JP2023144832A - Resin for decorative sheet containing ionomer - Google Patents

Abstract

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

Description

The present invention relates to a resin for decorative sheets with good chemical resistance and a decorative board using the resin for decorative sheets. More specifically, the present invention relates to a decorative sheet with excellent chemical resistance, heat resistance, and abrasion resistance in a well-balanced manner. This invention relates to an ionomer suitable as a resin that can provide

In recent years, ionomers have been widely used as resins for decorative sheets. This ionomer is an ionic copolymer consisting of an olefin such as ethylene and an unsaturated carboxylic acid such as acrylic acid, methacrylic acid, or maleic acid. It is neutralized with metal ions (Patent Document 1).

Conventionally, heat resistance, scratch resistance, and chemical resistance have been required for the skin materials of building interior materials (fittings, floors, walls, etc.), the interior and exterior of automobiles, and the skin materials of daily necessities. is known to use films containing ionomers. Specifically, a decorative sheet having a film containing an ionomer as a transparent resin layer may be used as the skin material.

Currently, commercially available ionomers include ``Surlyn (registered trademark)'', a sodium salt and zinc salt of ethylene-methacrylic acid copolymer developed by DuPont, and ``Surlyn (registered trademark)'', which is sold by Mitsui-Dow Polychemical Company. Hymilan (registered trademark)" and the like are known.

The ethylene-unsaturated carboxylic acid copolymer used as the base resin for these currently commercially available ionomers is a polar polymer made by polymerizing ethylene and a polar group-containing monomer such as an unsaturated carboxylic acid using a high-pressure radical polymerization method. Group-containing olefin copolymers have been used. The molecular structure of this polar group-containing olefin copolymer produced by high-pressure radical polymerization is a structure with many long chain branches and short chain branches irregularly, as shown in the image diagram shown in Figure 1. It has the disadvantage of insufficient chemical resistance, heat resistance, and abrasion resistance.

Patent Document 2 discloses a method of crosslinking an ionomer by irradiating the ionomer with an electron beam for the purpose of improving heat resistance.

US Patent No. 3,264,272 JP2020-050724A

Although these methods have yielded ionomers with excellent heat resistance, only heat resistance and abrasion resistance have been substantially studied, and there is no description regarding chemical resistance, which is originally required for decorative sheets. do not have. Further, crosslinking with electron beams leads to an increase in cost. In view of the above circumstances, there has been a desire for an ionomer that independently has excellent chemical resistance and has excellent abrasion resistance, heat resistance, and chemical resistance in a well-balanced manner, and a resin for decorative sheets using the same.

In view of the state of the prior art, the purpose of the present application is to provide a resin for decorative sheets using an ionomer that has significantly superior chemical resistance and has good chemical resistance, abrasion resistance, and heat resistance. do.

In order to solve the above problem, the present inventors have developed a linear structure that has a phase angle δ of 50 degrees to 75 degrees at the absolute value G* of the complex modulus of elasticity measured with a rotational rheometer = 0.1 MPa. We have discovered that certain ionomers have better chemical resistance, abrasion resistance, and heat resistance than conventional ionomers whose base resin is an olefin copolymer containing polar groups produced by high-pressure radical polymerization, and we have developed a specific ionomer for use in decorative sheets. It has been found that this method has the effect of improving the physical properties required for resins.

That is, the present invention provides a structural unit (A) derived from ethylene and/or an α-olefin having 3 to 20 carbon atoms, and a structural unit (B) derived from a monomer having a carboxyl group and/or a dicarboxylic acid anhydride group. In the copolymer (P) containing as an essential structural unit, at least a part of the carboxyl group and/or dicarboxylic acid anhydride group is at least one metal ion selected from Group 1, Group 2, or Group 12 of the Periodic Table. is converted into a metal-containing carboxylate containing , and is characterized in that the phase angle δ at the absolute value of the complex modulus G ^* = 0.1 MPa measured with a rotary rheometer is 50 degrees to 75 degrees. A resin for decorative sheets containing ionomer.
Further, in one aspect of the present invention, the number of methyl branches calculated by ¹³ C-NMR of the copolymer (P) is 50 or less per 1,000 carbons.
In one aspect of the present invention, the copolymer (P) contains 1 to 20 mol% of the structural unit (B) in the copolymer.
In one aspect of the present invention, the structural unit (A) is a structural unit derived from ethylene.
One aspect of the present invention is characterized in that the copolymer (P) is produced using a transition metal catalyst containing a transition metal from Groups 8 to 11 of the periodic table. Furthermore, one aspect of the present invention is characterized in that the transition metal catalyst is a transition metal catalyst consisting of a phosphorus sulfonic acid or phosphophenol ligand and nickel or palladium.
In one aspect of the present invention, the copolymer (P) has a crystallinity of 50% or less, preferably 10% or less.
Furthermore, one aspect of the present invention is a resin composition for a decorative sheet, comprising the resin for a decorative sheet. Moreover, one aspect of the present invention is a resin layer for a decorative sheet using the resin for a decorative sheet or the resin composition for a decorative sheet. Furthermore, one aspect of the present invention is a decorative sheet made of a laminate including at least a base material layer and the resin layer, and a laminate made of a laminate including a decorative laminate base material and the decorative sheet. It is a decorative board.

According to the present invention, by using an ionomer that has a substantially linear structure, it has much better chemical resistance than when using a conventional ionomer that has a multi-branched structure. It is possible to provide a resin for decorative sheets that has well-balanced and excellent abrasion resistance and heat resistance.

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

The present invention essentially comprises a structural unit (A) derived from ethylene and/or an α-olefin having 3 to 20 carbon atoms, and a structural unit (B) derived from a monomer having a carboxyl group and/or a dicarboxylic acid anhydride group. At least a part of the carboxyl group and/or dicarboxylic acid anhydride group in the copolymer (P) contained as a unit contains at least one metal ion selected from Group 1, Group 2, or Group 12 of the Periodic Table. Contains an ionomer that has been converted into a metal-containing carboxylic acid salt and has a phase angle δ of 50 degrees to 75 degrees at an absolute value G* of complex modulus of elasticity of 0.1 MPa measured with a rotary rheometer. , a resin for decorative sheets.

Hereinafter, the decorative sheet resin of the present invention and the ionomer related thereto will be explained in detail for each item. In addition, in this specification, "(meth)acrylic acid" means acrylic acid or methacrylic acid. Furthermore, in this specification, "~" indicating a numerical range is used to include the numerical values written before and after it as a lower limit value and an upper limit value. Moreover, in this specification, a copolymer means a binary or more copolymer containing at least one type of unit (A) and at least one type of unit (B).
In addition, in this specification, the ionomer includes the structural unit (A) and a structural unit (B') in which at least a part of the structural unit (B) is converted to a metal-containing carboxylate, Furthermore, it refers to an ionomer of a binary or more copolymer which may further contain the structural unit (B).

1. Ionomer The ionomer of the present invention comprises a structural unit (A) derived from ethylene and/or an α-olefin having 3 to 20 carbon atoms, and a structural unit (B) derived from a monomer having a carboxyl group and/or a dicarboxylic acid anhydride group. ) as essential structural units, a copolymer (P) in which these are substantially linearly randomly copolymerized is used as a base resin, and the carboxyl group and/or dicarboxylic acid anhydride group of the structural unit (B) is used as a base resin. is characterized in that at least a part of it is converted into a metal-containing carboxylate containing at least one metal ion selected from Groups 1, 2, or 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 α-olefins having 3 to 20 carbon atoms.
The α-olefin related to the present invention is an α-olefin having 3 to 20 carbon atoms and is represented by the structural formula: CH ₂ =CHR ¹⁸ (R ¹⁸ is a hydrocarbon group having 1 to 18 carbon atoms, and is a straight-chain structure or may have branches). The α-olefin preferably has 3 to 12 carbon atoms.

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. etc., and ethylene may also be used. As ethylene, ethylene derived from petroleum raw materials as well as non-petroleum raw materials such as vegetable raw materials can be used.
Further, the structural unit (A) may be one type or multiple types.
Examples of the combination of the two types include ethylene-propylene, ethylene-1-butene, ethylene-1-hexene, ethylene-1-octene, propylene-1-butene, propylene-1-hexene, and propylene-1-octene. can be mentioned.
Examples of the three combinations include ethylene-propylene-1-butene, ethylene-propylene-1-hexene, ethylene-propylene-1-octene, propylene-1-butene-hexene, and propylene-1-butene-1-octene. etc.

In the present invention, the structural unit (A) preferably essentially contains ethylene, and may further contain one or more α-olefins having 3 to 20 carbon atoms, if necessary.
Ethylene in the structural unit (A) may be 50 to 100 mol%, 70 to 100 mol%, or 90 to 100 mol%, based on the total mol of the structural unit (A). good.
From the viewpoint of chemical resistance, the first 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 acid anhydride group. Note that the structural unit (B) represents the same structure as the structural unit derived from a monomer having a carboxy group and/or a dicarboxylic acid anhydride group, and as described in the production method below, it does not necessarily include a carboxy group and/or a dicarboxylic acid anhydride group. Alternatively, it may not be produced using a monomer having a dicarboxylic anhydride group.

Examples of structural units derived from monomers having a carboxyl group include acrylic acid, methacrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, norbornenedicarboxylic acid, bicyclo[2, Unsaturated carboxylic acids such as 2,1]hept-2-ene-5,6-dicarboxylic acid, and structural units derived from monomers having dicarboxylic anhydride groups include, for example, maleic anhydride and 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, 2,7-octadien-1-ylsuccinic anhydride, and other unsaturated dicarboxylic anhydrides.
The structural unit derived from a monomer having a carboxyl group and/or a dicarboxylic acid anhydride group is preferably acrylic acid, methacrylic acid, or 5-norbornene-2,3-dicarboxylic anhydride from the viewpoint of industrial availability. Examples include structural units derived from substances, and in particular, structural units derived from acrylic acid.
Further, the number of structural units derived from monomers having carboxyl groups and/or dicarboxylic acid anhydride groups may be one type or multiple types.

Note that the dicarboxylic anhydride group may react with moisture in the air and open the ring, and a portion of the dicarboxylic acid anhydride group may become dicarboxylic acid. However, within the scope of the invention, the dicarboxylic anhydride group may be The ring may be open.

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

［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 monomer

[In general formula (1), T ¹ to T ³ each independently represent 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, or 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 of ~20, a hydrocarbon group having 3 to 20 carbon atoms substituted with an ester group having 2 to 20 carbon atoms, a 1 carbon group substituted with a halogen atom -20 hydrocarbon group, C1-20 alkoxy group, C6-20 aryl group, C2-20 ester group, C3-20 silyl group, halogen atom, or a substituent selected from the group consisting of cyano group,
^T4 is 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, or an ester group having 2 to 20 carbon atoms. Substituted hydrocarbon group having 3 to 20 carbon atoms, halogen atom-substituted hydrocarbon group having 1 to 20 carbon atoms, alkoxy group having 1 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, 2 carbon atoms The substituent is selected from the group consisting of an ester group having 1 to 20 carbon atoms, a silyl group having 3 to 20 carbon atoms, a halogen atom, or a cyano group. ]

The carbon skeletons of the hydrocarbon groups, substituted alkoxy groups, substituted ester groups, alkoxy groups, aryl groups, ester groups, and silyl groups related to T ¹ to T ⁴ may have branches, rings, and/or unsaturated bonds. good.
The lower limit of the number of carbon atoms in the hydrocarbon group related to T ¹ to T ⁴ may be 1 or more, and the upper limit may be 20 or less, and 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, and may be 10 or less.
The lower limit of the number of carbon atoms in the substituted ester group regarding T ¹ to T ⁴ may be 2 or more, and the upper limit may be 20 or less, and may be 10 or less.
The lower limit of the number of carbon atoms in the alkoxy group related to T ¹ to T ⁴ may be 1 or more, and the upper limit may be 20 or less, and may be 10 or less.
The lower limit of the number of carbon atoms in the aryl group related to T ¹ to T ⁴ may be 6 or more, and the upper limit may be 20 or less, and 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, and may be 10 or less.
The lower limit of the number of carbon atoms in the silyl group related to T ¹ to T ⁴ may be 3 or more, and the upper limit may be 18 or less, and may be 12 or less. Examples of the silyl group include trimethylsilyl group, triethylsilyl group, trin-propylsilyl group, triisopropylsilyl group, dimethylphenylsilyl group, methyldiphenylsilyl group, and 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, and T ¹ to T ³ are Both may be hydrogen atoms.
Furthermore, from the viewpoint of chemical resistance, T ⁴ may be an ester group having 2 to 20 carbon atoms.

Specific examples of the acyclic monomer include (meth)acrylic acid ester, etc., where T ⁴ is an ester group having 2 to 20 carbon atoms.
When T ⁴ is an ester group having 2 to 20 carbon atoms, examples of the acyclic monomer include a compound 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, and may have a branch, a ring, and/or an unsaturated bond. R ²² is a hydrocarbon group having 1 to 20 carbon atoms, and may have a branch, a ring, and/or an unsaturated bond. Furthermore, a heteroatom may be contained at any position within ^R22 .
Examples of the compound 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. Further examples include acrylic esters in which R ²¹ is a hydrogen atom or methacrylic esters in which R ²¹ is a methyl group.
Specific examples of compounds represented by the structural formula: CH ₂ =C(R ²¹ )CO ₂ (R ²² ) include methyl (meth)acrylate, ethyl (meth)acrylate, and n-(meth)acrylate. -Propyl, 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, Examples include 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. In particular, n-butyl acrylate (nBA), isobutyl acrylate (iBA), and t-butyl acrylate (tBA) may be used.
Note that the number of acyclic monomers may be one type or 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 monomer

[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 combined to form a divalent organic group, and R ⁹ or R ¹⁰ and R ¹¹ or R ¹² each have a ring. It may be formed.
Further, 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, ethylidene norbornene, norbornadiene, tetracyclododecene, tricyclo[4.3.0.1 ^2,5 ], tricyclo[4.3.0. Examples include compounds having a cyclic olefin skeleton such as 2 ^- norbornene (NB) and tetracyclo[6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, etc.

(4) Metal ion Examples of the metal ion of the carboxylic acid base include divalent metal ions selected from the group consisting of Group 1, Group 2, and Group 12 of the periodic table, and specifically, lithium ( Li), sodium (Na), potassium (K), rubidium (Rb), beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), radium (Ra), and Examples include zinc (Zn) ions, and from the viewpoint of ease of handling, sodium (Na), magnesium (Mg), calcium (Ca), or zinc (Zn) ions may also be used.
The carboxylic acid group can be added to the copolymer by, for example, hydrolyzing or thermally decomposing the ester group of the copolymer, or by reacting it with a compound containing the above-mentioned metal ion while hydrolyzing or thermally decomposing the ester group of the copolymer. It can be obtained by converting the ester group moiety of into a metal-containing carboxylate.
Note that the number of metal ions may be one type or multiple types.

(5) Copolymer (P)
The copolymer (P) serving as the base resin of the ionomer used in the present invention contains a structural unit (A) derived from ethylene and/or an α-olefin having 3 to 20 carbon atoms, and a carboxyl group and/or dicarboxylic acid anhydride. The structural unit (B) derived from a monomer having a group is an essential structural unit, and further optionally contains an optional structural unit (C), and each of these structural units is copolymerized in a substantially linear manner, preferably randomly. It is characterized by being copolymerized. "Substantially linear" refers to a state in which the copolymer has no branching or a branched structure appears infrequently, so that the copolymer can be considered to be linear. Specifically, it refers to a state in which the phase angle δ of the copolymer is 50 degrees or more.

The copolymer related to the present invention must contain one or more types of structural units (A) and one or more types of structural units (B), and must contain two or more types of monomer units in total, and other structural units (C ) may be included.
The structural units and amount of structural units of the copolymer related to the present invention will be explained.
A structure derived from one molecule each of ethylene and/or an α-olefin having 3 to 20 carbon atoms (A), a monomer (B) having a carboxyl group and/or a dicarboxylic acid anhydride group, and an arbitrary monomer (C), Defined as one structural unit in a copolymer.
The amount of structural units is the ratio of each structural unit expressed in mol% when the total amount of structural units in the copolymer is 100 mol%.

Amount of structural units of ethylene and/or α-olefin having 3 to 20 carbon atoms (A):
The lower limit of the structural unit amount of the structural unit (A) related to the present invention is 60.0 mol% or more, preferably 70.0 mol% or more, more preferably 80.0 mol% or more, still more preferably 85.0 mol% or more, and More preferably 90.0 mol% or more, particularly preferably 95.0 mol% or more, and the upper limit is 99.0 mol% or less, preferably 98.0 mol% or less, more preferably 97.0 mol% or less, still more preferably 96.0 mol% or less. Selected from 5 mol% or less.
If the amount of structural units derived from ethylene and/or α-olefin (A) having 3 to 20 carbon atoms is less than 60.0 mol%, the copolymer will have poor toughness, and if it is more than 99.0 mol%, the copolymer will have poor toughness. The degree of crystallinity may increase and the transparency may deteriorate.

- Structural unit amount of monomer (B) having carboxyl group and/or dicarboxylic acid anhydride group:
The lower limit of the structural unit amount of the structural unit (B) related to the present invention is 1.0 mol% or more, preferably 2.0 mol% or more, more preferably 3.0 mol% or more, still more preferably 3.5 mol% or more, 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, most preferably 5.3 mol%. Selected from:
If the amount of structural units derived from the monomer (B) having a carboxyl group and/or a dicarboxylic acid anhydride group is less than 1.0 mol%, the copolymer will not have sufficient adhesion to a highly polar dissimilar material; If the amount is more than 20.0 mol%, sufficient mechanical properties of the copolymer may not be obtained.
Further, the monomer having a carboxyl group and/or dicarboxylic acid anhydride group may be used alone, or two or more types may be used in combination.

・Amount of structural units of other monomers (C):
The upper limit of the structural unit amount of the structural unit (C) related to the present invention is 20.0 mol% or less, preferably 15.0 mol% or less, more preferably 10.0 mol% or less, still more preferably 5.0 mol% or less, especially It is preferably selected from 3.0 mol% or less, and there is no particular restriction on the lower limit, and it may be 0 mol%. When the amount of structural units derived from the arbitrary monomer (C) is 20.0 mol % or less, sufficient mechanical properties of the copolymer are likely to be obtained.
Furthermore, the arbitrary monomer (C) used may be used alone or in combination of two or more types.

Number of branches per 1,000 carbons of copolymer (P):
In the copolymer of the present invention, in order to increase the elastic modulus and obtain sufficient mechanical properties, the upper limit of the number of methyl branches calculated by ¹³ C-NMR is 50 or less per 1,000 carbons. The number may be 5.0 or less, 1.0 or less, 0.5 or less, and the lower limit is not particularly limited. good. The upper limit of the number of ethyl branches per 1,000 carbon atoms may be 3.0 or less, 2.0 or less, 1.0 or less, or 0.5 The lower limit is not particularly limited, and the lower the number, the better. Furthermore, the upper limit of the number of butyl branches per 1,000 carbons may be 7.0 or less, 5.0 or less, 3.0 or less, or 0.5 The lower limit is not particularly limited, and the lower the number, the better.

Method for measuring the amount of structural units derived from monomers having a carboxy group and/or dicarboxylic acid anhydride group and acyclic monomers and the number of branches in the copolymer:
The amount of structural units derived from the monomer having a carboxy group and/or dicarboxylic acid anhydride group and the acyclic monomer in the copolymer of the present invention, and the number of branches per 1,000 carbon atoms are determined by the ¹³ C-NMR spectrum. It can be found using ¹³ C-NMR is measured by the following method.
200 to 300 mg of the sample was dissolved in 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)) 2.4 ml and hexamethyldisiloxane, which is a reference substance for chemical shift, are placed in an NMR sample tube with an inner diameter of 10 mmφ, purged with nitrogen, sealed, and heated to dissolve as a homogeneous solution as an NMR measurement sample. shall be.
NMR measurements are carried out at 120° C. using an AV400M NMR apparatus manufactured by Bruker Japan Co., Ltd. equipped with a 10 mmφ cryoprobe.
¹³ C-NMR is measured using a reverse gate decoupling method at a sample temperature of 120° C., a pulse angle of 90°, a pulse interval of 51.5 seconds, and an integration count of 512 or more times.
For the chemical shift, the ¹³ C signal of hexamethyldisiloxane is set at 1.98 ppm, and the chemical shifts of other ¹³ C signals are based on this.
In the obtained ^13C -NMR, the amount of structural units of each monomer in the copolymer and the number of branches can be analyzed by identifying signals specific to the monomers or branches possessed by the copolymer and comparing their intensities. can do. The positions of signals specific to monomers or branches can be determined with reference to known materials, or can be independently identified depending on the sample. Such analysis techniques can be commonly performed by those skilled in the art.

・Weight average molecular weight (Mw) and molecular weight distribution (Mw/Mn):
The lower limit of the weight average molecular weight (Mw) of the copolymer related to the present invention is usually 1,000 or more, preferably 6,000 or more, more preferably 10,000 or more, and the upper limit is usually 2,000 or more, and more preferably 10,000 or more. 000,000 or less, preferably 1,500,000 or less, more preferably 1,000,000 or less, particularly preferably 800,000 or less, 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 not be sufficient, and if the Mw exceeds 2,000,000, the melt viscosity of the copolymer will be extremely high, and the copolymer will have insufficient physical properties such as mechanical strength and impact resistance. It may be difficult to form the combined product.

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

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

An example of the GPC measurement method related to the present invention is as follows.
(Measurement condition)
Model used: Waters 150C
Detector: FOXBORO MIRAN1A IR detector (measurement wavelength: 3.42 μm)
Measurement temperature: 140℃
Solvent: Orthodichlorobenzene (ODCB)
Column: Showa Denko AD806M/S (3 columns)
Flow rate: 1.0mL/min Injection volume: 0.2mL
(Preparation of sample)
For the sample, a 1 mg/mL solution was prepared using ODCB (containing 0.5 mg/mL BHT (2,6-di-t-butyl-4-methylphenol)) and heated at 140°C for about 1 hour. and dissolve.
(Calculation of molecular weight (M))
The standard polystyrene method is used, and the retention capacity is converted to molecular weight using a standard polystyrene calibration curve prepared in advance. The standard polystyrene used is, for example, brands (F380, F288, F128, F80, F40, F20, F10, F4, F1, A5000, A2500, A1000) manufactured by Tosoh Corporation, and monodispersed polystyrene (S-7300 manufactured by Showa Denko). , 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 created by injecting 0.2 mL of a solution dissolved in ODCB (containing 0.5 mg/mL BHT) so that each concentration is 0.5 mg/mL. As the calibration curve, a cubic equation obtained by approximation using the least squares method, or a quartic equation obtained by approximating the logarithm of elution time and molecular weight is used. The following numerical value is used for the viscosity formula [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 an endothermic curve measured by a differential scanning calorimeter (DSC). The maximum peak temperature is the height from the baseline when multiple peaks are shown in the endothermic curve obtained when the vertical axis is heat flow (mW) and the horizontal axis is temperature (℃) in DSC measurement. Indicates the temperature of the peak where is the maximum, and if there is one peak, indicates 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 will not be sufficient, and if it is higher than this range, the adhesiveness may be poor.
In the present invention, the melting point is determined by, for example, using a DSC (DSC7020) manufactured by SII Nanotechnology Co., Ltd., packing approximately 5.0 mg of a sample into an aluminum pan, and heating the sample to 200°C at a rate of 10°C/min. It can be determined from the absorption curve when the temperature is maintained isothermally at ℃ for 5 minutes, lowered to 20℃ at a rate of 10℃/min, held isothermally at 20℃ for 5 minutes, and then raised again to 200℃ at a rate of 10℃/min. .

・Crystallinity (%):
In the copolymer of the present invention, the degree of crystallinity observed by differential scanning calorimetry (DSC) is not particularly limited, but preferably exceeds 0%. More preferably, it exceeds 5%, and still more preferably 7% or more. If the crystallinity is 0%, the copolymer may not have sufficient toughness. The degree of crystallinity is also an index of transparency, and although transparency is preferable, the upper limit of the degree of crystallinity is not particularly limited.
In the present invention, the degree of crystallinity can be determined by determining the heat of fusion (ΔH) from the area of the endothermic melting peak obtained by DSC measurement using the same procedure as the measurement of the melting point above, and calculating the heat of fusion by determining the heat of fusion of high-density polyethylene (HDPE). It can be determined by dividing by the heat of fusion of the crystal, 293 J/g.

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

In addition, the copolymer related to the present invention includes a structural unit (A) of ethylene and/or an α-olefin having 3 to 20 carbon atoms, and a structural unit (B) of a monomer having a carboxyl group and/or a dicarboxylic acid anhydride group. , and random copolymers, block copolymers, and graft copolymers of the structural unit (C) of any monomer. Among these, random copolymers that can contain a large amount of the structural unit (B) may be used.
An example (1) of the molecular structure of a common ternary copolymer is shown below.
A random copolymer has a structural unit (A) of ethylene and/or an α-olefin having 3 to 20 carbon atoms and a carboxyl group and/or a dicarboxylic acid anhydride group in the molecular structure example (1) shown below. The probability that the monomer structural unit (B) and any monomer structural unit (C) will find each structural unit at a certain arbitrary position in the molecular chain is independent of the type of adjacent structural unit. It is a combination.
As shown below, the molecular structure example (1) of the copolymer is a monomer having a structural unit (A) of ethylene and/or an α-olefin having 3 to 20 carbon atoms and a carboxyl group and/or a dicarboxylic acid anhydride group. The structural unit (B) and the structural unit (C) of an arbitrary monomer form a random copolymer.

For reference, example (2) of the molecular structure of a copolymer into which a structural unit (B) of a monomer having a carboxyl group and/or a dicarboxylic acid anhydride group is introduced by graft modification shows that ethylene and/or 3 carbon atoms A part of the copolymer obtained by copolymerizing ~20 α-olefin structural units (A) and arbitrary monomer structural units (C) is a monomer having a carboxyl group and/or a dicarboxylic acid anhydride group. The structural unit (B) is graft-modified.

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

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

Further, the copolymer related to the present invention is preferably produced in the presence of a transition metal catalyst from the viewpoint of having a linear molecular structure.
It is known that the molecular structure of a copolymer differs depending on the production method, such as polymerization using a high-pressure radical polymerization process or polymerization using a metal catalyst.
This difference in molecular structure can be controlled by selecting the manufacturing method, but it can also be controlled by the complex modulus measured with a rotary rheometer, as described in JP-A-2010-150532. Molecular structure can be estimated.

・Phase angle δ at absolute value G ^* = 0.1 MPa of complex modulus:
In the copolymer of the present invention, the lower limit of the phase angle δ at the absolute value G ^* =0.1 MPa of the complex modulus measured with a rotary rheometer may be 50 degrees or more, and may be 51 degrees or more. The angle may be 54 degrees or more, 56 degrees or more, 58 degrees or more, and the upper limit may be 75 degrees or less, or 70 degrees or less.
More specifically, if the phase angle δ (G ^* = 0.1 MPa) at the absolute value G ^* = 0.1 MPa of the complex modulus measured with a rotary rheometer is 50 degrees or more, the molecular structure of the copolymer is a linear structure that does not contain any long chain branches or a structure that contains a small amount of long chain branches that does not affect mechanical strength.
In addition, if the phase angle δ (G ^* = 0.1 MPa) at the absolute value of the complex modulus G ^* = 0.1 MPa measured with a rotary rheometer is lower than 50 degrees, the molecular structure of the copolymer has long chain branching. It exhibits a structure containing excessive amounts of carbon dioxide, resulting in poor mechanical strength.
The phase angle δ at the absolute value G ^* =0.1 MPa of the complex modulus measured with a rotary rheometer is influenced by both the molecular weight distribution and the long chain branching. However, limited to copolymers with Mw/Mn≦4, more preferably Mw/Mn≦3, it is an indicator of the amount of long chain branching, and the more long chain branches included in the molecular structure, the more δ(G ^* = 0.1 MPa) value becomes smaller. Note that if the Mw/Mn of the copolymer is 1.5 or more, the δ (G ^* = 0.1 MPa) value will never exceed 75 degrees even if the molecular structure does not include long chain branches. do not have.

The method for measuring the complex modulus of elasticity is as follows.
The sample was placed in a hot press mold with a thickness of 1.0 mm, and after preheating for 5 minutes in a hot press machine with a surface temperature of 180°C, residual gas in the molten resin was degassed by repeating pressurization and depressurization. Apply pressure to 4.9 MPa and hold for 5 minutes. Thereafter, the sample was transferred to a press machine with a surface temperature of 25° C., and cooled by being held at a pressure of 4.9 MPa for 3 minutes to create a press plate made of the sample with a thickness of about 1.0 mm. The sample was a pressed plate made into a circle with a diameter of 25 mm, and the dynamic viscoelasticity was measured under the following conditions in a nitrogen atmosphere using an ARES type rotary rheometer manufactured by Rheometrics as a measuring device for dynamic viscoelasticity. Measure.
・Plate: φ25mm parallel plate ・Temperature: 160℃
・Distortion amount: 10%
・Measurement angular frequency range: 1.0×10 ^-2 to 1.0×10 ² rad/s
・Measurement interval: 5 points/decade
Plot the phase angle δ against the common logarithm logG ^* of the absolute value G ^* (Pa) of the complex modulus of elasticity, and calculate the value of δ (degrees) at the point corresponding to logG ^* =5.0 as δ(G ^* =0 .1 MPa). If there is no point corresponding to logG ^* =5.0 among the measurement points, the δ value at logG ^* =5.0 is determined by linear interpolation using two points around logG ^* =5.0. Furthermore, when logG ^* <5 at all measurement points, the δ value at logG ^* =5.0 is extrapolated and determined using a quadratic curve using the values of the three points with the largest logG ^* value.

- Regarding production of copolymer The copolymer related to the present invention is preferably produced in the presence of a transition metal catalyst from the viewpoint of making the molecular structure linear.

・Polymerization catalyst The type of polymerization catalyst used in the production of the copolymer related to the present invention is one that can copolymerize the structural unit (A), the structural unit (B), and any structural unit (C). Although not particularly limited, examples include transition metal compounds of Groups 5 to 11 having a chelating ligand.
Specific examples of preferred transition metals include vanadium atom, niobium atom, tantalum atom, chromium atom, molybdenum atom, tungsten atom, manganese atom, iron atom, platinum atom, ruthenium atom, cobalt atom, rhodium atom, nickel atom, and palladium atom. , copper atoms, etc. Among these, transition metals of Groups 8 to 11 are preferred, transition metals of Group 10 are more preferred, and nickel (Ni) and palladium (Pd) are particularly preferred. These metals may be used alone or in combination.
The chelating ligand has at least two atoms selected from the group consisting of P, N, O, and S, and is bidentate or multidentate. Contains a ligand and is electronically neutral or anionic. Structures of chelating ligands are illustrated in a review by Brookhart et al. (Chem. Rev., 2000, 100, 1169).
Preferably, the chelating ligand includes a bidentate anionic P, O ligand. Examples of bidentate anionic P, O ligands include phosphorus sulfonic acid, phosphorus carboxylic acid, phosphorus phenol, and phosphorus enolate. Other examples of the chelating ligand include bidentate anionic N, O ligands. Examples of bidentate anionic N, O ligands include salicylaldoiminate and pyridinecarboxylic acid. Other chelating ligands include diimine ligands, diphenoxide ligands, diamide ligands, and the like.

［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 that may have a substituent is coordinated. Ru.

[In structural formula (a) and structural formula (b),
M represents a transition metal belonging to any of Groups 5 to 11 of the periodic table of elements, ie, various transition metals as described above.
X ¹ represents oxygen, sulfur, -SO ₃ -, or -CO ₂ -.
Y ¹ represents carbon or silicon.
n represents an integer of 0 or 1.
E ¹ represents phosphorus, arsenic or antimony.
R ⁵³ and R ⁵⁴ each independently represent hydrogen or a hydrocarbon group which may contain a hetero atom having 1 to 30 carbon atoms.
R ⁵⁵ each independently represents hydrogen, halogen, or a hydrocarbon group which may contain a heteroatom having 1 to 30 carbon atoms.
R ⁵⁶ and R ⁵⁷ are each independently hydrogen, halogen, a hydrocarbon group which may contain a heteroatom having 1 to 30 carbon atoms, 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 hydrogen or a hydrocarbon group having 1 to 20 carbon atoms.
R ⁵² represents a hydrocarbon group having 1 to 20 carbon atoms.
M' represents an alkali metal, an alkaline earth metal, ammonium, quaternary ammonium or phosphonium, x represents an integer from 0 to 3, and y represents an integer from 0 to 2.
Note that R ⁵⁶ and R ⁵⁷ may be connected to each other to form an alicyclic ring, an aromatic ring, or a heterocycle containing a heteroatom selected from oxygen, nitrogen, or sulfur. At this time, the number of ring members is 5 to 8, and the ring may or may not have a substituent.
L ¹ represents a ligand coordinated to M.
Furthermore, R ⁵³ and L ¹ may be combined with 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。］ More preferred 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 elements, ie, various transition metals as described above.
X ¹ represents oxygen, sulfur, -SO ₃ -, or -CO ₂ -.
Y ¹ represents carbon or silicon.
n represents an integer of 0 or 1.
E ¹ represents phosphorus, arsenic or antimony.
R ⁵³ and R ⁵⁴ each independently represent hydrogen or a hydrocarbon group which may contain a hetero atom having 1 to 30 carbon atoms.
R ⁵⁵ each independently represents hydrogen, halogen, or a hydrocarbon group which may contain a heteroatom having 1 to 30 carbon atoms.
R ⁵⁸ , R ⁵⁹ , R ⁶⁰ and R ⁶¹ each independently represent hydrogen, halogen, a hydrocarbon group which may contain a hetero atom having 1 to 30 carbon atoms, 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 hydrogen or a hydrocarbon group having 1 to 20 carbon atoms.
R ⁵² represents a hydrocarbon group having 1 to 20 carbon atoms.
M' represents an alkali metal, an alkaline earth metal, ammonium, quaternary ammonium or phosphonium, x represents an integer from 0 to 3, and y represents an integer from 0 to 2.
Note that a plurality of groups appropriately selected from R ⁵⁸ to R ⁶¹ are connected to each other to form an alicyclic ring, an aromatic ring, or a heterocycle containing a heteroatom selected from oxygen, nitrogen, or sulfur. Good too. At this time, the number of ring members is 5 to 8, and the ring may or may not have a substituent.
L ¹ represents a ligand coordinated to M.
Furthermore, R ⁵³ and L ¹ may be combined with each other to form a ring. ]

Here, as catalysts for Groups 5 to 11 transition metal compounds having chelating ligands, catalysts such as so-called SHOP catalysts and Drent catalysts are typically known.
A SHOP-based catalyst is a catalyst in which a phosphorus-based ligand having an aryl group that may have a substituent is coordinated to nickel metal (see, for example, WO2010-050256).
Further, the Drent-based catalyst is a catalyst in which a phosphorus-based ligand having an aryl group that may have a substituent is coordinated to palladium metal (see, for example, JP-A-2010-202647).

・Polymerization method of copolymer:
The method of polymerizing the copolymer related to the present invention is not limited.
Polymerization methods include slurry polymerization in which at least part of the produced polymer becomes a slurry in a medium, bulk polymerization in which the liquefied monomer itself is used as a medium, gas phase polymerization in a vaporized monomer, or liquefaction at high temperature and high pressure. Examples include high-pressure ionic polymerization in which at least a portion of the produced polymer is dissolved in the monomer.
The polymerization format may be batch polymerization, semi-batch polymerization, or continuous polymerization.
Furthermore, living polymerization may be performed, or polymerization may be performed while chain transfer is occurring simultaneously.
Furthermore, during polymerization, a so-called chain shuttling agent (CSA) may be used in combination to perform chain shuttling reaction or cooperative chain transfer polymerization (CCTP).
Specific manufacturing processes and conditions are disclosed in, for example, Japanese Patent Laid-Open Nos. 2010-260913 and 2010-202647.

・Method for introducing carboxyl group and/or dicarboxylic acid anhydride group into copolymer:
The method of introducing carboxyl groups and/or dicarboxylic acid anhydride groups into the copolymer related to the present invention is not particularly limited.
A carboxyl group and/or a dicarboxylic acid anhydride group can be introduced by various methods without departing from the gist of the present invention.
Methods for introducing carboxyl groups and/or dicarboxylic acid anhydride groups include, for example, a method of directly copolymerizing a comonomer having a carboxyl group and/or a dicarboxylic acid anhydride group, or a method of copolymerizing other monomers and then modifying them to form carboxyl groups. Examples include a method of introducing a group and/or a dicarboxylic acid anhydride group.

Methods for introducing carboxyl groups and/or dicarboxylic acid anhydride groups through modification include, for example, when introducing carboxylic acid, a method in which acrylic acid ester is copolymerized and then hydrolyzed to convert into carboxylic acid, and acrylic acid t- Examples include a method in which butyl is copolymerized and then converted into carboxylic acid by thermal decomposition.

In the above-mentioned hydrolysis or thermal decomposition, a conventionally known acid/base catalyst may be used as an additive for promoting the reaction. Acid/base catalysts are not particularly limited, but include hydroxides of alkali metals and alkaline earth metals such as sodium hydroxide, potassium hydroxide, and lithium hydroxide; alkali metals and alkaline earth metals such as sodium hydrogen carbonate and sodium carbonate; Carbonates of similar metals, solid acids such as montmorillonite, inorganic acids such as hydrochloric acid, nitric acid, and sulfuric acid, organic acids such as formic acid, acetic acid, benzoic acid, citric acid, p-toluenesulfonic acid, trifluoroacetic acid, and trifluoromethanesulfonic acid, etc. can be used as appropriate.
From the viewpoints of reaction promotion effect, price, corrosivity of equipment, etc., sodium hydroxide, potassium hydroxide, sodium carbonate, para-toluenesulfonic acid, and trifluoroacetic acid are preferred, and para-toluenesulfonic acid and trifluoroacetic acid are more preferred.

(6) Ionomer The ionomer according to the present invention is such that at least a part of the carboxyl group and/or dicarboxylic acid anhydride group of the structural unit (B) of the copolymer of the present invention is from Group 1, Group 2, or Group 12 of the Periodic Table. It is converted into a metal-containing carboxylate containing at least one selected metal ion, and the phase angle δ at the absolute value of the complex modulus G ^* = 0.1 MPa measured with a rotary rheometer is 50 degrees to 75 degrees. It is an ionomer with a substantially linear structure.

- Structure of ionomer Since the ionomer related to the present invention has a substantially linear structure like the copolymer related to the present invention, the absolute value of the complex modulus G ^* = 0.1 MPa measured with a rotary rheometer. The phase angle δ is in the range of 50 degrees to 75 degrees. When the phase angle δ (G ^* =0.1 MPa) is lower than 50 degrees, the molecular structure of the ionomer exhibits a structure containing too many long chain branches, resulting in poor mechanical strength. Furthermore, even when the molecular structure does not include long chain branches, the δ (G ^* =0.1 MPa) value does not exceed 75 degrees.
In the ionomer of the present invention, from the viewpoint of improving mechanical strength, the lower limit of the phase angle δ is preferably 51 degrees or more, more preferably 54 degrees or more, and still more preferably 56 degrees or more. It is preferably 58 degrees or more, and even more preferably, the upper limit is not particularly limited, and the closer it is to 75 degrees, the better.

-Metal ions The metal ions contained in the ionomer related to the present invention can include metal ions used in conventionally known ionomers. The metal ion is preferably a metal ion of Group 1, Group 2 or Group 12 of the periodic table, such as Li ⁺ , Na ⁺ , K ⁺ , Rb ⁺ , Be ²⁺ , Mg ²⁺ , Ca ²⁺ , Sr ²⁺ , Ba ²⁺ , Ra ²⁺ , and Zn ²⁺ is more preferred. Particularly preferred are Na ⁺ , K ⁺ , Mg ²⁺ , Ca ²⁺ , Ba ²⁺ and Zn ²⁺ , and more preferably at least one selected from the group consisting of Na ⁺ , Mg ⁺ and Zn ²⁺ .
Two or more types of these metal ions can be mixed and included if necessary.

・Neutralization degree (mol%)
The metal ion content preferably includes an amount that neutralizes at least some or all of the carboxyl groups and/or dicarboxylic anhydride groups in the copolymer as the base polymer, and preferably includes The degree of neutralization is 1 to 90 mol%, more preferably 5 to 85 mol%, even more preferably 10 to 80 mol%.
The degree of neutralization is determined from the ratio of the total mol amount of metal ion valence x mol amount to the total mol amount of carboxy groups that may be contained in the carboxy groups and/or dicarboxylic acid anhydride groups in the copolymer. be able to.
When forming a carboxylic acid salt, the dicarboxylic acid anhydride group opens the ring to become a dicarboxylic acid, so the total mol amount of the carboxylic groups is calculated assuming that there are 2 mol of carboxyl groups per 1 mol of the dicarboxylic anhydride group. . Further, assuming that divalent metal ions such as Zn ²⁺ can form a salt with 2 mol of carboxyl groups per 1 mol, the total mol amount of molecules of the degree of neutralization is calculated from 2×mol amount.
When the degree of neutralization is high, the tensile strength and tensile failure stress of the ionomer are high, and the tensile failure strain is low, but the melt flow rate (MFR) of the ionomer tends to be low. On the other hand, when the degree of neutralization is low, an ionomer with a suitable MFR can be obtained, but the tensile modulus and tensile stress at break are low, and the tensile break strain tends to be high.
If the degree of neutralization is lower than 1 mol%, the toughness (strength and impact resistance) of the ionomer may be insufficient, and if the degree of neutralization is higher than 90 mol%, the heat resistance may be insufficient.

・Chemical resistance of ionomer:
In the ionomer of the present invention, it is preferable that the mass increase rate as determined by the immersion test described in JIS K7114 (2001) is low, since the impact resistance of the ionomer is sufficient. The mass increase rate, which is a criterion for evaluating chemical resistance, is taken into account for each solvent, since the frequency of practical use and expected applications differ depending on the solvent. Because ammonia is reactive and has a small molecular weight, it has a greater effect on the amount of ionomer than other solvents. Further, since ethanol is used for disinfection, it is used frequently in practical use and comes into contact with a large amount. Therefore, it is preferable that these solvents have higher resistance than other solvents, that is, have a lower mass increase rate. Specifically, in the case of toluene, it is preferably less than 30%, more preferably less than 20%, and even more preferably less than 15%. In the case of ammonia, it is preferably less than 10%, more preferably less than 5%, and even more preferably less than 3.5%. In the case of ethyl acetate, it is preferably less than 5%, more preferably less than 4.0%, and even more preferably less than 3.5%. In the case of ethanol, it is preferably less than 1.5%, more preferably less than 1.3%, and even more preferably less than 1.0%. In the case of Fuel C, it is preferably less than 40%, more preferably less than 30%, and even more preferably less than 25%.

- Abrasion resistance of ionomer In the ionomer of the present invention, the abrasion loss amount described in JIS K7204-1999 is preferably less than 15 mg, and less than 7.0 mg, since the ionomer has sufficient abrasion resistance. More preferably, it is, and even more preferably less than 5.0 mg.

・Ionomer crystallinity (%):
In the ionomer of the present invention, the lower limit of the degree of crystallinity observed by differential scanning calorimetry (DSC) is preferably greater than 0%, and more preferably greater than 5%, in order to ensure sufficient toughness of the ionomer. It is preferably 7% or more, and from the viewpoint of the transparency of the ionomer, the upper limit is preferably 50% or less, more preferably 40% or less, and even more preferably 35% or less. . Note that the degree of crystallinity is an indicator of transparency, and it can be judged that the lower the degree of crystallinity of the ionomer, the better the transparency.

Since the ionomer of the present invention is excellent in chemical resistance, abrasion resistance, and heat resistance, it is preferable that the ionomer further has at least one of the above-mentioned chemical resistance, abrasion resistance, and heat resistance.

・Production method of ionomer The ionomer related to the present invention is ethylene and/or α-olefin having 3 to 20 carbon atoms obtained by the method of introducing a carboxyl group and/or dicarboxylic acid anhydride group into a copolymer as described above. / A conversion step in which a copolymer of unsaturated carboxylic acid is treated 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 it into a metal-containing carboxylate salt. It may be obtained by In addition, the ionomer related to the present invention is produced by heating ethylene and/or an α-olefin having 3 to 20 carbon atoms/unsaturated carboxylic acid ester copolymer to remove at least some of the ester groups in the copolymer from the periodic table. It may be obtained through a heating conversion step of converting into a metal-containing carboxylic acid salt containing at least one metal ion selected from Group 1, Group 2, or Group 12.

When producing an ionomer after introducing a carboxyl group and/or a dicarboxylic acid anhydride group into a polymer, the production method is, for example, as follows. That is, a metal ion supply source is prepared by kneading a substance that captures metal ions, such as an ethylene/(meth)acrylic acid ((M)AA) copolymer, and a metal salt, with some heating. It can be obtained by adding the metal ion supply source to the precursor resin in an amount that provides a desired degree of neutralization and kneading the mixture.

In the heat conversion step, (i) ethylene and/or the α-olefin having 3 to 20 carbon atoms/unsaturated carboxylic acid ester copolymer is heated, and the ethylene and/or the 3 to 20 carbon atoms are hydrolyzed or thermally decomposed. After forming an α-olefin/unsaturated carboxylic acid copolymer with a carbon number of ~20, by reacting it with a compound containing a metal ion of group 1, group 2, or group 12 of the periodic table, the ethylene and/or the copolymer with a carbon number of 3 to The carboxylic acid in the α-olefin/unsaturated carboxylic acid copolymer of 20 may be converted into the metal-containing carboxylate, and (ii) ethylene and/or α-olefin having 3 to 20 carbon atoms/ By heating an unsaturated carboxylic acid ester copolymer and reacting it with a compound containing a metal ion of Group 1, Group 2 or Group 12 of the Periodic Table while hydrolyzing or thermally decomposing the ester group of the copolymer. , the ester group moiety in the ethylene and/or α-olefin having 3 to 20 carbon atoms/unsaturated carboxylic acid ester copolymer may be converted to the metal-containing carboxylate.

Further, the metal ion-containing compound may be an oxide, hydroxide, carbonate, bicarbonate, acetate, formate, etc. of a metal from Group 1, Group 2, or Group 12 of the Periodic Table.
The compound containing metal ions may be supplied to the reaction system in the form of granules or fine powder, or may be supplied to the reaction system after being dissolved or dispersed in water or an organic solvent. A masterbatch using a polymer or olefin copolymer as a base polymer may be prepared and supplied to the reaction system. In order to make the reaction proceed smoothly, it is preferable to prepare a masterbatch and supply it to the reaction system.

Furthermore, the reaction with a compound containing metal ions may be carried out by melt-kneading using various types of equipment such as a vent extruder, a Banbury mixer, or a roll mill, and the reaction may be carried out in a batch or continuous manner. It is preferable to carry out the reaction continuously using an extruder equipped with a degassing device, such as a vent extruder, because the reaction can be carried out smoothly by discharging water and carbon dioxide by-produced by the reaction using a degassing device. .
When reacting with a compound containing metal ions, a small amount of water may be injected to accelerate 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 should be the temperature at which the ester becomes a carboxylic acid; if the heating temperature is too low, the ester becomes a carboxylic acid. If it is not converted to acid and the concentration is too high, decarbonylation and decomposition of the copolymer will proceed. Therefore, the heating temperature in the present invention is preferably 80°C to 350°C, more preferably 100°C to 340°C, even more preferably 150°C to 330°C, even more preferably 200°C to 320°C.

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

In the above step, although there is no particular restriction on the reaction atmosphere, it is generally preferable to carry out the reaction under an inert gas stream. Examples of inert gases that can be used include nitrogen, argon, and carbon dioxide atmospheres. A small amount of oxygen or air may be mixed in.

There is no particular restriction on the reactor used in the above step, and any method is not limited as long as it can stir the copolymer substantially uniformly. A glass container equipped with a stirrer or an autoclave (AC) may be used, or a conventionally known device such as a Brabender plastograph, single or twin screw extruder, high-power screw kneader, Banbury mixer, kneader, roll, etc. Any kneader can be used.

Whether metal ions have been introduced into the ionomer base 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). can do. The degree of neutralization can also be determined by calculating from the molar ratio mentioned above, as well as by 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 carboxylic acid base. , can be confirmed.

・Additives The ionomer related to the present invention includes conventionally known antioxidants, ultraviolet absorbers, lubricants, antistatic agents, colorants, pigments, crosslinking agents, blowing agents, and cores, within the scope of the gist of the present invention. Additives such as additives, flame retardants, conductive materials, and fillers may be added. These additives can be appropriately selected from materials used in the decorative sheet, and constitute the resin composition for the decorative sheet.

- Decorative sheet One embodiment of the present invention is composed of a laminate including at least a base sheet layer and a resin layer for a decorative sheet (resin layer of the present invention) using a resin or resin composition containing the above-mentioned ionomer. It is a decorative sheet. By including the resin layer of the present invention, the decorative sheet can have good chemical resistance, abrasion resistance, and heat resistance. The decorative sheet may further have a pattern layer, an adhesive layer, a surface protection layer, a primer layer, etc. laminated thereon. The resin layer of the present invention is usually provided between the adhesive layer and the surface protection layer.

<Base material sheet>
Examples of the base sheet include various resin films, paper, and resin-impregnated paper. A resin film made of thermoplastic resin is preferably used. Specific examples of thermoplastic resins include polyolefin resins such as polyethylene and polypropylene, acrylic resins such as acrylic esters and methacrylic esters, polyvinyl chloride, polyethylene terephthalate, polybutylene terephthalate, polyamide, polycarbonate, and polyethylene terephthalate. Examples include phthalate, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, and ethylene-acrylic acid ester copolymer.

Various additives such as colorants, fillers, matting agents, foaming agents, flame retardants, lubricants, antistatic agents, antioxidants, ultraviolet absorbers, light stabilizers, etc. are added to the base sheet as necessary. It may also contain an agent. Further, the surface of the base sheet may be subjected to corona discharge treatment according to known methods and conditions, if necessary, in order to improve the adhesion of the ink forming the picture pattern layer.
The thickness of the base sheet can be appropriately set depending on the purpose of the final product, how it is used, etc., but it is generally preferably in the range of 50 to 250 μm.

<Picture pattern layer>
The pattern layer imparts a desired pattern or design to the decorative sheet. The type of pattern is not limited, and any pattern such as wood grain pattern, stone grain pattern, sand grain pattern, tiling pattern, brickwork pattern, cloth pattern, leather drawing pattern, geometric figures, letters, symbols, abstract patterns, etc. can be used. can be attached.
The method of forming the pattern layer is not particularly limited. For example, by a printing method using an ink obtained by dissolving a known coloring agent such as a dye, an inorganic or organic pigment, a fluorescent pigment, etc. together with a binder resin in a solvent or dispersing it in a dispersion medium, the surface of the base sheet is printed. can be formed into

Examples of the printing method used to form the pattern layer include inkjet printing, gravure printing, offset printing, screen printing, flexographic printing, electrostatic printing, and the like. In addition, when forming a pattern layer that is solid over the entire surface, examples of methods include gravure coating, gravure reverse coating, roll coating, knife coating, air knife coating, die coating, lip coating, and comma coating. , various coating methods such as a kiss coating method, a flow coating method, and a dip coating method. In addition to these methods, for example, hand drawing, suminagashi, photography, transfer, laser beam drawing, electron beam drawing, partial vapor deposition of metal, etching, etc. can also be used, and multiple image forming methods can be used in combination. You can.
The thickness of the pattern layer is not particularly limited and can be set appropriately depending on the product characteristics, but the layer thickness at the time of coating is generally about 0.1 to 10 μm.

<Adhesive layer>
The adhesive layer is a layer that is laminated between the pattern layer and the resin layer of the present invention to bond them together. The adhesive used in the adhesive layer can be appropriately selected depending on the components constituting the pattern layer or the resin layer of the present invention. For example, various adhesives including polyurethane resin, polyacrylic resin, polycarbonate resin, epoxy resin, etc. can be used. Any means for exerting adhesive strength is also applicable. In addition to reaction-curing adhesives, hot-melt adhesives, ionizing radiation-curing adhesives, ultraviolet-curing adhesives, and the like may also be used. Further, if necessary, known adhesion-facilitating treatments such as corona discharge treatment, plasma treatment, degreasing treatment, and surface roughening treatment can be applied to the adhesive surface.
Although it is preferable to use a transparent resin for the adhesive layer, it may not be completely transparent but may be semitransparent as long as the pattern layer is visible.

The adhesive layer can be formed, for example, by applying an adhesive onto the picture pattern layer, drying it once, and then laminating the resin of the present invention. The method of applying the adhesive is not particularly limited, and the methods mentioned above for forming the pattern layer, such as roll coating, can be employed.
The thickness of the adhesive layer varies depending on the transparent protective layer, the type of adhesive used, etc., but is generally about 0.1 to 30 μm.

<Transparent surface protective layer>
A transparent surface protective layer may be formed on the resin layer of the present invention. The components of the resin forming the transparent surface protective layer are not particularly limited, but preferably contain an ionizing radiation curable resin or a two-part curable urethane resin. Ionizing radiation curable resins or two-component curable urethane resins are preferred, as they have characteristics that can easily improve abrasion resistance, impact resistance, stain resistance, scratch resistance, weather resistance, and the like.

As the ionizing radiation-curable resin, a resin that can be polymerized and crosslinked by irradiation with ionizing radiation such as ultraviolet rays and electron beams can be used. Examples include compounds having radically polymerizable unsaturated groups such as (meth)acryloyl groups and (meth)acryloyloxy groups, and cationically polymerizable functional groups such as epoxy groups in the molecule. Specific examples include polymers of monofunctional monomers such as methyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and phenoxyethyl (meth)acrylate, diethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, and diethylene glycol di(meth)acrylate. Polymers of polyfunctional monomers such as pentaerythritol tetra(meth)acrylate, isoprene (meth)acrylate, epoxy(meth)acrylate, polyester(meth)acrylate, urethane(meth)acrylate, melamine(meth)acrylate, silicone(meth)acrylate Examples include (meth)acrylate modified resins such as acrylate.

As a method for curing the ionizing radiation curable resin, methods known to those skilled in the art can be used. The curing reaction is usually carried out using ultraviolet light or electron beams. For example, ultraviolet sources such as mercury lamps, carbon arc lamps, black lights, metal halide lamps, various electron beam accelerators such as Cockcroft-Walton type, Vandegraft type, resonant transformer type, insulated core transformer type, dynamitron type, high frequency type, etc. electron beam sources can be used.

Although the two-component curable urethane resin is not particularly limited, those containing a polyol component having a hydroxyl group as a main component and an isocyanate component can be used.

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

<Primer layer>
A primer layer may be laminated between the surface protective layer and the resin layer of the present invention. The primer layer has the function of improving the adhesion between the two. The primer layer is mainly composed of a binder resin, and may contain additives such as an ultraviolet absorber and a light stabilizer, if necessary.
Binder resins include urethane resin, acrylic polyol resin, acrylic resin, ester resin, amide resin, styrene resin, urethane-acrylic copolymer, vinyl chloride-vinyl acetate copolymer, chlorinated propylene resin, nitrocellulose resin, acetic acid. Resin such as cellulose resin is used. These may be used alone or in combination. The thickness of the primer layer is preferably 1 μm or more and 10 μm or less.

＜＜Processing＞＞
The decorative sheet may be further processed by embossing, anti-virus processing, etc. on the side of the transparent surface protective layer. Embossing is performed to give the decorative sheet a desired texture such as a wood grain pattern. For example, after the transparent protective layer is heated and softened, it is pressed and shaped with an embossing plate having an uneven pattern of a desired shape, and then cooled and fixed to give a texture. Embossing can be performed with a known single-fed or rotary embossing machine.
Antiviral processing can be performed by including an antiviral agent in the layer laminated on the outermost surface of the decorative sheet. Antiviral agents include inorganic antiviral agents formed by incorporating metal ions such as silver ions, copper ions, and zinc ions into substances such as zeolite, apatite, and zirconia, and 2-(4-thiazolyl)-benzimidazole. , 10,10-oxybisphenoxanodine, pyridine-2-thiol-oxide, and other organic antiviral agents or resins in which cationic polymers are kneaded can be used. In terms of antiviral effects, inorganic antiviral agents containing silver are preferred.

- Decorative board One aspect of the present invention is a decorative board composed of a laminate including a decorative board base material and a decorative sheet of the present invention. The base material of the decorative board is appropriately selected depending on the application. Examples include wood fiberboard, particle board, plywood, cork sheet, cork-containing composite substrate, thermoplastic resin board, and the like. These decorative board base materials may be used alone or in combination of two or more, laminated and adhered with an adhesive if necessary. Further, the shape of the base material is not particularly limited, and plate materials such as flat plates and curved plates made of various materials, three-dimensional articles, sheets, etc. can be used in any shape and thickness.
The lamination method for laminating the decorative sheet and the decorative laminate base material is not limited, and methods known to those skilled in the art, such as a method of adhering each with an adhesive, can be employed. The adhesive may be appropriately selected from known adhesives depending on the type of adherend.

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.
Note that measurements and evaluations of physical properties in Examples and Comparative Examples were carried out by the methods shown below.
Moreover, no data in the table means not measured, and not detected means less than the detection limit.

<Measurement and evaluation>
(1) Measurement of phase angle δ (G* = 0.1 MPa) at absolute value of complex modulus G* = 0.1 MPa 1) Preparation and measurement of sample Place the sample in a hot press mold with a thickness of 1.0 mm. After preheating for 5 minutes in a heat press with a surface temperature of 180° C., residual gas in the molten resin was degassed by repeating pressurization and depressurization, and the resin was further pressurized at 4.9 MPa and held for 5 minutes. Thereafter, the sample was transferred to a press machine with a surface temperature of 25° C., and cooled by being held at a pressure of 4.9 MPa for 3 minutes, thereby producing a press plate consisting of a sample having a thickness of about 1.0 mm. The sample was a pressed plate made into a circle with a diameter of 25 mm, and the dynamic viscoelasticity was measured under the following conditions in a nitrogen atmosphere using an ARES type rotary rheometer manufactured by Rheometrics as a measuring device for dynamic viscoelasticity. It was measured.
・Plate: φ25mm (diameter) Parallel plate ・Temperature: 160℃
・Distortion amount: 10%
・Measurement angular frequency range: 1.0×10-2 to 1.0×102 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 modulus of elasticity, and the value of δ (degrees) at the point corresponding to logG*=5.0 is calculated 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 determined by linear interpolation using two points around logG*=5.0. Further, when logG*<5 at all of the measurement points, the δ value at logG*=5.0 was extrapolated using a quadratic curve using the values of the three points with the largest logG* value.

(2) Measurement of weight average molecular weight (Mw) and molecular weight distribution parameter (Mw/Mn) Weight average molecular weight (Mw) was determined by gel permeation chromatography (GPC). Further, the molecular weight distribution parameter (Mw/Mn) was calculated by further determining the number average molecular weight (Mn) by gel permeation chromatography (GPC) and using the ratio of Mw and Mn, Mw/Mn.
Measurements were performed according to the following procedures and conditions.

1) Sample Pretreatment When the sample contained a carboxylic acid group, it was subjected to an esterification treatment such as methyl esterification using diazomethane, trimethylsilyl (TMS) diazomethane, etc., and used for measurement. In addition, when the sample contained a carboxylic acid group, it was treated with an acid to modify the carboxylic acid group into a carboxylic acid group, and then subjected to the above-mentioned esterification treatment and used for measurement.

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

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

4) Calibration curve Column calibration was performed using Showa Denko 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 (0.07 mg/ml solutions each), n-eicosane and n-tetracontane were measured under the same conditions as above, and the elution time and logarithm of molecular weight were calculated. It was approximated by a quartic equation. In addition, the following formula was used for conversion of polystyrene molecular weight (MPS) and polyethylene molecular weight (MPE).
MPE=0.468×MPS

(3) Melt flow rate (MFR)
MFR was measured according to Table 1-Condition 7 of JIS K-7210 (1999) at a temperature of 190° C. and a load of 21.18 N (=2.16 kg). Moreover, "<0.01" in the table means that the resin did not flow under the test conditions and could not be measured.

(4) Melting point and crystallinity The melting point is indicated by the peak temperature of an endothermic curve measured by a differential scanning calorimeter (DSC). The measurement was carried out using a DSC (DSC7020) manufactured by SII Nanotechnology Co., Ltd. under the following measurement conditions.
Approximately 5.0 mg of the sample was packed in an aluminum pan, heated to 200°C at a rate of 10°C/min, held at 200°C for 5 minutes, and then lowered to 30°C at a rate of 10°C/min. After holding at 30°C for 5 minutes, the temperature is raised again at 10°C/min. Among the absorption curves, the maximum peak temperature is taken as the melting point Tm, and the heat of fusion (ΔH) is calculated from the melting endothermic peak area. The degree of crystallinity (%) was determined by dividing by the heat of fusion of perfect crystals of high-density polyethylene (HDPE), 293 J/g.

(5) Method for measuring the amount of structural units derived from a monomer having a carboxyl group and/or a dicarboxylic acid anhydride group, and the number of branches per 1,000 carbon atoms The carboxy group in the copolymer of the present invention and The amount of structural units derived from a monomer having/or a dicarboxylic anhydride group and an acyclic monomer, and the number of branches per 1,000 carbon atoms are determined using a ¹³ C-NMR spectrum. ¹³ C-NMR was measured by the following method.
200 to 300 mg of the sample was dissolved in 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)) 2.4 ml and hexamethyldisiloxane, which is a reference material for chemical shift, are placed in an NMR sample tube with an inner diameter of 10 mmφ, purged with nitrogen, sealed, and heated to dissolve as a homogeneous solution as an NMR measurement sample. And so.
NMR measurements were carried out at 120° C. using an AV400M NMR apparatus manufactured by Bruker Japan Co., Ltd. equipped with a 10 mmφ cryoprobe.
¹³ C-NMR was measured using 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 integration count of 512 or more times.
For the chemical shift, the ¹³ C signal of hexamethyldisiloxane was set at 1.98 ppm, and the chemical shifts of other ¹³ C signals were based on this.

1) Pretreatment of Sample When a sample contained a carboxylic acid base, the sample was treated with an acid to modify the carboxylic acid base into a carboxyl group, and then used for measurement. Further, when the sample contains a carboxyl group, an esterification treatment such as methyl esterification using diazomethane, trimethylsilyl (TMS) diazomethane, etc. may be performed as appropriate.

2) Calculation of the amount of structural units derived from a monomer having a carboxy group and/or a dicarboxylic acid anhydride group and an acyclic monomer <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) × 100/[I (tBA) + I (E)]
Here, I(tBA) and I(E) are quantities represented by the following formulas, respectively.
I(tBA)=I _79.6-78.8
I(E)=(I _180.0~135.0 +I _120.0~5.0 -I(tBA)×7)/2

In addition, when the structural unit amount of each monomer is shown as "<0.1" including an inequality sign, it is present as a structural unit in the copolymer, but considering the significant figures, it is less than 0.1 mol%. It means quantity.

3) Calculation of the number of branches per 1,000 carbons There are two types of copolymers: isolated type in which branches exist alone in the main chain, complex type (face-to-face type in which branches face each other through the main chain, branched type). There are two types: a branched-branch type with branches in the chain, and a chain type.
Below is an example of an ethyl branch structure. In addition, in the facing type example, R represents an alkyl group.

The number of branches per 1,000 carbons is determined by substituting one of the following I(B1), I(B2), and I(B4) into the I (branching) term of the following formula. B1 represents a methyl branch, B2 represents an ethyl branch, and B4 represents a butyl branch. The number of methyl branches is determined using I(B1), the number of ethyl branches is determined using I(B2), and the number of butyl branches is determined using I(B4).
Number of branches (number/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 to 135.0} + I _{120.0 to 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 indicates the integrated intensity, and the numerical value of the subscript of I indicates the range of chemical shift. 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.
Attribution was made with reference to non-patent documents Macromolecules 1984, 17, 1756-1761 and Macromolecules 1979, 12, 41.
In addition, when each branch number is shown as "<0.1" including an inequality sign, it exists as a structural unit in the copolymer, but the amount is less than 0.1 mol% considering the significant figures. It means that. Moreover, not detected means below the detection limit.

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

(7) Measurement of mass increase rate 1) Chemical resistance test sample The sample was placed in a hot press mold with a thickness of 1.0 mm, and after preheating for 5 minutes in a hot press machine with a surface temperature of 180°C, pressurization and depressurization were performed. By repeating this process, residual gas in the molten resin was degassed, and the pressure was further increased to 4.9 MPa and held for 5 minutes. Thereafter, the sample was transferred to a press machine with a surface temperature of 25° C., and cooled by being held at a pressure of 4.9 MPa for 3 minutes, thereby producing a press plate consisting of a sample having a thickness of about 1.0 mm.
2) Chemical resistance test conditions Using the above test piece, mass change rate (%) was measured under the following conditions in accordance with JIS K 7114-2001. Fuel C is JIS fuel oil C with isooctane/toluene=1:1 (weight ratio).
・Soaking time:
Toluene, aqueous ammonia, ethyl acetate, ethanol 72 hours Fuel C 168 hours・Soaking temperature:
Toluene, aqueous ammonia, ethyl acetate, ethanol 23℃
FuelC 60℃
・Container: 240ml glass bottle ・Immersion solvent amount: 200ml
The following formula was used for the mass increase rate (%).
・Mass increase rate (%) = (sample weight after immersion m2 - sample weight before immersion m1)/sample weight before immersion m1

(8) Measurement of wear amount 1) Preparation method of wear test sample The sample was placed in a heat press mold with dimensions: 150 mm x 150 mm and thickness 1 mm, and after preheating for 5 minutes in a heat press machine with a surface temperature of 180 ° C. By repeating pressurization and depressurization, the sample was melted and residual gas in the sample was degassed, and the sample was further pressurized to 4.9 MPa and held for 3 minutes. Thereafter, the molded plate was gradually cooled at a rate of 10° C./min while a pressure of 4.9 MPa was applied, and when the temperature decreased to around room temperature, the molded plate was taken out from the mold. The obtained molded plate was conditioned for 48 hours or more in an environment with a temperature of 23±2°C and a humidity of 50±5°C. The press plate after conditioning was cut out into a circular shape with a diameter of about 115 mm, and a hole with a diameter of about 6.5 mm was punched in the center to prepare a wear test sample.

2) Abrasion test conditions Using the above test piece, the amount of abrasion loss (mg) was measured under the following conditions in accordance with JIS K 7204-1999.
・Equipment: Taber abrasion tester (rotary ablation tester) _ Manufactured by Toyo Seiki Seisakusho Co., Ltd. ・Abrasion wheel: CS-17
・Rotation speed: 60 rotations/min
・Test number: 1000 rotations ・Load: 4.9N

<Synthesis of metal complexes>
Synthesis of B-423/Ni complex The B-423/Ni complex was prepared using the following 2-bis(2,6-dimethoxyphenyl)phosphano-6-(2, 6-diisopropylphenyl)phenol ligand (B-423) was used. According to Example 1 of Patent No. 2019/156764, B-423 and Ni(COD)2 were combined using bis(1,5-cyclooctadiene)nickel(0) (referred to as Ni(COD)2). A nickel complex (B-423/Ni) in which B-423/Ni reacted in a one-to-one ratio was synthesized.

<(Production Example 1 to Production Example 4): Production of ionomer-based resin precursor>
An ethylene/tBu acrylic acid copolymer was produced using a transition metal complex (B-423/Ni complex). A copolymer was produced with reference to Production Example 1 or Production Example 3 described in JP-A-2016-79408, and the metal complex species, the amount of metal complex, the amount of aluminum compound (trioctylaluminium (TNOA)), and toluene were Table 1 shows the production conditions and the production results, which were changed as appropriate, such as amount, comonomer type, comonomer amount, ethylene partial pressure, polymerization temperature, and polymerization time, and Table 2 shows the physical properties of the obtained copolymer.

<(Resin 1 to Resin 2): Production of ionomer-based resin>
40 g of the obtained copolymers of Production Examples 1 and 2, 0.8 g of p-toluenesulfonic acid monohydrate, and 185 ml of toluene were placed in a 500 ml separable flask, and the mixture was stirred at 105° C. for 4 hours. After 185 ml of ion-exchanged water was added, stirred, and allowed to stand still, the aqueous layer was extracted. Thereafter, ion-exchanged water was repeatedly added and extracted until the pH of the extracted aqueous layer became 5 or higher. 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 peak around 850 cm ^-1 derived from the tBu group disappeared, the peak around 1730 cm ^-1 derived from the carbonyl group of the ester decreased, and the carbonyl of the carboxylic acid (dimer) disappeared. An increase in the peak around 1700 cm ⁻¹ originating from the group was observed.
Thereby, decomposition of t-Bu ester and generation of carboxylic acid were confirmed, and ionomer base resins 1 and 2 were obtained. Table 3 shows the physical properties of the obtained resin.

<Examples 1 to 9: Production of ionomer>
1) Preparation of Na ion supply source Ethylene/methacrylic acid (MAA) copolymer (Mitsui-Dow Polychemical Co., Ltd.) was added to a roller mixer R60 model Laboplastomill (manufactured by Toyo Seiki Co., Ltd.) equipped with a small mixer with a capacity of 60 ml. A Na ion source was prepared by adding 22 g of Nucrel N1050H (manufactured by Nucrel N1050H) and 18 g of sodium carbonate, and kneading them at 180° C. and 40 rpm for 3 minutes.

2) Preparation of Zn ion supply source Ethylene/methacrylic acid (MAA) copolymer (Mitsui-Dow Polychemical Co., Ltd.) was added to a roller mixer R60 model Laboplastomill (manufactured by Toyo Seiki Co., Ltd.) equipped with a small mixer with a capacity of 60 ml. A Zn ion source was prepared by adding 21.8 g of Nucrel N1050H (manufactured by Nucrel N1050H), 18 g of zinc oxide, and 0.2 g of zinc stearate, and kneading the mixture at 180° C. and 40 rpm for 3 minutes.

3): Preparation of ionomer 40 g of Resin 1 to Resin 6 were put into a roller mixer R60 model Laboplastomill manufactured by Toyo Seiki Co., Ltd. equipped with a small mixer with a capacity of 60 ml, and the mixture was kneaded and dissolved at 160° C. and 40 rpm for 3 minutes. Ta. Thereafter, a Na ion supply source and a Zn ion supply source were added to obtain a desired degree of neutralization, and kneading was performed at 250° C. and 40 rpm for 5 minutes.
In the IR spectrum of the obtained resin, the peak around 1700 cm ^-1 derived from the carbonyl group of the carboxylic acid (dimer) decreased, and the peak around 1560 cm ^-1 derived from the carbonyl group of the carboxylic acid base increased. was. It was confirmed that the ionomer with the desired degree of neutralization was produced from the amount of decrease in the peak around 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): Ionomer base resin E/AA
Resin 1, which is an ionomer-based resin, was used as an ionomer with a degree of neutralization of 0%. The physical properties are shown in Tables 6 and 7.

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

(Comparative Example 3): E/MAA-based binary ionomer A copolymer of ethylene, methacrylic acid, and Na methacrylate, an ionomer resin produced by a high-pressure radical process (manufactured by Mitsui-Dow Polychemical Co., Ltd.) :HIMILAN HIM1605) was used as a reference ionomer. The physical properties are shown in Tables 6 and 7.

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

(Comparative Example 5): E/MAA-based binary ionomer ethylene, methacrylic acid, and Zn methacrylate copolymer ionomer resin produced by a high-pressure radical process (manufactured by Mitsui Dow Polychemical Co., Ltd. Brand: HIMILAN HIM1650) was used as a reference ionomer. The physical properties are shown in Tables 6 and 7.

The evaluation criteria in Tables 5 and 7 will be explained.
1) Chemical resistance Regarding toluene, a mass increase rate of less than 15% was rated as ○, a mass increase rate of 15% or more and less than 20% was rated as Δ, and a mass increase rate of 20% or more was rated as ×. Regarding ammonia water, a mass increase rate of less than 3.5% was rated as ○, a mass increase rate of 3.5% or more and less than 5% was rated as Δ, and a mass increase rate of 5% or more was rated as ×. Regarding ethyl acetate, a mass increase rate of less than 4.5% was rated ○, a mass increase rate of 4.5% or more and less than 6% was rated Δ, and a mass increase rate of 6% or more was rated ×. Regarding ethanol, a mass increase rate of less than 1% was rated as ○, a mass increase rate of 1% or more and less than 1.5% was rated as Δ, and a mass increase rate of 1.5% or more was rated as ×. Regarding Fuel C, a mass increase rate of less than 25% was marked as ○, a mass increase rate of 25% or more and less than 40% was marked as Δ, and a mass increase rate of 40% or more was marked as ×.

2) Abrasion resistance Abrasion loss less than 5 mg is rated as ○, 5 mg or more and 10 mg or less is △, and 10 mg or more is rated as ×.

3) Heat resistance A melting point of 95°C or higher is rated as ○, a value of 93°C or higher and lower than 95°C is Δ, and a melting point of lower than 93°C is rated x.

<Consideration of results of Examples and Comparative Examples>
[Comparison of the ionomer of the present invention and conventional ionomer]
Examples 1 to 9 are ionomers made of a base resin produced with a specific transition metal catalyst and a metal ion source, so their molecular structure is substantially linear, and the phase angle δ (G*= 0.1 MPa) is 50° or more. On the other hand, in Comparative Examples 1 and 2, base resin 1 or 2 is used as is, and its molecular structure is substantially linear, and the phase angle δ (G*=0.1 MPa) is 50° or more. , the degree of neutralization of metal ions is 0%. Comparative Examples 3 to 5 are commercially available ionomers made of a base resin and a metal ion source produced by a high-pressure radical method, so their molecular structure has many long chain branches and a complex modulus of elasticity. The phase angle δ at the absolute value G*=0.1 MPa (phase angle δ (G*=0.1 MPa)) is less than 50°.
Example 6 and Comparative Example 5, Example 8 and Comparative Example 3, and Example 9 and Comparative Example 4 have the same content of structural unit (B), metal type, and degree of neutralization, and are directly compared.・Since evaluation is possible, the comparison will be explained below.

The ionomers of Examples 6, 8, and 9 and the ionomers of Comparative Examples 5, 3, and 4 were different from each other. Compared to Comparative Example 4, the mass change rate during Fuel C immersion is lower, the amount of wear is much lower, and the melting point is also higher. Therefore, the ionomers of Examples 6, 8, and 9 have better chemical resistance, abrasion resistance, and heat resistance than the ionomers of Comparative Examples 5, 3, and 4.
This means that the linear ionomer of the present invention, which has a phase angle δ (G*=0.1 MPa) of 50° or more, has better chemical resistance, abrasion resistance, and heat resistance than conventional hyperbranched ionomers. It shows that it is excellent.

[About the metal ion species and neutralization degree of the ionomer in the present invention]
Comparative Example 1 is the base resin of Examples 1 to 6, Comparative Example 2 is the base resin of Examples 7 to 9, and corresponds to the case where the degree of neutralization by metal ions is 0%. Examples 1 to 9, in which the degree of neutralization is not 0%, have much less wear than Comparative Examples 1 and 2, in which the degree of neutralization is 0%. This indicates that the ionomer of the present application having a substantially linear structure has excellent chemical resistance, abrasion resistance, and heat resistance regardless of the metal type.

[About the composition, degree of neutralization, and metal ion species of the ionomer in the present invention]
Examples 1 to 9 are ionomers with different base resin compositions, degrees of neutralization, and metal ion species, but all have higher melting points, lower mass change rates, and lower wear amounts than the conventional ionomers of comparative examples. There are far fewer.
This means that the ionomer of the present invention, which has a substantially linear structure, has relatively good chemical resistance, abrasion resistance, and heat resistance, regardless of the base resin composition, degree of neutralization, and metal ion species. It has been shown to be excellent.

The reason why the ionomer of the present application has better wear resistance and chemical resistance than conventional ionomers is probably due to the difference in molecular structure. The ionomer of the present application has a substantially linear molecular structure as shown in Figure 2, whereas the conventional ionomer has a multi-branched molecular structure with many long chain branches as shown in Figure 1. are doing. In the case of a multi-branched molecular structure, compared to a linear molecular structure, the molecule has a large number of molecular chain ends. The abrasion test is a test in which the surface is deformed and destroyed using a worn ring with irregularities, but when deformation is applied, it is the molecular chain ends that trigger the breakage, so it is better to use straight rings with a small number of molecular chain ends. It is thought that a chain structure has better wear resistance than a multi-branched structure having many molecular chain ends.
Chemical resistance depends on the ease with which the solvent penetrates, so if there are many molecular ends due to the multi-branched structure, the molecules will move more easily, making it easier for the solvent to penetrate. For this reason, it is thought that a linear structure with a small number of molecular chain terminals has better chemical resistance and wear resistance than a multi-branched structure with a large number of molecular terminals.

Claims (12)

Contains as essential structural units a structural unit (A) derived from ethylene and/or an α-olefin having 3 to 20 carbon atoms, and a structural unit (B) derived from a monomer having a carboxyl group and/or a dicarboxylic acid anhydride group. A metal-containing carboxyl group in which at least a part of the carboxyl group and/or dicarboxylic acid anhydride group in the copolymer (P) contains at least one metal ion selected from Group 1, Group 2, or Group 12 of the Periodic Table. For a decorative sheet containing an ionomer, which is converted into an acid salt and has a phase angle δ of 50 degrees to 75 degrees at the absolute value of complex modulus G ^* =0.1 MPa measured with a rotary rheometer. resin. The resin for decorative sheets according to claim 1, wherein the number of methyl branches calculated by ¹³ C-NMR of the copolymer (P) is 50 or less per 1,000 carbons. The resin for decorative sheets according to claim 1 or 2, wherein the copolymer (P) contains 1 to 20 mol% of the structural unit (B) in the copolymer. The resin for decorative sheets according to any one of claims 1 to 3, wherein the structural unit (A) is a structural unit derived from ethylene. The decorative sheet according to any one of claims 1 to 4, wherein the copolymer (P) is produced using a transition metal catalyst containing a transition metal from Groups 8 to 11 of the periodic table. Resin for use. 6. The resin for decorative sheets according to claim 5, wherein the transition metal catalyst is a transition metal catalyst consisting of phosphorus sulfonic acid or phosphophenol ligand and nickel or palladium. The resin for decorative sheets according to any one of claims 1 to 6, wherein the copolymer (P) has a crystallinity of 50% or less. The resin for decorative sheets according to any one of claims 1 to 6, wherein the copolymer (P) has a crystallinity of 10% or more. A resin composition for decorative sheets, comprising the resin for decorative sheets according to any one of claims 1 to 8. A resin layer for a decorative sheet using the resin for a decorative sheet or the resin composition for a decorative sheet according to any one of claims 1 to 9. A decorative sheet comprising a laminate comprising at least a base layer and the resin layer according to claim 10. A decorative board comprising a laminate comprising a decorative board base material and the decorative sheet according to claim 11.