JP2021001332A - Ethylene ionomer for soft sheet and molding thereof - Google Patents

Abstract

To provide an ethylene ionomer for soft sheets that has flexibility, wear resistance, impact resistance, and transparency in a balanced manner and a molding thereof.SOLUTION: An ethylene ionomer for soft sheets contains an ionomer that is substantially linear and has a phase angle δ of 50°-75° in a complex modulus of elasticity absolute value G*=0.1 MPa, as measured with a rotating-type rheometer, wherein a melt flow rate (MFR) is 0.1-15 g/10 min at a temperature of 190°C and a load of 2.16 kg; a tensile elasticity is 20-350 MPa; a tensile impact strength is 700 KJ/m2 or more; a wear resistance in a wear test is less than 10 mg; and a haze is 0.1-30%.SELECTED DRAWING: None

Description

The present invention relates to an ethylene ionomer for a soft sheet and a molded product thereof, which uses a novel ionomer and has an excellent balance of flexibility, abrasion resistance, impact resistance, and transparency.

The ethylene-based ionomer is a resin using an ethylene-unsaturated carboxylic acid copolymer as a base resin and intermolecularly bonded with metal ions such as sodium and zinc (Patent Document 1). It is tough, highly elastic, flexible, and has features such as wear resistance and transparency.
Currently, as commercially available ethylene-based ionomers, the ethylene-methacrylic acid copolymer sodium salt and zinc salt "Surlyn (registered trademark)" developed by DuPont, and Mitsui Dow Polychemical Co., Ltd. sell them. "Hymilan (registered trademark)" and the like are known. Further, Patent Document 2 discloses a molded product containing an ionomer, which is characterized by having good optical characteristics.

However, in each of the ethylene-unsaturated carboxylic acid copolymers of the base resin used in these currently commercially available ethylene ionomers, a polar group-containing monomer such as ethylene and an unsaturated carboxylic acid is used by a high-pressure radical polymerization method. A polar group-containing olefin copolymer polymerized by the above is used. The high-pressure radical polymerization method has an advantage that it can be polymerized at low cost regardless of the type of the monomer containing a polar group. However, the molecular structure of the polar group-containing olefin copolymer produced by the high-pressure radical polymerization method is a structure having many long-chain branches and short-chain branches irregularly as shown in the image diagram shown in FIG. , There is a drawback that the strength is insufficient.

On the other hand, conventionally, a method for producing a polar group-containing olefin copolymer having a linear molecular structure using a polymerization method using a catalyst has been sought, as shown in the image diagram shown in FIG. Group-containing monomers are generally difficult to polymerize because they are catalytic poisons, and in fact, it has been difficult for many years to obtain polar group-containing olefin copolymers having desired physical properties by an industrially inexpensive and stable method. Was there.
However, in recent years, by using a new catalyst and a new production method developed by the applicants of the present application and the like, a polar group-containing olefin copolymer having a substantially linear molecular structure can be obtained industrially at low cost and stably. A method has been proposed.
Then, as a method for producing a polar group-containing olefin copolymer serving as a base resin for ethylene-based ionomers, a copolymer of ethylene and t-butyl acrylate was produced using a late-period transition metal catalyst, and the obtained polar group was obtained. It has been reported by the applicants of the present application that the contained olefin copolymer was successfully modified into an ethylene-acrylic acid copolymer by heat or acid treatment and then reacted with a metal ion to produce a binary ionomer. (Patent Document 3).

U.S. Pat. No. 3,264,272 Special Table 2011-524918 Japanese Unexamined Patent Publication No. 2016-79408

Applications of the soft soft sheet include a cushioning sheet that suppresses damage due to contact between objects and a vibration-proof sheet that suppresses the transmission of vibration. Generally, a sheet made of silicone rubber is often used for such applications, but since the silicone rubber sheet is very expensive, there are expectations for a soft sheet that is inexpensive and can be used for general purposes. large.
Since the soft sheet is supposed to be used as described above, flexibility and wear resistance are considered to be important, and depending on the situation, impact resistance that can withstand breakage such as "tear" is required. Conceivable. Further, in order to further improve the degree of freedom of the situation / place / place of use, it is considered that good optical characteristics, particularly transparency, are also important performances.

However, the ionomer described in Patent Document 1 does not have sufficient resistance to impact, and according to the present inventors, it also has poor wear resistance. In Patent Document 2, in addition to the optical characteristics, an improvement in mechanical properties called "stress crack test" is shown, but other mechanical properties are not mentioned. In general, it is difficult to estimate other mechanical properties such as impact resistance and wear resistance from the results of stress crack tests.
In view of the situation of the prior art, an object of the present application is to provide an ethylene ionomer for a soft sheet and a molded product thereof, which has an excellent balance of flexibility, wear resistance, impact resistance, and transparency balance.

As a result of repeated studies by the present inventors to solve the above problems, by molding a resin composition for a soft sheet using a specific ionomer resin, the physical properties required for the soft sheet are significantly higher than expected. It was found that it has an excellent effect on.
The ethylene-based ionomer of Patent Document 3 is a novel ethylene-based ionomer that has a substantially linear molecular structure as a base resin and also has a function as an ionomer, and its physical properties and the like are many conventional. Unlike ethylene ionomers, which have a branched molecular structure, their unique properties and suitable applications are unknown. The present invention is based on the finding that a resin composition containing a substantially linear ethylene-based ionomer has an excellent effect on improving the physical properties required for a soft-based sheet.

That is, according to the first invention of the present invention, it is an ethylene ionomer for a soft sheet, and the ionomer is a structural unit (A) derived from ethylene and / or an α-olefin having 3 to 20 carbon atoms. , At least one of the carboxyl group and / or the dicarboxylic acid anhydride group in the copolymer (P) containing the structural unit (B) derived from the monomer having a carboxyl group and / or the dicarboxylic acid anhydride group as an essential structural unit. The part is converted into a metal-containing carboxylate containing at least one metal ion selected from Group 1, Group 2, or Group 12 of the periodic table, and has the following properties (a) to (f). An ethylene ionomer for a soft sheet is provided, which is characterized by the above.
(A) The phase angle δ at the absolute value G ^* = 0.1 MPa of the complex elastic modulus measured by the rotary rheometer is 50 to 75 degrees.
(B) The melt flow rate (MFR) at a temperature of 190 ° C. and a load of 2.16 kg is 0.1 to 15 g / 10 minutes.
(C) The tensile elastic modulus is 20 to 350 MPa.
(D) The tensile impact strength is 700 KJ / m ² or more.
(E) The amount of abrasion resistance in the wear test is less than 10 mg.
(F) The haze is 0.1 to 30%.

Further, according to the second invention of the present invention, in the first invention, the number of methyl branches calculated by ¹³ C-NMR of the copolymer (P) in the ionomer is 50 per 1,000 carbons. An ethylene ionomer for a soft sheet is provided, which is characterized by having no more than one.

Further, according to the third invention of the present invention, in the first invention, the number of methyl branches calculated by ¹³ C-NMR of the copolymer (P) in the ionomer is 5 per 1,000 carbons. An ethylene ionomer for a soft sheet is provided, which is characterized by having no more than one.

Further, according to the fourth invention of the present invention, in any one of the first to third inventions, the copolymer (P) in the ionomer contains the structural unit (B) 2 to 2 in the copolymer. Provided is an ethylene-based ionomer for a soft-based sheet, which comprises 20 mol%.

Further, according to the fifth invention of the present invention, in any one of the first to fourth inventions, the structural unit (A) in the ionomer is a structural unit derived from ethylene, which is soft. Ethylene ionomers for based sheets are provided.

Further, according to the sixth invention of the present invention, in any one of the first to fifth inventions, the transition metal catalyst in which the copolymer (P) in the ionomer contains a transition metal of groups 8 to 11 of the periodic table. Provided is an ethylene ionomer for a soft sheet, which is characterized by being produced using the above.

Further, according to the seventh invention of the present invention, in the sixth invention, the transition metal catalyst is a transition metal catalyst composed of a phosphorus sulfonic acid or a phosphorus phenol ligand and nickel or palladium. , Ethylene ionomers for soft sheets are provided.

Further, according to the eighth invention of the present invention, in any one of the first to seventh inventions, the copolymer (P) is further other than the structural unit (A) and the structural unit (B). Provided is an ethylene ionomer for a soft sheet, which is a copolymer containing a structural unit (C), which is a compound having one or more carbon-carbon double bonds in its molecular structure, as an essential structural unit. To.
Further, according to the ninth invention of the present invention, in the eighth invention, the acyclic monomer in which the structural unit (C) in the copolymer (P) is a (meth) acrylic acid ester, or An ethylene ionomer for a soft sheet, which is a cyclic monomer which is a norbornene-based olefin, is proposed.
Further, according to the tenth invention of the present invention, the structural unit (A) derived from ethylene and / or α-olefin having 3 to 20 carbon atoms and
At least a part of the carboxyl group and / or the dicarboxylic acid anhydride group in the copolymer (P) containing the structural unit (B) derived from the monomer having a carboxyl group and / or the dicarboxylic acid anhydride group as an essential structural unit. Is converted to a metal-containing carboxylate containing at least one metal ion selected from Group 1, Group 2, or Group 12 of the Periodic Table.
An ethylene-based ionomer resin composition for a soft sheet, which comprises an ionomer having a phase angle δ at an absolute value G ^* = 0.1 MPa of a complex elastic modulus measured by a rotary rheometer of 50 to 75 degrees. Is provided.
Further, according to the eleventh invention of the present invention, the ethylene ionomer for a soft sheet according to any one of the first to ninth inventions, or the ethylene ionomer resin composition for a soft sheet according to the tenth invention. A molded body is provided using.

INDUSTRIAL APPLICABILITY According to the present invention, an ethylene ionomer for a soft sheet having an excellent balance of flexibility, abrasion resistance, impact resistance, and transparency and a molded product thereof can be obtained. The ionomer according to the present invention, which has a substantially linear structure, is useful because a soft sheet having an excellent balance of flexibility, abrasion resistance, impact resistance, and transparency as compared with conventional materials can be obtained. ..

It is an image diagram of the molecular structure of the polybranched olefin copolymer polymerized by the high pressure radical method polymerization process. It is an image diagram of the molecular structure of the linear olefin copolymer polymerized by using a metal catalyst.

The present invention requires 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 a structural unit, a structural unit (C), which is a compound having one or more carbon-carbon double bonds in the molecular structure, is included as a structural unit, and these are copolymerized substantially linearly, preferably. Using the randomly copolymerized copolymer (P) as the base resin, at least a part of the carboxyl group and / or dicarboxylic acid anhydride group of the structural unit (B) is selected from Group 1, Group 2, or Group 12 of the periodic table. It is a soft sheet using an ionomer, which is characterized in that it is converted into a metal-containing carboxylate containing at least one kind of metal ion.

Hereinafter, ionomers and their uses related to the present invention will be described in detail for each item. In addition, in this specification, "(meth) acrylic acid" means acrylic acid or methacrylic acid. Further, in the present specification, "~" indicating a numerical range is used to mean that the numerical values described before and after the numerical range are included as the lower limit value and the upper limit value. Further, in the present specification, the copolymer means a copolymer of two or more systems including at least one unit (A) and at least one unit (B).
Further, in the present specification, the ionomer includes the structural unit (A) and the structural unit (B') in which at least a part of the structural unit (B) is converted into a metal-containing carboxylate. Further, it means an ionomer of a binary or higher copolymer which may further contain the structural unit (B).

1. 1. Ionomer The ionomer of the present invention is 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 an essential structural unit, and in some cases, a structural unit (C) which is a compound having one or more carbon-carbon double bonds in the molecular structure is included as a structural unit, and these are substantially linearly copolymerized. A copolymer (P) obtained by polymerization, preferably a random copolymerization, is used as a base resin, and at least a part of the carboxyl group and / or the dicarboxylic acid anhydride group of the structural unit (B) is Group 1 or Group 2 of the periodic table, or It is characterized in that it is converted into a metal-containing carboxylate containing at least one metal ion selected from Group 12.

(1) Structural unit (A)
The structural unit (A) is at least one structural unit selected from the group consisting of a structural unit derived from ethylene and a structural unit derived from an α-olefin having 3 to 20 carbon atoms.
The α-olefin according to the present invention is an α-olefin having 3 to 20 carbon atoms 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. It may be structural or have branches). The number of carbon atoms of the α-olefin is more preferably 3 to 12.

Specific examples of the structural unit (A) include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 3-methyl-1-butene, and 4-methyl-1-pentene. Etc., and may be ethylene. As the ethylene, ethylene derived from a non-petroleum raw material such as a plant raw material can be used as well as ethylene derived from a petroleum raw material.
Further, the structural unit (A) may be of one type or a plurality of types.
Examples of the combination of the two include ethylene-propylene, ethylene-1-butene, ethylene-1-hexene, ethylene-1-octene, propylene-1-butene, propylene-1-hexene, and propylene-1-octene. Can be mentioned.
The three combinations include, for example, ethylene-propylene-1-butene, ethylene-propylene-1-hexene, ethylene-propylene-1-octene, propylene-1-butene-hexene, and propylene-1-butene-1-octene. And so on.

In the present invention, the structural unit (A) preferably contains ethylene indispensably, and may further contain one or more α-olefins having 3 to 20 carbon atoms, if necessary.
The ethylene content in the structural unit (A) may be 65 to 100 mol% or 70 to 100 mol% with respect to the total mol of the structural unit (A).
From the viewpoint of impact resistance, the early 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. The structural unit (B) has the same structure as the structural unit derived from the monomer having a carboxy group and / or a dicarboxylic acid anhydride group, and is not necessarily a carboxy group and / or as described in the production method described later. Alternatively, it does not have to be produced using a monomer having a dicarboxylic acid anhydride group.

Specific examples of the structural unit derived from the monomer 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. Examples thereof include unsaturated carboxylic acids such as bicyclo [2,2,1] hept-2-ene-5,6-dicarboxylic acid, and examples of the structural unit derived from the monomer having a dicarboxylic acid anhydride group include maleic anhydride. , Itaconic anhydride, Citraconic anhydride, Tetrahydrophthalic acid anhydride, 5-Norbornene-2,3-dicarboxylic acid anhydride, 3,6-epoxy-1,2,3,6-tetrahydrophthalic acid anhydride, Tetracyclo [6 .2.1.1 ^3,6 . 0 ^2,7 ] Examples thereof include unsaturated dicarboxylic acid anhydrides such as dodeca-9-ene-4,5-dicarboxylic acid anhydride and 2,7-octadien-1-ylsuccinic anhydride.
As a structural unit derived from a monomer having a carboxyl group and / or a dicarboxylic acid anhydride group, acrylic acid, methacrylic acid, 5-norbornene-2,3-dicarboxylic acid anhydride are preferable from the viewpoint of industrial availability. In particular, acrylic acid may be used.
Further, the structural unit derived from the monomer having a carboxyl group and / or a dicarboxylic acid anhydride group may be one kind or a plurality of kinds.

The dicarboxylic acid anhydride group may react with water in the air to open a ring and partially become a dicarboxylic acid. However, as long as the gist of the present invention is not deviated, the dicarboxylic acid anhydride group may be used. The ring may be opened.

(3) Other structural units (C)
The copolymer (P) according to the present invention may contain a structural unit (A) and a structural unit (C) other than the structural unit represented by the structural unit (B). As the monomer giving the structural unit (C), any monomer can be used as long as it is not the same as the monomer giving the structural unit (A) and the structural unit (B). Any monomer that gives the structural unit (C) is not limited as long as it is a compound having one or more carbon-carbon double bonds in the molecular structure, but for example, an acyclic monomer represented by the general formula (1) or a general monomer. Examples thereof include a cyclic monomer represented by the formula (2).
Compared to the binary copolymer consisting of only the structural unit (A) and the structural unit (B), the melting point is obtained by using a ternary or more multipolymer containing the structural unit (C) component as the base resin of the ionomer. Ionomers with a lower degree of crystallinity can be obtained, the balance between rigidity and toughness is improved, and sheets with excellent transparency and gloss can be obtained. The structural unit (C) may be based on one type of monomer, or may be used in combination of two or more types of monomers.

・ Acyclic monomer

[In the general formula (1), T ^{1 to} T ³ are independently hydrogen atoms, hydrocarbon groups having 1 to 20 carbon atoms, hydrocarbon groups having 1 to 20 carbon atoms substituted with hydroxyl groups, and 1 carbon atoms. 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, and a carbon number 1 substituted with a halogen atom. ~ 20 hydrocarbon groups, 1 to 20 carbons alkoxy groups, 6 to 20 carbons aryl groups, 2 to 20 carbons ester groups, 3 to 20 carbons silyl groups, halogen atoms, or It is a substituent selected from the group consisting of cyano groups.
T ⁴ 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, and an ester group having 2 to 20 carbon atoms. Substituted hydrocarbon groups with 3 to 20 carbon atoms, hydrocarbon groups with 1 to 20 carbon atoms substituted with halogen atoms, alkoxy groups with 1 to 20 carbon atoms, aryl groups with 6 to 20 carbon atoms, 2 carbon atoms It is a substituent selected from the group consisting of an ester group of ~ 20, a silyl group having 3 to 20 carbon atoms, a halogen atom, or a cyano group. ]

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

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

In the ionomer of the present invention, T ¹ and T ² may be a hydrogen atom, T ³ may be a hydrogen atom or a methyl group, and T ^{1 to} T ³ may be, from the viewpoint of ease of production. Both may be hydrogen atoms.
Further, from the viewpoint of impact resistance, T ⁴ may be an ester group having 2 to 20 carbon atoms.

Specific examples of the acyclic monomer include cases where T ⁴ containing a (meth) acrylic acid ester or the like 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 branched, ring, and / or unsaturated bond. Furthermore, a heteroatom may be contained at any position in R ²² .
Structural formula: Examples of the compound represented by CH ₂ = C (R ²¹ ) CO ₂ (R ²² ) include a compound in which R ²¹ is a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms. Further, an acrylic acid ester in which R ²¹ is a hydrogen atom or a methacrylic acid ester in which R ²¹ is a methyl group can be mentioned.
Structural formula: Specific examples of the compound represented by CH ₂ = C (R ²¹ ) CO ₂ (R ²² ) include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, 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 thereof include phenyl (meth) acrylate, toluyl (meth) acrylate, and benzyl (meth) acrylate.
Specific examples of the compounds include methyl acrylate, ethyl acrylate, n-butyl acrylate (nBA), isobutyl acrylate (iBA), t-butyl acrylate (tBA), 2-ethylhexyl acrylate and the like. In particular, n-butyl acrylate (nBA), isobutyl acrylate (iBA), and t-butyl acrylate (tBA) may be used.
The acyclic monomer may be one kind or a plurality of kinds.

・ Cyclic monomer

[In the 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 be integrated to form a divalent organic group, respectively, and R ⁹ or R ¹⁰ and R ¹¹ or R ¹² may ring each other. It may be formed.
Further, n indicates 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, and cyclics such as norbornene, vinylnorbornene, etilidennorbornene, norbornadiene, tetracyclododecene, and tricyclo [4.3.0.1 ^2,5 ] deca-3-ene. Examples thereof include compounds having an olefin skeleton, 2-norbornene (NB), and tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] Dodeca-4-en or the like may be used.

(4) Copolymer (P)
The copolymer (P) used as the base resin of the ionomer used in the present invention contains a structural unit (A) derived from ethylene and / or α-olefin having 3 to 20 carbon atoms, and a carboxyl group and / or a dicarboxylic acid anhydride. A structural unit (B) derived from a monomer having a group is included as an essential structural unit, and in some cases, any structural unit (C) other than the above (A) and (B) is included, and each of these structural units is substantially. It is characterized in that it is linearly copolymerized, preferably randomly copolymerized. "Substantially linear" means that the copolymer does not have a branch or a branched structure appears infrequently, and the copolymer can be regarded as a linear state. Specifically, it refers to a state in which the phase angle δ of the copolymer is 50 degrees or more under the conditions described later.

The copolymer (P) according to the present invention needs to contain one or more structural units (A) and one or more structural units (B), and contains a total of two or more monomer units. ) And (B) may be included, but it is preferable that the copolymer contains such a structural unit (C).
The structural unit and the amount of the structural unit of the copolymer according to the present invention will be described.
Ethylene and / or α-olefin (A) having 3 to 20 carbon atoms, monomer (B) having a carboxyl group and / or dicarboxylic acid anhydride group, and any monomer (C) other than (A) and (B). A structure derived from each molecule is defined as one structural unit in the copolymer.
Then, when the total structural unit in the copolymer is 100 mol%, the ratio of each structural unit is expressed in mol%, which is the structural unit amount.

-Structural unit amount of ethylene and / or α-olefin (A) having 3 to 20 carbon atoms:
The lower limit of the structural unit amount of the structural unit (A) according 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 further. It is more preferably 90.0 mol% or more, particularly preferably 92.0 mol% or more, and the upper limit is 97.9 mol% or less, preferably 97.5 mol% or less, more preferably 97.0 mol% or less, still more preferably 96. It is selected from 5 mol% or less.
If the amount of structural unit derived from ethylene and / or α-olefin (A) having 3 to 20 carbon atoms is less than 60.0 mol%, the toughness of the copolymer is inferior, and if it is more than 97.9 mol%, the copolymer The crystallinity of ethylene is high, and the transparency may be poor.

-Structural unit amount of the monomer (B) having a carboxyl group and / or a dicarboxylic acid anhydride group:
The lower limit of the structural unit amount of the structural unit (B) according to the present invention is 2.0 mol% or more, preferably 2.9 mol% or more, more preferably 5.1 mol% or more, and the upper limit is 20.0 mol% or less. It is preferably selected from 15.0 mol% or less, more preferably 10.0 mol% or less, still more preferably 8.0 mol% or less, particularly preferably 6.0 mol% or less, and most preferably 5.6 mol% or less.
If the amount of the structural unit derived from the monomer (B) having a carboxyl group and / or a dicarboxylic acid anhydride group is less than 2.0 mol%, the adhesiveness of the copolymer to a highly polar dissimilar material is not sufficient. If it 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 a dicarboxylic acid anhydride group used may be used alone, or two or more kinds may be used in combination.

-Structural unit amount of any monomer (C):
When the component of the ionomer of the present invention contains an arbitrary monomer (C) other than the above (A) or (B), the lower limit of the structural unit amount of the structural unit (C) according to the present invention is 0.001 mol%. As described above, it is preferably 0.010 mol% or more, more preferably 0.020 mol% or more, still more preferably 0.1 mol% or more, still more preferably 1.9 mol% or more, and particularly preferably 2.0 mol% or more. The upper limit is selected from 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, and particularly preferably 3.6 mol% or less.
When the amount of the structural unit derived from the arbitrary monomer (C) is 0.001 mol% or more, the flexibility of the copolymer tends to be sufficient, and when it is 20.0 mol% or less, the mechanical properties of the copolymer are sufficient. Easy to obtain.
Further, any monomer used may be used alone, or two or more kinds may be used in combination.

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

Method for measuring the amount of structural units derived from the monomer having a carboxy group and / or the dicarboxylic acid anhydride group in the multiple copolymer and the acyclic monomer, and the number of branches:
The amount of structural units derived from the monomer having a carboxy group and / or the dicarboxylic acid anhydride group in the multiple copolymer of the present invention and the acyclic monomer, and the number of branches per 1,000 carbons are ¹³ C-NMR spectra. Is obtained using. ¹³ C-NMR is measured by the following method.

200 to 300 mg of sample is mixed with o-dichlorobenzene (C ₆ H ₄ Cl ₂ ) and deuterated benzene bromide (C ₆ D ₅ Br) mixed solvent (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, replaced with nitrogen, sealed, and heat-dissolved to form a uniform solution for NMR measurement. And.
The NMR measurement is performed at 120 ° C. using an AV400M type NMR apparatus of Bruker Japan Co., Ltd. equipped with a 10 mmφ cryoprobe.
¹³ C-NMR measures the sample temperature at 120 ° C., the pulse angle at 90 °, the pulse interval at 51.5 seconds, the number of integrations at 512 times or more, and the reverse gate decoupling method.
The chemical shift sets the ¹³ C signal of hexamethyldisiloxane to 1.98 ppm, and the chemical shift of the signal by other ¹³ C is based on this.
In the obtained ¹³ C-NMR, the monomer or the signal peculiar to the branching of the multiplex copolymer was identified, and the intensities thereof were compared. By comparing the strength, the structural unit amount and the number of branches of each monomer in the multiplex copolymer Can be analyzed. The position of the signal peculiar to the monomer or branch can be referred to a known material, or can be uniquely identified depending on the sample. Such an analysis method can be generally 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 according 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,. It is 0,000,000 or less, preferably 1500,000 or less, more preferably 1,000,000 or less, particularly preferably 800,000 or less, and most preferably 100,000 or less.
If Mw is less than 1,000, the physical properties such as mechanical strength and impact resistance of the copolymer are not sufficient, and if Mw exceeds 2,000,000, the melt viscosity of the copolymer becomes very high and the copolymer weight is equal. Molding of coalescence may be difficult.

The ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the copolymer according to the present invention is usually 1.5 to 4.0, preferably 1.6 to 3.5, and further. It is preferably in the range of 1.9 to 2.3. If Mw / Mn is less than 1.5, various processability including molding of the copolymer is not sufficient, and if it exceeds 4.0, the mechanical properties of the copolymer may be inferior.
Further, in the present specification, (Mw / Mn) may be expressed as a molecular weight distribution parameter.

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

An example of the GPC measuring method according to the present invention is as follows.
(Measurement condition)
Model used: Waters 150C
Detector: MIRAN1A / IR detector manufactured by FOXBORO (measurement wavelength: 3.42 μm)
Measurement temperature: 140 ° C
Solvent: Ortodichlorobenzene (ODCB)
Column: Showa Denko AD806M / S (3)
Flow velocity: 1.0 mL / min Injection volume: 0.2 mL
(Sample preparation)
As a sample, prepare a 1 mg / mL solution using ODCB (containing 0.5 mg / mL BHT (2,6-di-t-butyl-4-methylphenol)), and it takes about 1 hour at 140 ° C. And dissolve.
(Calculation of molecular weight (M))
It is performed by the standard polystyrene method, and the conversion from the holding capacity to the molecular weight is performed using a calibration curve prepared in advance using standard polystyrene. The standard polystyrene used is, for example, a brand of (F380, F288, F128, F80, F40, F20, F10, F4, F1, A5000, A2500, A1000) manufactured by Tosoh Corporation, and monodisperse polystyrene manufactured by Showa Denko (S-7300). , S-3900, S-1950, S-1460, S-1010, S-565, S-152, S-66.0, S-28.5, S-5.05, 0.07 mg / ml each. Solution) and so on. 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 is 0.5 mg / mL. For the calibration curve, a cubic equation obtained by approximating the least squares method, or a logarithmic approximation of the elution time and the molecular weight using a quaternary equation is used. The following numerical values are used for the viscosity formula [η] = K × Mα used for conversion to the molecular weight (M).
Polystyrene (PS): K = 1.38 × 10 ^-4 , α = 0.7
Polyethylene (PE): K = 3.92 × 10 ^-4 , α = 0.733
Polypropylene (PP): K = 1.03 × 10 ^-4 , α = 0.78

-Melting point (Tm, ° C):
The melting point of the copolymer according to the present invention is indicated by the maximum peak temperature of the endothermic curve measured by a differential scanning calorimeter (DSC). 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 the heat flow (mW) and the horizontal axis is the temperature (° C) in the DSC measurement. Indicates the maximum peak temperature, and when there is one peak, it indicates the peak temperature.
The melting point is preferably 50 ° C. to 140 ° C., more preferably 60 ° C. to 138 ° C., and most preferably 70 ° C. to 135 ° C. If it is lower than this range, the heat resistance is not sufficient, and if it is higher than this range, the adhesiveness may be inferior.
In the present invention, for example, using DSC (DSC7020) manufactured by SII Nanotechnology Co., Ltd., about 5.0 mg of a sample is packed in an aluminum pan, and the temperature is raised to 200 ° C. at 10 ° C./min to 200. It can be obtained from the absorption curve when the temperature is kept isothermal at 10 ° C./min for 5 minutes, the temperature is lowered to 20 ° C. at 10 ° C./min, the temperature is kept isothermal at 20 ° C. for 5 minutes, and then the temperature is raised again to 200 ° C. ..

-Crystallinity (%):
In the copolymer of the present invention, the crystallinity observed by differential scanning calorimetry (DSC) is not particularly limited, but is preferably more than 0% and 30% or less, more than 0% and 25. % Or less is more preferable, more than 5% and 25% or less are particularly preferable, and 5% or more and 20% or less are most preferable.
When the crystallinity is 0%, the toughness of the copolymer is not sufficient, and when the crystallinity is higher than 30%, the transparency of the copolymer is inferior. The crystallinity is an index of transparency, and it can be judged that the lower the crystallinity of the copolymer, the better the transparency.
In the present invention, for the crystallinity, for example, the heat of fusion (ΔH) is obtained from the heat of fusion peak area obtained by DSC measurement in the same procedure as the measurement of the melting point, and the heat of fusion is the perfect heat of fusion 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 according 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 the structural unit (B) of the monomer, or any structural unit (C) other than (A) and (B).

Further, the copolymer according to the present invention is 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, graft copolymers, etc. of the structural unit (C) of any monomer. Among these, a random copolymer capable of containing a large amount of the structural unit (B) may be used.
An example of the molecular structure (1) of a general ternary copolymer is shown below.
The random copolymer has a structural unit (A) of ethylene and / or α-olefin having 3 to 20 carbon atoms in the molecular structure example (1) shown below, and a carboxyl group and / or a dicarboxylic acid anhydride group. The probability that the structural unit (B) of the monomer and the structural unit (C) of any monomer find each structural unit at a position in an arbitrary molecular chain is a copolymer regardless of the type of the adjacent structural unit. It is a coalescence.
As described 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) of the above and the structural unit (C) of an arbitrary monomer form a random copolymer.

In addition, if the molecular structure example (2) of the copolymer into which the structural unit (B) of the monomer having a carboxyl group and / or the dicarboxylic acid anhydride group is introduced by graft modification is also posted for reference, ethylene and / or the number of carbon atoms is 3. A part of the copolymer obtained by copolymerizing the structural unit (A) of α-olefin of ~ 20 and the structural unit (C) of any monomer is a monomer having a carboxyl group and / or a dicarboxylic acid anhydride group. It is graft-modified to the structural unit (B).

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

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 ( It is preferable that the total content [Z] (mol%) of B) and the structural unit (C) of any monomer satisfies the following formula (I).
50 <Tm <-3.74 × [Z] +130 ... (I)
When the melting point (Tm, ° C) of the copolymer is higher than -3.74 x [Z] +130 (° C), the random copolymerization is low, so the mechanical properties such as impact strength are inferior, and the melting point is higher than 50 ° C. If it is low, the heat resistance may be inferior.

Further, the copolymer according to the present invention is preferably produced in the presence of a transition metal catalyst from the viewpoint of making its molecular structure linear.
It is known that the molecular structure of a copolymer differs depending on the production method, such as polymerization by a high-pressure radical polymerization method process or polymerization using a metal catalyst.
This difference in molecular structure can be controlled by selecting the production method, but for example, as described in Japanese Patent Application Laid-Open No. 2010-150532, the complex elastic modulus measured by a rotary rheometer can also be used. The molecular structure can be estimated.

-Phase angle δ at absolute value G ^* = 0.1 MPa of complex elastic 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 elastic modulus measured by the rotary rheometer may be 50 degrees or more, and 51 degrees or more. It may be 54 degrees or more, 56 degrees or more, 58 degrees or more, an upper limit of 75 degrees or less, or 70 degrees or less.
More specifically, when the phase angle δ (G ^* = 0.1 MPa) at the absolute value G ^* = 0.1 MPa of the complex elastic modulus measured by the 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 that contains a small amount of long-chain branches that do not affect the mechanical strength. Shown.
Further, when the phase angle δ (G ^* = 0.1 MPa) at the absolute value G ^* = 0.1 MPa of the complex elastic modulus measured by the rotary rheometer is lower than 50 degrees, the molecular structure of the copolymer has a long-chain branch. The structure is excessively contained, and the mechanical strength is inferior.
The phase angle δ at the absolute value G ^* = 0.1 MPa of the complex elastic modulus measured by the rotary rheometer is affected by both the molecular weight distribution and the long chain branching. However, if it is limited to a copolymer having Mw / Mn ≦ 4, more preferably Mw / Mn ≦ 3, it can be an index of the amount of long-chain branching, and the more long-chain branching contained in the molecular structure, the more δ (G ^*). = 0.1 MPa) The value becomes smaller. If the Mw / Mn of the copolymer is 1.5 or more, the δ (G ^* = 0.1 MPa) value may exceed 75 degrees even if the molecular structure does not include long-chain branches. Absent.

The method for measuring the complex elastic modulus is as follows.
The sample is placed in a heat press mold having a thickness of 1.0 mm, preheated in a heat press machine having a surface temperature of 180 ° C. for 5 minutes, and then pressurized and depressurized repeatedly to degas the residual gas in the molten resin. Pressurize at 4.9 MPa and hold for 5 minutes. Then, the sample is transferred to a press machine having a surface temperature of 25 ° C. and cooled by holding at a pressure of 4.9 MPa for 3 minutes to prepare a press plate composed of a sample having a thickness of about 1.0 mm. A press plate made of a sample is processed into a circle with a diameter of 25 mm, and a dynamic viscoelasticity is 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 characteristics. Measure.
・ Plate: φ25mm Parallel plate ・ Temperature: 160 ℃
・ Distortion amount: 10%
-Measurement angular frequency range: 1.0 x 10 ^{-2 to} 1.0 x 10 ² rad / s
・ Measurement interval: 5 points / decade
The phase angle δ is plotted against the common logarithm logG ^* of the absolute value G ^* (Pa) of the complex elastic modulus, and the value of δ (degrees) of the point corresponding to logG ^* = 5.0 is δ (G ^* = 0). .1 MPa). When there is no point corresponding to log G ^* = 5.0 in the measurement point, log G ^* = 5.0 with two points before and after obtaining the δ value in log G ^* = 5.0 by linear interpolation. When all the measurement points are logG ^* <5, the δ value at logG ^* = 5.0 is subtracted from the quadratic curve using the values of the three points from the largest logG ^* value.

-Production of Copolymer The copolymer according to the present invention is preferably produced in the presence of a transition metal catalyst from the viewpoint of making its molecular structure linear.
-Polymerization catalyst The type of polymerization catalyst used in the production of the copolymer according to the present invention is that the structural unit (A), the structural unit (B), and any structural unit (C) can be copolymerized. If there is, the present invention is not particularly limited, and examples thereof include Group 5 to 11 transition metal compounds having a chelating ligand.
Specific examples of preferable 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 atom and the like. Among these, the transition metal of Group 8 to 11 is preferable, the transition metal of Group 10 is more preferable, and nickel (Ni) and palladium (Pd) are particularly preferable. These metals may be single or in combination of two or more.
The chelating ligand has at least two atoms selected from the group consisting of P, N, O, and S and is bidentate or multidentate. It contains a ligand and is electronically neutral or anionic. A review by Brookhard et al. Illustrates the structure of chelating ligands (Chem. Rev., 2000, 100, 1169).
The chelating ligand preferably includes bidentate anionic P and O ligands. Examples of the bidentate anionic P and O ligands include phosphorus sulfonic acid, phosphorus carboxylic acid, phosphorus phenol, and phosphorus enolate. Other examples of chelating ligands include bidentate anionic N and O ligands. Examples of the bidentate anionic N and O ligands include salicylic aldoiminate and pyridinecarboxylic acid. Other examples of the chelating ligand include a diimine ligand, a diphenoxide ligand, and a diamide ligand.

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 arylarcin compound or an arylantimon compound which may have a substituent is coordinated. To.


[In the structural formula (a) and the structural formula (b),
M represents a transition metal belonging to any of Group 5 to 11 of the periodic table of elements, that is, 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 a hydrocarbon group that may contain hydrogen or a heteroatom having 1 to 30 carbon atoms.
R ⁵⁵ represents a hydrocarbon group that may independently contain hydrogen, halogen, or a heteroatom having 1 to 30 carbon atoms.
R ⁵⁶ and R ⁵⁷ are hydrocarbon groups, OR ⁵² , CO ₂ R ⁵² , CO ₂ M', C (O), which may independently contain hydrogen, halogen, and a heteroatom having 1 to 30 carbon atoms, respectively. 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 represents 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, a quaternary ammonium or phosphonium, x represents an integer from 0 to 3, and y represents an integer from 0 to 2.
R ⁵⁶ and R ⁵⁷ may be linked to each other to form an alicyclic ring, an aromatic ring, or a heterocycle containing a hetero atom 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.
Further, R ⁵³ and L ¹ may be bonded to each other to form a ring. ]

More preferably, the complex serving as a polymerization catalyst is a transition metal complex represented by the following structural formula (c).

[In structural formula (c),
M represents a transition metal belonging to any of Group 5 to 11 of the periodic table of elements, that is, 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 a hydrocarbon group that may contain hydrogen or a heteroatom having 1 to 30 carbon atoms.
R ⁵⁵ represents a hydrocarbon group that may independently contain hydrogen, halogen, or a heteroatom having 1 to 30 carbon atoms.
R ⁵⁸ , R ⁵⁹ , R ⁶⁰ and R ⁶¹ are hydrocarbon groups, OR ⁵² , CO ₂ R ⁵² and CO ₂ M, which may independently contain hydrogen, halogen and heteroatoms having 1 to 30 carbon atoms, respectively. ', 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' represents _{PO 3 M '2, P (} O) (oR 52) 2 M' or 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, a quaternary ammonium or phosphonium, x represents an integer from 0 to 3, and y represents an integer from 0 to 2.
A plurality of groups appropriately selected from R ^{58 to} R ⁶¹ are linked to each other to form an alicyclic ring, an aromatic ring, or a heterocycle containing a hetero atom selected from oxygen, nitrogen, or sulfur. May be good. 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.
Further, R ⁵³ and L ¹ may be bonded to each other to form a ring. ]

Here, as a catalyst of the transition metal compound of Group 5 to 11 having a chelating ligand, a catalyst such as a so-called SHOP-based catalyst and a Drent-based catalyst is typically known.
The SHOP-based catalyst is a catalyst in which a phosphorus-based ligand having an aryl group, which may have a substituent, is coordinated to a nickel metal (see, for example, WO2010-05256).
Further, the Drent-based catalyst is a catalyst in which a phosphorus-based ligand having an aryl group, which may have a substituent, is coordinated with a palladium metal (see, for example, Japanese Patent Application Laid-Open No. 2010-202647).

-Polymer polymerization method:
The method for polymerizing the copolymer according to the present invention is not limited.
As a polymerization method, slurry polymerization in which at least a part of the produced polymer becomes a slurry in a medium, bulk polymerization using the liquefied monomer itself as a medium, vapor phase polymerization performed in a vaporized monomer, or liquefaction at high temperature and high pressure. Examples thereof include high-pressure ionic polymerization in which at least a part of the produced polymer is dissolved in the monomer.
The polymerization form may be any of batch polymerization, semi-batch polymerization, and continuous polymerization.
Further, the living polymerization may be carried out, or the polymerization may be carried out while causing chain transfer.
Further, at the time of polymerization, a so-called chain shutting agent (CSA) may be used in combination to carry out a chain shutdown reaction or a coordinative chain transfer polymerization (CCTP).
Specific manufacturing processes and conditions are disclosed in, for example, JP-A-2010-260913 and JP-A-2010-202647.

-Method of introducing a carboxyl group and / or a dicarboxylic acid anhydride group into the copolymer:
The method for introducing a carboxyl group and / or a dicarboxylic acid anhydride group into the copolymer according 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.
The method for introducing a carboxyl group and / or a dicarboxylic acid anhydride group is, for example, a method of directly copolymerizing a comonomer having a carboxyl group and / or a dicarboxylic acid anhydride group, or another monomer having a functional group producing a carboxyl group. Examples thereof include a method of introducing a carboxyl group and / or a dicarboxylic acid anhydride group by modification after copolymerization.

As a method for introducing a carboxyl group and / or a dicarboxylic acid anhydride group by modification, for example, in the case of introducing a carboxylic acid, a method in which an acrylic acid ester as a precursor is copolymerized and then hydrolyzed to change to a carboxylic acid. , A method of copolymerizing t-butyl acrylate as a precursor and then converting it into a carboxylic acid by thermal decomposition.

A conventionally known acid / base catalyst may be used as an additive for accelerating the reaction during the above-mentioned hydrolysis or thermal decomposition. The acid / base catalyst is not particularly limited, but for example, hydroxides of alkali metals and alkaline earth metals such as sodium hydroxide, potassium hydroxide and lithium hydroxide, alkali metals such as sodium hydrogencarbonate and sodium carbonate, and alkaline soil. Carbonates of similar metals, solid acids such as montmorillonite, inorganic acids such as hydrochloric acid, nitrate and sulfuric acid, organic acids such as formic acid, acetic acid, benzoic acid, citric acid, paratoluene sulfonic acid, trifluoroacetic acid and trifluoromethanesulfonic acid. Can be used as appropriate.
Sodium hydroxide, potassium hydroxide, sodium carbonate, paratoluenesulfonic acid, and trifluoroacetic acid are preferable, and paratoluenesulfonic acid and trifluoroacetic acid are more preferable, from the viewpoints of reaction promoting effect, price, device corrosiveness, and the like.

(5) Ionomer In the ionomer according to the present invention, at least a part of the carboxyl group and / or the dicarboxylic acid anhydride group of the structural unit (B) in the copolymer (P) is Group 1 or Group 2 of the Periodic Table. Alternatively, it is an ionomer having a substantially linear structure converted into a metal-containing carboxylate containing at least one metal ion selected from Group 12. The ionomer is obtained by allowing a metal salt to act on the ionomer base resin as described later, and at that time, a reaction that breaks the molecular chain of the polymer does not usually occur. For this reason, structural parameters such as comonomer molar ratio, degree of branching, and randomness are usually conserved between the ionomer-based resin and the ionomer.

-Structure of ionomer Since the ionomer according to the present invention has a substantially linear structure like the copolymer according to the present invention, the absolute value G ^* = 0.1 MPa of the complex elastic modulus measured by the rotary rheometer. The phase angle δ in the above is 50 to 75 degrees.
When the phase angle δ (G ^* = 0.1 MPa) is lower than 50 degrees, the molecular structure of the ionomer shows a structure containing an excessive number of long-chain branches, and the mechanical strength becomes inferior. As described above, if Mw / Mn ≦ 4, the value of the phase angle δ is an index of the amount of long chain branching. When the Mw / Mn of the ionomer is 1.5 or more, the δ (G ^* = 0.1 MPa) value does not exceed 75 degrees even if the molecular structure does not include a long chain branch.
In the ionomer of the present invention, the lower limit of the phase angle δ is preferably 51 degrees or more, more preferably 54 degrees or more, and further preferably 56 degrees or more, from the viewpoint of improving the mechanical strength. It is more preferable that the temperature is 58 degrees or higher, and the upper limit is not particularly limited, and the closer it is to 75 degrees, the better.
・ Melting point of ionomer (Tm, ℃)
The melting point (Tm, ° C.) of the ionomer according to the present invention is preferably 50 ° C. to 140 ° C., more preferably 60 ° C. to 138 ° C., and most preferably 70 ° C. to 135 ° C. If it is lower than this range, the heat resistance is not sufficient, and if it is higher than this range, the moldability may be inferior.
Among the ionomers according to the present invention, the ionomer based on a binary copolymer composed of only the structural unit (A) and the structural unit (B) has a melting point of 90 ° C. or higher, preferably 95 ° C. or higher, more preferably 100. The temperature of the ionomer based on the ternary copolymer of ternary or higher is less than 100 ° C, preferably less than 95 ° C, and more preferably less than 90 ° C.

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

・ Neutralization degree (mol%)
The content of the metal ion preferably includes an amount that neutralizes at least a part or all of the carboxyl group and / or the dicarboxylic acid anhydride group in the copolymer as the base polymer, and a preferable degree of neutralization (average). The degree of neutralization) is 5 to 95 mol%, more preferably 10 to 90 mol%, still more preferably 20 to 80 mol%, and particularly preferably 10 to 40 mol%.
The degree of neutralization is determined from the ratio of the total mol amount of the valence of the metal ion x the mol amount to the total mol amount of the carboxy group and / or the dicarboxylic acid anhydride group in the copolymer. be able to.
Since the dicarboxylic acid anhydride group opens a ring to become a dicarboxylic acid when forming a carboxylic acid salt, the total mol amount of the carboxy group is determined assuming that 1 mol of the dicarboxylic acid anhydride group has 2 mol of carboxy group. .. Further, assuming that a divalent metal ion such as Zn ²⁺ can form a salt with 2 mol of a carboxy group per 1 mol, the total mol amount of molecules having a degree of neutralization is calculated by the amount of 2 × mol.
When the degree of neutralization is high, the tensile strength and tensile fracture stress of the ionomer are high, and the tensile fracture strain is small, but the melt flow rate (MFR) of the ionomer tends to be small. On the other hand, when the degree of neutralization is low, an ionomer having an appropriate MFR can be obtained, but the tensile elastic modulus and the tensile fracture stress tend to be low, and the tensile fracture strain tends to be high.
The degree of neutralization can be calculated from the amount of the carboxyl group and / or the dicarboxylic acid anhydride group and the molar ratio of the added metal ions.

-Method for producing ionomer The ionomer according to the present invention is ethylene and / or α-olefin having 3 to 20 carbon atoms obtained by the method for introducing a carboxyl group and / or a dicarboxylic acid anhydride group into the copolymer as described above. / A conversion step of treating an unsaturated carboxylic acid copolymer with a metal salt containing at least one metal ion selected from Group 1, Group 2, or Group 12 of the Periodic Table to convert it into a metal-containing carboxylic acid salt. It may be obtained by passing. Further, the ionomer according to the present invention heats ethylene and / or an α-olefin / unsaturated carboxylic acid ester copolymer having 3 to 20 carbon atoms, and displays at least a part of the ester groups in the copolymer in the periodic table. It may be obtained by undergoing a heat conversion step of converting into a metal-containing carboxylate containing at least one metal ion selected from Group 1, Group 2, or Group 12.

When an ionomer is produced after introducing a carboxyl group and / or a dicarboxylic acid anhydride group into the polymer, the production method thereof is, for example, as follows. That is, a substance that traps metal ions such as an ethylene / methacrylic acid (MAA) copolymer and a metal salt are optionally heated and kneaded to prepare a metal ion supply source, and then the metal ion is supplied to an ionomer base resin. It can be obtained by adding an amount of the source to a desired degree of neutralization and kneading.

Further, in the heat conversion step, (i) ethylene and / or an α-olefin / unsaturated carboxylic acid ester copolymer having 3 to 20 carbon atoms is heated, and ethylene and / or carbon atoms are 3 by hydrolysis or thermal decomposition. After making an α-olefin / unsaturated carboxylic acid copolymer of ~ 20, the ethylene and / or carbon number 3 is reacted by reacting with a compound containing a metal ion of Group 1, Group 2, or Group 12 of the periodic table. The carboxylic acid in the ~ 20 α-olefin / unsaturated carboxylic acid copolymer may be converted to the metal-containing carboxylic acid salt, and (ii) ethylene and / or the α-olefin having 3 to 20 carbon atoms. / The unsaturated carboxylic acid ester copolymer is heated, and the ester group of the copolymer is hydrolyzed or thermally decomposed to react with a compound containing metal ions of Group 1, Group 2, or Group 12 of the periodic table. As a result, the ester group portion in the ethylene and / or α-olefin / unsaturated carboxylic acid ester copolymer having 3 to 20 carbon atoms may be converted into the metal-containing carboxylic acid salt.

The compound containing a metal ion may be an oxide, hydroxide, carbonate, bicarbonate, acetate, formate or the like of a metal of Group 1, Group 2, or Group 12 of the Periodic Table.
The compound containing a metal ion 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, and the ethylene / unsaturated carboxylic acid copolymer may be used. A master batch using a polymer or an olefin copolymer as a base polymer may be prepared and supplied to the reaction system. In order to allow the reaction to proceed smoothly, a method of preparing a masterbatch and supplying it to the reaction system is preferable.

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

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

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

In the above step, the reaction atmosphere is not particularly limited, but it is generally preferable to carry out the step under an inert gas stream. Nitrogen, argon, and carbon dioxide atmospheres can be used as examples of the inert gas. There may be a small amount of oxygen or air mixed in.

The reactor used in the above step is not particularly limited, but is not limited as long as it is a method capable of stirring the copolymer substantially uniformly, and a glass container equipped with a stirrer or an autoclave (AC) is used. Alternatively, any conventionally known kneader such as a brabender plastograph, a single-screw or twin-screw extruder, a strong screw kneader, a Banbury mixer, a kneader, a roll, etc. can be used.

Whether or not metal ions were introduced into the ionomer-based resin and became ionomers was confirmed by measuring the IR spectrum of the obtained resin and examining the decrease in the peak derived from the carbonyl group of the carboxylic acid (dimer). can do. Similarly, the degree of neutralization is calculated from the above-mentioned molar ratio, and 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.

・ MFR:
In the ionomer of the present invention, the melt flow rate (MFR) at a temperature of 190 ° C. and a load of 2.16 kg is 0.1 to 30 g / 10 minutes, preferably 0.1 to 15 g / 10 minutes, more preferably. Is 0.5 to 20 g / 10 minutes.
When the MFR of the ionomer is in this range, the molecular weight is high and sufficient wear resistance can be obtained. In addition, injection molding, extrusion molding, and the like do not increase the resin pressure during molding, and molding is easy.

・ Tension modulus:
In the ionomer of the present invention, the tensile elastic modulus is 20 to 350 MPa, preferably 20 to 300 MPa.
When the tensile elastic modulus of the ionomer is in this range, the adhesiveness of the soft sheet is good. In addition, the ionomer can be manufactured without making the design in terms of elastic modulus difficult.

・ Tensile impact strength:
In the ionomer of the present invention, the tensile impact strength is 700 KJ / m ² or more, preferably 800 KJ / m ² or more.
When the tensile impact strength of the ionomer is within this range, the risk of damage to the soft sheet is reduced even if the soft sheet is rubbed with large deformation. The upper limit of tensile impact strength is not particularly limited as long as it can be obtained from materials used by those skilled in the art.

・ Amount of wear in wear test:
In the ionomer of the present invention, the amount of wear in the wear test is less than 10 mg, preferably 9 mg or less. The conditions of the wear test are as described later.
When the amount of wear in the wear test is within this range, the surface of the soft sheet is less likely to be damaged even when repeated rubbing / compression forces are applied, and the generation of wear debris can be suppressed satisfactorily. It is possible to reduce the risk of contamination and contamination of other products.

・ Haze:
In the ionomer of the present invention, the haze is 0.1 to 30%, preferably 0.1 to 20%.
When the haze of the ionomer is 30% or less, the transparency is not deteriorated and the ionomer can be used without any restrictions on the environment and usage, which is preferable. On the other hand, ionomers with a haze of less than 0.1% are difficult to manufacture, and ionomers with a lower limit of 0.1% can be manufactured without using special conditions, which is sufficient. Practical.

-Resin composition The ionomer of the present invention may be used alone or as a resin composition containing other resin components. Hereinafter, in the present invention, the term "resin composition containing ionomer" when used in a molded product includes a composition containing ionomer alone or other resin components, additives and the like. The other resin components that can be blended in the ionomer resin composition of the present invention are not particularly limited as long as they are compatible with ionomer and do not impair the effects of the present invention as the resin composition for soft sheets. For example, high-density polyethylene, medium-density polyethylene, low-density polyethylene, ethylene-vinyl acetate copolymer, ethylene-acrylic acid ester copolymer, other ionomers and the like can be mentioned. Further, two or more kinds of materials can be used in combination. The blending amount of these resin components is not particularly limited as long as the effects of the present invention are not impaired.
The resin composition of the present invention is characterized by containing the specific ionomer according to the present application, preferably from the range of 1 to 100% by weight, optionally in combination with the intended use and other conditions. You can choose the amount.
As the content in the resin composition, the ionomer of the present invention is preferably contained in an amount of 10% by weight or more, more preferably 30% by weight or more, further preferably 50% by weight or more, and 60% by weight. It is particularly preferable that the content is by weight% or more. The upper limit value can be arbitrarily selected from 100% by weight or less, 90% by weight or less, 70% by weight or less, 50% by weight or less, or 40% by weight or less.
The higher the content of the specific ionomer according to the present invention in the resin composition, the more excellent physical properties and the like due to the use of the ionomer can be sufficiently exhibited, but other processability and requirements are required. The blending amount can be arbitrarily selected from the viewpoints of physical properties and cost.

-Additives For ionomers related to the present invention, conventionally known antioxidants, ultraviolet absorbers, lubricants, antistatic agents, antiblocking agents, colorants, pigments, cross-linking agents, as long as the gist of the present invention is not deviated. Additives such as foaming agents, nucleating agents, flame retardants, conductive materials, and fillers may be blended.

In the ionomer used in the present invention, various additives and polymer components to be added or blended are mixed by using a Henschel mixer, a super mixer, a tumbler type mixer or the like as necessary, and then uniaxial or biaxial extrusion is performed. It may be pelletized by heating and kneading with a machine, a kneader or the like.

2. 2. Molded product (soft sheet)
One embodiment of the present invention relates to a soft sheet-shaped molded product molded by using the resin composition containing the ionomer.
The thickness of the sheet can be arbitrarily selected depending on the intended use, but is usually 250 μm or more, preferably 500 μm or more. In the present specification, the thickness is not particularly limited, and a sheet (sheet-shaped molded product) in which the thickness is sufficiently small compared to the length in the remaining biaxial direction and the surface having no thickness direction is exclusively used for the use is used. ). If the molded product of the present invention is bendable and has a sheet shape, the surface portion thereof can take any shape such as a quadrilateral, a circle, or a triangle. Therefore, the "sheet" of the present invention means not only a sheet in a narrow sense (thickness of 250 μm or more) but also a tape or the like. Further, those skilled in the art can appropriately adopt an appropriate sheet thickness depending on the application.

By molding the resin composition containing the ionomer of the present invention into a sheet, a molded body of a soft sheet can be obtained. As a method for producing the sheet, a method known to those skilled in the art can be used. In addition to molding with a general mold, various T-die sheet molding methods, press molding methods and the like can be mentioned.

The molded product of the present embodiment has a known use as a sheet using a conventional ethylene resin or ionomer, or an application of another sheet material which has not been conventionally used in an ethylene resin, for example, as a sheet for replacing a silicone rubber sheet. It can be used as a single layer or laminated with other materials.
Examples of applications include sanitary materials, protective sheets, steel wire coating materials, mats, antifouling sheets, dustproof sheets and the like.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.
The measurement and evaluation of the physical properties in Examples and Comparative Examples were carried out by the methods shown below. Further, not detected in the table means less than the detection limit.

<Measurement and evaluation>
(1) Measurement of phase angle δ (G ^* = 0.1 MPa) at absolute value G ^* = 0.1 MPa of complex elastic modulus 1) Preparation and measurement of sample Place the sample in a heat press mold with a thickness of 1.0 mm. After preheating in a hot press machine having a surface temperature of 180 ° C. for 5 minutes, the residual gas in the molten resin was degassed by repeating pressurization and depressurization, further pressurized at 4.9 MPa, and held for 5 minutes. Then, it was transferred to a press machine having a surface temperature of 25 ° C. and cooled by holding it at a pressure of 4.9 MPa for 3 minutes to prepare a press plate composed of a sample having a thickness of about 1.0 mm. A press plate made of a sample is processed into a circle with a diameter of 25 mm, and a dynamic viscoelasticity is 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 characteristics. It was measured.
・ Plate: φ25mm (diameter) Parallel plate ・ Temperature: 160 ℃
・ Distortion amount: 10%
-Measurement angular frequency range: 1.0 x 10 ^{-2 to} 1.0 x 10 ² rad / s
・ Measurement interval: 5 points / decade
The phase angle δ is plotted against the common logarithm logG ^* of the absolute value G ^* (Pa) of the complex elastic modulus, and the value of δ (degrees) of the point corresponding to logG ^* = 5.0 is δ (G ^* = 0). .1 MPa). When there is no point corresponding to log G ^* = 5.0 in the measurement point, log G ^* = 5.0 with two points before and after to determine the δ value in log G ^* = 5.0 by linear interpolation. When all the measurement points were logG ^* <5, the δ value at logG ^* = 5.0 was subtracted from the quadratic curve using the values of the three points from the largest logG ^* value.

(2) Measurement of Weight Average Molecular Weight (Mw) and Molecular Weight Distribution Parameter (Mw / Mn) The weight average molecular weight (Mw) was determined by gel permeation chromatography (GPC). The molecular weight distribution parameter (Mw / Mn) was further determined by gel permeation chromatography (GPC) to obtain a number average molecular weight (Mn), and was calculated by the ratio of Mw to Mn and Mw / Mn.
The measurement was performed according to the following procedure and conditions.

1) Pretreatment of the sample When the sample contained a carboxylic acid group, esterification treatment such as methyl esterification using diazomethane or trimethylsilyl (TMS) diazomethane was performed and used for the measurement. When the sample contained a carboxylic acid base, an acid treatment was performed to modify the carboxylic acid base into a carboxylic acid group, and then the above esterification treatment was performed and used for the measurement.

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

3) Measurement Connect Showa Denko's high-temperature GPC columns Showex HT-G x 1 and HT-806M x 2 to the Alliance GPCV2000 type manufactured by Waters, and use o-dichlorobenzene as the eluent at a temperature of 145 ° C. The measurement was performed at a flow rate of 1.0 mL / min.

4) Calibration curve Column calibration is performed by Showa Denko monodisperse polystyrene (S-7300, S-3900, S-1950, S-1460, S-1010, S-565, S-152, S-66.0, (0.07 mg / ml solution of each of S-28.5 and S-5.05), n-icosane and n-tetracontane were measured under the same conditions as above, and the elution time and the logarithm of the molecular weight were measured. It was approximated by a quaternary equation. The following formula was used to convert the polystyrene molecular weight ( _MPS ) and the polyethylene molecular weight ( _MPE ).
_{M PE} = 0.468 × M _PS

(3) Melt flow rate (MFR)
The MFR was measured according to Table 1-Condition 7 of JIS K-7210 (1999) under the conditions of a temperature of 190 ° C. and a load of 2.16 kg.

(4) Tensile Elastic Modulus A sheet having a thickness of 1 mm was prepared by the method (cooling method A) described in JIS K7151 (1995), and the sample was punched out to prepare 5B according to JIS K7162 (1994). A tensile test was performed under the condition of a temperature of 23 ° C. according to JIS K7161 (1994) using a small-sized test piece, and the tensile elastic modulus was measured. The test speed was 10 mm / min.

(5) Melting point and crystallinity The melting point is indicated by the peak temperature of the endothermic curve measured by a differential scanning calorimeter (DSC). A DSC (DSC7020) manufactured by SII Nanotechnology Co., Ltd. was used for the measurement, and the measurement was carried out under the following measurement conditions.
About 5.0 mg of the sample was packed in an aluminum pan, heated to 200 ° C. at 10 ° C./min, held at 200 ° C. for 5 minutes, and then lowered to 30 ° C. at 10 ° C./min. Of the absorption curve when the temperature is raised again at 10 ° C./min after holding at 30 ° C. for 5 minutes, the maximum peak temperature is set to the melting point Tm, the heat of fusion (ΔH) is obtained from the heat absorption peak area for melting, and the heat of fusion is obtained. The crystallinity (%) was determined by dividing the total crystal of high-density polyethylene (HDPE) by the heat of fusion of 293 J / g.

(6) Monomer having a carboxy group and / or a dicarboxylic acid anhydride group, and a method for measuring the amount of structural units derived from an acyclic monomer and the number of branches per 1,000 carbons The carboxy group in the multiple copolymer of the present invention. And / or the amount of structural units derived from the monomer having a dicarboxylic acid anhydride group and the acyclic monomer, and the number of branches per 1,000 carbons can be determined using a ¹³ C-NMR spectrum. ¹³ C-NMR was measured by the following method.
200 to 300 mg of sample is mixed with o-dichlorobenzene (C ₆ H ₄ Cl ₂ ) and deuterated benzene bromide (C ₆ D ₅ Br) mixed solvent (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, replaced with nitrogen, sealed, and heat-dissolved to form a uniform solution for NMR measurement samples. And said.
The NMR measurement was performed at 120 ° C. using an AV400M type NMR apparatus of Bruker Japan Co., Ltd. equipped with a 10 mmφ cryoprobe.
¹³ C-NMR was measured by the 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 number of 512 times or more.
For the chemical shift, the ¹³ C signal of hexamethyldisiloxane was set to 1.98 ppm, and the chemical shift of the signal due to other ¹³ C was based on this.

1) Pretreatment of sample When the sample contained a carboxylic acid base, it was used for the measurement after the carboxylic acid base was denatured into a carboxy group by performing acid treatment. When the sample contains a carboxy group, esterification treatment such as methyl esterification using diazomethane or trimethylsilyl (TMS) diazomethane may be appropriately performed.

2) Calculation of the amount of structural unit derived from a monomer having a carboxy group and / or a dicarboxylic acid anhydride group and an acyclic monomer

<E / tBA / iBA>
The quaternary carbon signal of the t-butyl acrylate group of tBA is 79.6 to 78.8 ppm in the ¹³ C-NMR spectrum, the methylene signal of the isobutoxy group of iBA is 70.5 to 69.8 ppm, and the methyl signal of the isobutoxy group is. It is detected at 19.5 to 18.9 ppm. Using these signal intensities, the amount of comonomer was calculated from the following formula.
Total tBA (mol%) = I (tBA) x 100 / [I (tBA) + I (iBA) + I (E)]
Total iBA (mol%) = I (iBA) x 100 / [I (tBA) + I (iBA) + I (E)]
Here, I (tBA), I (iBA), and I (E) are quantities represented by the following formulas, respectively.
I (tBA) = I _79.6-78.8
I (iBA) = (I _70.5-69.8 + I _19.5-18.9 ) / 3
I (E) = (I _{180.0 to 135.0} + I _{120.0 to 5.0-} I (iBA) x 7-I (tBA) x 7) / 2

<E / tBA / NB>
The quaternary carbon signal of the t-butyl acrylate group of tBA is detected at 79.6 to 78.8 ppm in the ¹³ C-NMR spectrum, and the methine carbon signal of NB is detected at 41.9 to 41.1 ppm. Using these signal intensities, the amount of comonomer was calculated from the following formula.
Total tBA (mol%) = I (tBA) x 100 / [I (tBA) + I (NB) + I (E)]
Total amount of NB (mol%) = I (NB) x 100 / [I (tBA) + I (NB) + I (E)]
Here, I (tBA), I (NB), and I (E) are quantities represented by the following formulas, respectively.
I (tBA) = I _79.6-78.8
I (NB) = (I _41.9-41.1 ) / 2
I (E) = (I _{180.0 to 135.0} + I _{120.0 to 5.0-} I (NB) x 7-I (tBA) x 7) / 2

When the structural unit amount of each monomer is indicated by "<0.1" including the inequality sign, it exists as a structural unit in the multi-dimensional copolymer, but it is less than 0.1 mol% in consideration of significant figures. Means that it is the amount of.

3) Calculation of the number of branches per 1,000 carbons There are two types of multiple copolymers: isolated type, which has a single branch in the main chain, and composite type (face-to-face type, in which branches and branches face each other via the main chain. There are branched-branch types and chain types with branches in the branched chain.
The following is an example of the structure of the ethyl branch. In the face-to-face type example, R represents an alkyl group.

The number of branches per 1,000 carbons is obtained by substituting any of the following I (B1), I (B2), and I (B4) into the I (branch) term of the following equation. B1 represents a methyl branch, B2 represents an ethyl branch, and B4 represents a butyl branch. The number of methyl branches is determined by using I (B1), the number of ethyl branches is determined by using I (B2), and the number of butyl branches is determined by using I (B4).
Number of branches (per 1,000 carbons) = I (branches) x 1000 / I (total)
Here, I (total), I (B1), I (B2), and I (B4) are quantities represented by the following equations.
I (total) = I _{180.0 to 135.0} + I _{120.0 to 5.0}
I (B1) = (I _{20.0 to 19.8} + I _{33.2 to 33.1} + I _{37.5 to 37.3} ) / 4
I (B2) = I _{8.6 to 7.6} + I _{11.8 to 10.5}
I (B4) = I _{14.3 to 13.7} -I _{32.2 to 32.0}
Here, I indicates the integrated intensity, and the subscript value of I indicates the range of the chemical shift. For example, I _180.0 to 135.0 indicate the integrated intensity of the ¹³ C signal detected between 180.0 ppm and 135.0 ppm.
Attribution was based on the non-patent documents Macromolecules 1984, 17, 1756-1761 and Macromolecules 1979, 12, 41.
When the number of branches is indicated by "<0.1" including the inequality sign, the amount is less than 0.1 mol% in consideration of significant figures, although it exists as a constituent unit in the multiple copolymer. It means that there is.

(7) Infrared absorption spectrum A sample is melted at 180 ° C. for 3 minutes and compression molded to prepare a film having 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 Made by JASCO Corporation Measurement method: Transmission method Detector: TGS (Triglycine sulfate)
Number of integrations: 16 to 512 times Resolution: 4.0 cm ^-1
Measurement wavelength: 5000-500 cm ^-1

(8) Tensile impact strength 1) Method for preparing a tensile impact strength test sample The sample is placed in a 1 mm thick heat press mold, preheated in a heat press machine with a surface temperature of 180 ° C. for 5 minutes, and then pressurized. The sample was melted by repeating the reduced pressure, the residual gas in the sample was degassed, the pressure was further increased at 4.9 MPa, and the sample was held for 5 minutes. Then, it was gradually cooled at a rate of 10 ° C./min under a pressure of 4.9 MPa, and when the temperature dropped to around room temperature, the molded plate was taken out from the mold. The state of the obtained molded plate was adjusted for 48 hours or more in an environment of a temperature of 23 ± 2 ° C. and a humidity of 50 ± 5 ° C. A test piece in the shape of ASTM D1822 Type-S was punched out from the press plate after adjusting the state to prepare a tensile impact strength test sample.

2) Tensile impact strength test conditions Using the above test piece, the tensile impact strength was measured with reference to Method B of JIS K 7160-1996. The only difference from JIS K 7160-1996 is the shape of the test piece. Regarding other measurement conditions, the test was carried out by a method according to JIS K 7160-1996.

(9) Measurement of wear amount 1) Preparation method of wear test sample The sample is placed in a heating press mold having dimensions: 150 mm × 150 mm and a thickness of 1 mm, and after preheating for 5 minutes in a heat press machine having a surface temperature of 180 ° C. By repeating pressurization and depressurization, the sample was melted and the residual gas in the sample was degassed, further pressurized at 4.9 MPa, and held for 3 minutes. Then, it was gradually cooled at a rate of 10 ° C./min under a pressure of 4.9 MPa, and when the temperature dropped to around room temperature, the molded plate was taken out from the mold. The state of the obtained molded plate was adjusted for 48 hours or more in an environment of a temperature of 23 ± 2 ° C. and a humidity of 50 ± 5 ° C. The pressed plate after adjusting the state was cut out into a circle with a diameter of about 115 mm, and a hole with a diameter of about 6.5 mm was made in the center to prepare a wear test sample.

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

(10) Haze 1) Method for adjusting the press plate of the sample The sample is placed in a mold for a heating press having dimensions: 50 mm × 60 mm and a thickness of 0.5 mm, preheated in a heat press machine having a surface temperature of 180 ° C. for 5 minutes, and then added. Residual gas in the sample was degassed by repeating pressure and depressurization, further pressurized at 4.9 MPa, and held for 3 minutes. Then, it was transferred to a press machine having a surface temperature of 25 ° C. and cooled by holding it at a pressure of 4.9 MPa for 3 minutes to prepare a press plate having a thickness of about 0.5 mm.
2) Haze measurement conditions Using the above test piece, haze was measured in accordance with JIS K 7136-2000.

<Synthesis of metal complex>
(1) Synthesis of B-27DM / Ni complex The B-27DM / Ni complex has the following 2-bis (2,6-dimethoxyphenyl) phosphane according to Synthesis Example 4 described in International Publication No. 2010/050256. A 6-pentafluorophenylphenol ligand (B-27DM) was used. B-27DM and Ni (COD) using bis (1,5-cyclooctadiene) nickel (0) (referred to as Ni (COD) ₂ ) according to Example 1 of International Publication No. 2010/050256. A nickel complex (B-27DM / Ni) in which ₂ was reacted 1: 1 was synthesized.

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

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

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

(Ii) Synthesis of Compound 3 Iso-PrMgCl (2M, 5.25 ml) was added to a solution of Compound 2 (2.64 g, 10.0 mmol) in THF (5.0 ml) at 0 ° C. After stirring the reaction mixture at 25 ° C. for 1 hour, PCL ₃ (618 mg, 4.50 mmol) was added at −78 ° C.
The reaction mixture was heated to 25 ° C. over 3 hours to give a yellow suspension. The solvent was distilled off under reduced pressure to obtain a yellow solid. This mixture was used in the next reaction without purification.

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

(Iv) Synthesis of Compound 7 Compound 5 (5.00 g, 27.5 mmol), Compound 6 (4.42 g, 18.3 mmol), Pd ₂ (dba) ₃ (168 mg, 0.183 mmol), s-Phos (2). - dicyclohexylphosphino-2 ', 6'-dimethoxy _{biphenyl) (376mg, 0.916mmol), K} 3 PO 4 (7.35g, 34.6mmol) and was weighed in a reaction vessel was added toluene (40 ml). The solution was reacted at 110 ° C. for 12 hours to give a black suspension.
H ₂ O (50ml) was added, and extracted with EtOAc (55ml × 3).
The organic layer was washed with saline (20 ml) and dehydrated with Na ₂ SO ₄ .
The organic layer was filtered to distill off the solvent under reduced pressure, and then purified by a silica gel column to obtain 1.3 g of an oily substance.

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

(Vi) Synthesis of B-423 HCl / EtOAc (4M, 50 ml) was added to a solution of compound 8 (2.9 g, 4.8 mmol) in dichloromethane (20 ml) at 0 ° C. A solution was obtained.
After distilling off the solvent under reduced pressure, dichloromethane (50 ml) was added. Washing with saturated aqueous NaHCO ₃ solution (100 ml) gave 2.5 g of B-423. The NMR attribution values of the obtained ligand B-423 are shown below.
[NMR]
^{1 1} H NMR (CDCl ₃ , δ, ppm): 7.49 (t, 1H), 7.33 (t, 1H), 7.22 (m, 4H), 6.93 (d, 1H), 6. 81 (t, 1H), 6.49 (dd, 4H), 6.46 (br, 1H), 3.56 (s, 12H), 2.63 (sept, 2H), 1.05 (d, 6H) ), 1.04 (d, 6H);
³¹ P NMR (CDCl ₃ , δ, ppm): -61.6 (s).

2) Synthesis of B-423 / Ni complex The B-423 / Ni complex uses a B-423 ligand and is bisacetylacetonatonickel (II) according to Example 1 of International Publication No. 2010/050256. ) (Refered to be Ni (acac) ₂ ) was used to synthesize a nickel complex (B-423 / Ni) in which B-423 and Ni (acac) ₂ reacted 1: 1.

<(Manufacturing Examples 1 and 2): Production of ionomer-based resin precursor>
Ethylene / acrylic acid tBu / acrylic acid ester copolymers and ethylene / acrylic acid tBu / norbornene copolymers were produced using transition metal complexes (B-27DM / Ni complex or 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 a metal catalyst species, a metal catalyst amount, a trioctyl aluminum (TNOA) amount, a toluene amount, and a comonomer type were produced. Table 1 shows the production conditions and production results that were appropriately changed, such as the amount of comonomer, ethylene partial pressure, polymerization temperature, and polymerization time, and Table 2 shows the physical properties of the obtained copolymer. However, not detected in the table means less than the detection limit.

<(Resin 1, 2): Manufacture of ionomer-based resin>
40 g of the obtained copolymers of Production Examples 1 and 2, 0.8 g of paratoluenesulfonic acid monohydrate, and 185 ml of toluene were placed in a separable flask having a capacity of 500 ml, and the mixture was stirred at 105 ° C. for 4 hours. After adding 185 ml of ion-exchanged water, stirring and allowing to stand, the aqueous layer was extracted. After that, the ion-exchanged water was repeatedly added and extracted until the pH of the extracted aqueous layer became 5 or more. The solvent was distilled off from the remaining solution under reduced pressure, and the mixture was dried until it became constant.
In the IR spectrum of the obtained resin, the peak near 850 cm ^-1 derived from the tBu group disappeared, the peak near 1730 cm ^-1 derived from the carbonyl group of the ester decreased, and the carbonyl of the carboxylic acid (dimer). An increase in the peak around 1700 cm ^-1 derived from the group was observed.
As a result, the decomposition of t-Bu ester and the formation of carboxylic acid were confirmed, and ionomer-based resins 1 and 2 were obtained. Table 3 shows the physical characteristics of the obtained resin. However, not detected in the table means less than the detection limit. Here, "E", "AA", "iBA", and "NB" in the following table represent the structural units of the copolymer, "ethylene", "acrylic acid", "i-butyl acrylate", and "norbornene", respectively. ..

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

2) Preparation of Zn ion supply source Labplast mill manufactured by Toyo Seiki Co., Ltd. equipped with a small mixer with a capacity of 60 ml: Ethylene / methacrylic acid (MAA) copolymer (Mitsui / Dow Polychemical Co., Ltd.) on roller mixer R60 type A Zn ion supply source was prepared by adding 21.8 g of (brand: Nucle N1050H), 18 g of zinc oxide and 0.2 g of zinc stearate, and kneading at 180 ° C. and 40 rpm for 3 minutes.

3): Preparation of ionomer Labplast mill manufactured by Toyo Seiki Co., Ltd. equipped with a small mixer with a capacity of 60 ml: 40 g of resins 1 and 2 was added to a roller mixer R60 type and kneaded at 160 ° C. and 40 rpm for 3 minutes to dissolve it. .. Then, a Na ion supply source or a Zn ion supply source was added so as to have 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 near 1700 cm ^-1 derived from the carbonyl group of the carboxylic acid (dimer) decreased, and the peak near 1560 cm ^-1 derived from the carbonyl group of the carboxylic acid base increased. Was there. It was confirmed that an ionomer having a desired degree of neutralization could be 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 characteristics of the obtained ionomer are shown in Tables 4 and 5.

(Comparative Example 1): E / MAA-based binary ionomer A copolymer of ethylene, methacrylic acid, and Na methacrylate, which is an ionomer resin manufactured by a high-pressure radical process (a brand manufactured by Mitsui Dow Polychemical Co., Ltd.). : HIMILAN HIM1555) was used as a reference ionomer. The physical characteristics are shown in Tables 4 and 5.

(Comparative Example 2): E / MAA-based binary ionomer A copolymer of ethylene, methacrylic acid, and Na methacrylate, which is an ionomer resin produced by a high-pressure radical process (a brand manufactured by Mitsui Dow Polychemical Co., Ltd.). : HIMILAN HI M1605) was used as a reference ionomer. The physical characteristics are shown in Tables 4 and 5.

<Discussion of the results of Examples and Comparative Examples>
As described above, when comparing Examples 1 to 3 and Comparative Examples 1 and 2 from the results shown in Table 5, the ethylene ionomer that does not satisfy the specific requirements of the ethylene ionomer for the soft sheet of the present invention is flexible. The balance of wear resistance, impact resistance, and transparency is inferior to that of the ethylene ionomers of Examples 1 to 3.
Compared with these comparative examples, the ethylene ionomer for a soft sheet and its molded product according to the present invention have a good balance of flexibility, abrasion resistance, impact resistance, and transparency as shown in Examples 1 to 3. It was confirmed that.

According to the present invention, it is possible to provide a soft sheet made of ethylene-based ionomer, which is suitable for a cushioning sheet or a vibration-proof sheet.
That is, the molded product using the ethylene-based ionomer of the present invention has an excellent balance of flexibility, wear resistance, impact resistance, and transparency, and is therefore very useful in industry.

Claims (11)

An ethylene ionomer for a soft sheet, the ionomer has a structural unit (A) derived from ethylene and / or an α-olefin having 3 to 20 carbon atoms, and a carboxyl group and / or a dicarboxylic acid anhydride group. At least a part of the carboxyl group and / or the dicarboxylic acid anhydride group in the copolymer (P) containing the structural unit (B) derived from the monomer as an essential structural unit is Group 1, Group 2, or Group 12 of the periodic table. An ethylene ionomer for a soft sheet, which is converted into a metal-containing carboxylate containing at least one metal ion selected from the above and has the following properties (a) to (f).
(A) The phase angle δ at the absolute value G ^* = 0.1 MPa of the complex elastic modulus measured by the rotary rheometer is 50 to 75 degrees.
(B) The melt flow rate (MFR) at a temperature of 190 ° C. and a load of 2.16 kg is 0.1 to 15 g / 10 minutes.
(C) The tensile elastic modulus is 20 to 350 MPa.
(D) The tensile impact strength is 700 KJ / m ² or more.
(E) The amount of abrasion resistance in the wear test is less than 10 mg.
(F) The haze is 0.1 to 30%. The soft sheet according to claim 1, wherein the number of methyl branches calculated by ¹³ C-NMR of the copolymer (P) in the ionomer is 50 or less per 1,000 carbons. Ethylene ionomer. The soft sheet according to claim 1, wherein the number of methyl branches calculated by ¹³ C-NMR of the copolymer (P) in the ionomer is 5 or less per 1,000 carbons. Ethylene ionomer. The soft sheet according to any one of claims 1 to 3, wherein the copolymer (P) in the ionomer contains 2 to 20 mol% of the structural unit (B) in the copolymer. Ethylene ionomer for. The ethylene-based ionomer for a soft sheet according to any one of claims 1 to 4, wherein the structural unit (A) in the ionomer is a structural unit derived from ethylene. The invention according to any one of claims 1 to 5, wherein the copolymer (P) in the ionomer is produced using a transition metal catalyst containing a transition metal of Groups 8 to 11 of the periodic table. Ethylene ionomer for soft sheets. The ethylene ionomer for a soft sheet according to claim 6, wherein the transition metal catalyst is a transition metal catalyst composed of a phosphorus sulfonic acid or a phosphorus phenol ligand and nickel or palladium. A structural unit (C) in which the copolymer (P) is a compound having one or more carbon-carbon double bonds in the molecular structure other than the structural unit (A) and the structural unit (B). The ethylene ionomer for a soft sheet according to any one of claims 1 to 7, which is a copolymer contained as an essential structural unit. The eighth aspect of the present invention, wherein the structural unit (C) in the copolymer (P) is a non-cyclic monomer which is a (meth) acrylic acid ester or a cyclic monomer which is a norbornene-based olefin. Ethylene ionomer for soft sheets. A structural unit (A) derived from ethylene and / or an α-olefin having 3 to 20 carbon atoms, and
At least a part of the carboxyl group and / or the dicarboxylic acid anhydride group in the copolymer (P) containing the structural unit (B) derived from the monomer having a carboxyl group and / or the dicarboxylic acid anhydride group as an essential structural unit. Is converted to a metal-containing carboxylate containing at least one metal ion selected from Group 1, Group 2, or Group 12 of the Periodic Table.
An ethylene-based ionomer resin composition for a soft sheet, which comprises an ionomer having a phase angle δ at an absolute value G ^* = 0.1 MPa of a complex elastic modulus measured by a rotary rheometer of 50 to 75 degrees. .. A molded product using the ethylene ionomer for a soft sheet according to any one of claims 1 to 9 or the ethylene ionomer resin composition for a soft sheet according to claim 10.