JP2021008612A - Resin for glass laminate - Google Patents

Abstract

To provide a resin for glass laminate including an ionomer which is excellent in balance among impact resistance, transparency and adhesion.SOLUTION: In a resin for glass laminate including an ionomer, at least a part of a carboxyl group and/or a dicarboxylic acid anhydride group in a copolymer (P) containing a structural unit (A) derived from ethylene and/or α-olefin having 3-20 carbon atoms and a structural unit (B) derived from a monomer having a carboxyl group and/or a dicarboxylic acid anhydride group as essential constitutional units is converted into a metal-containing carboxylate containing at least one metal ion selected from group I, group II or group XII of the periodic table, and a phase angle δ at an absolute value G* of 0.1 MPa of a complex elastic modulus measured by a rotary type rheometer is 50-75 degrees.SELECTED DRAWING: None

Description

The present invention relates to a resin for a glass laminate using a novel ionomer.

The ethylene 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 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.

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 unsaturated carboxylic acid is added by a high-pressure radical polymerization method. A polymerized polar group-containing olefin copolymer 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 this 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. It has the disadvantage of being insufficient in strength. Therefore, conventional commercially available ionomers using a polar group-containing olefin copolymer polymerized by a high-pressure radical polymerization method as a base resin have insufficient impact resistance.

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, etc., 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 2).

Ethylene-based ionomers are also used as a resin layer for glass laminates, and applications include laminated glass interlayer films and solar cell encapsulants. Laminated glass is laminated glass in which two or more glass plates are bonded via a resin interlayer film. Laminated glass is used as automobile windshields, instrument monitor glass, and building material glass. By providing the interlayer film, the flexibility of the interlayer film and the adhesiveness to the glass provide safety advantages such as prevention of cracking of the glass and prevention of scattering of fragments when the interlayer film is broken. Therefore, the laminated glass interlayer film is required to have transparency, impact resistance, and adhesiveness to glass. Laminated glass using an ethylene ionomer as an interlayer film is described in Patent Documents 3 and 4.

The solar cell encapsulant is a material that adheres to both the front and back surfaces of a power generation element composed of a solar cell and an interconnector to seal the element in the solar cell module. The power generation element adheres to the light receiving layer and the back surface layer of the solar cell module via this sealing material. A glass layer called a cover glass is generally used as the light receiving layer, and a weather resistant resin film is used as the back surface layer. The encapsulant in the solar cell module is required to have high transparency so that the incident light passing through the light receiving layer reaches the solar cell without loss and a function of protecting the power generation element from the impact from the outside world. Patent Document 5 describes a solar cell encapsulant whose adhesiveness is improved by adding a silane coupling agent to an ethylene ionomer.

U.S. Pat. No. 3,264,272 Japanese Unexamined Patent Publication No. 2016-79408 Japanese Unexamined Patent Publication No. 2018-193261 Japanese Unexamined Patent Publication No. 2016-188158 Japanese Unexamined Patent Publication No. 2009-248377

As described above, the laminated glass interlayer film and the solar cell encapsulant are required to have high impact resistance, high transparency, and high adhesiveness to glass. Ionomer is one of the materials under consideration. Although patent documents 3 and 4 describe laminated glass in which a silane coupling agent is added to an ethylene-based ionomer to improve adhesiveness, an ionomer resin is used. Since there has never been an example of improving the adhesiveness by improving a single unit, there was room for improvement in terms of cost and productivity. In addition, the impact resistance is still not sufficient, and there is no example in which the impact resistance is improved by improving the resin alone. Even in the ionomer described in Patent Document 5, it is not an example in which the adhesive strength is improved by the resin alone, the impact resistance is still not sufficient, and there is no example in which the impact resistance is improved by improving the resin alone.

In view of the situation of the prior art, an object of the present application is to provide a resin for a glass laminate containing an ionomer having an excellent balance of impact resistance, transparency and adhesiveness.

As a result of repeated studies by the present inventors to solve the above problems, by using a specific ionomer resin, a significantly superior effect to the required physical properties such as impact resistance, transparency, and adhesiveness can be obtained. Found to have.
The ethylene-based ionomer described in Patent Document 2 is a novel ethylene-based ionomer in which the base resin has a substantially linear molecular structure and also functions as an ionomer, and its physical properties and the like are conventional. Unlike ethylene ionomers, which have a multi-branched molecular structure, their unique properties and suitable applications were unknown. The present invention is based on the finding that a resin containing a substantially linear ethylene-based ionomer has an excellent effect on improving the physical properties required as a resin layer used for a glass laminate.

That is, the present invention is as shown in the following [1] to [13].
[1] 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.
A resin for a glass laminate containing an ionomer, wherein a phase angle δ at an absolute value G ^* = 0.1 MPa of a complex elastic modulus measured by a rotary rheometer is 50 degrees to 75 degrees.
[2] The glass laminate according to [1], wherein the number of methyl branches calculated by ¹³ C-NMR of the copolymer (P) is 50 or less per 1,000 carbons. It is a resin.
[3] The glass laminate according to [1], wherein the number of methyl branches calculated by ¹³ C-NMR of the copolymer (P) is 5 or less per 1,000 carbons. It is a resin.
[4] The glass laminate according to any one of [1] to [3], wherein the copolymer (P) contains 2 to 20 mol% of the structural unit (B) in the copolymer. Resin for use.
[5] The resin for a glass laminate according to any one of [1] to [4], wherein the structural unit (A) is a structural unit derived from ethylene.
[6] Described in any one of [1] to [5], wherein the copolymer (P) is produced using a transition metal catalyst containing a transition metal of Groups 8 to 11 of the periodic table. This is a resin for glass laminates.
[7] The resin for a glass laminate according to [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.
[8] The resin film for a glass laminate, which comprises using the resin for a glass laminate according to any one of the above [1] to [7].
[9] A resin film for a glass interlayer film, which comprises using the resin for a glass laminate according to any one of the above [1] to [7].
[10] A resin film for a solar cell encapsulant, characterized in that the resin for a glass laminate according to any one of the above [1] to [7] is used.
[11] The glass laminate is characterized in that the resin film for the glass laminate of the above [8] is laminated.
[12] The laminated glass is characterized in that the resin film for the glass interlayer film of the above [9] is laminated.
[13] The solar cell module is characterized in that the resin film for the solar cell encapsulant according to the above [10] is laminated.

The resin for a glass laminate containing an ionomer of the present invention, which has a substantially linear structure, has a better balance of impact resistance, transparency, and adhesiveness than the existing resin for a glass laminate made of polyethylene or an ionomer resin. Excellent.

It is an image figure 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. It is a figure which shows the relationship between the tensile impact strength and the adhesive strength to glass of Examples 1-10 and Comparative Examples 1-2.

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 resin for a glass laminate using an ionomer, which is characterized by being converted into a metal-containing carboxylate containing at least one kind of metal ion.

Hereinafter, ionomers related to the present invention, resins for glass laminates using ionomers, uses thereof, and the like 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.

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, and bicyclo [2. 2,1] Unsaturated carboxylic acids such as hept-2-ene-5,6-dicarboxylic acid can be mentioned, and examples of the structural unit derived from the monomer having a dicarboxylic acid anhydride group include maleic anhydride and itaconic anhydride. , Citraconic anhydride, tetrahydrophthalic anhydride, 5-norbornene-2,3-dicarboxylic acid anhydride, 3,6-epoxy-1,2,3,6-tetrahydrophthalic 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 moisture 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) used in the present invention includes a binary copolymer consisting of only a structural unit (A) and a structural unit (B), a structural unit (A) and a structural unit (B), and other than these. A multi-dimensional copolymer further containing a structural unit (C) can be used, but preferably a multi-dimensional copolymer further containing a structural unit (C) other than the structural unit (A) and the structural unit (B). It is a copolymer. As the monomer giving the structural unit (C), any monomer can be used as long as it is not included in the structural unit (A) and the monomer giving the structural unit (B). The 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) described later or Examples thereof include a cyclic monomer represented by the general formula (2).
Compared to the binary copolymer consisting of only the structural unit (A) and the structural unit (B), by using a ternary or more multi-polymer copolymer containing the structural unit (C) component as the base resin of the ionomer, the ionomer is used. The physical properties of the resin can be controlled more finely. In particular, it is advantageous because the impact resistance can be further improved. 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.

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

[In 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 group. A hydrocarbon group having 2 to 20 carbon atoms substituted with an alkoxy group of ~ 20, a hydrocarbon group having 3 to 20 carbon atoms substituted with an ester group having 2 to 20 carbon atoms, 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. ]

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 groups 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 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.

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

[In 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, such as norbornene, vinylnorbornene, etilidennorbornene, norbornadiene, tetracyclododecene, tricyclo [4.3.0.1 ^2,5 ], and tricyclo [4.3.0. 1 ^{2, 5} ] Compounds having a cyclic olefin skeleton such as deca-3-ene are mentioned, and 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 is 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 entire 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 units 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 copolymer (P) is provided with structural units other than the structural units (A) and (B), the lower limit of the structural unit amount of the structural unit (C) according to the present invention is preferably 0.001 mol% or more. It is 0.010 mol% or more, more preferably 0.020 mol% or more, further preferably 0.1 mol% or more, even more preferably 1.5 mol% or more, particularly preferably 2.9 mol% or more, and the upper limit is 20. It is selected from 0.0 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 2.9 mol% or less.
When the amount of the structural unit derived from the arbitrary monomer (C) is in this range, the flexibility of the copolymer becomes more sufficient and more sufficient mechanical properties can be obtained.
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 (P):
In the copolymer 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. There may be 5.0 or less, 1.0 or less, 0.5 or less, and the lower limit is not particularly limited, and the smaller the number, the more. Good. 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 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 copolymer of the present invention and the acyclic monomer, and the number of branches per 1,000 carbons are ¹³ C-NMR spectra. Obtained using. ¹³ C-NMR is measured by the following method.
Sample 200-300 mg in a mixed solvent (C ₆ H ₄ Cl ₂ / C ₆ D ₅ Br = 2 /) of o-dichlorobenzene (C ₆ H ₄ Cl ₂ ) and benzene dehydride (C ₆ D ₅ Br) 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 structural unit amount and the number of branches of each monomer in the copolymer were analyzed by identifying the monomer or the signal peculiar to the branching of the copolymer and comparing the intensities thereof. can do. 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 ,000,000 or less, preferably 1,500,000 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 the number average molecular weight (Mn) of the copolymer according to the present invention can be 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. at 10 ° C./min. ..

-Crystallinity (%):
In the copolymer of the present invention, the crystallinity observed by differential scanning calorimetry (DSC) is not particularly limited, but is preferably more than 0% and 30% or less, more than 0% and 25. % Or less is more preferable, more than 5% and 25% or less are particularly preferable, and 7% or more and 24% or less are most preferable.
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 heat of fusion of a complete crystal of high-density polyethylene (HDPE). It can be obtained by dividing by 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 any monomer form a random copolymer.

If the molecular structure example (2) of the copolymer in 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 contains a small amount of long-chain branches that do not affect the mechanical strength, and is a substantially linear structure. 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 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 either 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).
Preferred examples of the chelating ligand include 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.

［構造式（ａ）、及び構造式（ｂ）において、
Ｍは、元素の周期表の第５〜１１族のいずれかに属する遷移金属、即ち前述したような種々の遷移金属を表す。
Ｘ^１は、酸素、硫黄、−ＳＯ_３−、又は−ＣＯ_２−を表す。
Ｙ^１は、炭素又はケイ素を表す。
ｎは、０又は１の整数を表す。
Ｅ^１は、リン、砒素又はアンチモンを表す。
Ｒ^５３及びＲ^５４は、それぞれ独立に、水素又は炭素数１ないし３０のヘテロ原子を含有してもよい炭化水素基を表す。
Ｒ^５５は、それぞれ独立に、水素、ハロゲン、又は炭素数１ないし３０のヘテロ原子を含有してもよい炭化水素基を表す。
Ｒ^５６及びＲ^５７は、それぞれ独立に、水素、ハロゲン、炭素数１ないし３０のヘテロ原子を含有してもよい炭化水素基、ＯＲ^５２、ＣＯ_２Ｒ^５２、ＣＯ_２Ｍ’、Ｃ（Ｏ）Ｎ（Ｒ^５１）_２、Ｃ（Ｏ）Ｒ^５２、ＳＲ^５２、ＳＯ_２Ｒ^５２、ＳＯＲ^５２、ＯＳＯ_２Ｒ^５２、Ｐ（Ｏ）（ＯＲ^５２）_２−ｙ（Ｒ^５１）_ｙ、ＣＮ、ＮＨＲ^５２、Ｎ（Ｒ^５２）_２、Ｓｉ（ＯＲ^５１）_３−ｘ（Ｒ^５１）_ｘ、ＯＳｉ（ＯＲ^５１）_３−ｘ（Ｒ^５１）_ｘ、ＮＯ_２、ＳＯ_３Ｍ’、ＰＯ_３Ｍ’_２、Ｐ（Ｏ）（ＯＲ^５２）_２Ｍ’又はエポキシ含有基を表す。
Ｒ^５１は、水素又は炭素数１ないし２０の炭化水素基を表す。
Ｒ^５２は、炭素数１ないし２０の炭化水素基を表す。
Ｍ’は、アルカリ金属、アルカリ土類金属、アンモニウム、４級アンモニウム又はフォスフォニウムを表し、ｘは、０から３までの整数、ｙは、０から２までの整数を表す。
なお、Ｒ^５６とＲ^５７が互いに連結し、脂環式環、芳香族環、又は酸素、窒素、若しくは硫黄から選ばれるヘテロ原子を含有する複素環を形成してもよい。この時、環員数は５〜８であり、該環上に置換基を有していても、有していなくてもよい。
Ｌ^１は、Ｍに配位したリガンドを表す。
また、Ｒ^５３とＬ^１が互いに結合して環を形成してもよい。］ The structure of the metal complex obtained from the chelating ligand is represented by the following structural formula (a) or (b) in which an arylphosphine compound, an arylarcin compound or an arylantimon compound which may have a substituent is coordinated. Ru.

[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 each independently a hydrocarbon group which may contain hydrogen, halogen, or a heteroatom having 1 to 30 carbon atoms, OR ⁵² , CO ₂ R ⁵² , CO ₂ M', C (O). N (R ⁵¹ ) ₂ , C (O) R ⁵² , SR ⁵² , SO ₂ R ⁵² , SOR ⁵² , OSO ₂ R ⁵² , P (O) (OR ⁵² ) _2-y (R ⁵¹ ) _y , CN, NHR _{^{52, N (R 52) 2}} , Si (OR 51) 3-x (R 51) x, OSi (OR 51) 3-x (R 51) x, NO 2, SO 3 M ', PO 3 M' 2 , P (O) (OR ⁵² ) ₂ M'or 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. ]

［構造式（ｃ）において、
Ｍは、元素の周期表の第５〜１１族のいずれかに属する遷移金属、即ち前述したような種々の遷移金属を表す。
Ｘ^１は、酸素、硫黄、−ＳＯ_３−、又は−ＣＯ_２−を表す。
Ｙ^１は、炭素又はケイ素を表す。
ｎは、０又は１の整数を表す。
Ｅ^１は、リン、砒素又はアンチモンを表す。
Ｒ^５３及びＲ^５４は、それぞれ独立に、水素又は炭素数１ないし３０のヘテロ原子を含有してもよい炭化水素基を表す。
Ｒ^５５は、それぞれ独立に、水素、ハロゲン、又は炭素数１ないし３０のヘテロ原子を含有してもよい炭化水素基を表す。
Ｒ^５８、Ｒ^５９、Ｒ^６０及びＲ^６１は、それぞれ独立に、水素、ハロゲン、炭素数１ないし３０のヘテロ原子を含有してもよい炭化水素基、ＯＲ^５２、ＣＯ_２Ｒ^５２、ＣＯ_２Ｍ’、Ｃ（Ｏ）Ｎ（Ｒ^５１）_２、Ｃ（Ｏ）Ｒ^５２、ＳＲ^５２、ＳＯ_２Ｒ^５２、ＳＯＲ^５２、ＯＳＯ_２Ｒ^５２、Ｐ（Ｏ）（ＯＲ^５２）_２−ｙ（Ｒ^５１）_ｙ、ＣＮ、ＮＨＲ^５２、Ｎ（Ｒ^５２）_２、Ｓｉ（ＯＲ^５１）_３−ｘ（Ｒ^５１）_ｘ、ＯＳｉ（ＯＲ^５１）_３−ｘ（Ｒ^５１）_ｘ、ＮＯ_２、ＳＯ_３Ｍ’、ＰＯ_３Ｍ’_２、Ｐ（Ｏ）（ＯＲ^５２）_２Ｍ’又はエポキシ含有基を表す。
Ｒ^５１は、水素又は炭素数１ないし２０の炭化水素基を表す。
Ｒ^５２は、炭素数１ないし２０の炭化水素基を表す。
Ｍ’は、アルカリ金属、アルカリ土類金属、アンモニウム、４級アンモニウム又はフォスフォニウムを表し、ｘは、０から３までの整数、ｙは、０から２までの整数を表す。
なお、Ｒ^５８〜Ｒ^６１から適宜選択された複数の基が互いに連結し、脂環式環、芳香族環、又は酸素、窒素、若しくは硫黄から選ばれるヘテロ原子を含有する複素環を形成してもよい。このとき、環員数は５〜８であり、該環上に置換基を有していても、有していなくてもよい。
Ｌ^１は、Ｍに配位したリガンドを表す。
また、Ｒ^５３とＬ^１が互いに結合して環を形成してもよい。］ More preferably, the complex serving as 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 for the transition metal compounds of Groups 5 to 11 having a chelating ligand, catalysts such as so-called SHOP-based catalysts and Drent-based catalysts are 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).
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, JP-A-2010-20647).

-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. Carbonic acid of similar metals, solid acid such as montmorillonite, inorganic acid such as hydrochloric acid, nitric acid, sulfuric acid, organic acid such as formic acid, acetic acid, benzoic acid, citric acid, paratoluenesulfonic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, etc. Can be used as appropriate.
Sodium hydroxide, potassium hydroxide, sodium carbonate, trifluoroacetic acid, and paratoluenesulfonic acid are preferable, and trifluoroacetic acid and paratoluenesulfonic 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 converted to a metal-containing carboxylic acid salt containing at least one metal ion selected from Group 12, and the phase angle δ at the absolute value G ^* = 0.1 MPa of the heteroelasticity measured by a rotary leometer is determined. It is an ionomer having a substantially linear structure at 50 to 75 degrees. 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 ionomer-based resins and ionomers.

-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 of the complex elastic modulus measured by the rotary rheometer G ^* = 0.1 MPa. 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. Further, even when the molecular structure does not include a long chain branch, the δ (G ^* = 0.1 MPa) value does not exceed 75 degrees.
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 preferably 58 degrees or more, 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 adhesiveness 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 10 to 80 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.

・ Haze (%)
The ethylene-based ionomer resin of the present invention preferably has a haze value (%) measured according to JIS K 7136-2000 of 25% or less, more preferably 20% or less. When the haze (%) is 25% or less, the transparency of the molded product becomes better, which is more preferable in applications such as window glass and solar cell modules where transparency is required.

・ Tensile impact strength (kJ / m ² )
The ethylene-based ionomer resin of the present invention preferably has a tensile impact strength of 700 kJ / m ² or more, preferably 720 kJ or more, as measured with reference to the B method of JIS K 7160-1996, from the viewpoint of sufficient impact resistance. more preferably / ^{m 2} or more, still more preferably 800KJ / ^{m 2} or more, particularly preferably 1000 kJ / ^{m 2} or more.

・ Adhesive strength (N / 10mm)
The ethylene-based ionomer resin of the present invention is preferably 2.0 N / 10 mm or more, more preferably 2.3 N / 10 mm or more, and more preferably 2.5 N / 10 mm or more, from the viewpoint that the adhesive strength measured by the tensile tester described below becomes sufficient. It is more preferably 10 mm or more, and even more preferably 3.0 N / 10 mm or more.

-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 metal ion supply source is prepared by heating and kneading a metal ion trapping substance such as an ethylene / methacrylic acid (MAA) copolymer and a metal salt in some cases, and then supplying the metal ion 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 forming an α-olefin / unsaturated carboxylic acid copolymer of ~ 20, the ethylene and / or carbon number 3 is formed 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 α-olefin / unsaturated carboxylic acid copolymer of ~ 20 may be converted to the metal-containing carboxylic acid salt, and (ii) ethylene and / or 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, may be dissolved or dispersed in water or an organic solvent, and then supplied to the reaction system. 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 at which the ethylene and / or α-olefin / unsaturated carboxylic acid ester copolymer having 3 to 20 carbon atoms is heated 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 a metal ion was introduced into an ionomer-based resin and became an ionomer 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.

2. 2. Resin film for glass laminate and glass laminate The ionomer according to the present invention can be used for the resin film constituting at least one layer of the glass laminate. "Glass laminate" refers to a laminate having a multilayer structure of two or more layers, of which at least one layer is glass. Therefore, the glass laminate in the present invention is a structure having at least one glass layer and at least one resin layer containing an ionomer according to the present invention (hereinafter, the layer is also referred to as an “ionomer resin layer”). Preferably, the glass layer and the ionomer resin layer are in direct contact. The material used for the other layers can be freely selected by those skilled in the art depending on the use of the glass laminate.

The resin film for a glass laminate of the present invention is a film containing a resin for a glass laminate containing the ionomer. Here, the term "membrane" generally refers to a structure having a thickness that can be ignored with respect to the area, but in the present invention, the term "membrane" is used as a film in a narrow sense (generally a thickness of 250 μm or less) or a sheet. Not only that, it is treated as including plate-like objects. Further, regardless of the flexibility of the film, even if it is hard and has a specific shape, it is not particularly limited as long as it can form a laminated body. The surface portion of the film can take any shape such as a quadrilateral, a circle, or a triangle.

The resin film for a glass laminate may consist of only the ionomer, but if necessary, an antioxidant, an ultraviolet absorber, a light stabilizer, a flame retardant, a dye, a pigment, a plasticizer, an antioxidant, etc. Additives such as inorganic particles, fluorescent agents, heat ray absorbers, heat ray reflectors, modified silicone oils, moisture resistant agents, and antiblocking agents may be contained as adhesive force adjusting agents. Further, other resins may be contained in order to provide effects such as absorption of ultraviolet rays / infrared rays, soundproofing, and moisture proofing as long as the effects of the present invention are not impaired. The resin that can be used can be freely selected by those skilled in the art according to the use of the laminate.

Further, the resin film for the glass laminate itself may have a plurality of layers. That is, it may have a single-layer structure consisting of only the ionomer resin layer, or may have a multi-layer structure in which the ionomer resin layer and another layer (one layer or two or more layers) are laminated. As the other layer, an adhesive layer containing a resin exhibiting adhesiveness to glass, such as a polyvinyl acetal resin, may be provided, although it is not always necessary.

The material, manufacturing method, layer thickness, etc. of the glass layer can be freely designed according to the application. When a plurality of glass layers are present in the glass laminate, each layer may be the same material or a different material. The glass laminate is a structure having at least one ionomer resin layer and one glass layer as described above, but the glass laminate has a structure in which the glass layers and the ionomer resin layers are alternately laminated. May be good. An adhesive layer may be provided between each glass layer and the ionomer resin layer, or another layer may be provided depending on the use of the glass laminate. Further, the glass layer does not have to be the outermost layer in the laminated body, and layers made of other materials may be laminated.

As a method for producing the glass laminate, a method known to those skilled in the art can be used. The flat glass layer and the ionomer resin layer may be separately manufactured and then bonded, or the ionomer resin may be uniformly applied to the glass layer and then cured.
The glass laminate of the present invention may be combined with another plate-like body to provide a hollow layer in the middle. That is, a gas layer or a vacuum layer is provided in the structure by facing the glass laminate of the present invention and another plate-like body at a certain interval, sealing the ends and, in some cases, degassing. be able to.

3. 3. Resin film for glass interlayer film, laminated glass The resin for glass laminate of the present invention can be suitably used for a resin film for glass interlayer film. That is, the resin film for a glass interlayer film is located between the two glass layers to form a laminated body of at least three layers. Preferably, the resin film for a glass interlayer film has at least one surface, more preferably both surfaces, in contact with the glass layer. In order for the resin for glass interlayer film to be effective in preventing cracking of glass and scattering of fragments when broken, it is preferable that the adhesive strength measured under the conditions described below is 2.0 N / 10 mm or more. It is more preferably 2.3 N / 10 mm or more, further preferably 2.5 N / 10 mm or more, and even more preferably 3.0 N / 10 mm or more. One aspect of the present invention is a laminated glass in which a resin for a glass laminate containing the ionomer is used as a resin film for a glass interlayer film. The laminated glass of the present invention can be used as laminated glass for window glass, automobile windshield, monitor glass, building material glass, security glass and the like.

The resin film for a glass interlayer film of the present invention may have a single-layer structure composed of only an ionomer resin layer, or a multilayer structure in which the above-mentioned ionomer resin layer and another layer (one layer or two or more layers) are laminated. You may.

The other layers are not particularly limited, but for example, polyvinyl acetal resin, ethylene-vinyl acetate copolymer resin, ethylene-acrylic copolymer resin, polyurethane resin, polyurethane resin containing sulfur element, polyvinyl alcohol resin, chloride. Examples thereof include a layer containing a thermoplastic resin other than the ionomer resin, such as a vinyl resin and a polyethylene terephthalate resin. Among them, polyvinyl acetal resin is used because it exhibits excellent adhesiveness to glass when used in combination with a plasticizer, and a resin film capable of exhibiting various functions can be obtained by blending various additives. The containing layer is suitable.

The laminated glass is a laminated body having a structure of at least three layers by sandwiching a resin film for a glass interlayer film (ionomer resin layer) between two glass layers. The laminated glass may have a structure in which glass layers and ionomer resin layers are alternately laminated.

4. Resin film for solar cell encapsulant and solar cell module The resin for glass laminate of the present invention can be suitably used for the resin film for solar cell encapsulant.

The resin film for a solar cell encapsulant of the present invention may contain additives such as a light stabilizer, an ultraviolet absorber, and a silane coupling agent, if necessary.
As the light stabilizer, it is preferable to add a hindered amine-based light stabilizer. Hindered amine-based light stabilizers capture radical species that are harmful to the polymer and prevent the generation of new radicals. There are many types of hindered amine-based light stabilizers, from low molecular weight compounds to high molecular weight compounds, but conventionally known compounds can be used without particular limitation.
Examples of the ultraviolet absorber include various types such as benzophenone type, benzotriazole type, triazine type, and salicylic acid ester type.
Examples of the silane coupling agent include vinyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, and 3-acryloxypropyltrimethoxysilane, which are mainly adhered to the upper protective material of the solar cell and the solar cell element. It can be used for the purpose of improving force.

In addition, other additional optional ingredients can be blended as long as the object of the present invention is not significantly impaired. Examples of such optional components include antioxidants, crystal nucleating agents, clearing agents, lubricants, colorants, dispersants, fillers, fluorescent whitening agents, etc. used in ordinary polyolefin resin materials. Can be done.

By using the resin film for the solar cell encapsulant of the present invention, the solar cell module can be manufactured by fixing the solar cell element together with the upper and lower protective materials. As such a solar cell module, various types can be exemplified. For example, an upper transparent protective material / encapsulant / solar cell element / encapsulant / lower protective material sandwiched between both sides of the solar cell element, formed on the inner peripheral surface of the lower substrate protective material On a solar cell element having a structure in which a sealing material and an upper transparent protective material are formed on the solar cell element, or on a solar cell element formed on the inner peripheral surface of the upper transparent protective material, for example, a fluororesin-based transparent protective material. Examples thereof include an amorphous solar cell element having a structure in which a sealing material and a lower protective material are formed on the one produced by sputtering or the like.

As described above, the resin for a glass laminate of the present invention and its use have been described with specific examples, but the resin for a glass laminate of the present invention, a film made of the resin, and a glass laminate have been given as specific examples. It is not limited to things. A person skilled in the art can appropriately design, change, improve, etc., without departing from the spirit of the present invention.

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, no data in the table means unmeasured, and not detected means less than the detection limit.

<Measurement and evaluation>
(1) Measurement of phase angle δ (G ^* = 0.1 MPa) at absolute value 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 Senshu Kagaku's 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, S-28.5 and S-5.05, 0.07 mg / ml solutions each), n-icosane and n-tetracontane were measured under the same conditions as above, and the elution time and molecular weight logarithmic values 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 under the conditions of a temperature of 190 ° C. and a load of 21.18 N (= 2.16 kg) according to Table 1-Condition 7 of JIS K-7210 (1999).

(4) 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.

(5) 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 and the carboxy group in the copolymer of the present invention / 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.
Sample 200-300 mg in a mixed solvent (C ₆ H ₄ Cl ₂ / C ₆ D ₅ Br = 2 /) of o-dichlorobenzene (C ₆ H ₄ Cl ₂ ) and benzene dehydride (C ₆ D ₅ Br) 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 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 carboxylic acid base was contained in the sample, 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 structural unit amount derived from a monomer having a carboxy group and / or a dicarboxylic acid anhydride group and an acyclic monomer <E / tBA>
The quaternary carbon signal of the t-butyl acrylate group of tBA is detected at 79.6-78.8 in the ¹³ C-NMR spectrum. Using these signal intensities, the amount of comonomer was calculated from the following formula.
Total tBA (mol%) = I (tBA) x 100 / [I (tBA) + I (E)]
Here, I (tBA) and I (E) are quantities represented by the following formulas, respectively.
I (tBA) = I _79.6-78.8
I (E) = (I _{180.0 to 135.0} + I _{120.0 to 5.0-} I (tBA) x 7) / 2

<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 copolymer, but it is less than 0.1 mol% in consideration of significant figures. It means that it is a quantity.

3) Calculation of the number of branches per 1,000 carbons There are two types of copolymers: isolated type, in which a single branch exists in the main chain, and composite type (face-to-face type, in which branches face each other via the main chain, and branches. There are branched-branch types and chain types with branches in the 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 numerical value of the subscript 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, it exists as a constituent unit in the copolymer, but the amount is less than 0.1 mol% in consideration of significant figures. Means that. Further, not detected means less than the detection limit.

(6) Infrared absorption spectrum The 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

(7) Tensile Impact Strength 1) Tensile Impact Strength Test Sample Preparation Method Place the sample in a 1 mm thick heating press mold, preheat it in a heat press machine with a surface temperature of 180 ° C for 5 minutes, and then pressurize and reduce the pressure. By repeating the process, the sample was melted and the residual gas in the sample was degassed, further pressurized at 4.9 MPa, and held for 5 minutes. Then, with a pressure of 4.9 MPa applied, the mixture was gradually cooled at a rate of 10 ° C./min, 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 Tensile impact strength was measured using the above test piece 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.

(8) 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.

(9) Glass Adhesive Strength The glass adhesive strength was measured by superimposing a sample processed on a press plate and float plate glass and vacuum laminating them to prepare a laminate, and performing a peeling test. The method of adjusting the press plate and the laminate and the method of measuring the adhesive strength will be described in order.

1) Method for adjusting the press plate of the sample Place the sample in a mold for heating press with dimensions: 50 mm x 60 mm and thickness 0.5 mm, preheat it in a heat press machine with a surface temperature of 180 ° C for 5 minutes, and then pressurize and depressurize. By repeating the process, the residual gas in the sample was degassed, 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) Method for adjusting flat glass As the glass plate, a commercially available float flat glass manufactured by the float method was used. In the float method, molten glass is poured onto molten tin, and the glass is cooled and solidified on the molten tin to obtain a flat glass with high smoothness. Tin was present on the lower surface of the float plate glass manufactured by such a float method, that is, the surface that was in contact with molten tin (hereinafter, bottom surface), and the surface that was not in contact with molten tin (hereinafter, top). The surface) is characterized by a larger amount of silanol groups. In addition, since the silanol group of glass has the property of adsorbing hydrocarbon-based substances existing in the atmosphere, it is desirable to wash the plate glass used for the adhesion test immediately before the test. Based on the above, in the present invention, the 2.5 mm-thick float plate glass is washed with a neutral detergent before the test, dried at 70 ° C., cut to a size of 50 mm × 60 mm, and the sample press plate is used using the top surface. Was glued.

3) Method for manufacturing a laminate of a sample and a plate glass Using a vacuum laminator (manufactured by NPC Co., Ltd.), the press plate and the top surface of the plate glass were heated at a heating temperature of 180 ° C. and a heating time of 10 minutes. After laminating under the conditions, it was sandwiched between two aluminum plates and rapidly cooled for 3 minutes to obtain a two-kind, two-layer laminate. A slit having a width of 10 mm was inserted in the sheet portion of this laminate to prepare a test piece.

4) Adhesive strength measurement method of the laminate Using the laminate obtained by the method of manufacturing the laminate as a test piece, peel it off at a take-up speed of 50 mm / min using a Tensiron (manufactured by Toyo Seiki Co., Ltd.) tensile tester. The maximum stress was determined as the adhesive strength (N / 10 mm).

<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.

<(Manufacturing Example 1): Production of ionomer-based resin precursor>
An ethylene / tBu acrylate / norbornene copolymer was produced using a transition metal complex (B-27DM / 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.

<(Resin 1): Production of ionomer-based resin-1>
40 g of the obtained copolymer of Production Example 1, 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 the t-Bu ester and the formation of the carboxylic acid were confirmed, and the ionomer base resin 1 was obtained. Table 3 shows the physical characteristics of the obtained resin.

<Ionomer 1-Ionomer 4: Production of Ionomer-1>
1) 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 Nucle® (registered trademark) N1050H), 18 g of zinc oxide and 0.2 g of zinc stearate, and kneading at 180 ° C. and 40 rpm for 3 minutes.

2): Preparation of ionomer Toyo Seiki Co., Ltd.'s Labplast Mill: Roller Mixer R60 equipped with a small mixer with a capacity of 60 ml was charged with 40 g of resin 1 and kneaded at 160 ° C. and 40 rpm for 3 minutes to dissolve. Then, the 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 Zn methacrylate, which is an ionomer resin manufactured by a high-pressure radical process (a brand manufactured by Mitsui Dow Polychemical Co., Ltd.). : HIMILAN (registered trademark) HIM1706) 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 Zn methacrylate, which is an ionomer resin manufactured by a high-pressure radical process (a brand manufactured by Mitsui Dow Polychemical Co., Ltd.). : HIMILAN (registered trademark) HIM1707) 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>
Since Comparative Examples 1 and 2 are ionomers composed of a base resin produced by the high-pressure radical method and a metal ion source, their molecular structure has many long-chain branches, and the absolute value of the complex elastic modulus G ^* = 0. The phase angle δ at 1 MPa is less than 50 °. On the other hand, since Examples 1 to 10 are ionomers composed of a base resin produced by a specific transition metal catalyst and metal ions, their molecular structure is substantially linear and the phase angle δ (G ^* =). 0.1 MPa) is 50 ° or more.
From the measurement results shown in Table 5, it can be seen that in the examples of the laminate of the present invention, the resin layer is firmly adhered to the glass layer, and the transparency and tensile impact strength are also high. Comparative Example 1 and Example 4, and Comparative Example 2 and Example 7 are existing ionomers having the same acid content and neutralization degree, respectively, but the comparative examples have the same transparency but adhesion as compared with the examples. Inferior in strength and tensile impact strength.
This means that the ionomer of the present invention having a phase angle δ (G ^* = 0.1 MPa) of 50 ° or more is relatively superior to the conventional ionomer in the balance of transparency, adhesive strength and tensile impact strength. Shown.

[Regarding the composition, neutralization degree, and metal ion species of ionomers in the present invention]
Examples 1 to 10 are ionomers having different base resin compositions, neutralization degrees, and Kinzo ion species, but all have desired transparency (haze), desired adhesive performance (adhesive strength), and desired adhesive strength. All of the strengths (tensile impact strength) are satisfied, and the adhesive strength and tensile impact strength are superior to those of Comparative Examples 1 and 2 of the existing ionomers.
As shown in FIG. 3, the multidimensional ionomer of the present invention having a phase angle δ (G ^* = 0.1 MPa) of 50 ° or more has relatively transparency, adhesive strength and adhesive strength regardless of the degree of neutralization. It shows that the balance of tensile impact strength is excellent.
In the present invention, the desired haze may be at least 25% or less, preferably 20% or less, and the desired adhesive strength is preferably 2.0 N / 10 mm or more, more preferably 2.3 N / 10 mm. As mentioned above, it may be more preferably 2.5 N / 10 mm or more, further preferably 3.0 N / 10 mm or more, and the desired tensile impact strength is preferably 700 kJ / m ² or more, more preferably 720 kJ / m ^2. The above is more preferably 800 kJ / m ² or more, and particularly preferably 1000 kJ / m ² or more.

From the comparison between the examples and the comparative examples, the ionomer of the present invention exhibits an excellent balance of transparency, adhesiveness, and impact resistance, which was not found in conventional ionomers, due to its characteristic molecular structure. It turned out.

If the resin for a glass laminate containing an ionomer of the present invention is used, a laminated glass having excellent adhesiveness and impact resistance while maintaining the same transparency as the conventional resin for a glass laminate containing an ionomer. It is expected that interlayer films and solar cell module encapsulants can be obtained. Laminated glass is expected to improve safety while maintaining visibility, and is considered to have high utility value as automobile glass and architectural glass. If it is a solar cell module, it is expected that the durability can be improved without lowering the conversion efficiency.

Claims (13)

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.
A resin for a glass laminate containing an ionomer, wherein the phase angle δ at the absolute value G ^* = 0.1 MPa of the complex elastic modulus measured by a rotary rheometer is 50 degrees to 75 degrees. The resin for a glass laminate according to claim 1, wherein the number of methyl branches calculated by ¹³ C-NMR of the copolymer (P) is 50 or less per 1,000 carbons. The resin for a glass laminate according to claim 1, wherein the number of methyl branches calculated by ¹³ C-NMR of the copolymer (P) is 5 or less per 1,000 carbons. The resin for a glass laminate according to any one of claims 1 to 3, wherein the copolymer (P) contains the structural unit (B) in an amount of 2 to 20 mol% in the copolymer. .. The resin for a glass laminate according to any one of claims 1 to 4, wherein the structural unit (A) is a structural unit derived from ethylene. The glass laminate according to any one of claims 1 to 5, wherein the copolymer (P) is produced using a transition metal catalyst containing a transition metal of groups 8 to 11 of the periodic table. Body resin. The resin for a glass laminate 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 resin film for a glass laminate, which comprises using the resin for a glass laminate according to any one of claims 1 to 7. A resin film for a glass interlayer film, which comprises using the resin for a glass laminate according to any one of claims 1 to 7. A resin film for a solar cell encapsulant, which comprises using the resin for a glass laminate according to any one of claims 1 to 7. A glass laminate according to claim 8, wherein the resin film for the glass laminate is laminated. A laminated glass characterized in that the resin film for a glass interlayer film according to claim 9 is laminated. The solar cell module according to claim 10, wherein the resin film for the solar cell encapsulant is laminated.

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