Resin for glass laminates

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

[Technical Field]

[0001] The present invention relates to a resin for glass laminates using a novel ionomer. [Background technology]

[0002] Ethylene-based ionomers are resins that use ethylene-unsaturated carboxylic acid copolymers as the base resin and are intermolecularly bonded by metal ions such as sodium and zinc (Patent Document 1).They are characterized by their toughness, elasticity, flexibility, abrasion resistance, transparency, etc. Currently, commercially available ethylene-based ionomers include "Surlyn (registered trademark)," a sodium salt or zinc salt of ethylene-methacrylic acid copolymer developed by DuPont, and "Himilan (registered trademark)," sold by Mitsui Dow Polychemicals.

[0003] However, the ethylene-unsaturated carboxylic acid copolymers used as the base resins in these currently commercially available ethylene-based ionomers all use polar-group-containing olefin copolymers obtained by high-pressure radical polymerization of ethylene and polar-group-containing monomers such as unsaturated carboxylic acids. High-pressure radical polymerization has the advantage of being relatively inexpensive and allows for the polymerization of any polar-group-containing monomer. However, the molecular structure of the polar-group-containing olefin copolymers produced by this high-pressure radical polymerization method, as shown in Figure 1, has the disadvantage of having many irregular long-chain branches and short-chain branches, resulting in insufficient strength. Therefore, conventional commercially available ionomers using polar-group-containing olefin copolymers polymerized by high-pressure radical polymerization as the base resin have insufficient impact resistance.

[0004] Meanwhile, methods have been explored for producing polar group-containing olefin copolymers with a linear molecular structure, as shown in the image in Figure 2, using a polymerization method that uses a catalyst. However, polar group-containing monomers generally act as catalyst poisons, making polymerization difficult. In fact, it has long been considered difficult to obtain polar group-containing olefin copolymers with the desired physical properties using an industrially inexpensive and stable method. However, in recent years, a method has been proposed for industrially obtaining polar group-containing olefin copolymers having a substantially linear molecular structure at low cost and in a stable manner by using a new catalyst and a new production method developed by the present applicant and others. The present applicants have reported that they have succeeded in producing a polar group-containing olefin copolymer, which serves as the base resin for ethylene-based ionomers, by using a late transition metal catalyst to produce a copolymer of ethylene and t-butyl acrylate, modifying the resulting polar group-containing olefin copolymer by heat or acid treatment to form an ethylene-acrylic acid copolymer, and then reacting it with metal ions to produce a binary ionomer (Patent Document 2).

[0005] Ethylene-based ionomers are also used as resin layers in glass laminates, and examples of their applications include laminated glass interlayers and solar cell encapsulants. Laminated glass is a laminated glass formed by bonding two or more glass sheets together via a resin interlayer. Laminated glass is used as automobile windshields, instrument monitor glass, and building glass. The provision of an interlayer provides safety benefits, such as preventing cracking of the glass and scattering of broken glass fragments, due to the flexibility of the interlayer and its adhesion to the glass. For this reason, laminated glass interlayers are required to have transparency, impact resistance, and adhesion to the glass. Laminated glass using an ethylene-based ionomer as an interlayer is described in Patent Document 3 and Patent Document 4.

[0006] A solar cell encapsulant is a material that adheres to both the front and back surfaces of a power generation element consisting of a solar cell and an interconnector in a solar cell module to seal the element. The power generation element is adhered to the light-receiving layer and back surface layer of the solar cell module via this encapsulant. 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 a solar cell module is required to have high transparency so that incident light passing through the light-receiving layer reaches the solar cell without loss, and to protect the power generation element from external impacts. Patent Document 5 describes a solar cell encapsulant whose adhesion is improved by adding a silane coupling agent to an ethylene-based ionomer. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] U.S. Patent No. 3,264,272 [Patent Document 2] Japanese Patent Application Laid-Open No. 2016-79408 [Patent Document 3] Japanese Patent Application Publication No. 2018-193261 [Patent Document 4] Japanese Patent Application Laid-Open No. 2016-188158 [Patent Document 5] Japanese Patent Application Laid-Open No. 2009-248377 Summary of the Invention [Problem to be solved by the invention]

[0008] Thus, laminated glass interlayers and solar cell encapsulants are required to have high impact resistance, high transparency, and high adhesion to glass. Ionomers are one of the materials being investigated. Patent Documents 3 and 4 describe laminated glass in which adhesiveness is improved by adding a silane coupling agent to an ethylene-based ionomer. However, there have been no examples of improving adhesiveness by improving the ionomer resin alone, leaving room for improvement in terms of cost and productivity. Furthermore, impact resistance is still insufficient, and there have been no examples of improving impact resistance by improving the resin alone. Even with the ionomer described in Patent Document 5, there are no examples of improving adhesive strength with the resin alone, and impact resistance is still insufficient, and there have been no examples of improving impact resistance by improving the resin alone.

[0009] In view of the state of the prior art, the present application aims to provide a resin for glass laminates containing an ionomer that has an excellent balance of impact resistance, transparency, and adhesiveness. [Means for solving the problem]

[0010] As a result of extensive investigations conducted by the present inventors to solve the above problems, they discovered that the use of a specific ionomer resin has a far superior effect than expected in terms of required physical properties such as impact resistance, transparency, and adhesiveness. The ethylene-based ionomer described in Patent Document 2 is a novel ethylene-based ionomer that has not been seen before, in which the base resin has a substantially linear molecular structure and also functions as an ionomer, and its physical properties, etc., are significantly different from those of conventional ethylene-based ionomers having a multi-branched molecular structure, and its unique characteristics and suitable applications were also unknown. The present invention is based on the discovery that a resin containing a substantially linear ethylene-based ionomer has an excellent effect in improving the physical properties required for a resin layer used in a glass laminate.

[0011] That is, the present invention is as set forth 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; a copolymer (P) containing, as an essential structural unit, a structural unit (B) derived from a monomer having a carboxyl group and / or a dicarboxylic acid anhydride group, in which at least a portion of the carboxyl groups and / or dicarboxylic acid anhydride groups are converted to a metal-containing carboxylate salt containing at least one metal ion selected from Group 1, Group 2, or Group 12 of the Periodic Table; Absolute value of complex modulus G measured by a rotational rheometer * The resin for glass laminates contains an ionomer characterized in that the phase angle δ at a pressure of 0.1 MPa is 50 degrees to 75 degrees. [2] The copolymer (P) 13 The resin for glass laminates according to [1], characterized in that the number of methyl branches calculated by C-NMR is 50 or less per 1,000 carbon atoms. [3] The copolymer (P) 13 The resin for glass laminates according to [1], characterized in that the number of methyl branches calculated by C-NMR is 5 or less per 1,000 carbon atoms. [4] The resin for a glass laminate according to any one of [1] to [3], wherein the copolymer (P) contains the structural unit (B) in an amount of 2 to 20 mol % in the copolymer. [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] The resin for glass laminates according to 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. [7] The resin for glass laminates according to [6], wherein the transition metal catalyst is a transition metal catalyst comprising a phosphorus sulfonic acid or phosphorus phenol ligand and nickel or palladium. [8] A resin film for a glass laminate, characterized by using any one of the resins for a glass laminate described in [1] to [7] above. [9] A resin film for glass interlayers, characterized by using the resin for glass laminates according to any one of [1] to [7] above.

[10] A resin film for solar cell encapsulant, characterized by using the resin for glass laminate of any one of [1] to [7] above.

[11] A glass laminate characterized by being laminated with the resin film for glass laminates according to [8] above.

[12] Laminated glass characterized by being laminated with the resin film for glass interlayer film according to [9] above.

[13] A solar cell module characterized by laminating the resin film for solar cell encapsulant according to

[10] above. [Effects of the Invention]

[0012] A resin for glass laminates containing the ionomer of the present invention, which has a substantially linear structure, has a better balance of impact resistance, transparency, and adhesiveness than existing resins for glass laminates made of polyethylene or ionomer resins. [Brief explanation of the drawings]

[0013] [Figure 1] FIG. 1 is an image of the molecular structure of a hyperbranched olefin copolymer polymerized by a high-pressure radical polymerization process. [Figure 2] FIG. 1 is an image of the molecular structure of a linear olefin copolymer polymerized using a metal catalyst. [Figure 3] FIG. 1 is a graph showing the relationship between tensile impact strength and adhesive strength to glass in Examples 1 to 10 and Comparative Examples 1 and 2. DETAILED DESCRIPTION OF THE INVENTION

[0014] The present invention provides a resin for glass laminates using an ionomer, characterized in that the base resin is a copolymer (P) obtained by copolymerizing, preferably randomly copolymerizing, structural units (A) derived from ethylene and / or an α-olefin having 3 to 20 carbon atoms and structural units (B) derived from a monomer having a carboxyl group and / or a dicarboxylic anhydride group as essential structural units, and optionally further comprising, as a structural unit, structural units (C) which are compounds having one or more carbon-carbon double bonds in the molecular structure, these structural units being copolymerized in a substantially linear manner, and at least a portion of the carboxyl groups and / or dicarboxylic anhydride groups in structural units (B) are converted to a metal-containing carboxylate containing at least one metal ion selected from Groups 1, 2, and 12 of the Periodic Table.

[0015] The ionomer according to the present invention, the resin for glass laminates using the ionomer, and their applications will be described in detail below. In this specification, "(meth)acrylic acid" means acrylic acid or methacrylic acid. In this specification, the symbol "to" indicating a numerical range is used to mean that the numerical values ​​before and after the symbol are the lower and upper limits. In this specification, the term "copolymer" means a binary or higher copolymer containing at least one type of unit (A) and at least one type of unit (B). In addition, in this specification, the term "ionomer" refers to an ionomer of a binary or higher copolymer that contains the structural unit (A) and a structural unit (B') in which at least a portion of the structural unit (B) has been converted to a metal-containing carboxylate, and that may further contain the structural unit (B).

[0016] 1. Ionomer The ionomer of the present invention is characterized in that it comprises, as a base resin, a copolymer (P) which contains, as essential structural units, structural units (A) derived from ethylene and / or an α-olefin having 3 to 20 carbon atoms and structural units (B) derived from a monomer having a carboxyl group and / or a dicarboxylic anhydride group, and optionally also contains, as a structural unit, structural units (C) which are compounds having one or more carbon-carbon double bonds in the molecular structure, and which are copolymerized, preferably randomly, in a substantially linear chain, and in which at least a portion of the carboxyl groups and / or dicarboxylic anhydride groups of the structural units (B) are converted to a metal-containing carboxylate containing at least one metal ion selected from Groups 1, 2, and 12 of the Periodic Table.

[0017] (1) Structural unit (A) The structural unit (A) is at least one structural unit selected from the group consisting of structural units derived from ethylene and structural units derived from an α-olefin having 3 to 20 carbon atoms. The α-olefins involved in the present invention have the structural formula: CH₂=CHR 18 is an α-olefin having 3 to 20 carbon atoms (R 18 is a hydrocarbon group having 1 to 18 carbon atoms, which may have a linear or branched structure. The α-olefin more preferably has 3 to 12 carbon atoms.

[0018] Specific examples of the structural unit (A) include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 3-methyl-1-butene, and 4-methyl-1-pentene, and may be ethylene. As the ethylene, ethylene derived from petroleum raw materials or non-petroleum raw materials such as plant raw materials can be used. The structural unit (A) may be of one type or of multiple types. Examples of combinations of the two include ethylene-propylene, ethylene-1-butene, ethylene-1-hexene, ethylene-1-octene, propylene-1-butene, propylene-1-hexene, and propylene-1-octene. Examples of combinations of the three include ethylene-propylene-1-butene, ethylene-propylene-1-hexene, ethylene-propylene-1-octene, propylene-1-butene-hexene, and propylene-1-butene-1-octene.

[0019] In the present invention, the structural unit (A) preferably contains ethylene as an essential component, and may further contain one or more α-olefins having 3 to 20 carbon atoms, if necessary. The amount of ethylene in the structural unit (A) may be 65 to 100 mol % or 70 to 100 mol % based on the total moles of the structural unit (A). In terms of impact resistance, the structural unit (A) may be a structural unit derived from ethylene.

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

[0021] Examples of structural units derived from monomers having a carboxyl group include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, norbornene dicarboxylic acid, and bicyclo[2,2,1]hept-2-ene-5,6-dicarboxylic acid. Examples of structural units derived from monomers having a dicarboxylic acid anhydride group include maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, 3,6-epoxy-1,2,3,6-tetrahydrophthalic anhydride, and tetracyclo[6.2.1.1 3,6 .0 2,7] Examples of the unsaturated dicarboxylic acid anhydrides include dodec-9-ene-4,5-dicarboxylic acid anhydride and 2,7-octadien-1-yl succinic acid anhydride. As the structural unit derived from a monomer having a carboxyl group and / or a dicarboxylic acid anhydride group, from the viewpoint of ease of industrial availability, preferred examples include acrylic acid, methacrylic acid, and 5-norbornene-2,3-dicarboxylic acid anhydride, and particularly acrylic acid. Furthermore, the structural unit derived from a monomer having a carboxyl group and / or a dicarboxylic anhydride group may be of one type or of multiple types.

[0022] The dicarboxylic anhydride group may react with moisture in the air to open the ring and convert a portion of the group into a dicarboxylic acid. However, the dicarboxylic anhydride group may be ring-opened within the scope of the present invention.

[0023] (3) Other structural units (C) The copolymer (P) used in the present invention may be a binary copolymer consisting of only the structural unit (A) and the structural unit (B), or a multicomponent copolymer containing the structural unit (A), the structural unit (B), and a structural unit (C) other than these. However, a multicomponent copolymer containing a structural unit (C) other than the structural units represented by the structural units (A) and (B) is preferred. Any monomer can be used to provide the structural unit (C), as long as it is not included in the monomers that provide the structural units (A) and (B). The monomer that provides the structural unit (C) is not limited as long as it is a compound having one or more carbon-carbon double bonds in its molecular structure. Examples of the monomer that provides the structural unit (C) include acyclic monomers represented by the general formula (1) shown below and cyclic monomers represented by the general formula (2) shown below. Compared to a binary copolymer consisting only of structural units (A) and (B), the use of a ternary or higher multi-component copolymer containing structural unit (C) as the base resin of an ionomer allows for more precise control of the physical properties of the ionomer resin. This is particularly advantageous because it allows for even greater improvement in impact resistance. The structural unit (C) may be based on one type of monomer, or two or more types of monomers may be used in combination.

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

[0025] T 1 ~T 4 The carbon skeleton of the hydrocarbon group, substituted alkoxy group, substituted ester group, alkoxy group, aryl group, ester group, and silyl group may have a branch, a ring, and / or an unsaturated bond. T1 ~T 4 The lower limit of the number of carbon atoms in the hydrocarbon group may be 1 or more, and the upper limit may be 20 or less, or may be 10 or less. T 1 ~T 4 The lower limit of the number of carbon atoms in the substituted alkoxy group may be 1 or more, and the upper limit may be 20 or less, or may be 10 or less. T 1 ~T 4 The lower limit of the number of carbon atoms in the substituted ester group may be 2 or more, and the upper limit may be 20 or less, or may be 10 or less. T 1 ~T 4 The lower limit of the number of carbon atoms in the alkoxy group in the above formula may be 1 or more, and the upper limit may be 20 or less, or may be 10 or less. T 1 ~T 4 The lower limit of the number of carbon atoms in the aryl group in the above formula may be 6 or more, and the upper limit may be 20 or less, or may be 11 or less. T 1 ~T 4 The lower limit of the number of carbon atoms in the ester group in the above formula may be 2 or more, and the upper limit may be 20 or less, or may be 10 or less. T 1 ~T 4 The lower limit of the number of carbon atoms in the silyl group in the above formula may be 3 or more, and the upper limit may be 18 or less, or may be 12 or less. Examples of the silyl group include a trimethylsilyl group, a triethylsilyl group, a tri-n-propylsilyl group, a triisopropylsilyl group, a dimethylphenylsilyl group, a methyldiphenylsilyl group, and a triphenylsilyl group.

[0026] In the ionomer of the present invention, from the viewpoint of ease of production, T 1 and T 2 may be a hydrogen atom, T 3 may be a hydrogen atom or a methyl group, T 1 ~T 3 However, either may be a hydrogen atom. In addition, from the viewpoint of impact resistance, T4 may be an ester group having 2 to 20 carbon atoms.

[0027] Specific examples of the acyclic monomer include T monomers containing (meth)acrylic acid esters, etc. 4 is an ester group having 2 to 20 carbon atoms. T 4 is an ester group having 2 to 20 carbon atoms, the acyclic monomer may be an ester group having the structural formula: CH2=C(R 21 )CO2(R 22 ) where R 21 is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, which may have a branched structure, a ring, and / or an unsaturated bond. 22 is a hydrocarbon group having 1 to 20 carbon atoms, which may have a branched, cyclic, and / or unsaturated bond. 22 It may contain a heteroatom at any position within the group. Structural formula: CH2=C(R 21 )CO2(R 22 ) as a compound represented by R 21 is a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms. 21 is a hydrogen atom or an acrylic acid ester in which R 21 is a methyl group. Structural formula: CH2=C(R 21 )CO2(R 22 Specific examples of the compound represented by the formula (I) include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, cyclohexyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, octadecyl (meth)acrylate, phenyl (meth)acrylate, toluyl (meth)acrylate, and benzyl (meth)acrylate. Specific compounds include methyl acrylate, ethyl acrylate, n-butyl acrylate (nBA), isobutyl acrylate (iBA), t-butyl acrylate (tBA), and 2-ethylhexyl acrylate, and in particular may be n-butyl acrylate (nBA), isobutyl acrylate (iBA), and t-butyl acrylate (tBA). The acyclic monomer may be of one type or of multiple types.

[0028] Cyclic Monomers [ka] [In general formula (2), R 1 ~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 combine with each other to form a divalent organic group, R 9 or R 10 and R 11 or R 12 may form a ring together. Furthermore, n represents 0 or a positive integer, and when n is 2 or more, R 5 ~R 8 may be the same or different in each repeating unit.

[0029] Examples of the cyclic monomer include norbornene-based olefins, such as norbornene, vinylnorbornene, ethylidenenorbornene, norbornadiene, tetracyclododecene, tricyclo[4.3.0.1 2,5 ], tricyclo[4.3.0.1 2,5 ]dec-3-ene, and compounds having a cyclic olefin skeleton such as 2-norbornene (NB) and tetracyclo[6.2.1.1 3,6 .0 2,7 ]dodec-4-ene and the like.

[0030] (4) Copolymer (P) The copolymer (P) used in the present invention, which serves as the base resin for the ionomer, contains, as essential constituent units, structural units (A) derived from ethylene and / or an α-olefin having 3 to 20 carbon atoms and structural units (B) derived from a monomer having a carboxyl group and / or a dicarboxylic anhydride group, and optionally further contains an optional structural unit (C) other than (A) and (B), characterized in that these structural units are copolymerized, preferably randomly copolymerized, in a substantially linear chain. The term "substantially linear" refers to a state in which the copolymer has no branches or the frequency of branched structures is low, and the copolymer can be considered linear. Specifically, this refers to a state in which the phase angle δ of the copolymer is 50 degrees or greater under the conditions described below.

[0031] The copolymer (P) according to the present invention must contain at least one type of structural unit (A) and at least one type of structural unit (B), for a total of two or more types of monomer units. It may also contain any structural unit (C) other than (A) and (B), but is preferably a multi-component copolymer containing such a structural unit (C). The structural units and amounts of the structural units of the copolymer according to the present invention will be explained below. A structure derived from one molecule of each of ethylene and / or an α-olefin having 3 to 20 carbon atoms (A), a monomer (B) having a carboxyl group and / or a dicarboxylic anhydride group, and an arbitrary monomer (C) other than (A) and (B) is defined as one structural unit in the copolymer. The amount of structural units is the ratio of each structural unit expressed in mol % when the total structural units in the copolymer is taken as 100 mol %.

[0032] Amount of structural units of ethylene and / or α-olefin having 3 to 20 carbon atoms (A): The structural unit amount of the structural unit (A) according to the present invention has a lower limit of 60.0 mol% or more, preferably 70.0 mol% or more, more preferably 80.0 mol% or more, even more preferably 85.0 mol% or more, still more preferably 90.0 mol% or more, and particularly preferably 92.0 mol% or more, and an upper limit of 97.9 mol% or less, preferably 97.5 mol% or less, more preferably 97.0 mol% or less, and even more preferably 96.5 mol% or less. If the amount of structural units derived from ethylene and / or an α-olefin (A) having 3 to 20 carbon atoms is less than 60.0 mol%, the toughness of the copolymer will be poor, and if it is more than 97.9 mol%, the crystallinity of the copolymer will be high, which may result in poor transparency.

[0033] Amount of structural units of monomer (B) having a carboxyl group and / or a dicarboxylic anhydride group: The amount of the structural unit (B) according to the present invention is selected from the following: a lower limit of 2.0 mol% or more, preferably 2.9 mol% or more, and more preferably 5.1 mol% or more; and an upper limit of 20.0 mol% or less, preferably 15.0 mol% or less, more preferably 10.0 mol% or less, even more preferably 8.0 mol% or less, particularly preferably 6.0 mol% or less, and most preferably 5.6 mol% or less. If the amount of structural units derived from the monomer (B) having a carboxyl group and / or a dicarboxylic anhydride group is less than 2.0 mol%, the copolymer may not have sufficient adhesion to highly polar different materials, and if it is more than 20.0 mol%, the copolymer may not have sufficient mechanical properties. Furthermore, the monomer having a carboxyl group and / or a dicarboxylic anhydride group to be used may be used alone or in combination of two or more kinds.

[0034] Amount of structural units of any monomer (C): When copolymer (P) contains structural units other than the structural units (A) and (B), the structural unit amount of the structural unit (C) according to the present invention is selected from the following: a lower limit of 0.001 mol% or more, preferably 0.010 mol% or more, more preferably 0.020 mol% or more, even more preferably 0.1 mol% or more, still more preferably 1.5 mol% or more, and particularly preferably 2.9 mol% or more; and an upper limit of 20.0 mol% or less, preferably 15.0 mol% or less, more preferably 10.0 mol% or less, even more preferably 5.0 mol% or less, and particularly preferably 2.9 mol% or less. When the amount of the structural unit derived from the optional monomer (C) is within this range, the flexibility of the copolymer becomes more sufficient, and more satisfactory mechanical properties are obtained. Furthermore, any of the monomers used may be used alone or in combination of two or more kinds.

[0035] Number of branches per 1,000 carbon atoms in copolymer (P): In the copolymer of the present invention, in order to increase the elastic modulus and obtain sufficient mechanical properties, 13 The number of methyl branches calculated by C-NMR per 1,000 carbon atoms may be an upper limit of 50, 5.0, 1.0, or 0.5, with no particular lower limit, and the lower limit is the better. The number of ethyl branches per 1,000 carbon atoms may be an upper limit of 3.0, 2.0, 1.0, or 0.5, with no particular lower limit, and the lower limit is the better. The number of butyl branches per 1,000 carbon atoms may be an upper limit of 7.0, 5.0, 3.0, or 0.5, with no particular lower limit, and the lower limit is the better.

[0036] Method for measuring the amount of structural units derived from monomers having a carboxy group and / or a dicarboxylic anhydride group and acyclic monomers in copolymers, and the number of branches: The amount of structural units derived from the monomer having a carboxy group and / or a dicarboxylic anhydride group and the acyclic monomer in the copolymer of the present invention, and the number of branches per 1,000 carbon atoms are 13 It can be determined using C-NMR spectroscopy. 13 C-NMR is measured by the following method. 200-300 mg of sample is placed in an NMR sample tube with an inner diameter of 10 mm, together with 2.4 ml of a mixed solvent of o-dichlorobenzene (C6H4Cl2) and deuterated bromide benzene (C6D5Br) (C6H4Cl2 / C6D5Br = 2 / 1 (volume ratio)) and hexamethyldisiloxane, a chemical shift reference substance, and the tube is purged with nitrogen, sealed, and heated to dissolve into a homogeneous solution, which is used as the NMR measurement sample. NMR measurements are carried out at 120°C using an AV400M NMR instrument manufactured by Bruker Japan Ltd. equipped with a 10 mmφ cryoprobe. 13 C-NMR is measured using the inverse gate decoupling method with a sample temperature of 120°C, a pulse angle of 90°, a pulse interval of 51.5 seconds, and an accumulation count of 512 or more. The chemical shifts are those of hexamethyldisiloxane. 13 The C signal was set to 1.98 ppm, and the other 13 The chemical shift of the C signal is based on this. obtained 13 In C-NMR, signals specific to the monomers or branches in the copolymer are identified and their intensities are compared, allowing the amount of structural units of each monomer in the copolymer and the number of branches to be analyzed. The positions of the signals specific to the monomers or branches can be determined by reference to publicly known materials, or can be independently identified depending on the sample. Such analytical techniques are commonly known to those skilled in the art.

[0037] Weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn): The weight average molecular weight (Mw) of the copolymer according to the present invention has a lower limit of usually 1,000 or more, preferably 6,000 or more, and more preferably 10,000 or more, and an upper limit of usually 2,000,000 or less, preferably 1,500,000 or less, even 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 copolymer will not have sufficient physical properties such as mechanical strength and impact resistance, and if Mw exceeds 2,000,000, the copolymer will have an extremely high melt viscosity, which may make it difficult to mold the copolymer.

[0038] The ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the copolymer according to the present invention is usually in the range of 1.5 to 4.0, preferably 1.6 to 3.5, and more preferably 1.9 to 2.3. If Mw / Mn is less than 1.5, the copolymer may have insufficient processability in molding and other processes, while if it exceeds 4.0, the copolymer may have poor mechanical properties. In this specification, (Mw / Mn) may be expressed as a molecular weight distribution parameter.

[0039] The weight average molecular weight (Mw) and number average molecular weight (Mn) of the copolymer according to the present invention are determined by gel permeation chromatography (GPC). The molecular weight distribution parameter (Mw / Mn) is calculated by determining the number average molecular weight (Mn) by gel permeation chromatography (GPC) and then calculating the ratio of Mw to Mn, Mw / Mn.

[0040] An example of the GPC measurement method according to the present invention is as follows. (Measurement conditions) Model used: Waters 150C Detector: FOXBORO MIRAN1A IR detector (measurement wavelength: 3.42 μm) Measurement temperature: 140℃ Solvent: orthodichlorobenzene (ODCB) Column: Showa Denko AD806M / S (3 columns) Flow rate: 1.0mL / min Injection volume: 0.2mL (Sample preparation) A 1 mg / mL solution of the sample is prepared using ODCB (containing 0.5 mg / mL of BHT (2,6-di-t-butyl-4-methylphenol)), and the sample is dissolved at 140° C. for about 1 hour. (Calculation of molecular weight (M)) The standard polystyrene method was used, and the conversion from retention volume to molecular weight was performed using a calibration curve prepared using standard polystyrenes. Examples of standard polystyrenes used include those manufactured by Tosoh Corporation (F380, F288, F128, F80, F40, F20, F10, F4, F1, A5000, A2500, A1000) and monodisperse polystyrenes manufactured by Showa Denko (S-7300, S-3900, S-1950, S-1460, S-1010, S-565, S-152, S-66.0, S-28.5, S-5.05, each in a 0.07 mg / mL solution). A calibration curve was prepared by injecting 0.2 mL of a solution of each of the polystyrenes dissolved in ODCB (containing 0.5 mg / mL BHT) at 0.5 mg / mL. The calibration curve is a cubic equation obtained by approximating using the least squares method, or a quartic equation obtained by approximating the logarithm of the elution time and molecular weight. The following values ​​are used for the viscosity equation [η] = K × Mα used to convert to molecular weight (M): Polystyrene (PS): K = 1.38 x 10 -4 , α=0.7 Polyethylene (PE): K = 3.92 x 10 -4 , α=0.733 Polypropylene (PP): K = 1.03 x 10 -4 , α=0.78

[0041] Melting point (Tm, °C): The melting point of the copolymer according to the present invention is indicated by the maximum peak temperature of the endothermic curve measured by a differential scanning calorimeter (DSC). When the endothermic curve obtained in the DSC measurement shows multiple peaks with heat flow (mW) on the vertical axis and temperature (°C) on the horizontal axis, the maximum peak temperature refers to the temperature of the peak with the greatest height from the baseline. When there is only one peak, the maximum peak temperature refers to the temperature of that peak. The melting point is preferably 50° C. to 140° C., more preferably 60° C. to 138° C., and most preferably 70° C. to 135° C. If it is lower than this range, heat resistance may be insufficient, and if it is higher than this range, adhesiveness may be poor. In the present invention, the melting point can be determined from the absorption curve obtained by using, for example, a DSC (DSC7020) manufactured by SII Nanotechnology Inc., packing approximately 5.0 mg of a sample into an aluminum pan, heating it to 200°C at 10°C / min, holding it isothermally at 200°C for 5 minutes, cooling it to 20°C at 10°C / min, holding it isothermally at 20°C for 5 minutes, and then heating it again to 200°C at 10°C / min.

[0042] Crystallinity (%): In the copolymer of the present invention, the crystallinity observed by differential scanning calorimetry (DSC) is not particularly limited, but is preferably more than 0% and not more than 30%, more preferably more than 0% and not more than 25%, particularly preferably more than 5% and not more than 25%, and most preferably 7% or more and not more than 24%. The crystallinity can be determined, for example, by determining the heat of fusion (ΔH) from the area of ​​the melting endothermic peak obtained by DSC measurement using the same procedure as in the measurement of the melting point, and dividing the heat of fusion by the heat of fusion of perfectly crystalline high-density polyethylene (HDPE), 293 J / g.

[0043] Copolymer molecular structure: The molecular chain terminals of the copolymer according to the present invention may be structural units (A) of ethylene and / or an α-olefin having 3 to 20 carbon atoms, structural units (B) of a monomer having a carboxyl group and / or a dicarboxylic anhydride group, or any structural unit (C) other than (A) and (B).

[0044] The copolymer according to the present invention may be a random copolymer, block copolymer, or graft copolymer of a structural unit (A) of ethylene and / or an α-olefin having 3 to 20 carbon atoms, a structural unit (B) of a monomer having a carboxyl group and / or a dicarboxylic anhydride group, and a structural unit (C) of an arbitrary monomer. Among these, a random copolymer that can contain a large amount of the structural unit (B) may be used. An example of the molecular structure of a typical ternary copolymer (1) is shown below. A random copolymer is a copolymer of the structural unit (A) of ethylene and / or an α-olefin having 3 to 20 carbon atoms, the structural unit (B) of a monomer having a carboxyl group and / or a dicarboxylic anhydride group, and the structural unit (C) of an arbitrary monomer, as shown in the molecular structure example (1) below, in which the probability of finding each structural unit at any position in a molecular chain is independent of the type of the adjacent structural unit. As shown below, in the example molecular structure (1) of the copolymer, structural units (A) of ethylene and / or an α-olefin having 3 to 20 carbon atoms, structural units (B) of a monomer having a carboxyl group and / or a dicarboxylic anhydride group, and structural units (C) of any monomer form a random copolymer. [ka]

[0045] For reference, an example of the molecular structure (2) of a copolymer into which structural unit (B) of a monomer having a carboxyl group and / or a dicarboxylic anhydride group has been introduced by graft modification is also shown. A part of the copolymer in which structural unit (A) of ethylene and / or an α-olefin having 3 to 20 carbon atoms and structural unit (C) of an arbitrary monomer are copolymerized is graft modified with structural unit (B) of a monomer having a carboxyl group and / or a dicarboxylic anhydride group. [ka]

[0046] Furthermore, the random copolymerization of a copolymer can be confirmed by various methods, and methods for determining the random copolymerization from the relationship between the comonomer content and melting point of the copolymer are described in detail in JP 2015-163691 A and JP 2016-079408 A. From these documents, it can be determined that the randomness is low when the melting point (Tm, °C) of the copolymer is higher than -3.74 × [Z] + 130 (where [Z] is the comonomer content / mol%).

[0047] The random copolymer according to the present invention preferably has a melting point (Tm, °C) measured by differential scanning calorimetry (DSC) and a total content [Z] (mol %) of the structural unit (B) of the monomer having a carboxyl group and / or a dicarboxylic anhydride group and the structural unit (C) of any monomer, which satisfy the following formula (I): 50 <Tm<-3.74×[Z]+130···(I) If the melting point of the copolymer (Tm, °C) is higher than -3.74 × [Z] + 130 (°C), the random copolymerization is low, resulting in poor mechanical properties such as impact strength, and if the melting point is lower than 50°C, the heat resistance may be poor.

[0048] Furthermore, the copolymer according to the present invention is preferably produced in the presence of a transition metal catalyst, from the viewpoint of making the molecular structure linear. It is known that the molecular structure of the copolymer varies depending on the production method, such as polymerization by a high-pressure radical polymerization process or polymerization using a metal catalyst. The difference in molecular structure can be controlled by selecting the production method, but the molecular structure can also be estimated from the complex modulus measured with a rotational rheometer, as described in JP 2010-150532 A, for example.

[0049] · Absolute value of complex elastic modulus G * Phase angle δ at =0.1MPa: In the copolymer of the present invention, the absolute value of the complex modulus G measured by a rotational rheometer * The phase angle δ at σ = 0.1 MPa may have a lower limit of 50 degrees or more, 51 degrees or more, 54 degrees or more, 56 degrees or more, or 58 degrees or more, and an upper limit of 75 degrees or less, or 70 degrees or less. More specifically, the absolute value of the complex modulus G measured with a rotational rheometer * = 0.1MPa at the phase angle δ(G * = 0.1 MPa) is 50 degrees or higher, the molecular structure of the copolymer is a linear structure that does not contain any long chain branches, or a substantially linear structure that contains a small amount of long chain branches that does not affect the mechanical strength. In addition, the absolute value of the complex modulus G measured by a rotational rheometer * = 0.1MPa at the phase angle δ(G * = 0.1 MPa) is lower than 50 degrees, the molecular structure of the copolymer will contain excessive long chain branches, resulting in poor mechanical strength. Absolute value of complex modulus G measured by a rotational rheometer * The phase angle δ at Mw / Mn = 0.1 MPa is affected by both the molecular weight distribution and long chain branching. However, it is an indicator of the amount of long chain branching for copolymers with Mw / Mn ≦ 4, more preferably Mw / Mn ≦ 3. The more long chain branches there are in the molecular structure, the lower the δ(G *= 0.1 MPa) value is small. If the Mw / Mn of the copolymer is 1.5 or more, the δ(G * =0.1MPa) value never exceeds 75 degrees.

[0050] The complex elastic modulus is measured as follows. The sample is placed in a 1.0 mm thick heat press mold and preheated for 5 minutes in a heat press at a surface temperature of 180°C. Residual gas in the molten resin is degassed by repeatedly applying and depressurizing pressure. The sample is then pressurized to 4.9 MPa and held for 5 minutes. The sample is then transferred to a press at a surface temperature of 25°C and cooled by holding at 4.9 MPa for 3 minutes to create a pressed plate made of the sample with a thickness of approximately 1.0 mm. The pressed plate made of the sample is cut into a 25 mm diameter circle to serve as the sample. A Rheometrics ARES rotational rheometer is used to measure dynamic viscoelastic properties under the following conditions in a nitrogen atmosphere. Plate: φ25mm parallel plate ·Temperature: 160℃ Distortion: 10% Measurement angular frequency range: 1.0 x 10 -2 ~1.0×10 2 rad / s Measurement interval: 5 points / decade Absolute value of complex modulus G * Common logarithm logG of (Pa) * Plot the phase angle δ against logG * = 5.0, the value of δ (degrees) is * = 0.1 MPa). * If there is no point corresponding to =5.0, logG * Using two points around =5.0, logG * The δ value at logG = 5.0 is calculated by linear interpolation. * <5, logG * Using the three largest values, logG is calculated using a quadratic curve. * The δ value at =5.0 is extrapolated.

[0051] Copolymer production The copolymer according to the present invention is preferably produced in the presence of a transition metal catalyst, from the viewpoint of making the molecular structure linear. Polymerization catalyst The type of polymerization catalyst used in producing the copolymer according to the present invention is not particularly limited as long as it is capable of copolymerizing the structural unit (A), the structural unit (B), and the optional structural unit (C). For example, a transition metal compound of Groups 5 to 11 having a chelating ligand can be used. Specific examples of preferred transition metals include vanadium atom, niobium atom, tantalum atom, chromium atom, molybdenum atom, tungsten atom, manganese atom, iron atom, platinum atom, ruthenium atom, cobalt atom, rhodium atom, nickel atom, palladium atom, and copper atom. Among these, transition metals of Groups 8 to 11 are preferred, transition metals of Group 10 are more preferred, and nickel (Ni) and palladium (Pd) are particularly preferred. These metals may be used alone or in combination. Chelating ligands have at least two atoms selected from the group consisting of P, N, O, and S, and include bidentate or multidentate ligands, and are electronically neutral or anionic. Examples of chelating ligand structures are provided in a review by Brookhart et al. (Chem. Rev., 2000, 100, 1169). The chelating ligand preferably includes a bidentate anionic P,O ligand. Examples of bidentate anionic P,O ligands include phosphorus sulfonic acid, phosphorus carboxylic acid, phosphorus phenol, and phosphorus enolate. Other examples of the chelating ligand include a bidentate anionic N,O ligand. Examples of the bidentate anionic N,O ligand include salicylaldiminate and pyridinecarboxylic acid. Other examples of the chelating ligand include a diimine ligand, a diphenoxide ligand, and a diamide ligand.

[0052] The structure of the metal complex obtained from the chelating ligand is represented by the following structural formula (a) or (b), in which an arylphosphine compound, an arylarsine compound, or an arylantimony compound, which may have a substituent, is coordinated. [ka] [ka] [In structural formula (a) and structural formula (b), M represents a transition metal belonging to any of Groups 5 to 11 of the periodic table of the elements, that is, the various transition metals mentioned above. X 1 represents oxygen, sulfur, -SO3-, or -CO2-. Y 1 represents carbon or silicon. n represents an integer of 0 or 1. E 1 represents phosphorus, arsenic or antimony. R 53 and R 54 each independently represents hydrogen or a hydrocarbon group having 1 to 30 carbon atoms which may contain a heteroatom. R 55 each independently represents hydrogen, halogen, or a hydrocarbon group having 1 to 30 carbon atoms which may contain a heteroatom. R 56 and R 57 each independently represents hydrogen, halogen, a hydrocarbon group having 1 to 30 carbon atoms which may contain a heteroatom, OR 52 , CO2R 52 , CO2M', C(O)N(R 51 )2, C(O)R 52 , S.R. 52 , SO2R 52 , SOR 52 , OSO2R 52 , P(O)(OR 52 ) 2-y (R 51 ) y , CN, NHR 52 , N(R 52)2, Si(OR 51 ) 3-x (R 51 ) x , OSi(OR 51 ) 3-x (R 51 ) x , NO2, SO3M', PO3M'2, P(O)(OR 52 )2M' or an epoxy-containing group. R 51 represents hydrogen or a hydrocarbon group having 1 to 20 carbon atoms. R 52 represents a hydrocarbon group having 1 to 20 carbon atoms. M' represents an alkali metal, an alkaline earth metal, ammonium, a quaternary ammonium, or a phosphonium; x represents an integer of 0 to 3; and y represents an integer of 0 to 2. In addition, R 56 and R 57 may be linked to each other to form an alicyclic ring, an aromatic ring, or a heterocyclic ring containing a heteroatom selected from oxygen, nitrogen, and sulfur, in which case the ring has 5 to 8 members and may or may not have a substituent on the ring. L 1 represents a ligand coordinated to M. Also, R 53 and L 1 may be bonded to each other to form a ring.

[0053] More preferably, the complex that serves as the polymerization catalyst is a transition metal complex represented by the following structural formula (c). [ka] [In structural formula (c), M represents a transition metal belonging to any of Groups 5 to 11 of the periodic table of the elements, that is, the various transition metals mentioned above. X 1 represents oxygen, sulfur, -SO3-, or -CO2-. Y 1 represents carbon or silicon. n represents an integer of 0 or 1. E1 represents phosphorus, arsenic or antimony. R 53 and R 54 each independently represents hydrogen or a hydrocarbon group having 1 to 30 carbon atoms which may contain a heteroatom. R 55 each independently represents hydrogen, halogen, or a hydrocarbon group having 1 to 30 carbon atoms which may contain a heteroatom. R 58 , R 59 , R 60 and R 61 each independently represents hydrogen, halogen, a hydrocarbon group having 1 to 30 carbon atoms which may contain a heteroatom, OR 52 , CO2R 52 , CO2M', C(O)N(R 51 )2, C(O)R 52 , S.R. 52 , SO2R 52 , SOR 52 , OSO2R 52 , P(O)(OR 52 ) 2-y (R 51 ) y , CN, NHR 52 , N(R 52 )2, Si(OR 51 ) 3-x (R 51 ) x , OSi(OR 51 ) 3-x (R 51 ) x , NO2, SO3M', PO3M'2, P(O)(OR 52 )2M' or an epoxy-containing group. R 51 represents hydrogen or a hydrocarbon group having 1 to 20 carbon atoms. R 52 represents a hydrocarbon group having 1 to 20 carbon atoms. M' represents an alkali metal, an alkaline earth metal, ammonium, a quaternary ammonium, or a phosphonium; x represents an integer of 0 to 3; and y represents an integer of 0 to 2. In addition, R 58 ~R 61A plurality of groups appropriately selected from the above may be linked to each other to form an alicyclic ring, an aromatic ring, or a heterocyclic ring containing a heteroatom selected from oxygen, nitrogen, or sulfur, in which case the ring has 5 to 8 members and may or may not have a substituent on the ring. L 1 represents a ligand coordinated to M. Also, R 53 and L 1 may be bonded to each other to form a ring.

[0054] Here, typical catalysts of transition metal compounds of Groups 5 to 11 having a chelating ligand include so-called SHOP-based catalysts and Drent-based catalysts. The SHOP catalyst is a catalyst in which a phosphorus-based ligand having an aryl group which may have a substituent is coordinated to nickel metal (see, for example, WO2010-050256). Furthermore, Drent-based catalysts are catalysts in which a phosphorus-based ligand having an aryl group which may have a substituent is coordinated to palladium metal (see, for example, JP-A-2010-202647).

[0055] Copolymerization method: The method for polymerizing the copolymer according to the present invention is not limited. Examples of the polymerization method include slurry polymerization in which at least a portion of the produced polymer becomes a slurry in a medium, bulk polymerization in which liquefied monomer itself is used as a medium, gas phase polymerization carried out in vaporized monomer, and high pressure ionic polymerization in which at least a portion of the produced polymer is dissolved in monomer liquefied at high temperature and pressure. The polymerization method may be any of batch polymerization, semi-batch polymerization, and continuous polymerization. Furthermore, living polymerization may be carried out, or polymerization may be carried out while chain transfer occurs simultaneously. Furthermore, during polymerization, a so-called chain shuttling agent (CSA) may be used in combination to carry out a chain shuttling reaction or coordinated chain transfer polymerization (CCTP). Specific manufacturing processes and conditions are disclosed in, for example, Japanese Patent Application Laid-Open Nos. 2010-260913 and 2010-202647.

[0056] Method for introducing carboxyl groups and / or dicarboxylic anhydride groups into copolymers: The method for introducing a carboxyl group and / or a dicarboxylic anhydride group into the copolymer according to the present invention is not particularly limited, and the carboxyl group and / or the dicarboxylic anhydride group can be introduced by various methods within the scope of the present invention. Examples of methods for introducing a carboxyl group and / or a dicarboxylic anhydride group include a method of directly copolymerizing a comonomer having a carboxyl group and / or a dicarboxylic anhydride group, and a method of copolymerizing another monomer having a functional group that generates a carboxyl group, and then introducing a carboxyl group and / or a dicarboxylic anhydride group by modification.

[0057] Examples of methods for introducing a carboxyl group and / or a dicarboxylic anhydride group by modification include, for example, when introducing a carboxylic acid, a method in which an acrylic acid ester as a precursor is copolymerized and then hydrolyzed to convert it into a carboxylic acid, and a method in which t-butyl acrylate as a precursor is copolymerized and then thermally decomposed to convert it into a carboxylic acid.

[0058] A conventionally known acid-base catalyst may be used as an additive to promote the hydrolysis or thermal decomposition reaction. The acid-base catalyst is not particularly limited, and examples thereof include alkali metal or alkaline earth metal hydroxides such as sodium hydroxide, potassium hydroxide, and lithium hydroxide; alkali metal or alkaline earth metal carbonates such as sodium bicarbonate and sodium carbonate; solid acids such as montmorillonite; inorganic acids such as hydrochloric acid, nitric acid, and sulfuric acid; and organic acids such as formic acid, acetic acid, benzoic acid, citric acid, paratoluenesulfonic acid, trifluoroacetic acid, and trifluoromethanesulfonic acid. From the viewpoint of reaction acceleration effect, cost, corrosion resistance to equipment, etc., sodium hydroxide, potassium hydroxide, sodium carbonate, trifluoroacetic acid, and paratoluenesulfonic acid are preferred, and trifluoroacetic acid and paratoluenesulfonic acid are more preferred.

[0059] (5) Ionomer The ionomer according to the present invention is a copolymer (P) in which at least a portion of the carboxyl groups and / or dicarboxylic anhydride groups of the structural unit (B) is converted into a metal-containing carboxylate salt containing at least one metal ion selected from Groups 1, 2, and 12 of the periodic table, and the absolute value G of the complex modulus measured with a rotational rheometer is * = 0.1 MPa, the phase angle δ is 50 to 75 degrees, and it is an ionomer with a substantially linear structure. As described below, ionomers are obtained by reacting a metal salt with an ionomer base resin, and reactions that sever the polymer molecular chains do not usually occur during this process. Therefore, structural parameters such as the comonomer molar ratio, degree of branching, and randomness are usually preserved between the ionomer base resin and the ionomer.

[0060] Ionomer structure The ionomer according to the present invention has a substantially linear structure similar to the copolymer according to the present invention, and therefore the absolute value of the complex modulus G measured by a rotational rheometer * The phase angle δ at pressure = 0.1 MPa is 50 to 75 degrees. The phase angle δ(G * = 0.1 MPa) is lower than 50 degrees, the molecular structure of the ionomer contains excessive long chain branches, resulting in poor mechanical strength. Even if the molecular structure does not contain long chain branches, * =0.1MPa) value never exceeds 75 degrees. In the ionomer of the present invention, from the viewpoint of improving the mechanical strength, the lower limit of the phase angle δ is preferably 51 degrees or more, more preferably 54 degrees or more, even more preferably 56 degrees or more, and still more preferably 58 degrees or more. The upper limit is not particularly limited, and the closer to 75 degrees the better.

[0061] Melting point of ionomer (Tm, °C) The melting point (Tm, °C) of the ionomer according to the present invention is preferably 50 to 140°C, more preferably 60 to 138°C, and most preferably 70 to 135°C. If the melting point is lower than this range, the heat resistance may be insufficient, and if the melting point is higher than this range, the adhesiveness may be poor. Of the ionomers related to the present invention, ionomers based on a binary copolymer consisting only of structural unit (A) and structural unit (B) have a melting point of 90°C or higher, preferably 95°C or higher, and more preferably 100°C or higher, while ionomers based on ternary or higher multi-component copolymers have a melting point of less than 100°C, preferably less than 95°C, and more preferably less than 90°C.

[0062] Metal ions The metal ions contained in the ionomer according to the present invention are not particularly limited and may include metal ions used in conventionally known ionomers. Among these, metal ions are preferably ions of metals in Groups 1, 2, or 12 of the periodic table, and Li + , Na + , K. + , Rb + , Cs + , Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ and Zn 2+ At least one selected from the group consisting of is more preferred. Particularly preferred is Li + , Na + , K. + , Mg 2+ , Ca 2+ , and Zn 2+ , more preferably Na + , and Zn2+ At least one selected from the group consisting of: Two or more of these metal ions may be mixed and contained as needed.

[0063] ·Neutralization degree (mol%) The metal ion content is preferably an amount that neutralizes at least a part or all of the carboxyl groups and / or dicarboxylic anhydride groups in the copolymer as the base polymer, and the preferred degree of neutralization (average degree of neutralization) is 5 to 95 mol%, more preferably 10 to 90 mol%, and even more preferably 10 to 80 mol%. The degree of neutralization can be determined from the ratio of the total molar amount of the valence × molar amount of metal ions to the total molar amount of carboxy groups that may be contained in the carboxy groups and / or dicarboxylic anhydride groups in the copolymer. When forming a carboxylate, the dicarboxylic anhydride group opens its ring to form a dicarboxylic acid, so the total molar amount of the carboxyl groups is calculated assuming that there are 2 mol of carboxyl groups per mol of dicarboxylic anhydride group. 2+ For divalent metal ions such as those mentioned above, 1 mole can form a salt with 2 moles of carboxyl groups, and the total molar amount of molecules with a degree of neutralization is calculated by 2 x the molar amount. A high degree of neutralization results in an ionomer with high tensile strength and tensile stress at break and low tensile strain at break, but tends to result in a low melt flow rate (MFR).On the other hand, a low degree of neutralization results in an ionomer with a moderate MFR, but tends to result in a low tensile modulus and tensile stress at break and high tensile strain at break.

[0064] Haze (%) The ethylene ionomer resin of the present invention preferably has a haze value (%) measured in accordance with JIS K 7136-2000 of 25% or less, more preferably 20% or less. A haze (%) of 25% or less improves the transparency of molded articles, making it preferable for applications requiring transparency, such as window glass and solar cell modules.

[0065] Tensile impact strength (kJ / m 2 ) The ethylene ionomer resin of the present invention has a tensile impact strength of 700 kJ / m, as measured in accordance with Method B of JIS K 7160-1996, from the viewpoint of providing sufficient impact resistance. 2 It is preferable that the concentration is 720 kJ / m or more. 2 More preferably, it is 800 kJ / m or more. 2 More preferably, it is 1000 kJ / m or more. 2 More preferably, it is equal to or greater than this.

[0066] ·Adhesive strength (N / 10mm) The ethylene-based ionomer resin of the present invention preferably has an adhesive strength of 2.0 N / 10 mm or more, more preferably 2.3 N / 10 mm or more, even more preferably 2.5 N / 10 mm or more, and even more preferably 3.0 N / 10 mm or more, in order to ensure sufficient adhesive strength as measured by a tensile tester described below.

[0067] -Ionomer manufacturing method The ionomer of the present invention may be obtained by a conversion step in which a copolymer of ethylene and / or an α-olefin having 3 to 20 carbon atoms / unsaturated carboxylic acid, obtained by the above-mentioned method for introducing carboxyl groups and / or dicarboxylic anhydride groups into the copolymer, is treated with a metal salt containing at least one metal ion selected from Group 1, Group 2, or Group 12 of the periodic table to convert it into a metal-containing carboxylate. Alternatively, the ionomer of the present invention may be obtained by a heat conversion step in which an ethylene and / or an α-olefin having 3 to 20 carbon atoms / unsaturated carboxylic acid ester copolymer is heated to convert at least a portion of the ester groups in the copolymer into a metal-containing carboxylate containing at least one metal ion selected from Group 1, Group 2, or Group 12 of the periodic table.

[0068] When an ionomer is produced after introducing carboxyl groups and / or dicarboxylic anhydride groups into a polymer, the production method is, for example, as follows: A metal ion source is prepared by kneading, optionally with heating, a metal salt with a substance that captures metal ions, such as an ethylene / methacrylic acid (MAA) copolymer, and then the metal ion source is added to an ionomer base resin in an amount that achieves the desired degree of neutralization, followed by kneading.

[0069] The thermal conversion step may also involve (i) heating an ethylene and / or C3-20 α-olefin / unsaturated carboxylic acid ester copolymer to hydrolyze or pyrolyze it into an ethylene and / or C3-20 α-olefin / unsaturated carboxylic acid copolymer, and then reacting the copolymer with a compound containing a metal ion of Group 1, 2, or 12 of the periodic table to convert the carboxylic acid in the copolymer into the metal-containing carboxylate; or (ii) heating an ethylene and / or C3-20 α-olefin / unsaturated carboxylic acid ester copolymer to hydrolyze or pyrolyze the ester groups in the copolymer while reacting the copolymer with a compound containing a metal ion of Group 1, 2, or 12 of the periodic table to convert the ester group moieties in the copolymer into the metal-containing carboxylate.

[0070] The compound containing a metal ion may be an oxide, hydroxide, carbonate, bicarbonate, acetate, formate, etc. of a metal of Group 1, 2, or 12 of the periodic table. The compound containing a metal ion may be supplied to the reaction system in the form of particles or fine powder, or may be dissolved or dispersed in water or an organic solvent and then supplied to the reaction system, or a masterbatch may be prepared using an ethylene / unsaturated carboxylic acid copolymer or an olefin copolymer as a base polymer and then supplied to the reaction system. To ensure smooth reaction, it is preferable to prepare a masterbatch and then supply it to the reaction system.

[0071] Furthermore, the reaction with the metal ion-containing compound may be carried out by melt-kneading using various types of equipment such as a vented extruder, a Banbury mixer, or a roll mill, and the reaction may be carried out batchwise or continuously. Since the reaction can be carried out smoothly by discharging water and carbon dioxide gas by-produced in the reaction using a degassing device, it is preferable to carry out the reaction continuously using an extruder equipped with a degassing device such as a vented extruder. In the reaction with the compound containing metal ions, a small amount of water may be injected to promote the reaction.

[0072] The temperature at which the ethylene and / or C3-20 α-olefin / unsaturated carboxylic acid ester copolymer is heated may be any temperature at which the ester is converted to a carboxylic acid, but if the heating temperature is too low, the ester will not be converted to a carboxylic acid, and if the heating temperature is too high, decarbonylation or decomposition of the copolymer may occur. Therefore, the heating temperature in the present invention is preferably in the range of 80°C to 350°C, more preferably 100°C to 340°C, even more preferably 150°C to 330°C, and even more preferably 200°C to 320°C.

[0073] The reaction time varies depending on the heating temperature, the reactivity of the ester group moiety, etc., but is usually 1 minute to 50 hours, more preferably 2 minutes to 30 hours, even more preferably 2 minutes to 10 hours, still more preferably 2 minutes to 3 hours, and particularly preferably 3 minutes to 2 hours.

[0074] In the above steps, the reaction atmosphere is not particularly limited, but it is generally preferable to carry out the reaction under a stream of inert gas. Examples of inert gases that can be used include nitrogen, argon, and carbon dioxide. A small amount of oxygen or air may be present.

[0075] The reactor used in the above step is not particularly limited, and any method can be used as long as it can stir the copolymer substantially uniformly. A glass vessel or autoclave (AC) equipped with a stirrer may be used, or any conventionally known kneader such as a Brabender Plastograph, a single-screw or twin-screw extruder, a high-intensity screw kneader, a Banbury mixer, a kneader, or a roll may be used.

[0076] Whether or not metal ions have been introduced into an ionomer-based resin and it has become an ionomer can be confirmed by measuring the IR spectrum of the resulting resin and examining the decrease in the peak due to the carbonyl group of the carboxylic acid (dimer). Similarly, the degree of neutralization can be confirmed by calculating from the molar ratio mentioned above, as well as examining the decrease in the peak due to the carbonyl group of the carboxylic acid (dimer) and the increase in the peak due to the carbonyl group of the carboxylate salt group.

[0077] 2. Resin film for glass laminate and glass laminate The ionomer according to the present invention can be used in a resin film constituting at least one layer of a glass laminate. A "glass laminate" refers to a laminate having a multilayer structure of two or more layers, at least one of which is glass. Therefore, the glass laminate according to the present invention is a structure having at least one glass layer and one resin layer containing the ionomer according to the present invention (hereinafter, this layer may also be referred to as an "ionomer resin layer"). Preferably, the glass layer and the ionomer resin layer are in direct contact with each other. Materials used for the other layers can be freely selected by those skilled in the art depending on the application of the glass laminate.

[0078] The resin film for glass laminates of the present invention is a film containing the resin for glass laminates containing the ionomer. Here, the term "film" generally refers to a structure having a thickness negligible relative to its area, but in the present invention, the term "film" is used to include not only films (generally 250 μm thick) and sheets in the narrow sense, but also plate-like objects. Furthermore, regardless of the flexibility of the film, there are no particular limitations as long as it is rigid and has a specific shape, as long as it can form a laminate. The surface of the film can have any shape, such as a quadrilateral, circle, or triangle.

[0079] The resin film for glass laminates may consist solely of the ionomer, but may also contain additives such as antioxidants, ultraviolet absorbers, light stabilizers, flame retardants, dyes, pigments, plasticizers, antistatic agents, inorganic particles, fluorescent agents, heat ray absorbers, heat ray reflectors, modified silicone oil as an adhesion adjuster, moisture-resistant agents, and antiblocking agents, as needed. Furthermore, other resins may be included to impart effects such as ultraviolet and infrared absorption, soundproofing, and moisture prevention, as long as the effects of the present invention are not impaired. Those skilled in the art can freely select the resins that can be used depending on the intended use of the laminate.

[0080] The resin film for a glass laminate itself may have multiple layers. That is, it may have a single-layer structure consisting of only an ionomer resin layer, or a multilayer structure in which the ionomer resin layer is laminated with other layers (one or more layers). As the other layer, an adhesive layer containing a resin that exhibits adhesiveness to glass, such as a polyvinyl acetal resin, may be provided, although this is not necessarily required.

[0081] The material, manufacturing method, layer thickness, etc. of the glass layer can be freely designed depending on the application. When a glass laminate has multiple glass layers, each layer may be made of the same material or different materials. As described above, the glass laminate is a structure having at least one ionomer resin layer and one glass layer, but the glass laminate may also have a structure in which glass layers and ionomer resin layers are alternately laminated. An adhesive layer may be provided between each glass layer and the ionomer resin layer, or other layers may be provided depending on the application of the glass laminate. Furthermore, the glass layer does not need to be the outermost layer in the laminate, and layers made of other materials may be further laminated thereon.

[0082] The glass laminate can be manufactured by any method known to those skilled in the art. A flat glass layer and an ionomer resin layer may be manufactured separately and then bonded together, 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 therebetween. That is, by placing the glass laminate of the present invention and another plate-like body opposite each other with a certain gap between them, sealing the edges and optionally evacuating the air, a gas layer or a vacuum layer can be provided in the structure.

[0083] 3. Resin film for glass interlayer, laminated glass The resin for glass laminates of the present invention can be suitably used as a resin film for glass interlayers. That is, the resin film for glass interlayers is positioned between two glass layers to form a laminate of at least three layers. Preferably, the resin film for glass interlayers is in contact with the glass layers on at least one side, more preferably on both sides. In order for the resin for glass interlayers to be effective in preventing cracking of the glass and scattering of broken glass fragments, the adhesive strength measured under the conditions described below is preferably 2.0 N / 10 mm or more, more preferably 2.3 N / 10 mm or more, even more 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 laminated glass using the resin for glass laminates containing the ionomer as a resin film for glass interlayers. The laminated glass of the present invention can be used as laminated glass for window glass, automobile windshields, monitor glass, building glass, security glass, and the like.

[0084] The resin film for glass interlayers of the present invention may have a single-layer structure consisting of only an ionomer resin layer, or may have a multilayer structure in which the ionomer resin layer is laminated with other layers (one or more layers).

[0085] The other layer is not particularly limited, and examples thereof include layers containing thermoplastic resins other than ionomer resins, such as polyvinyl acetal resins, ethylene-vinyl acetate copolymer resins, ethylene-acrylic copolymer resins, polyurethane resins, polyurethane resins containing elemental sulfur, polyvinyl alcohol resins, vinyl chloride resins, polyethylene terephthalate resins, etc. Among these, layers containing polyvinyl acetal resins are preferred because they exhibit excellent adhesion to glass when used in combination with a plasticizer, and a resin film that can exhibit various functions can be obtained by blending various additives therein.

[0086] Laminated glass is a laminate having a structure of at least three layers, in which two glass layers sandwich a resin film for glass interlayers (ionomer resin layer). The laminated glass may have a structure in which glass layers and ionomer resin layers are alternately laminated.

[0087] 4. Resin film for solar cell encapsulant and solar cell module The resin for glass laminates of the present invention can be suitably used as a resin film for solar cell encapsulant.

[0088] 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 blend a hindered amine light stabilizer. The hindered amine light stabilizer captures radical species harmful to the polymer and prevents the generation of new radicals. There are many types of hindered amine light stabilizers, ranging from low molecular weight to high molecular weight compounds, and any conventionally known compound can be used without any particular limitation. Examples of ultraviolet absorbers include various types such as benzophenone-based, benzotriazole-based, triazine-based, and salicylic acid ester-based. Examples of silane coupling agents include vinyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, and 3-acryloxypropyltrimethoxysilane, and they can be used mainly for the purpose of improving the adhesive strength between the upper protective material of the solar cell and the solar cell element.

[0089] Other optional components may also be added to the polyolefin resin composition within the scope of the present invention, such as antioxidants, crystal nucleating agents, clarifying agents, lubricants, colorants, dispersants, fillers, and fluorescent whitening agents, which are commonly used in polyolefin resin materials.

[0090] By using the resin film for solar cell encapsulant of the present invention, a solar cell module can be produced by fixing a solar cell element together with upper and lower protective materials. Examples of such solar cell modules include those configured such that the solar cell element is sandwiched between encapsulants from both sides, such as upper transparent protective material / encapsulant / solar cell element / encapsulant / lower protective material; those configured such that an encapsulant and upper transparent protective material are formed on a solar cell element formed on the inner peripheral surface of a lower substrate protective material; and those configured such that an encapsulant and lower protective material are formed on a solar cell element formed on the inner peripheral surface of an upper transparent protective material, for example, an amorphous solar cell element formed on a fluororesin-based transparent protective material by sputtering or the like.

[0091] As described above, the resin for glass laminates of the present invention and its uses have been described with reference to specific examples, but the resin for glass laminates of the present invention, and the film and glass laminate made thereof are not limited to the specific examples given above. Those skilled in the art can design, modify, improve, etc. as appropriate within the scope of the present invention. [Example]

[0092] EXAMPLES The present invention will be explained in more detail below with reference to examples and comparative examples, but the present invention is not limited to these examples. The physical properties in the examples and comparative examples were measured and evaluated by the methods shown below. In the tables, "no data" means that no measurement was performed, and "not detected" means that the value was below the detection limit.

[0093] <Measurement and Evaluation> (1) Absolute value of complex elastic modulus G * = 0.1MPa at the phase angle δ(G * =0.1MPa) 1) Sample preparation and measurement The sample was placed in a 1.0 mm thick heat press mold and preheated for 5 minutes in a heat press at a surface temperature of 180°C. Residual gas in the molten resin was removed by repeatedly applying and depressurizing pressure to 4.9 MPa and holding for 5 minutes. The sample was then transferred to a press at a surface temperature of 25°C and cooled by holding at 4.9 MPa for 3 minutes to produce a pressed plate made of the sample with a thickness of approximately 1.0 mm. The pressed plate made of the sample was cut into a 25 mm diameter circle and used as a sample. Dynamic viscoelasticity was measured using a Rheometrics ARES rotational rheometer under a nitrogen atmosphere under the following conditions: Plate: φ25mm (diameter) parallel plate ·Temperature: 160℃ Distortion: 10% Measurement angular frequency range: 1.0 x 10 -2 ~1.0×10 2 rad / s Measurement interval: 5 points / decade Absolute value of complex modulus G * Common logarithm logG of (Pa) * Plot the phase angle δ against logG * = 5.0, the value of δ (degrees) is * = 0.1 MPa). * If there is no point corresponding to =5.0, logG * Using two points around =5.0, logG * The δ value at logG = 5.0 was calculated by linear interpolation. * <5, logG * Using the three largest values, logG is calculated using a quadratic curve. * The δ value at δ = 5.0 was extrapolated.

[0094] (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), and the molecular weight distribution parameter (Mw / Mn) was calculated from the ratio of Mw to Mn, Mw / Mn, obtained by further determining the number average molecular weight (Mn) by gel permeation chromatography (GPC). The measurements were carried out according to the following procedures and conditions.

[0095] 1) Sample pretreatment If the sample contained a carboxylic acid group, it was subjected to esterification treatment, such as methyl esterification using diazomethane or trimethylsilyl (TMS) diazomethane, before use in the measurement. If the sample contained a carboxylic acid base, it was treated with an acid to modify the carboxylic acid base to a carboxylic acid group, and then subjected to the above-mentioned esterification treatment before use in the measurement.

[0096] 2) Preparation of sample solution 3 mg of sample and 3 mL of o-dichlorobenzene were weighed into a 4 mL vial, and the vial was capped with a screw cap and a Teflon (registered trademark) septum, and then shaken for 2 hours at 150°C using a Senshu Scientific SSC-7300 high-temperature shaker. After shaking, it was visually confirmed that there were no insoluble components.

[0097] 3) Measurement A Waters Alliance GPCV2000 was connected to one Showdex HT-G and two Showdex HT-806M high-temperature GPC columns, and measurements were performed using o-dichlorobenzene as the eluent at a temperature of 145°C and a flow rate of 1.0 mL / min.

[0098] 4) Calibration curve The column was calibrated using monodisperse polystyrene (S-7300, S-3900, S-1950, S-1460, S-1010, S-565, S-152, S-66.0, S-28.5, S-5.05, each 0.07 mg / ml solution) manufactured by Showa Denko, n-eicosane, and n-tetracontane under the same conditions as above, and the logarithm of the elution time and molecular weight was approximated by a quartic equation. PS) and polyethylene molecular weight (M PE ) was converted using the following formula: M PE =0.468×M PS

[0099] (3) Melt flow rate (MFR) The MFR was measured in accordance with Table 1-Condition 7 of JIS K-7210 (1999) at a temperature of 190°C and a load of 21.18N (=2.16kg).

[0100] (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). Measurements were performed using a DSC (DSC7020) manufactured by SII Nano Technology, Inc. under the following measurement conditions: Approximately 5.0 mg of sample was placed in an aluminum pan, heated to 200°C at 10°C / min, held at 200°C for 5 minutes, and then cooled to 30°C at 10°C / min. After holding at 30°C for 5 minutes, the sample was again heated at 10°C / min. The maximum peak temperature of the absorption curve obtained during this period was taken as the melting point Tm, and the heat of fusion (ΔH) was calculated from the area of ​​the melting endothermic peak. The degree of crystallinity (%) was calculated by dividing this heat of fusion by the heat of fusion of 293 J / g for perfectly crystalline high-density polyethylene (HDPE).

[0101] (5) Method for measuring the amount of structural units derived from monomers having a carboxyl group and / or a dicarboxylic anhydride group, and acyclic monomers, and the number of branches per 1,000 carbon atoms The amount of structural units derived from monomers having a carboxy group and / or a dicarboxylic anhydride group and acyclic monomers in the copolymer of the present invention, and the number of branches per 1,000 carbon atoms are 13 It can be determined using C-NMR spectroscopy. 13 C-NMR was measured by the following method. 200-300 mg of sample was placed in an NMR sample tube with an inner diameter of 10 mm, together with 2.4 ml of a mixed solvent of o-dichlorobenzene (C6H4Cl2) and deuterated bromide benzene (C6D5Br) (C6H4Cl2 / C6D5Br = 2 / 1 (volume ratio)) and hexamethyldisiloxane, a chemical shift reference substance, and the tube was purged with nitrogen, then sealed and heated to dissolve, creating a homogeneous solution that was used as the NMR measurement sample. NMR measurements were carried out at 120°C using a Bruker AV400M NMR instrument equipped with a 10 mm diameter cryoprobe. 13 C-NMR was measured using the inverse gate decoupling method at a sample temperature of 120°C, a pulse angle of 90°, a pulse interval of 51.5 seconds, and an accumulation count of 512 or more. The chemical shifts are those of hexamethyldisiloxane. 13 The C signal was set to 1.98 ppm, and the other 13 The chemical shift of the C signal was based on this.

[0102] 1) Sample pretreatment If the sample contained a carboxylate group, it was treated with an acid to convert the carboxylate group to a carboxyl group before use. If the sample contained a carboxyl group, it may be subjected to an appropriate esterification treatment, such as methyl esterification using diazomethane or trimethylsilyl (TMS) diazomethane.

[0103] 2) Calculation of the amount of structural units derived from monomers having a carboxyl group and / or a dicarboxylic anhydride group, and acyclic monomers <e tba> The quaternary carbon signal of the t-butyl acrylate group of tBA is 13 It is detected at 79.6 to 78.8 in the C-NMR spectrum. Using these signal intensities, the amount of comonomer was calculated according to the following formula. Total amount of tBA (mol%) = I(tBA) × 100 / [I(tBA) + I(E)] Here, I(tBA) and I(E) are the quantities shown in the following formulas. I(tBA)=I 79.6~78.8 I(E)=(I 180.0~135.0 +I 120.0~5.0 -I(tBA)×7) / 2

[0104] <e tba iba> The quaternary carbon signal of the t-butyl acrylate group of tBA is 13 The methylene signal of the isobutoxy group of iBA is detected at 70.5 to 69.8 ppm, and the methyl signal of the isobutoxy group is detected at 19.5 to 18.9 ppm in the C-NMR spectrum. Using these signal intensities, the amount of comonomer was calculated using the following formula. Total amount of tBA (mol%) = I(tBA) × 100 / [I(tBA) + I(iBA) + I(E)] Total amount of iBA (mol%)=I(iBA)×100 / [I(tBA)+I(iBA)+I(E)] Here, I(tBA), I(iBA), and I(E) are the quantities shown in the following formulas. I(tBA)=I 79.6~78.8 I(iBA)=(I 70.5~69.8 +I 19.5~18.9 ) / 3 I(E)=(I 180.0~135.0 +I 120.0~5.0 -I(iBA)×7-I(tBA)×7) / 2

[0105] <e tba nb> The quaternary carbon signal of the t-butyl acrylate group of tBA is 13 The C-NMR spectrum shows a signal at 79.6 to 78.8 ppm, 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 using the following formula: Total amount of tBA (mol%) = I(tBA) × 100 / [I(tBA) + I(NB) + I(E)] Total amount of NB (mol%) = I(NB) × 100 / [I(tBA) + I(NB) + I(E)] Here, I(tBA), I(NB), and I(E) are the quantities shown in the following formulas. I(tBA)=I 79.6~78.8 I(NB)=(I 41.9~41.1 ) / 2 I(E)=(I 180.0~135.0 +I 120.0~5.0 -I(NB)×7-I(tBA)×7) / 2

[0106] When the amount of structural units of each monomer is indicated by "<0.1" including an inequality sign, this means that the monomer is present as a structural unit in the copolymer, but the amount is less than 0.1 mol % taking into account significant digits.

[0107] 3) Calculation of the number of branches per 1,000 carbon atoms Copolymers come in three types: isolated types, in which branches exist singly in the main chain; complex types (face-to-face types, in which branches face each other via the main chain; branched-branch types, in which branches exist within branched chains; and chain types). The following is an example of the structure of an ethyl branch: In the example of the face-to-face type, R represents an alkyl group.

[0108] [ka]

[0109] The number of branches per 1,000 carbons can be calculated by substituting either I(B1), I(B2), or I(B4) below into the I (branch) term in the following formula. B1 represents methyl branches, B2 represents ethyl branches, and B4 represents butyl branches. The number of methyl branches can be calculated using I(B1), the number of ethyl branches using I(B2), and the number of butyl branches using I(B4). Number of branches (per 1,000 carbon atoms) = I (branches) × 1,000 / I (total) Here, I(total), I(B1), I(B2), and I(B4) are quantities expressed by the following formulas. I(total)=I 180.0~135.0 +I 120.0~5.0 I(B1)=(I 20.0~19.8 +I 33.2~33.1 +I 37.5~37.3 ) / 4 I(B2)=I 8.6~7.6 +I 11.8~10.5 I(B4)=I 14.3~13.7 -I 32.2~32.0 where I is the integrated intensity, and the subscripts of I indicate the range of chemical shifts. For example, I 180.0~135.0 was detected between 180.0 ppm and 135.0 ppm. 13 The integrated intensity of the C signal is shown. The attribution was made with reference to the non-patent literature Macromolecules 1984, 17, 1756-1761 and Macromolecules 1979, 12, 41. When the number of branches is indicated as "<0.1" including an inequality sign, it means that the branch is present as a structural unit in the copolymer, but the amount is less than 0.1 mol% taking into account significant figures. Also, "not detected" means below the detection limit.

[0110] (6) Infrared absorption spectrum The sample was melted at 180°C for 3 minutes and compression molded to prepare a film with a thickness of about 50 µm. This film was analyzed by Fourier transform infrared spectroscopy to obtain an infrared absorption spectrum. Product name: FT / IR-6100 manufactured by JASCO Corporation Measurement method: transmission method Detector: TGS (Triglycine sulfate) Accumulation count: 16 to 512 times Resolution: 4.0cm -1 Measurement wavelength: 5000~500cm -1

[0111] (7) Tensile impact strength 1) Preparation method for tensile impact strength test samples The sample was placed in a 1mm thick heat press mold and preheated to a surface temperature of 180°C for 5 minutes. The sample was melted and degassed by repeatedly applying pressure and depressurizing the pressure. The mold was then pressurized to 4.9 MPa and held for 5 minutes. The mold was then gradually cooled at a rate of 10°C / min while still under pressure at 4.9 MPa. Once the temperature had dropped to near room temperature, the molded plate was removed. The resulting plate was conditioned for at least 48 hours at a temperature of 23±2°C and a humidity of 50±5°C. Test specimens conforming to ASTM D1822 Type-S were punched out of the conditioned press plate to prepare samples for tensile impact strength testing.

[0112] 2) Tensile impact strength test conditions Using the above test specimens, the tensile impact strength was measured with reference to Method B of JIS K 7160-1996. Note that the only difference from JIS K 7160-1996 was the shape of the test specimen. Other measurement conditions were in accordance with the method of JIS K 7160-1996.

[0113] (8) Hayes 1) How to adjust the press plate for the sample The sample was placed in a heat press mold measuring 50 mm x 60 mm and 0.5 mm thick, and preheated for 5 minutes in a heat press at a surface temperature of 180°C. Residual gas in the sample was removed by repeatedly applying and depressurizing pressure, and the sample was then pressurized to 4.9 MPa and held for 3 minutes. The sample was then transferred to a press at a surface temperature of 25°C and cooled by holding the pressure at 4.9 MPa for 3 minutes to produce a pressed plate approximately 0.5 mm thick. 2) Haze measurement conditions Using the above test piece, the haze was measured in accordance with JIS K 7136-2000.

[0114] (9) Glass adhesive strength The glass adhesive strength was measured by vacuum laminating a pressed plate sample and a float glass sheet to form a laminate, and then conducting a peel test. The methods for preparing the pressed plate and the laminate, and the method for measuring the adhesive strength are explained below.

[0115] 1) How to adjust the press plate for the sample The sample was placed in a heat press mold measuring 50 mm x 60 mm and 0.5 mm thick, and preheated for 5 minutes in a heat press at a surface temperature of 180°C. Residual gas in the sample was removed by repeatedly applying and depressurizing pressure, and the sample was then pressurized to 4.9 MPa and held for 3 minutes. The sample was then transferred to a press at a surface temperature of 25°C and cooled by holding the pressure at 4.9 MPa for 3 minutes to produce a pressed plate approximately 0.5 mm thick.

[0116] 2) How to adjust the glass sheets The glass plates used were commercially available float glass plates manufactured by the float process. In the float process, molten glass is poured onto molten tin, where it cools and solidifies, resulting in highly smooth glass plates. The lower surface of float glass plates manufactured by this float process, i.e., the surface that was in contact with the molten tin (hereinafter referred to as the bottom surface), contains tin, and is characterized by a higher amount of silanol groups than the surface that was not in contact with the molten tin (hereinafter referred to as the top surface). Furthermore, because silanol groups in glass have the property of adsorbing hydrocarbon-based substances present in the atmosphere, it is desirable to clean the glass plates used in adhesion tests immediately before the test. Based on the above, in this invention, 2.5 mm thick float glass plates were washed with a neutral detergent before the test, dried at 70°C, and cut to dimensions of 50 mm x 60 mm. The top surface was then bonded to the press plate sample.

[0117] 3) Manufacturing method of laminate of sample and plate glass Using a vacuum laminator (manufactured by NPC Corporation), the top surfaces of the press plate and the glass plate were laminated together at a heating temperature of 180°C for 10 minutes, then sandwiched between two aluminum plates and quenched for 3 minutes to obtain a two-layer, two-type laminate. A 10 mm wide slit was made in the sheet portion of this laminate to prepare a test specimen.

[0118] 4) Method for measuring adhesive strength of laminates The laminate obtained by the laminate manufacturing method was used as a test piece, and peeled at a take-up speed of 50 mm / min using a Tensilon (manufactured by Toyo Seiki Co., Ltd.) tensile tester, and the maximum stress was determined as the adhesive strength (N / 10 mm).

[0119] <Synthesis of metal complexes> (1) Synthesis of B-27DM / Ni complex The B-27DM / Ni complex was prepared according to Synthesis Example 4 described in WO 2010 / 050256, using the following 2-bis(2,6-dimethoxyphenyl)phosphano-6-pentafluorophenylphenol ligand (B-27DM). Following Example 1 of WO 2010 / 050256, a nickel complex (B-27DM / Ni) was synthesized in which B-27DM and Ni(COD)2 reacted in a 1:1 ratio using bis(1,5-cyclooctadiene)nickel(0) (referred to as Ni(COD)2). [ka]

[0120] <(Production 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). The copolymer was produced with reference to Production Example 1 or Production Example 3 described in JP 2016-79408 A. The production conditions, including the type and amount of metal catalyst, the amount of trioctylaluminum (TNOA), the amount of toluene, the type and amount of comonomer, the ethylene partial pressure, the polymerization temperature, and the polymerization time, were appropriately changed. The production results are shown in Table 1, and the physical properties of the resulting copolymer are shown in Table 2.

[0121] [Table 1]

[0122] [Table 2]

[0123] <(Resin 1): Production of ionomer-based resin-1> A 500 ml separable flask was charged with 40 g of the copolymer obtained in Production Example 1, 0.8 g of paratoluenesulfonic acid monohydrate, and 185 ml of toluene, and the mixture was stirred at 105°C for 4 hours. 185 ml of ion-exchanged water was added, stirred, and allowed to stand, after which the aqueous layer was extracted. Subsequently, the addition and extraction of ion-exchanged water was repeated until the pH of the extracted aqueous layer reached 5 or higher. The solvent was distilled off from the remaining solution under reduced pressure, and the solution was dried to a constant weight. In the IR spectrum of the obtained resin, a 850 cm derivative of the tBu group was observed. -1 The disappearance of the peak around 1730 cm originating from the carbonyl group of the ester -1 The decrease in the peak near 1700 cm originates from the carbonyl group of the carboxylic acid (dimer). -1 An increase in the peak around This confirmed the decomposition of t-Bu ester and the production of carboxylic acid, yielding ionomer base resin 1. The physical properties of the resulting resin are shown in Table 3.

[0124] [Table 3]

[0125] <Ionomer 1 to Ionomer 4: Ionomer Production-1> 1) Preparation of Zn ion source A Zn ion source was prepared by adding 21.8 g of ethylene / methacrylic acid (MAA) copolymer (Nucrel® N1050H, manufactured by Mitsui-Dow Polychemicals Co., Ltd.), 18 g of zinc oxide, and 0.2 g of zinc stearate to a Laboplastomill (Roller Mixer R60, manufactured by Toyo Seiki Co., Ltd.) equipped with a 60 ml small mixer, and kneading the mixture at 180°C and 40 rpm for 3 minutes.

[0126] 2): Preparation of ionomer 40 g of Resin 1 was placed in a Labo Plastomill (Roller Mixer R60) manufactured by Toyo Seiki Co., Ltd., equipped with a 60 ml small mixer, and dissolved by kneading at 160°C and 40 rpm for 3 minutes. Thereafter, a Zn ion source was added so as to achieve the desired degree of neutralization, and the mixture was kneaded at 250°C and 40 rpm for 5 minutes. In the IR spectrum of the obtained resin, the peak at 1700 cm originating from the carbonyl group of the carboxylic acid (dimer) was observed. -1 The peak around 1560 cm originating from the carbonyl group of the carboxylate group decreases. -1 The peak around 1700 cm originating from the carbonyl group of the carboxylic acid (dimer) increased. -1 The decrease in the peak near 0.01 was sufficient to confirm that an ionomer with the desired degree of neutralization had been produced. The physical properties of the resulting ionomer are shown in Tables 4 and 5.

[0127] [Table 4]

[0128] [Table 5]

[0129] (Comparative Example 1): E / MAA-based binary ionomer An ionomer resin (manufactured by Mitsui-Dow Polychemicals Co., Ltd., brand: HIMILAN (registered trademark) HIM1706) which is a copolymer of ethylene, methacrylic acid, and zinc methacrylate and produced by a high-pressure radical process was used as the reference ionomer. The physical properties are shown in Tables 4 and 5.

[0130] (Comparative Example 2): E / MAA-based binary ionomer An ionomer resin (manufactured by Mitsui-Dow Polychemicals Co., Ltd., brand: HIMILAN (registered trademark) HIM1707) which is a copolymer of ethylene, methacrylic acid, and zinc methacrylate and produced by a high-pressure radical process was used as the reference ionomer. The physical properties are shown in Tables 4 and 5.

[0131] <Consideration of the results of Examples and Comparative Examples> Comparative Examples 1 and 2 are ionomers made from a base resin produced by a high-pressure radical method and a metal ion source, and therefore their molecular structures have many long-chain branches and the absolute value of the complex modulus G * On the other hand, since Examples 1 to 10 are ionomers made of a base resin and metal ions produced using a specific transition metal catalyst, their molecular structures are substantially linear, and the phase angle δ (G * =0.1MPa) is 50° or more. The measurement results shown in Table 5 show that the resin layer in the laminate examples of the present invention is firmly bonded to the glass layer and has high transparency and tensile impact strength. Comparative Examples 1 and 4, and Comparative Examples 2 and 7 are existing ionomers with equivalent acid contents and degrees of neutralization, but the comparative examples have inferior adhesive strength and tensile impact strength compared to the examples, although they have equivalent transparency. This means that the phase angle δ(G * = 0.1 MPa) is 50° or more, the ionomer of the present invention is shown to be relatively superior in balance of transparency, adhesive strength and tensile impact strength compared to conventional ionomers.

[0132] [Ionomer Composition, Degree of Neutralization, and Metal Ion Species in the Present Invention] Examples 1 to 10 are ionomers with different base resin compositions, degrees of neutralization, and metal ion species, but all of them satisfy the desired transparency (haze), desired adhesive performance (adhesive strength), and desired strength (tensile impact strength), and have superior adhesive strength and tensile impact strength to Comparative Examples 1 and 2, which are existing ionomers. This is shown in Figure 3, where the phase angle δ(G * This indicates that the multi-component ionomer of the present invention, in which the tensile strength (=0.1 MPa) is 50° or more, is relatively excellent in the balance of transparency, adhesive strength, and tensile impact strength, regardless of the degree of neutralization. In the present invention, the desired haze is at least 25% or less, preferably 20% or less, the desired adhesive strength is preferably 2.0 N / 10 mm or more, more preferably 2.3 N / 10 mm or more, even more preferably 2.5 N / 10 mm or more, and still more preferably 3.0 N / 10 mm or more, and the desired tensile impact strength is preferably 700 kJ / m 2 More preferably, 720 kJ / m or more. 2 More preferably, it is 800 kJ / m or more. 2 or more, and particularly preferably 1000 kJ / m 2 Anything above that is fine.

[0133] From such a comparison between the Examples and Comparative Examples, it was found that the ionomer of the present invention, due to its characteristic molecular structure, exhibits an excellent balance of transparency, adhesiveness, and impact resistance that was not available in conventional ionomers. [Industrial Applicability]

[0134] By using a glass laminate resin containing the ionomer of the present invention, it is expected that laminated glass interlayers and solar cell module encapsulants can be obtained that have excellent adhesion and impact resistance while maintaining the same transparency as glass laminate resins containing conventional ionomers. In the case of laminated glass, it is expected that safety will be improved while maintaining visibility, and it is thought that it will be highly useful as automotive glass and architectural glass. In the case of solar cell modules, it is expected that durability will be improved without reducing conversion efficiency.< / e> < / e> < / e>

Claims

1. a copolymer (P) comprising, as essential structural units, structural units (A) derived from ethylene and / or an α-olefin having 3 to 20 carbon atoms and structural units (B) derived from a monomer having a carboxyl group and / or a dicarboxylic acid anhydride group, in which the structural unit amount of the structural units (A) is 96.5 mol % or less, and at least a portion of the carboxyl groups and / or dicarboxylic acid anhydride groups are converted to a metal-containing carboxylate containing at least one metal ion selected from Group 1, Group 2, or Group 12 of the Periodic Table, Absolute value of complex modulus G measured by a rotational rheometer ＊ = 0.1 MPa, the phase angle δ is 50 degrees to 75 degrees, and the glass adhesive strength measured according to the following method is 2.0 N / 10 mm or more. 1) Sample press plate adjustment method The ionomer sample was placed in a heat press mold with dimensions of 50 mm x 60 mm and a thickness of 0.5 mm, preheated for 5 minutes in a heat press at a surface temperature of 180°C, and then degassed by repeatedly applying and depressurizing pressure to remove residual gas from the sample. The sample was then further pressurized to 4.9 MPa and held for 3 minutes. The sample was then transferred to a press at a surface temperature of 25°C and cooled by holding at a pressure of 4.9 MPa for 3 minutes to produce a pressed plate with a thickness of approximately 0.5 mm. 2) How to adjust the glass plate The glass plate used was a commercially available float glass plate manufactured by the float process. Immediately before the test, the 2.5 mm thick float glass plate was washed with a neutral detergent, dried at 70°C, and cut to a size of 50 mm x 60 mm. The top surface of the glass plate was then bonded to the press plate of the sample. 3) Manufacturing method of laminate of sample and glass plate Using a vacuum laminator, the top surfaces of the press plate and the glass plate were laminated together at a heating temperature of 180°C for 10 minutes, then sandwiched between two aluminum plates and quenched for 3 minutes to obtain a two-layer, two-kind laminate. A 10 mm wide slit was made in the sheet portion of this laminate to prepare a test specimen. 4) Method for measuring adhesive strength of laminate The laminate obtained by the laminate manufacturing method is used as a test piece, and is peeled off at a take-up speed of 50 mm / min using a Tensilon tensile tester, and the maximum stress is determined as the glass adhesive strength (N / 10 mm).

2. The copolymer (P) １３ 2. The resin for glass laminates according to claim 1, wherein the number of methyl branches calculated by C-NMR is 50 or less per 1,000 carbon atoms.

3. The copolymer (P) １３ 2. The resin for glass laminates according to claim 1, wherein the number of methyl branches calculated by C-NMR is 5 or less per 1,000 carbon atoms.

4. 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%.

5. 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.

6. The resin for glass laminates according to any one of claims 1 to 5, characterized in that the copolymer (P) is produced using a transition metal catalyst containing a transition metal of Groups 8 to 11 of the periodic table.

7. 7. The resin for glass laminates according to claim 6, wherein the transition metal catalyst is a transition metal catalyst comprising a phosphorus sulfonic acid or phosphorus phenol ligand and nickel or palladium.

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