JP2015028164A - Multi-component polar group-containing olefin copolymer, adhesive and laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polar-group-containing olefin copolymer which is produced by an easy and efficient method and is sufficiently improved in mechanical physical properties and adhesiveness.SOLUTION: There is provided a multinary polar group-containing olefin copolymer having three or more monomer units comprising a nonpolar monomer (X1) unit selected from ethylene and an α-olefin having 3 to 10 carbon atoms, a polar monomer (Z1) unit selected from an epoxy group, a carboxyl group or a dicarboxylic acid anhydride group and the other noncyclic or cyclic monomer (Z2) unit as essential components, which is copolymerized in the presence of a transition metal catalyst.

Description

  The present invention relates to a polar group-containing olefin copolymer having excellent physical properties, and more specifically, a nonpolar monomer unit selected from ethylene and an α-olefin having 3 to 10 carbon atoms, an epoxy group, a carboxyl group, or a dicarboxylic acid anhydride. The present invention relates to a multi-component polar olefin copolymer comprising a polar monomer unit having a physical group and another monomer unit, and having significantly improved adhesion and impact resistance.

  In general, olefin-based resins have high mechanical strength, excellent impact resistance, long-term durability, chemical resistance, corrosion resistance, etc., are inexpensive, have excellent moldability, and are compatible with environmental issues and resource reusability. Therefore, it is used as an industrial material, and is formed into a film, a laminate, a container, a blow bottle, etc. by, for example, injection molding, extrusion molding, blow molding, etc., and used for a wide range of applications. Furthermore, by laminating with a base material such as a gas barrier material such as ethylene-vinyl alcohol copolymer (EVOH) or aluminum foil, in addition to the above properties, properties such as gas barrier properties can be added, High-performance packaging materials and containers can be obtained.

  However, olefin-based resins are generally non-polar, and when used in laminated materials, the disadvantage is that their adhesion strength to other types of highly polar dissimilar materials such as synthetic resins, metals, and wood is extremely low or not bonded. There is.

Therefore, in order to improve the adhesion with different polar materials, a method of grafting a polar group-containing monomer using an organic peroxide has been widely performed (for example, see Patent Document 1).
However, in this method, intermolecular crosslinking between olefinic resins and molecular chain scission of olefinic resins occur in parallel with the grafting reaction, so that the excellent physical properties of the olefinic resin are not maintained in the graft modified product. The problem occurs. For example, unnecessary long chain branching is introduced by intermolecular crosslinking, resulting in an increase in melt viscosity and broadening of the molecular weight distribution, which adversely affects adhesiveness and moldability. Further, the increase in the low molecular weight component of the olefin resin due to the molecular chain breakage presents the problem of causing eye strain and fuming during molding.

  Furthermore, by increasing the polar group content in the polar group-containing olefin copolymer, it is possible to increase the adhesion with different polar materials, but a large amount of polar group-containing monomer is grafted onto the olefin resin by graft modification. It is not easy to do. As a method for increasing the content of the polar group-containing monomer, for example, a method for increasing the amount of the polar group-containing monomer used for graft modification and the amount of the organic peroxide can be considered. When this method is used, it leads to further intermolecular crosslinking and molecular chain breakage of the olefin resin, and various physical properties such as mechanical properties, impact resistance, long-term durability, and moldability are impaired. In addition, the amount of unreacted polar group-containing monomers and organic peroxide decomposition products remaining in the olefin resin increases, leading to an accelerated deterioration of the olefin resin and an unpleasant odor. Occur. Therefore, there has been a limit to increase the content of the polar group-containing monomer in the olefin resin.

  By the way, as a means of incorporating polar group-containing monomers into olefinic resins without causing intermolecular crosslinking or gelation and molecular chain scission between olefinic resins, high pressure radical polymerization is used to polarize ethylene and polar groups. A method of copolymerizing a group-containing monomer to obtain a polar group-containing olefin copolymer is also disclosed (see Patent Documents 2 to 4). In addition, although the molecular structure example of the polar group containing olefin copolymer which introduce | transduced the polar group using the high pressure radical polymerization process is shown in FIG. 1 (a), the problem which generate | occur | produces by graft modification according to this method is As a result, it is possible to increase the content of the polar group-containing monomer in the polar group-containing olefin copolymer as compared with graft modification. However, since the polymerization process is a high-pressure radical method, the obtained polar group-containing olefin copolymer has a molecular structure having many long-chain branches and short-chain branches irregularly. For this reason, only a polar group-containing olefin copolymer having a low elastic modulus and low mechanical properties is obtained as compared with a polar group-containing olefin copolymer polymerized using a transition metal catalyst, and high strength is required. The range of application to the use is limited.

  On the other hand, when a conventional metallocene catalyst is used to copolymerize ethylene and a polar group-containing monomer, it has been said that catalytic polymerization activity is reduced and polymerization is difficult. A method of polymerizing a polar group-containing olefin copolymer in the presence of a catalyst coordinated to a transition metal has been proposed (see Patent Documents 5 to 8). According to these methods, although it has a high elastic modulus and mechanical strength compared with the polar group-containing olefin copolymer obtained by the high-pressure radical process, it is possible to increase the polar group content. 2 (b) and 3 (c) show image diagrams of the molecular structure of the polar group-containing olefin copolymer polymerized using a catalyst. The methods described in these documents are mainly methyl acrylate or ethyl acrylate. The main focus is on monomers containing acrylate groups such as acrylate, and copolymers of specific polar group-containing monomers such as vinyl acetate and ethylene or α-olefins. Polar group-containing olefin copolymers having these functional groups are Adhesiveness with dissimilar materials with high polarity is not sufficient. In addition, specific adhesion performance with different polar materials is not mentioned, and use as a specific polar group-containing olefin copolymer for the purpose of adhesion performance is not disclosed.

On the other hand, in general, epoxy groups, carboxyl groups or dicarboxylic anhydride groups are known as polar groups capable of expressing excellent adhesiveness with different polar materials, but in ordinary catalytic polymerization methods, It is difficult to copolymerize an epoxy group, carboxyl group or dicarboxylic anhydride group-containing comonomer, and at present, polar olefin copolymer containing mainly epoxy group, carboxyl group or dicarboxylic anhydride group which is commercially available The coalescence is due to the high pressure radical polymerization process.
In addition, as an example of the polar group-containing olefin copolymer polymerized without using the high-pressure radical polymerization process, a so-called masking method called a specific metallocene catalyst and a sufficient amount of organic aluminum (with a polar group-containing monomer) In the process invention that polymerizes in the presence of equimolar or more), 1,2-epoxy-9-decene or (2,7-octadien-1-yl) succinic anhydride is copolymerized with ethylene and 1-butene. The polar group-containing olefin copolymer is shown (see Patent Document 9).
However, according to the present invention, a large amount of organoaluminum is required for copolymerization of the polar group-containing olefin, and the production cost must be increased. In addition, a large amount of organoaluminum is present in the polar group-containing olefin copolymer as an impurity, causing deterioration of mechanical properties, discoloration, and promotion of deterioration, and further removing this leads to further cost increase. Furthermore, the effect of the invention is mainly to produce a polar group-containing olefin copolymer with high polymerization activity, and no specific adhesion performance with different polar materials is mentioned.
In addition, this patent document completely touches on the resin physical properties necessary for the polar group-containing olefin copolymer to obtain sufficient adhesiveness with different polar materials and the conditions for improving the adhesive properties and mechanical properties in a well-balanced manner. The use as a polar group-containing olefin copolymer that balances high adhesive performance and excellent mechanical properties is not disclosed.

  In view of the above prior art, it is apparent that development of a polar group-containing olefin copolymer produced by a simple and efficient polymerization method and having sufficiently improved mechanical properties and adhesiveness is desired. .

JP 50-004144 A Japanese Patent No. 2516003 JP 47-23490 A Japanese Patent Laid-Open No. 48-11388 JP 2010-202647 A JP 2010-150532 A JP 2010-150246 A JP 2010-260913 A Japanese Patent No. 4672214

  In view of the conventional problems described above as the background art, the object of the present invention is to dissimilarly dissimilar materials with high polarity, which are produced by any conventional method and which include each problem. An object of the present invention is to develop a polar group-containing olefin copolymer having excellent adhesion performance and excellent balance between adhesion and mechanical properties.

In order to solve the above problems, the present inventors have produced the copolymer by a simple and efficient production method in the production of a polar group-containing olefin copolymer, and the adhesion of the copolymer to a different material. In order to improve the performance, the method of polar group introduction, selection of polar group and polymerization catalyst, the molecular structure of the polar group-containing olefin copolymer, and the correlation between the structure of the copolymer and the adhesion performance were considered and examined. As a result of the verification, it was possible to find a polar group-containing olefin copolymer that was excellent in adhesion performance with different materials and sufficiently compatible with adhesiveness and mechanical properties, leading to the creation of the present invention.
That is, the multi-component polar olefin copolymer of the present invention having an extremely narrow molecular weight distribution in a specific range and having a melting point in a specific range is characterized by a dramatic improvement in terms of the balance between adhesiveness and mechanical properties. Yes.

  Specifically, it is selected from one or more nonpolar monomer (X1) units selected from ethylene and an α-olefin having 3 to 10 carbon atoms and a monomer having an epoxy group, a carboxyl group or a dicarboxylic anhydride group. A multi-component polar group-containing olefin copolymer (provided that X1, Z1, X1, Z2) are characterized by comprising one or more polar monomer (Z1) units and any non-cyclic or cyclic monomer (Z2) unit. Each unit of Z2 is at least one essential component), and is characterized by having a linear and random molecular structure obtained by copolymerization in the presence of a transition metal catalyst. A multi-component polar group-containing olefin copolymer is defined as a basic invention (first invention).

  2nd invention of this invention is that the ratio of the weight average molecular weight (Mw) and number average molecular weight (Mn) calculated | required by gel permeation chromatography (GPC) is the range of 1.5-3.5. A multi-component polar group-containing olefin copolymer according to the first aspect of the invention.

  The third invention of the present invention is characterized in that the amount of aluminum (Al) contained in the multi-component polar group-containing olefin copolymer is 0 to 100,000 μg per 1 g of the copolymer, It is a multi-component polar group-containing olefin copolymer in the second invention.

  In the fourth aspect of the present invention, the melting point Tm (° C.) expressed by the temperature at the maximum peak position of the absorption curve measured by the differential scanning calorimetry (DSC) method is 50 <Tm <128-6. 0.0 [Z1] (provided that the monomer unit derived from Z1 is [Z1] (mol%)), the multi-component polar group-containing olefin copolymer according to the first to third inventions It is a coalescence.

  According to a fifth aspect of the present invention, the polar monomer (Z1) unit selected from monomers having an epoxy group, a carboxyl group or a dicarboxylic anhydride group is 0.001 to 19.999 mol%. The multi-component polar group-containing olefin copolymer in the fourth invention.

  A sixth invention of the present invention is the multi-component polar group-containing olefin copolymer according to the first to fifth inventions, wherein the nonpolar monomer (X1) unit is ethylene.

  The seventh invention of the present invention is the multicomponent system according to the first to sixth inventions, characterized in that the transition metal catalyst is a transition metal containing a chelating ligand and a Group 5-11 metal. It is a polar group-containing olefin copolymer.

  The eighth invention of the present invention is characterized in that the multi-component polar group-containing olefin copolymer is a transition metal catalyst in which a triarylphosphine or a triarylarsine compound is coordinated to palladium or nickel metal. It is a multi-component polar group-containing olefin copolymer in the seventh invention.

  The ninth invention of the present invention is an adhesive comprising the multi-component polar group-containing olefin copolymer in the first to eighth inventions.

  A tenth aspect of the present invention is a laminate including at least a multi-component polar group-containing olefin copolymer or a layer containing an adhesive in the first to ninth aspects, and a base material layer.

  In an eleventh aspect of the present invention, the base material layer is selected from olefin resins, highly polar thermoplastic resins, metals, vapor-deposited films of inorganic oxides, papers, cellophane, woven fabrics, and nonwoven fabrics. It is a laminated body in the tenth invention.

  According to a twelfth aspect of the present invention, the base material layer is a polyamide resin, a fluorine resin, or an ethylene-vinyl alcohol copolymer (EVOH). Is the body.

  Since the polar group-containing olefin copolymer of the present invention has a specific molecular structure and resin physical properties, it exhibits high adhesiveness with other base materials without impairing mechanical physical properties and other physical properties. This makes it possible to produce a useful laminate. Such remarkable effects are verified by the data of each example of the present invention described later and the comparison between each example and each comparative example.

  Further, the multi-component polar group-containing olefin copolymer having a specific molecular structure and resin properties according to the present invention is excellent not only in adhesiveness but also in mechanical and thermal properties, and can be applied as a useful multilayer molded article. Yes, it can be formed into a multilayer film, a multilayer blow bottle, etc. by various uses such as extrusion molding and blow molding, and can be used for a wide range of applications.

It is an image figure of the molecular structure of the olefin copolymer (a) polymerized by the high-pressure radical polymerization process. It is an image figure of the molecular structure of (b) when it is an olefin copolymer polymerized using a metal catalyst and does not have a long chain branch. It is an image figure of the molecular structure of (c) when it is a small amount of long chain branching with the olefin copolymer polymerized using the metal catalyst.

  Below, the multicomponent polar olefin copolymer in this invention, the adhesive material and laminated body using the same are demonstrated concretely and in detail for every item.

[I] Multi-component polar group-containing olefin copolymer (1) Multi-component polar group-containing olefin copolymer The multi-component polar group-containing olefin copolymer according to the present invention is ethylene and an α- having 3 to 10 carbon atoms. Three components comprising a nonpolar monomer (X1) selected from olefins, a polar group-containing monomer (Z1) selected from monomers having an epoxy group, a carboxyl group or a dicarboxylic anhydride group, and another monomer (Z2) Is a multi-component polar olefin copolymer. The multi-component polar group-containing olefin copolymer obtained by copolymerizing (X1), (Z1), and (Z2) is already known in graft polymerization, high-pressure radical polymerization and other polymerization methods described above. However, in the present invention, the known multi-component polar group-containing olefin copolymer is a random copolymer polymerized in the presence of a transition metal, and its molecular structure is substantially linear. Since it has the feature that it is in the form of a sheet and also has a requirement of having a special adhesive effect, it is significantly different from known copolymers.

(2) Nonpolar monomer (X1)
Examples of the nonpolar monomer (X1) related to the present invention include ethylene and / or an α-olefin having 3 to 10 carbon atoms.
Preferable specific examples include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 3-methyl-1-butene and 4-methyl-1-pentene. A specific example is ethylene. Moreover, one type of α-olefin may be used, or a plurality of α-olefins may be used in combination.
Examples of the two combinations include ethylene-propylene, ethylene-1-butene, ethylene-1-hexene, ethylene-1-octene, propylene-1-butene, propylene-1-hexene, and propylene-1-octene. .
Examples of the three combinations include ethylene-propylene-1-butene, ethylene-propylene-1-hexene, ethylene-propylene-1-octene, propylene-1-butene-hexene, and propylene-1-butene-1-octene. It is done.

(3) Polar monomer (Z1) containing epoxy group, carboxyl group or dicarboxylic anhydride group
The polar group-containing monomer (Z1) related to the present invention needs to contain an epoxy group, a carboxyl group or a dicarboxylic anhydride group. Highly polar thermoplastic such as polyamide resin, polyester resin, ethylene-vinyl alcohol copolymer (EVOH), adhesive fluororesin, etc., if it is an olefin copolymer having an epoxy group, a carboxyl group or a dicarboxylic anhydride group It becomes possible to laminate and adhere to a resin and a base material of a metal material such as aluminum or steel.

The polar group-containing monomer containing an epoxy group, a carboxyl group or a dicarboxylic anhydride group is preferably a polar group-containing monomer represented by the following structural formula (I) or structural formula (II).
Structural formula (I)

（構造式（Ｉ）中、Ｒ^１は水素原子または炭素数１〜１０のアルキル基、Ｒ^２、Ｒ^３、Ｒ^４はそれぞれ独立して、水素原子、炭化水素基、又はエポキシ基、カルボキシル基又はジカルボン酸無水物基を含む下記の特定の官能基を示し、Ｒ^２〜Ｒ^４のいずれか１つ以上がエポキシ基、カルボキシル基又はジカルボン酸無水物基を含む特定の官能基である。
特定の官能基：エポキシ基、カルボキシル基又はジカルボン酸無水物基を必須で含み、炭素原子、酸素原子、水素原子からなる分子構造を有した基）
構造式（ＩＩ）

(In the structural formula (I), R ¹ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R ² , R ³ and R ⁴ are each independently a hydrogen atom, a hydrocarbon group, an epoxy group or a carboxyl group. or indicate a specific functional group of the following including dicarboxylic acid anhydride group, or one of R ² to R ⁴ is a specific functional group containing an epoxy group, a carboxyl group or a dicarboxylic anhydride group.
Specific functional group: a group containing an epoxy group, a carboxyl group or a dicarboxylic anhydride group as essential, and having a molecular structure composed of a carbon atom, an oxygen atom and a hydrogen atom)
Structural formula (II)

（構造式（II）中、Ｒ^５〜Ｒ^８はそれぞれ独立して、水素原子、炭化水素基、又はエポキシ基、カルボキシル基又はジカルボン酸無水物基を含む下記の特定の官能基を示し、Ｒ^５〜Ｒ^８のいずれか１つはエポキシ基、カルボキシル基又はジカルボン酸無水物基を含む特定の官能基である。また、ｍは０〜２である。Ｚは炭素原子又は酸素原子から選択される原子である。特定の官能基：エポキシ基、カルボキシル基又はジカルボン酸無水物基を必須で含み、炭素原子、酸素原子、水素原子からなる分子構造を有した基）

(In Structural Formula (II), R ^{5 to} R ⁸ each independently represent a hydrogen atom, a hydrocarbon group, or the following specific functional group containing an epoxy group, a carboxyl group, or a dicarboxylic anhydride group, and R Any one of ^{5 to} R ⁸ is a specific functional group including an epoxy group, a carboxyl group or a dicarboxylic anhydride group, and m is 0 to 2. Z is selected from a carbon atom or an oxygen atom. Specific functional group: a group having an epoxy group, a carboxyl group, or a dicarboxylic anhydride group, and having a molecular structure composed of a carbon atom, an oxygen atom, and a hydrogen atom)

The molecular structure of the polar group-containing monomer is not particularly limited, but considering the ease of copolymerization in the presence of a transition metal catalyst and the handling of the polar group-containing monomer, the polar group-containing monomer represented by the structural formula (I) is More preferred. Furthermore, among the epoxy group, carboxyl group or dicarboxylic anhydride group-containing monomers represented by the structural formula (I), R1 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R2, R3 and R4 are each independently Any one of the following specific functional groups including a hydrogen atom, a hydrocarbon group, or an epoxy group, a carboxyl group, or a dicarboxylic anhydride group, and any one or more of R2 to R4 is an epoxy group A monomer having a specific functional group containing a carboxyl group or a dicarboxylic anhydride group is more preferable.
(Specific functional group: an epoxy group, a carboxyl group or a dicarboxylic anhydride group essential, and further including any one of a hydrocarbon group, a carbonyl group and an ether group, carbon atom, oxygen atom, hydrogen atom A group having a molecular structure consisting of

<Polar group-containing monomer containing epoxy group (Z1)>
Examples of the polar group-containing monomer containing an epoxy group include 5-hexene epoxide, 6-heptene epoxide, 7-octene epoxide, 8-nonene epoxide, 9-decene epoxide, 10-undecene epoxide, and 11-dodecene. Ω-alkenyl epoxides such as epoxide, 2-methyl-6-heptene epoxide, 2-methyl-7-octene epoxide, 2-methyl-8-nonene epoxide, 2-methyl-9-decene epoxide, 2-methyl- Ω-alkenyl epoxides having a branch in the molecular structure such as 10-undecene epoxide, allyl glycidyl ether, 2-methylallyl glycidyl ether, glycidyl ether of o-allylphenol, glycidyl ether of m-allylphenol, p-allyl Unsaturated glycidyl ethers such as glycidyl ether of phenol, 4-hydroxybutyrate (Meth) acrylate, acrylic acid, methacrylic acid, glycidyl p-styrylcarboxylate, endo-cis-bicyclo [2,2,1] hept-5-ene-2,3-dicarboxylic acid, endo-cis-bicyclo [ 2,2,1] hept-5-ene-2-methyl-2,3-dicarboxylic acid, itaconic acid, citraconic acid, butenetricarboxylic acid, glycidyl ester of unsaturated carboxylic acid, epoxy hexyl norbornene, epoxy cyclohexane norbornene , Cyclic olefins containing an epoxy group such as methyl glycidyl ether norbornene, 2- (o-vinylphenyl) ethylene oxide, 2- (p-vinylphenyl) ethylene oxide, 2- (o-allylphenyl) ethylene oxide, 2- (p -Allylphenyl) ethylene oxide, 2- o-vinylphenyl) propylene oxide, 2- (p-vinylphenyl) propylene oxide, 2- (o-allylphenyl) propylene oxide, 2- (p-allylphenyl) propylene oxide, p-glycidylstyrene, 3,4- Epoxy-1-butene, 3,4-epoxy-3-methyl-1-butene, 3,4-epoxy-1-pentene, 3,4-epoxy-3-methyl-1-pentene, 5,6-epoxy- Mention of monomers containing an epoxy group such as 1-hexene, vinylcyclohexene monoxide, allyl-2,3-epoxycyclopentyl ether, 2,3-epoxy-5-vinylnorbornane, 1,2-epoxy-4-vinylcyclohexane I can do it.
Among these, 1,2-epoxy-9-decene, 4-hydroxybutyl acrylate glycidyl ether, glycidyl methacrylate, 1,2-epoxy-4-vinylcyclohexane and the like represented by the following structural formula are particularly preferable.

１，２−ｅｐｏｘｙ−９−ｄｅｃｅｎｅ

1,2-epoxy-9-decene

４−ｈｙｄｒｏｘｙｂｕｔｙｌ ａｃｒｙｌａｔｅ ｇｌｙｃｉｄｙｌｅｔｈｅｒ

4-hydroxybutyryl glycidylether

ｇｌｙｃｉｄｙｌ ｍｅｔｈａｃｒｙｌａｔｅ

glycidyl methacrylate

１，２−ｅｐｏｘｙ−４−ｖｉｎｙｌｃｙｃｌｏｈｅｘａｎｅ

1,2-epoxy-4-vinylcyclohexane

  In a polar group-containing olefin copolymer using a monomer containing an epoxy group, cross-linking between molecular chains may occur due to a reaction between the contained epoxy groups. As long as it does not depart from the gist of the present invention, intermolecular chain crosslinking may occur.

<Polar group-containing monomer containing carboxyl group or dicarboxylic anhydride group>
Specific monomers containing a carboxyl group or dicarboxylic anhydride group include acrylic acid, methacrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, norbornene dicarboxylic acid, Unsaturated carboxylic acids such as bicyclo [2,2,1] hept-2-ene-5,6-dicarboxylic acid, maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, 5-norbornene-2, 3-dicarboxylic acid anhydride, 3,6-epoxy-1,2,3,6-tetrahydrophthalic acid anhydride, tetracyclo [6. 2. 1. 1 ^{3 , 6} . 0 ^{2 , 7} ] unsaturated carboxylic acid anhydrides such as dodeca-9-ene-4,5-dicarboxylic acid anhydride and 2,7-octadien-1-ylsuccinic acid anhydride.
Among these, 2,7-octadien-1-yl succinic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, 3,6-epoxy-1,2,3 represented by the following chemical formula 6-tetrahydrophthalic anhydride and the like are preferable.

２，７−オクタジエン−１−イルコハク酸無水物

2,7-octadiene-1-ylsuccinic anhydride

５−ノルボルネン−２，３−ジカルボン酸無水物

5-norbornene-2,3-dicarboxylic anhydride

３，６−エポキシ−１，２，３，６−テトラヒドロフタル酸無水物

3,6-epoxy-1,2,3,6-tetrahydrophthalic anhydride

  In a copolymer using an unsaturated dicarboxylic acid anhydride as a monomer, a dicarboxylic acid anhydride group contained therein may react with moisture in the air to open a ring, and a part thereof may be a dicarboxylic acid. As long as it does not depart from the gist of the present invention, the dicarboxylic anhydride group may be ring-opened.

  Furthermore, the polar group-containing monomer used may be used singly or in combination of two or more.

(4) Other monomer (Z2)
The other monomer (Z2) which is the third component can be any monomer as long as it is not the same as (X1) and (Z1). For example, when ethylene is selected as (X1), ethylene cannot be used as (Z2), but other α-olefins such as 1-butene and 1-hexene can be used. Similarly, when 4-hydroxybutyl glycidylether is selected as (Z1), for example, 4-hydroxybutyl acrylate monomer that is not 4-hydroxybutyryl glycidylether is an epoxy group-containing monomer or a monomer that contains an acid anhydride. I can do it.

The other monomer (Z2) is a compound that essentially contains a carbon-carbon double bond in the molecule, and has a substituent (polar group) containing an atom having an electronegativity different from that of the carbon atom. It is good and does not need to have.
Here, examples of polar groups include halogens, hydroxyl groups (—OH), carboxyl groups (—COOH), formyl groups (—CHO), alkoxy groups (—OR), ester groups (—COOR), nitrile groups ( -CN), an ether group (-O-), a carbonyl group (= CO), an epoxy group, and an acid anhydride group.

  The other monomer (Z2) according to the present invention is classified into an acyclic monomer or a cyclic monomer depending on the position of the carbon-carbon double bond in the molecule. In addition, as long as a carbon-carbon double bond is located in the non-cyclic part in a molecule | numerator, an acyclic monomer may have a cyclic structure in the said molecule | numerator.

(4-1) Acyclic monomer Examples of the acyclic monomer include α-olefin, unsaturated carboxylic acid, unsaturated carboxylic acid anhydride (when the carbon-carbon double bond is not cyclic), (meth) acrylic acid ester, and the like. Can be mentioned.

The α-olefin according to the present invention is an α-olefin having 3 to 20 carbon atoms and represented by the structural formula: CH ₂ ═CHR ¹⁸ (R ¹⁸ is a hydrocarbon group having 1 to ¹⁸ carbon atoms and linear The structure may be branched. Specific examples of the α-olefin include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 3-methyl-1-butene, 4-methyl-1-pentene, Vinylcyclohexene, 1,2-epoxy-4-vinylcyclohexane, styrene, 6-hydroxy-1-hexene, 8-hydroxy-1-octene, 9,10-oxy-1-decene, 7- (N, N-dimethyl) Amino) -1-peptene, 3-triethoxysilyl-1-propene, allyl alcohol, 2-allyloxyethanol, allyl acetate and the like, more preferably an α-olefin having 3 to 12 carbon atoms, Preferably, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 3-methyl-1-butene, 4 An α-olefin selected from methyl-1-pentene, and more preferably an α-olefin selected from propylene, 1-butene, 1-hexene and 1-octene. The α-olefin used for polymerization may be used alone or in combination of two or more.

  Specific examples of the unsaturated carboxylic acid include methacrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, norbornene dicarboxylic acid, bicyclo [2,2,1] hept-2- Examples include ene-5,6-dicarboxylic acid.

  Specific examples of the unsaturated carboxylic acid anhydride (when the carbon-carbon double bond is not cyclic) include itaconic anhydride and 2,7-octadien-1-yl succinic anhydride.

The (meth) acrylic acid ester related to the present invention is a compound represented by the structural formula: CH ₂ ═C (R ²¹ ) CO 2 (R ²² ). Here, R < ²¹ > is a hydrogen atom or a C1-C10 hydrocarbon group, and may have a branch, a ring, and / or an unsaturated bond. R ²² is a hydrocarbon group having 1 to 30 carbon atoms, and may have a branch, a ring, and / or an unsaturated bond. Furthermore, it may contain a hetero atom at any position within R ^22.
Preferable (meth) acrylic acid ester includes (meth) acrylic acid ester in which R ²¹ is a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms. More preferable examples include acrylic acid esters in which R ²¹ is a hydrogen atom or methacrylic acid esters in which R ²¹ is a methyl group.

Specific examples of (meth) acrylic acid ester include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and (meth) acrylic acid n. -Butyl, isobutyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, octyl (meth) acrylate, (meth) 2-ethylhexyl acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, phenyl (meth) acrylate, toluyl (meth) acrylate, benzyl (meth) acrylate, (meth ) Hydroxyethyl acrylate, hydroxybutyl (meth) acrylate, 1,4-cyclohe Sanmethanol mono (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether (4-HBAGE), 2-methoxyethyl (meth) acrylate, 3-methoxypropyl (meth) acrylate, (meth) acryl Examples include glycidyl acid, ethylene oxide (meth) acrylate, trifluoromethyl (meth) acrylate, (meth) acrylic acid-2-trifluoromethylethyl, perfluoroethyl (meth) acrylate, and the like.
A single (meth) acrylic acid ester may be used, or a plurality of (meth) acrylic acid esters may be used in combination.
Preferred compounds include methyl acrylate, ethyl acrylate, n-butyl acrylate, t-butyl acrylate, and (4-hydroxybutyl) acrylate glycidyl ether.

(4-2) Cyclic monomer Examples of the cyclic monomer include norbornene-based olefins and unsaturated carboxylic acid anhydrides (when the carbon-carbon double bond is cyclic), such as cyclopentene, cyclohexene, norbornene, and ethylidene norbornene. Examples of the compound having a cyclic olefin skeleton and derivatives thereof include compounds containing a hydroxyl group, an alkoxide group, a carboxylic acid group, an ester group, an aldehyde group, an acid anhydride group, and an epoxy group.

  Specific examples of the unsaturated carboxylic acid anhydride (when the carbon-carbon double bond is cyclic) include maleic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, 5-norbornene-2,3-dicarboxylic acid anhydride, 3,6-epoxy-1,2,3,6-tetrahydrophthalic anhydride, tetracyclo [6.2.13,6.02,7] dodec-9-ene-4,5-dicarboxylic anhydride Etc.

  Examples of the norbornene-based olefin include compounds represented by the following structural formula (E) and structural formula (F). Structural formula (E) is norbornene having an acid anhydride group (Diels-Alder reaction product of cyclopentadiene and maleic anhydride, that is, 5-norbornene-2,3-dicarboxylic acid anhydride), (F) is norbornene having a hydroxyl group.

(5) Amounts of structural units of monomers (X1), (Z1), (Z2) The multi-component polar group-containing olefin copolymer according to the present invention includes one or more types of (X1), (Z1), and (Z2). It is necessary to contain 3 or more types of monomer units in total.
The structural unit amount of (X1) is 80.000 mol% to 99.998 mol%, preferably 80.000 mol% to 99.98 mol%, more preferably 80.000 mol% to 99.94 mol%. The structural unit amount of (Z1) is 0.001 mol% to 19.999 mol%, preferably 0.01 mol% to 15.000 mol%, more preferably 0.02 mol% to 10.000 mol%, still more preferably 0.02 mol%. -5.000 mol%. The structural unit amount of (Z2) is 0.001 mol% to 19.999 mol%, preferably 0.01 mol% to 15.000 mol%, more preferably 0.02 mol% to 10.000 mol%, still more preferably 0.02 mol%. -5.000 mol%. (X1) + (Z1) + (Z2) must be 100 mol%.

In the multi-component olefin copolymer according to the present invention, when polymerized in the presence of a transition metal catalyst and ethylene is selected as (X1), the crystallinity of the copolymer depends on the content of monomers other than ethylene. Determined. For example, in the case of a copolymer of ethylene and (Z1), the content of (Z1) is a strong factor that determines the crystallinity of the copolymer.
By the way, in the examination process of the present invention, the present inventors have found that, in addition to the (Z1) content of the copolymer, the lower melting point shows higher adhesiveness as a factor affecting the adhesive performance. . That is, in order to further improve the adhesive performance, it is important to lower the melting point of the copolymer by containing (Z1) in an amount of 0.001 mol% or more and further containing another monomer (Z2). It was. (Z2) The main reason for copolymerizing the monomer into the copolymer is to control the melting point of the copolymer, and (Z2) the monomer is not limited for this reason. Further, the monomer (Z1) is often more expensive than the monomer (X1) or the monomer (Z2).
According to the present invention, once the minimum amount of monomer (Z1) necessary for improving the adhesiveness is determined, the melting point is lowered by further copolymerizing an appropriate amount of (Z2) monomer, and the adhesion performance is further improved. It can be increased.
It is not clear why the copolymer has a lower melting point and is more flexible so that the adhesiveness can be improved. However, JIS K6854-1-4 (1999) "Adhesive-Peeling bond strength test method" When carrying out a peel test as exemplified in the above, if the adhesive is flexible, the adhesive itself is greatly deformed, and the amount of deformation is measured as stress, resulting in high adhesion. I guess it is.
Furthermore, the present invention, which can arbitrarily adjust the melting point of the copolymer without changing the content of the polar group derived from the monomer (Z1), can improve the adhesion performance and mechanical properties of the copolymer, particularly impact resistance. It is possible to achieve both.

(6) Structural unit of multi-component polar group-containing olefin copolymer The structural unit and structural unit amount of the multi-component polar group-containing olefin copolymer according to the present invention will be described.
A structure derived from one molecule of ethylene and / or an α-olefin (X1) having 3 to 10 carbon atoms, an epoxy group, a carboxyl group or a dicarboxylic anhydride group-containing monomer (Z1), and another monomer (Z2), It is defined as one structural unit in the polar group-containing olefin copolymer. And what represented the ratio of each structural unit in a polar group containing olefin copolymer in mol% is a structural unit amount.

(7) Structural unit amount of epoxy group, carboxyl group or dicarboxylic anhydride group-containing monomer (Z1) The structural unit amount of (Z1) according to the present invention is usually in the range of 0.001 mol% to 19.999 mol%, preferably Is selected from the range of 0.01 mol% to 15.000 mol%, more preferably in the range of 0.02 mol% to 10.000 mol%, more preferably in the range of 0.02 mol% to 5.000 mol%. It is preferable to exist in the copolymer. If the amount of the structural unit derived from the polar group-containing monomer is less than this range, the adhesion with a different polar material is not sufficient, and if it is more than this range, sufficient mechanical properties cannot be obtained. Furthermore, the polar group-containing monomer used may be used alone or in combination of two or more.

(8) Measuring method of structural unit amount of polar group-containing monomer The structural unit amount of the polar group (epoxy group, carboxyl group or dicarboxylic anhydride group) in the multi-component polar group-containing olefin copolymer according to the present invention is ^1. It is determined using an H-NMR spectrum. ¹ H-NMR spectrum was measured by the following method.
200-250 mg of a sample having an inner diameter of 10 mmφ together with 2.4 ml of o-dichlorobenzene / deuterated benzene bromide (C ₆ D ₅ Br) = 4/1 (volume ratio) and hexamethyldisiloxane which is a reference substance of chemical shift The sample was placed in an NMR sample tube, purged with nitrogen, sealed, heated and dissolved, and subjected to NMR measurement as a uniform solution.
The NMR measurement was performed at 120 ° C. using a Bruker BioSpin Corporation AV400M NMR apparatus equipped with a 10 mmφ cryoprobe.
¹ H-NMR was measured at a pulse angle of 1 °, a pulse interval of 1.8 seconds, and an integration frequency of 1,024 times or more. The chemical shift was set so that the peak of methyl proton of hexamethyldisiloxane was 0.088 ppm, and the chemical shift of the peak due to other protons was based on this.
13C-NMR was measured by a proton complete decoupling method with a pulse angle of 90 °, a pulse interval of 20 seconds, and a cumulative number of 512 times or more. The chemical shift was set such that the methyl carbon peak of hexamethyldisiloxane was set to 1.98 ppm, and the chemical shifts of peaks due to other carbons were based on this.

The comonomer content was calculated | required with the following method from the structural unit amount 1H-NMR spectrum of the polar group containing monomer .
The integrated intensity sum of the peak due to the polar group-containing olefin copolymer in the range of the structural unit amount of 4-hydroxybutyl acrylate glycidyl ether (4-HBAGE) in the range of 0.3 to 3.1 ppm is I _A1 , 2.4, 2. When the sum of integrated intensities of peaks due to protons of 4-HBAGE contained in the copolymer generated at 6, 3.0, 3.3, 3.4, 3.5, and 4.1 ppm is I _X1 , It calculated | required according to the following formula | equation.
4-HBAGE content (mol%) = 40 × I _X1 / (I _A1 −0.6 × I _X1 )

The integrated intensity sum of the peak due to the polar group-containing olefin copolymer in the range of structural unit quantity 0.3~3.2ppm of glycidyl methacrylate (GMA) and _{I A3,} 2.5,2.6,3.1,3 .9, and the sum of integrated intensity of the peak due to protons of GMA contained in the copolymer produced in 4.3 ppm when the I _X3, was determined according to the following formula.

GMA content (mol%) = 80 × I _X3 / (I _A3 −0.8 × I _X3 )

Structural unit amount of norbornene-2,3-dicarboxylic acid anhydride (NB-DCA) When the polar group-containing monomer species is 5-norbornene-2,3-dicarboxylic acid anhydride, the polar group-containing monomer is at the end of the molecular chain. When introduced, it has the following structure A1 (hereinafter referred to as structure A1), and when introduced into the main chain of the molecular chain, it has the structure A2 (hereinafter referred to as structure A2). ^{In the 13} C-NMR spectrum, a peak of methylene carbon A1 _α adjacent to the double bond of structure A1 is detected near 33.6 ppm, and a peak of methine carbon A2 _br of structure A2 is detected near 42.1 ppm. In addition, a peak due to the main chain methylene carbon is detected in the vicinity of 29.9 ppm. For example, when the integrated intensity of the peak of carbon A1 _alpha near 33.6ppm was denoted as _{I 33.6} or the like, the content of the structural A1 and A2 are determined from the following equation 1,2.

Content of structure A1 (mol%)
= 2 × I _33.6 × 100 / (2 × I _33.6 + I _42.1 + I _29.9 ) ... formula-1
Structure A2 content (mol%)
= I _42.1 × 100 / (2 × I _33.6 + I _42.1 + I _29.9 ) ... Formula-2
The total structural unit amount of the polar group can be obtained as the sum of the structure A1 content and the structure A2 content obtained by the above formulas -1 and 2.

(9) Weight average molecular weight (Mw) and molecular weight distribution parameter (Mw / Mn) of multi-component polar group-containing olefin copolymer
The weight average molecular weight (Mw) of the multi-component polar group-containing olefin copolymer according to the present invention is usually 1,000 to 2,000,000, preferably 10,000 to 1,500,000, more preferably 20 ,. It is desirable that the range is from 3,000 to 1,000,000, preferably from 31,000 to 800,000, and more preferably from 35,000 to 800,000. If the Mw is less than 1,000, physical properties such as mechanical strength and impact resistance are not sufficient, and if the Mw exceeds 2,000,000, the melt viscosity becomes very high and the molding process becomes difficult.

The ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the multi-component polar group-containing olefin copolymer according to the present invention is usually 1.5 to 3.5, preferably 1.6. It is desirable to be in the range of -3.3, more preferably 1.7-3.0. If the Mw / Mn is less than 1.5, various workability including molding of the laminate is not sufficient, and if it exceeds 3.5, the adhesive strength is inferior. Moreover, (Mw / Mn) may be expressed as a molecular weight distribution parameter.

  The weight average molecular weight (Mw) according to the present invention is determined by gel permeation chromatography (GPC). The molecular weight distribution parameter (Mw / Mn) is a value obtained by further obtaining the number average molecular weight (Mn) by gel permeation chromatography (GPC), and calculating the ratio of Mw to Mn, Mw / Mn.

The GPC measurement method according to the present invention is as follows.
(Measurement conditions) Model used: 150C manufactured by Waters Inc. Detector: MIRAN1A / IR detector manufactured by FOXBORO (measurement wavelength: 3.42 μm) Measurement temperature: 140 ° C. Solvent: Orthodichlorobenzene (ODCB) Column: AD806M manufactured by Showa Denko KK / S (3) Flow rate: 1.0 mL / min Injection volume: 0.2 mL
(Preparation of sample) A sample was prepared by preparing a 1 mg / mL solution using ODCB (containing 0.5 mg / mL BHT (2,6-di-t-butyl-4-methylphenol)) at 140 ° C. It takes about 1 hour to dissolve.
(Calculation of molecular weight) The standard polystyrene method is used, and the conversion from the retention capacity to the molecular weight is performed using a calibration curve prepared in advance by standard polystyrene. The standard polystyrene used is a brand (F380, F288, F128, F80, F40, F20, F10, F4, F1, A5000, A2500, A1000) manufactured by Tosoh Corporation. A calibration curve is created by injecting 0.2 mL of a solution dissolved in ODCB (containing 0.5 mg / mL BHT) so that each is 0.5 mg / mL. The calibration curve uses a cubic equation obtained by approximation by the least square method. The viscosity equation [η] = K × Mα used for conversion to molecular weight uses the following numerical values.
PS: K = 1.38 × 10 −4, α = 0.7
PE: K = 3.92 × 10 −4, α = 0.733
PP: K = 1.03 × 10−4, α = 0.78

(10) Melting point The relationship between the melting point Tm (° C.) and the polar group-containing monomer content [Z1] (mol%) of the multi-component olefin copolymer according to the present invention is:
It is preferable that 50 <Tm <128-6.0 [Z1].
As a factor affecting the adhesive performance of the copolymer, in addition to the (Z1) content of the copolymer, it was found that the melting point of the copolymer has a great influence, and that the lower melting point shows higher adhesiveness. . However, as a result of investigation by the present inventors, for example, in the case of a binary copolymer of ethylene and (Z1) in which ethylene is selected as (X1), the melting point of the copolymer depends on the (Z1) content, and 128 It was extremely difficult to make it lower than −6.0 [Z1] (° C.), and there was a limit to the improvement of the adhesion performance.
Therefore, when the melting point of the copolymer according to the present invention exceeds 128-6.0 [Z1], improvement in adhesiveness is not expected and sufficient adhesiveness is hardly exhibited. Moreover, if melting | fusing point is less than 50 degreeC, it is hard to hold | maintain the minimum heat resistance required as an ethylene-type copolymer.

(11) Molecular structure of multi-component polar group-containing olefin copolymer The multi-component polar group-containing olefin copolymer according to the present invention is a random copolymer of (X1), (Z1), and (Z2).
Examples of the molecular structure of the multi-component polar group-containing olefin copolymer according to the present invention are shown in the following paragraphs. The random copolymer is the type of the adjacent structural unit that has a probability of finding each structural unit at a position in a given molecular chain of the A structural unit and B structural unit in the example of the molecular structure shown in the following paragraph. Is a copolymer unrelated to. Further, the molecular chain terminal of the polar group-containing olefin copolymer may be any one of (X1), (Z1), and (Z2). A represents a nonpolar monomer composed of (X1), and B represents a (Z1) or (Z2) monomer.

In addition, although the example of the molecular structure of the copolymer by which B structural unit graft-modified with respect to A structural unit was published as reference below, it is a structure different from the random copolymer of this invention.

  The multi-component polar group-containing olefin copolymer according to the present invention is characterized in that it is produced in the presence of a transition metal catalyst, and its molecular structure is linear. An image diagram of an olefin copolymer polymerized by a high-pressure radical polymerization process is shown in FIG. 1 (a), and an image diagram of an olefin copolymer polymerized using a metal catalyst is shown in FIGS. 2 (b) and 3 (c). As illustrated, the molecular structure varies depending on the production method. This difference in molecular structure can be controlled by selecting a production method. For example, as described in the patent publication “Japanese Patent Laid-Open No. 2010-150532”, the complex elastic modulus measured by a rotary rheometer is used. Can also be used to estimate the molecular structure. More specifically, when the phase angle δ (G * = 0.1 MPa) at the absolute value G * = 0.1 MPa of the complex elastic modulus measured with a rotary rheometer is 40 degrees or more, the molecular structure is (b ) Or a linear structure as shown in (c) and has no long chain branching (b) or a structure having a small amount of long chain branching that does not affect the mechanical strength. (C) is shown. Further, when the phase angle δ (G * = 0.1 MPa) at the absolute value G * = 0.1 MPa of the complex elastic modulus measured with a rotary rheometer is lower than 40 degrees, the molecular structure is shown in the structure (a). Such a structure containing an excessive amount of long chain branching is exhibited, and the mechanical strength is inferior. The phase angle δ at the absolute value G * = 0.1 MPa of the complex elastic modulus measured with a rotary rheometer is affected by both the molecular weight distribution and the long chain branching, but Mw / Mn ≦ 4, more preferably Mw / Mn ≦. If it is limited to three, it becomes an index of the amount of long chain branching, and the larger the long chain branching, the smaller the δ (G * = 0.1 MPa) value. In addition, if Mw / Mn is 1.5 or more, the δ (G * = 0.1 MPa) value does not exceed 75 degrees even when there is no long chain branching.

[II] Production of multi-component polar group-containing olefin copolymer The multi-component polar group-containing olefin copolymer according to the present invention is produced in the presence of a transition metal catalyst, and its molecular structure is Linear.

(1) Polymerization catalyst of multi-component polar group-containing olefin copolymer The type of polymerization catalyst used in the production of the multi-component polar group-containing olefin copolymer according to the present invention is (X1), (Z1), (Z2). Although it will not specifically limit if it can copolymerize, For example, the 5-11 group transition metal compound which has a chelating ligand is mentioned.
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, A copper atom etc. are mentioned.
Among these, vanadium atoms, iron atoms, platinum atoms, cobalt atoms, nickel atoms, palladium atoms, and rhodium atoms are preferable, and platinum atoms, cobalt atoms, nickel atoms, and palladium atoms are particularly preferable. These metals may be single or plural.
Furthermore, the transition metal of the transition metal complex of the present invention is an element in which M is selected from the group consisting of nickel (II), palladium (II), platinum (II), cobalt (II) and rhodium (III). However, from the viewpoint of polymerization activity, nickel (II) is particularly preferable from the viewpoint of polymerization activity. The chelating ligand has at least two atoms selected from the group consisting of P, N, O, and S, and is bidentate or multidentate. It contains a ligand and is electronically neutral or anionic. The structure is illustrated in a review by Brookhart et al. (Chem. Rev., 2000, 100, 1169).
Preferably, examples of the bidentate anionic P and O ligand include phosphorus sulfonic acid, phosphorus carboxylic acid, phosphorus phenol, and phosphorus enolate. Other examples of the bidentate anionic N and O ligand include salicyl. Examples include aldoiminate and pyridinecarboxylic acid, and other examples include diimine ligands, diphenoxide ligands, and diamide ligands.

  The structure of the metal complex obtained from the chelating ligand is represented by the following structural formulas (A) and / or (B) coordinated by an arylphosphine compound, arylarsine compound or arylantimony compound which may have a substituent. expressed.

(In Structural Formulas (A) and (B), M represents a transition metal belonging to any of Groups 5 to 11 of the periodic table of elements, that is, various transition metals as described above. X ¹ represents oxygen. Represents sulfur, —SO ₃ —, or —CO ₂ —, Y ¹ represents carbon or silicon, n represents 0 or an integer of ¹ , E ¹ represents phosphorus, arsenic, or antimony R ³ and R ⁴ each independently represent hydrogen or a hydrocarbon group that may contain a heteroatom having 1 to 30 carbon atoms, and R ⁵ each independently represents hydrogen, halogen, or a carbon atom having 1 to 30 carbon atoms. R ⁶ and R ⁷ each independently represents a hydrocarbon group that may contain a hetero atom, hydrogen, halogen, a hydrocarbon group that may contain a hetero atom having 1 to 30 carbon atoms, OR ² , CO ₂ R ² , CO ₂ M ′, C (O) N (R ¹ ) ₂ , _{^{C (O) R 2, SR}} 2, SO 2 R 2, SOR 2, OSO 2 R 2, P (O) (OR 2) 2-y (R 1) y, CN, NHR 2, N (R 2) ₂ , Si (OR ¹ ) _3-x (R ¹ ) _x , OSi (OR ¹ ) _3-x (R ¹ ) _x , NO ₂ , SO ₃ M ′, PO ₃ M ′ ₂ , P (O) (OR ² ) ₂ represents M ′ or an epoxy-containing group, M ′ represents an alkali metal, an alkaline earth metal, ammonium, quaternary ammonium, or phosphonium, x is an integer from 0 to 3, and y is 0 to 2 R ⁶ and R ⁷ may be connected to each other to form an alicyclic ring, an aromatic ring, or a heterocyclic ring containing a heteroatom selected from oxygen, nitrogen, and sulfur. At this time, the number of ring members is 5 to 8, and it may or may not have a substituent on the ring. There .R ¹ is .R ² representing a hydrocarbon group having 1 to hydrogen or carbon 20, .L ¹ representing a hydrocarbon group having 1 to 20 carbon atoms, represents a ligand coordinated to M. The R ³ and L ¹ may be bonded to each other to form a ring.)
More preferably, it is a transition metal complex represented by the following structural formula (C).

(In Structural Formula (C), M represents a transition metal belonging to any of Groups 5 to 11 of the periodic table of elements, that is, various transition metals as described above. X ¹ represents oxygen, sulfur, − Represents SO ₃ — or —CO ₂ —, Y ¹ represents carbon or silicon, n represents an integer of 0 or 1, E ¹ represents phosphorus, arsenic, or antimony, R ³ and R ⁴ Each independently represents hydrogen or a hydrocarbon group that may contain a heteroatom having 1 to 30 carbon atoms, and R ⁵ each independently contains hydrogen, a halogen, or a heteroatom having 1 to 30 carbon atoms. R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ are each independently hydrogen, halogen, a hydrocarbon group which may contain 1 to 30 carbon atoms, OR ² , CO ₂ R ² , CO ₂ M ′, C (O) N (R _{^{1) 2, C (O)}} R 2, SR 2, SO 2 R 2, SOR 2, OSO 2 R 2, P (O) (OR 2) 2-y (R 1) y, CN, NHR 2, N (R ² ) ₂ , Si (OR ¹ ) _3-x (R ¹ ) _x , OSi (OR ¹ ) _3-x (R ¹ ) _x , NO ₂ , SO ₃ M ′, PO ₃ M ′ ₂ , P (O) (OR ² ) ₂ M ′ or an epoxy-containing group, where M ′ represents an alkali metal, an alkaline earth metal, ammonium, quaternary ammonium, or phosphonium, x is an integer from 0 to 3, and y is , And represents an integer from 0 to 2. In addition, a plurality of groups appropriately selected from R ^{8 to} R ¹¹ are connected to each other, and an alicyclic ring, an aromatic ring, or a heteroatom selected from oxygen, nitrogen, and sulfur In this case, the number of ring members is 5 to 8, and May have a substituent, may .R ¹ need not have the .R ² representing a hydrocarbon group having 1 to hydrogen or carbon 20 represents a hydrocarbon group having 1 to 20 carbon atoms L ¹ represents a ligand coordinated to M. R ³ and L ¹ may be bonded to each other to form a ring.)

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

(2) Organometallic compound In the production of the multi-component polar group-containing olefin copolymer according to the present invention, the epoxy group, carboxyl group or dicarboxylic anhydride group-containing monomer and a small amount of organometallic compound are contacted, (X1), (Z1), and (Z2) are copolymerized in the presence of the transition metal catalyst to increase the polymerization activity.
The organometallic compound is an organometallic compound including a hydrocarbon group which may have a substituent, and can be represented by the following structural formula (H).
^{R 30 nM 30 X 30 m-} n structure (H)
(In the formula, R ³⁰ represents a hydrocarbon group which may have a substituent having 1 to 12 carbon atoms, and M ³⁰ represents Group 1, Group 2, Group 12 and Group 13 of the periodic table. A metal selected from the group consisting of: X ³⁰ represents a halogen atom or a hydrogen atom, m is a valence of M ³⁰ and n is 1 to m.)

Examples of the organometallic compound represented by the structural formula (H) include tri-n-butylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, tri-n-decylaluminum and other alkylaluminums, methylaluminum Examples include alkylaluminum halides such as dichloride, ethylaluminum dichloride, dimethylaluminum chloride, diethylaluminum chloride, and diethylaluminum ethoxide, and trialkylaluminum is preferably selected. More preferably, a trialkylaluminum having a hydrocarbon group having 4 or more carbon atoms, more preferably a trialkylaluminum having a hydrocarbon group having 6 or more carbon atoms, more preferably tri-n-hexylaluminum, -N-octylaluminum and tri-n-decylaluminum are selected, and tri-n-octylaluminum can be most preferably used.
The organometallic compound may be contacted in an amount such that the molar ratio to the polar group-containing comonomer is 10 ^{−5 to} 0.9, preferably 10 ^{−4 to} 0.2, and more preferably 10 ^{−4 to} 0.1. It is preferable from the viewpoint of polymerization activity and cost.

Aluminum (Al) content remaining in 1g of the multi-polar group-containing olefin copolymer according to the remaining amount present invention aluminum (Al) is preferably less 100,000 micrograms _Al / g, or less 70,000μg _Al / g , still more preferably less 20,000 _Al / g, or less and particularly preferably 10,000 _[Al / g, a preferable less 5,000 micrograms _Al / g, and more preferably less 1,000 .mu.g _Al / g 500 μg _{Al 2} / g or less is most preferable. When the amount is larger than this, the mechanical properties are deteriorated, the polymerization product is discolored and the deterioration is accelerated. Residual amounts of aluminum (Al) may have the smaller to the extent possible, for example, may be a very small amount of about 1 [mu] g _{Al / g,} it may be a 0 Pg _{Al / g.} In addition, μg _Al / g means that the amount of aluminum (Al) contained in 1 g of the multi-component polar group-containing olefin copolymer is expressed in μg.

Aluminum (Al) amount The amount of aluminum (Al) contained in the multi-component polar group-containing olefin copolymer according to the present invention is the same as the amount of aluminum contained in the alkylaluminum subjected to the polymerization. It can be calculated as a value divided by the yield of the containing olefin copolymer.

  The amount of aluminum (Al) contained in the multi-component polar group-containing olefin copolymer is calculated from the amount of alkylaluminum polymerized, and measured by fluorescent X-ray analysis or inductively coupled plasma emission (ICP) analysis. Also good. When using fluorescent X-ray analysis or ICP analysis, it can be measured, for example, by the following method.

(1) Fluorescent X-ray analysis 3 to 10 g of a measurement sample is weighed and heated and pressure-molded with a heating press to prepare a flat sample having a diameter of 45 mm. The measurement is performed on a portion having a central diameter of 30 mm of the flat sample, and measurement is performed under the following conditions using a scanning fluorescent X-ray analyzer “ZSX100e” (Rh tube 4.0 kW) manufactured by Rigaku Denki Kogyo.
・ X-ray output: 50kV-50mA
-Spectral crystal: PET
・ Detector: PC (proportional counter)
-Detection line: Al-Kα line The aluminum content can be determined from a calibration curve prepared in advance and the results measured under the above conditions. A calibration curve can be prepared by measuring the aluminum content of a plurality of polyethylene resins by ICP analysis and further subjecting these polyethylene resins to fluorescent X-ray analysis under the above conditions.

(2) Inductively coupled plasma emission (ICP) analysis measurement sample, 3 ml of special grade nitric acid, and 1 ml of hydrogen peroxide (hydrogen peroxide content 30% by weight) are placed in a Teflon (registered trademark) container and microwave decomposition equipment (milestone) Using General MLS-1200MEGA), the thermal decomposition operation is performed at a maximum of 500 W, and the measurement sample is made into a solution. The aluminum content can be measured by subjecting the measurement sample in solution to an ICP emission spectroscopic analyzer (IRIS-AP, manufactured by Thermo Jarrel Ash). The aluminum content is quantified using a calibration curve prepared using a standard solution having a known aluminum element concentration.

(3) Polymerization method of multi-component polar group-containing olefin copolymer The polymerization method of multi-component polar group-containing olefin copolymer according to the present invention is not limited. Slurry polymerization in which at least a part of the produced polymer becomes a slurry in the medium, bulk polymerization using the liquefied monomer itself as a medium, gas phase polymerization performed in the vaporized monomer, or a polymer produced in the monomer liquefied at high temperature and high pressure High-pressure ionic polymerization in which at least a part of the polymer is dissolved is preferably used. As the polymerization format, any of batch polymerization, semi-batch polymerization, and continuous polymerization may be used. Moreover, living polymerization may be sufficient and it may superpose | polymerize, combining chain transfer. Furthermore, so-called chain shunting agent (CSA) may be used in combination to perform chain shunting reaction or coordinative chain transfer polymerization (CCTP). Specific manufacturing processes and conditions are disclosed in, for example, JP 2010-260913 A and JP 2010-202647 A.

(4) Method for introducing polar group into multi-component polar group-containing olefin copolymer The method for introducing a polar group into multi-component polar group-containing olefin copolymer according to the present invention is not limited. The gist of the present invention is to use a multi-component polar group-containing olefin copolymer that is copolymerized in the presence of a transition metal catalyst, has a linear molecular structure, is a random copolymer, and has a specific polar group. is there. A specific polar group can be introduced by various methods without departing from the gist of the present invention. For example, a method of directly copolymerizing a polar group-containing comonomer having a specific polar group, a method of copolymerizing another polar group-containing comonomer, and then introducing a specific polar group by modification. As a method for introducing a specific polar group by modification, for example, when introducing a carboxylic acid, a method in which t-butyl acrylate is copolymerized and then converted into a carboxylic acid by thermal decomposition can be mentioned.

[IV] Additive The multi-component polar group-containing olefin copolymer according to the present invention includes an antioxidant, an ultraviolet absorber, a lubricant, an antistatic agent, a colorant, a pigment, and the like within a range not departing from the gist of the present invention. You may mix | blend additives, such as a crosslinking agent, a foaming agent, a nucleating agent, a flame retardant, a electrically conductive material, and a filler.

[V] Adhesive The multi-component polar group-containing olefin copolymer according to the present invention has a specific molecular structure and resin physical properties, and thus exhibits high adhesiveness with other substrates, and is industrially useful. Made it possible to produce laminates. That is, the adhesion performance with various base materials includes (X1), (Z1) and (Z2) as essential components, and is a multi-component polar group-containing olefin copolymer obtained by copolymerization in the presence of a transition metal catalyst. The amount of structural units derived from (Z1) in the multi-component polar group-containing olefin copolymer is usually in the range of 0.001 mol% to 19.999 mol%, preferably in the range of 0.01 mol% to 15.000 mol%. More preferably, it is sufficiently manifested in the range of 0.02 mol% to 10.000 mol%, more preferably in the range of 0.02 mol% to 5.000 mol%. Its superiority as an adhesive is demonstrated by the data of the examples described later and the comparison between the examples and the comparative examples.

[VI] Laminate (1) Material of Laminate The laminate according to the present invention is a laminate comprising a layer composed of a multi-component polar group-containing olefin copolymer (B) and a base material layer, Specific examples of the base material include high-density polyethylene, medium-density polyethylene, low-density polyethylene, ethylene-vinyl acetate copolymer, ethylene-acrylic acid ester copolymer and other polyethylene-based resins, ionomers, homopolypropylene resins, and propylene. Polypropylene resins such as copolymers with other α-olefins, olefin resins such as poly-1-butene, poly-4-methyl-1-pentene, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyacrylate, Vinyl polymers such as polyacrylonitrile, nylon 6, nylon 66, nylon 10, nylon 11, Niro 12, Polyamide resins such as nylon 610, polymetaxylylene adipamide, polyethylene terephthalate, polyethylene terephthalate / isophthalate, polybutylene terephthalate, polylactic acid, polybutylene succinate, polyester resins such as aromatic polyesters, polyvinyl alcohol , Ethylene / vinyl alcohol copolymer, polycarbonate resin, adhesive fluororesin, phenol resin, epoxy resin, urea resin, melamine resin, urea resin, alkyd resin, unsaturated polyester, polyurethane, thermosetting polyimide, etc. Thermoplastic resin film or sheet having a film-forming ability such as a cellulosic resin such as a resin or cellophane (stretched product or printed material thereof), aluminum, iron, copper, or a main component thereof. Metal foil or metal plate such as alloy, vapor-deposited film of inorganic oxide such as silica-deposited plastic film, alumina-deposited plastic film, vapor-deposited film of metal such as gold, silver and aluminum, or compounds other than these metal oxides And paper such as high-quality paper, kraft paper, paperboard, glassine paper, and synthetic paper, cellophane, woven fabric, and non-woven fabric.

The base material layer related to the present invention can be appropriately selected depending on the application and the type of the package. For example, if the package is a perishable food, such as polyamide, polyvinylidene chloride, ethylene-vinyl alcohol copolymer (EVOH), polyvinyl alcohol, polyester, transparency, rigidity, gas permeation resistance An excellent resin can be used. In addition, when the package is a confectionery or a fiber, it is preferable to use polypropylene having good transparency, rigidity, and water permeation resistance. When adapting to fuel tanks of automobiles, tubes, hoses, pipes, etc. through which fuel passes, resins having excellent fuel permeation prevention performance such as EVOH, polyamides, and fluororesins can be used.
Examples of the barrier resin include polyamide resin, polyester resin, EVOH, polyvinylidene chloride resin, polycarbonate resin, stretched polypropylene (OPP), stretched polyester (OPET), stretched polyamide, alumina vapor deposition film, silica vapor deposition film, and the like. Examples include metal, inorganic oxide vapor deposition films, metal vapor deposition films such as aluminum vapor deposition, and metal foils.

(2) Use of laminated body The laminated body concerning this invention is suitable as a packaging material of foodstuffs, for example. Specific examples of food include snacks such as potato chips, confectionery such as biscuits, rice crackers and chocolates, powder seasonings such as powdered soup, foods such as shavings and smoked foods, and the like. In addition, the pouch container can be formed by facing the ethylene copolymer layer surfaces of the laminate and heat-sealing at least a part thereof. Specifically, for example, water packaging, general bags, liquid soup bags, liquid paper containers, lami raw fabrics, special shaped liquid packaging bags (standing pouches, etc.), standard bags, heavy bags, semi heavy bags, wrap films, It is suitably used for sugar bags, oil packaging bags, various packaging containers for food packaging, infusion bags and the like.

(3) Manufacture of laminated body As a processing method of the laminated body related to the present invention, normal press molding, air-cooled inflation molding, air-cooled two-stage cooling inflation molding, high-speed inflation molding, flat die molding (T-die molding), water cooling Conventionally known methods such as extrusion molding such as inflation molding, laminating methods such as extrusion laminating processing, sand laminating processing, and dry laminating processing, blow molding, pressure forming, injection molding, and rotational molding may be mentioned.

(4) Laminate laminate The laminate laminate according to the present invention is a laminate that can be produced by a known laminating method such as extrusion lamination, sand laminating, dry laminating, etc. It is a laminate that can be produced by laminating a laminate material containing the multi-component polar group-containing olefin copolymer of the present invention and at least one base material layer. The laminate material according to the present invention is a resin material containing a multi-component polar group-containing olefin copolymer that can be subjected to various known laminating methods. Extrusion laminating is a molding method in which a molten resin film extruded from a T-die is continuously coated and pressure-bonded on a substrate, and coating and adhesion are performed simultaneously. Sand laminating is a method in which a molten resin is poured between paper and a film to be laminated, and the molten resin acts as an adhesive to bond and laminate. Dehumidify the ambient humidity in the vicinity of the adhesive and / or adhesive application roll for laminating the film to be laminated with the material, warm the temperature of the adhesive and / or adhesive application roll, or apply a film sheet This is a method of drying the mating surface.
In the sand laminating process and the dry laminating process, a barrier property is provided between the base material and the layer containing the olefin resin composition on the side on which the base material containing the olefin resin composition is formed. In order to improve, it is easy to laminate the aluminum foil, polyester film, various barrier films and the like. As the base material layer to be laminated with the laminating material according to the present invention, various kinds of materials as described above can be appropriately used.

[VII] Other uses The multi-component polar group-containing olefin copolymer according to the present invention is not only suitably used as the adhesive resin material, but also polyolefin resin such as polypropylene resin, polyamide resin, polyester resin, polycarbonate. Various resin modifiers such as resins, acrylic resins and polyvinyl chloride resins, or engineering plastics such as polyolefin resins such as polypropylene and polycarbonate resins, polyphenylene ether resins, polyamide resins, polyester resins, polyphenylene sulfide resins, and liquid crystal resins It is also suitably applied as a compatibilizing agent.

  In the following, the present invention will be described in detail by way of examples and comparative examples, and the rationality and significance of the configuration of the present invention and the prior art by comparing the data of each preferred example and the comparison between each example and each comparative example. Demonstrate excellence against The physical property test method of the polar group-containing olefin copolymer produced in the present invention and the test method of the obtained laminate are as follows.

(1) Amount of polar group-containing structural unit in multi-component polar group-containing olefin copolymer The amount of polar group-containing structural unit in multi-component polar group-containing olefin copolymer was determined using 1H-NMR spectrum. Details are described above.

(2) 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). Further, the molecular weight distribution parameter (Mw / Mn) was further calculated by the number average molecular weight (Mn) by gel permeation chromatography (GPC), and calculated by the ratio of Mw to Mn, Mw / Mn. Details are described above.

(3) Melting | fusing point Melting | fusing point is shown by the peak temperature of the endothermic curve measured with the differential scanning calorimeter (DSC). DSC (DSC7020) manufactured by SII Nano Technology Co., Ltd. was used for measurement, and the measurement was performed under the following measurement conditions.
About 5.0 mg of the sample was packed in an aluminum pan, increased 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 maintaining at 30 ° C. for 5 minutes, the maximum peak temperature in the absorption curve when the temperature was raised again at 10 ° C./min was taken as the melting point.

(4) Adhesive strength Adhesive strength is obtained by preparing a measurement sample processed into a press plate and various substrate films, making a laminate by superimposing the two types and hot pressing them, and performing a peel test. It was measured. The adjustment method / measurement method of each process will be described in order.

(1) Method for adjusting the press plate of the measurement sample The measurement sample is placed in a hot press mold having dimensions of 50 mm x 60 mm and a thickness of 0.5 mm, preheated for 5 minutes in a hot press machine having a surface temperature of 180 ° C, and then pressed. The residual gas in the molten resin was degassed by repeating the pressure reduction, and further pressurized at 4.9 MPa and held for 5 minutes. Then, it transferred to the press machine with a surface temperature of 25 degreeC, it cooled by hold | maintaining for 3 minutes with the pressure of 4.9 Mpa, and produced the press plate about 0.5 mm in thickness.

(2) Preparation method of EVOH film Using a multi-layer T-die molding machine, after forming a two-layer three-layer film with EVOH as the central layer and LLDPE as both outer layers, the LLDPE in the outer layer is peeled off, and EVOH having a thickness of 100 μm A single layer film was prepared. The film forming conditions are as follows.
Molding machine: 2 types, 3 layers T-die Molding temperature: 200 ° C. Layer structure: LLDPE / EVOH / LLDPE Film thickness: 300 μm (100 μm / 100 μm / 100 μm) Outer layer: LLDPE (manufactured by Nippon Polyethylene Co., Ltd. Brand: Novatec UF943) MFR = 2.0 g / 10 min, density = 0.937 / cm3 Intermediate layer: EVOH (manufactured by Kuraray Co., Ltd. Brand: EVAL F101B)

(3) Preparation method of polyamide film Using a multi-layer T-die molding machine, after forming a two-layer, three-layer multilayer film in which the center layer is polyamide and both outer layers are LLDPE, the outer layer LLDPE is peeled off to form a polyamide having a thickness of 100 μm. A single layer film was prepared. The film forming conditions are as follows.
Molding machine: 2 types, 3 layers T-die Molding temperature: 250 ° C. Layer structure: LLDPE / EVOH / LLDPE Film thickness: 300 μm (100 μm / 100 μm / 100 μm) Outer layer: LLDPE (manufactured by Nippon Polyethylene Co., Ltd. Brand: Novatec UF943) MFR = 2.0 g / 10 min, density = 0.937 / cm3 Intermediate layer: Polyamide (made by Toray Industries, Inc. Brand: Amilan CM1021FS)

(4) Fluorine resin film adjustment method Using a multi-layer T-die molding machine, after forming a two-layer, three-layer multilayer film in which the center layer is fluororesin and both outer layers are LLDPE, the outer layer LLDPE is peeled off to obtain a thickness of 100 μm. A fluororesin single layer film was prepared. The film forming conditions are as follows.
Molding machine: 2 types, 3 layers T-die Molding temperature: 230 ° C. Layer structure: LLDPE / EVOH / LLDPE Film thickness: 300 μm (100 μm / 100 μm / 100 μm) Outer layer: LLDPE (manufactured by Nippon Polyethylene Co., Ltd. Brand: Novatec UF943) MFR = 2.0 g / 10 min, density = 0.937 / cm3 Intermediate layer: Fluororesin (Daikin Industries, Ltd. Brand: NEOFLON EFEP RP-5000)

(5) Preparation method of laminate of EVOH film and measurement sample The measurement plate press plate obtained by the above press plate preparation method and the EVOH film obtained by the above EVOH film preparation method are 50 mm x 60 mm in size. The cut pieces were stacked and placed in a hot press mold having dimensions of 50 mm × 60 mm and a thickness of 0.5 mm, and pressed at 4.9 MPa for 3 minutes using a hot press machine having a surface temperature of 200 ° C. Then, it moved to the press machine with the surface temperature of 25 degreeC, it cooled by hold | maintaining for 3 minutes with the pressure of 4.9 MPa, and the laminated body of the press board of a measurement sample and EVOH was prepared.

(6) Preparation method of laminate of polyamide film and measurement sample The measurement sample press plate obtained by the above press plate preparation method and the polyamide film obtained by the above polyamide film preparation method have dimensions of 50 mm x 60 mm. The cut pieces were stacked and placed in a hot press mold having dimensions of 50 mm × 60 mm and a thickness of 0.5 mm, and pressed at 4.9 MPa for 5 minutes using a hot press machine having a surface temperature of 250 ° C. Then, it transferred to the press machine with a surface temperature of 25 degreeC, it cooled by hold | maintaining for 3 minutes with the pressure of 4.9 Mpa, and the laminated body of the press board and polyamide of the measurement sample was prepared.

(7) Preparation method of laminate of fluororesin film and measurement sample The press plate of the measurement sample obtained by the above press plate preparation method and the fluororesin film obtained by the above preparation method of the fluororesin film are 50 mm × The cut pieces of 60 mm were stacked, placed in a hot press mold having dimensions of 50 mm × 60 mm and a thickness of 0.5 mm, and pressed at 4.9 MPa for 3 minutes using a hot press with a surface temperature of 200 ° C. . Then, it transferred to the press machine with a surface temperature of 25 degreeC, it cooled by hold | maintaining for 3 minutes with the pressure of 4.9 MPa, and the laminated body of the press board of a measurement sample and a fluororesin was prepared.

(8) Measuring method of adhesive strength of laminate The laminate obtained by the method of preparing the laminate was cut into a width of 10 mm, and using a Tensilon (Toyo Seiki Co., Ltd.) tensile tester, the speed was 50 mm / min. The adhesive strength was measured by T-peeling. The unit of adhesive strength is indicated by gf / 10 mm. When the adhesive strength is very strong, the measurement sample layer or the base material layer yields and breaks during the peel test. This is a phenomenon that occurs because the adhesive strength of the laminate is higher than the lower one of the tensile break strength of the measurement sample layer or the base material layer, and the adhesiveness is very high. I can judge. When the adhesive strength cannot be measured due to this phenomenon, the result of the adhesive strength measurement in each example is described as “non-peelable”, and it is determined that the adhesive strength is higher than that measured for the numerical value of the adhesive strength.

(5) Tensile impact strength
(1) Tensile impact strength test sample preparation method The resin composition pellets of each Example and each Comparative Example were placed in a 1 mm thick hot press mold and preheated for 5 minutes in a hot press with a surface temperature of 230 ° C. Thereafter, the resin was melted by repeating pressurization and decompression, and the residual gas in the molten resin was deaerated, and further pressurized at 4.9 MPa and held for 5 minutes. Thereafter, the plate was gradually cooled at a rate of 10 ° C./min with a pressure of 4.9 MPa applied, and the molded plate was taken out of the mold when the temperature dropped to near room temperature. The obtained molded plate was conditioned for 48 hours or more in an environment of temperature 23 ± 2 ° C. and humidity 50 ± 5 ° C. A test piece having the shape of ASTM D1822 Type-S was punched out of the press plate after the state adjustment to obtain a tensile impact strength test sample.

Tensile Impact Strength Test Conditions Tensile impact strength was measured using the above test piece with reference to method B of JIS K 7160-1996. The only difference from JIS K 7160-1996 is the shape of the test piece. Regarding other measurement conditions, etc., the test was carried out by a method according to JIS K 7160-1996.

(6) Measurement of phase angle δ (G * = 0.1 MPa) at the absolute value G * = 0.1 MPa of the complex elastic modulus The sample was put into a mold for heating press having a thickness of 1.0 mm, and the heat at a surface temperature of 180 ° C. After preheating in a press for 5 minutes, the residual gas in the molten resin was degassed by repeating pressurization and decompression, and further pressurized at 4.9 MPa and held for 5 minutes. Then, it transferred to the press machine with a surface temperature of 25 degreeC, it cooled by hold | maintaining for 3 minutes with the pressure of 4.9 MPa, and the press plate which consists of a sample about 1.0 mm thick was created. A press plate made of a sample processed into a circular shape with a diameter of 25 mm is used as a sample, and a dynamic viscoelasticity is measured by using an ARES rotary rheometer manufactured by Rheometrics as a measuring device for dynamic viscoelasticity. It was measured.
・ Plate: φ25mm parallel plate ・ Temperature: 160 ℃
・ Distortion amount: 10%
Measurement angular frequency range: 1.0 × 10 ^{−2 to} 1.0 × 10 ² rad / s
・ Measurement interval: 5 points / decade
The phase angle δ is plotted against the common logarithm log G * of the absolute value G * (Pa) of the complex elastic modulus, and the value of δ (degree) at a point corresponding to log G * = 5.0 is set to δ (G * = 0). .1 MPa). When there was no point corresponding to log G * = 5.0 among the measurement points, the δ value at log G * = 5.0 was obtained by linear interpolation using two points around log G * = 5.0. Further, when all of the measurement points were logG * <5, the values were obtained by extrapolating the δ value at logG * = 5.0 with a quadratic curve using three values from the larger logG * value.

(7) Aluminum (Al) amount The amount of aluminum (Al) contained in the multi-component polar group-containing olefin copolymer is the same as the amount of aluminum (Al) contained in the alkylaluminum subjected to the polymerization. It can obtain | require by the method of calculating as a value remove | divided with the yield of the polar group containing olefin copolymer, and the method of measuring by a fluorescent X ray analysis.

(1) Method of calculating from alkylaluminum polymerization addition amount Specifically, it was calculated by the following formula.
Unit of aluminum (Al) content: μg _Al / g
(Μg _Al / g means that the amount of aluminum (Al) contained in 1 g of the multi-component polar group-containing olefin copolymer is expressed in μg.)
μg _Al = n × Mw (Al) × 10 ³ (μg)
n: Amount of alkylaluminum used for polymerization (mmol)
Mw (Al): Molecular weight of aluminum (Al) element (26.9 g / mol)

(2) Method of measuring by fluorescent X-ray analysis The amount of aluminum (Al) contained in the multi-component polar group-containing olefin copolymer was determined using fluorescent X-ray analysis. Details are described above.

[Example 1]
Synthesis of SHOP type ligand (B-27DM) According to the method described in WO2010-050256 (Synthesis Example 4), the following ligand B-27DM was obtained.

Formation of Complex 112 mg (200 μmol) of B-27DM was weighed into a 50 ml eggplant-shaped flask sufficiently purged with nitrogen. Next, 56 mg (200 μmol) of bis-1,5-cyclooctadiene nickel (0) (hereinafter referred to as Ni (COD) 2) was weighed into a 50 ml eggplant type flask, dissolved in 20 ml of dry toluene, and 10 mmol / l. A Ni (COD) 2 toluene solution was prepared. The total amount (20 ml) of Ni (COD) 2 toluene solution obtained here was added to an eggplant-shaped flask containing B-27DM, and stirred in a hot water bath at 40 ° C. for 30 minutes, whereby B-27DM and Ni (COD 20 ml of a 10 mmol / l solution of the reaction product of 2) was obtained.

(Ethylene / 4-hydroxybutyl acrylate glycidyl ether (4-HBAGE) / acrylic acid-n-butyl terpolymer)
In an autoclave with a stirring blade having an internal volume of 2.4 liters, 1000 ml of dry toluene, 36.6 mg (0.1 mmol) of tri-n-octylaluminum (TNOA), and 3.6 ml (20 mmol) of 4-HBAGE and acrylic 7.1 ml (50 mmol) of acid-n-butyl was charged. The temperature of the autoclave was raised to 80 ° C. while stirring, and nitrogen was supplied to 0.4 MPa. Then, ethylene was supplied to a pressure of 2.8 MPa so that the ethylene partial pressure was 2.4 MPa. After the temperature and pressure were stabilized, 10 ml (100 μmol) of the previously prepared B-27DM-Ni complex solution was injected with nitrogen to initiate copolymerization. During the reaction, the temperature was kept at 80 ° C., and ethylene was continuously supplied so that the pressure was maintained. After polymerization for 180 minutes, the reaction was stopped by cooling and depressurization. The reaction solution was poured into 1 liter of acetone to precipitate the polymer, and then collected by filtration, washing, and further dried under reduced pressure at 60 ° C. until a constant weight was obtained. The polar group-containing monomer remaining in was removed, and finally 19.4 g of the polar group-containing olefin copolymer was recovered. The polymerization conditions and polymerization results are shown in Table 1, and the physical property measurement results are shown in Table 2. In Table 2, “ND” means not measured. The polymerization activity was calculated on the assumption that B-27DM and Ni (COD) 2 reacted one-on-one to form a nickel complex.
Further, 4-HBAGE used for copolymerization was dehydrated with molecular sieve 3A.

[Example 2, Comparative Example 1, Comparative Example 2]
Among the methods described in Example 1, the polarities of Example 2, Comparative Example 1, and Comparative Example 2 were obtained by performing polymerization by changing the ligand amount, comonomer type, monomer concentration, polymerization temperature, and polymerization time, respectively. A group-containing olefin copolymer was prepared. The polymerization conditions and polymerization results are shown in Table 1, and the physical property measurement results are shown in Table 2. In Table 2, “ND” means not measured.

Example 3
Synthesis of SHOP type ligand (B-111) According to the method described in JP2013-038771 (Synthesis Example 1), the following ligand B-111 was obtained.

Formation of Complex 137 mg (200 μmol) of B-111 was weighed into a 50 ml eggplant-shaped flask sufficiently purged with nitrogen. Next, 56 mg (200 μmol) of bis-1,5-cyclooctadiene nickel (0) (hereinafter referred to as Ni (COD) 2) was weighed into a 50 ml eggplant type flask, dissolved in 20 ml of dry toluene, and 10 mmol / l. A Ni (COD) 2 toluene solution was prepared. The total amount (20 ml) of the Ni (COD) 2 toluene solution obtained here was added to an eggplant-shaped flask containing B-27DM, and stirred in a hot water bath at 40 ° C. for 30 minutes, whereby B-111 and Ni (COD 20 ml of a 10 mmol / l solution of reaction product 2) was obtained.

(Ethylene / 4-hydroxybutyl acrylate glycidyl ether (4-HBAGE) / acrylic acid-n-butyl terpolymer)
In an autoclave with a stirring blade having an internal volume of 2.4 liters, 1000 ml of dry toluene, 54.9 mg (0.15 mmol) of tri-n-octylaluminum (TNOA), and 3.96 ml (22 mmol) of 4-HBAGE and acrylic 19.9 ml (140 mmol) of acid-n-butyl was charged. While stirring, the temperature of the autoclave was raised to 70 ° C. and nitrogen was supplied to 0.4 MPa, and then ethylene was supplied to a pressure of 2.8 MPa so that the ethylene partial pressure was 2.4 MPa. After the temperature and pressure were stabilized, 18 ml (180 μmol) of the previously prepared B-111-Ni complex solution was injected with nitrogen to initiate copolymerization. During the reaction, the temperature was maintained at 70 ° C., and ethylene was continuously supplied so that the pressure was maintained. After polymerization for 120 minutes, the reaction was stopped by cooling and depressurization. The reaction solution was poured into 1 liter of acetone to precipitate the polymer, and then collected by filtration, washing, and further dried under reduced pressure at 60 ° C. until a constant weight was obtained. The polar group-containing monomer remaining in was removed, and 21.0 g of a polar group-containing olefin copolymer was finally recovered. The polymerization conditions and polymerization results are shown in Table 1, and the physical property measurement results are shown in Table 2. In Table 2, “ND” means not measured. The polymerization activity was calculated on the assumption that B-111 and Ni (COD) 2 reacted one-on-one to form a nickel complex.
Further, 4-HBAGE used for copolymerization was dehydrated with molecular sieve 3A.

Example 4
Among the methods described in Example 3, the polar group-containing olefin copolymer of Example 4 was prepared by performing polymerization by changing the ligand amount, comonomer type, monomer concentration, polymerization temperature, and polymerization time, respectively. did. The polymerization conditions and polymerization results are shown in Table 1, and the physical property measurement results are shown in Table 2. In Table 2, “ND” means not measured.

Example 5
Drent-based ligand: Synthesis of (2-isopropyl-phenyl) (2′-methoxy-phenyl) (2 ″ -sulfonyl-phenyl) phosphine (I) Tetrahydrofuran of benzenesulfonic anhydride (2 g, 12.6 mmol) 20 mL), normal butyllithium hexane solution (2.5 M, 10 mL, 25.3 mmol) was slowly added dropwise at 0 ° C., and the mixture was stirred for 1 hour while raising the temperature to room temperature. The reaction solution was cooled to −78 ° C., phosphorus trichloride (1.0 mL, 12.6 mmol) was added, and the mixture was stirred for 2 hours (reaction solution A).
Magnesium was dispersed in tetrahydrofuran (20 mL), 1-bromo-2-methoxybenzene (2.3 g, 12.6 mmol) was added, and the mixture was stirred at room temperature for 3 hours. This solution was added dropwise to the previous reaction solution A at −78 ° C. and stirred for 1 hour (reaction solution B).
To a solution of 1-bromo-2-isopropylbenzene (2.5 g, 12.6 mmol) in diethyl ether (20 mL), slowly add normal butyl lithium hexane solution (2.5 M, 5.0 mL, 12.6 mmol) at −30 ° C. And stirred at room temperature for 2 hours. This solution was added dropwise to the previous reaction solution B at −78 ° C. and stirred overnight at room temperature. LC-MS purity 60%.
Water (50 mL) was added, acidified with hydrochloric acid (PH <3), extracted with methylene chloride (100 mL), dried over sodium sulfate, and the solvent was evaporated. By recrystallization from methanol, 1.1 g of white target product (I) was obtained. Yield 22%.
1H NMR (CDCl3, ppm): 8.34 (t, J = 6.0 Hz, 1 H), 7.7-7.6 (m, 3 H), 7.50 (t, J = 6
.4 Hz, 1 H), 7.39 (m, 1 H), 7.23 (m, 1 H), 7.1-6.9 (m, 5 H), 3.75 (s, 3 H), 3.05
(m, 1 H), 1.15 (d, J = 6.8 Hz, 3 H), 1.04 (d, J = 6.4 Hz, 3 H) .31P NMR (CDCl3,
ppm): -10.5.

Complex Formation Complex Formation 100 μmol of palladium bisdibenzylideneacetone and phosphorus sulfonic acid ligand (I) were weighed in a 30 mL flask sufficiently purged with nitrogen, and dehydrated toluene (10 mL) was added. The catalyst slurry was prepared by processing for 10 minutes with a sonic vibrator.

(Ethylene / norbornene-2,3-dicarboxylic anhydride (NB-DCA) / acrylic acid-n-butyl terpolymer)
After substituting an autoclave with a stirring blade having an internal volume of 2.4 liters with purified nitrogen, dry toluene (1.0 liter), norbornene-2,3-dicarboxylic acid anhydride was 0.25 mol / L, acrylic acid-n -It charged so that butyl might be set to 0.25 mol / L. The temperature of the autoclave was raised to 80 ° C. while stirring and nitrogen was supplied to 0.3 MPa, and then ethylene was supplied to a pressure of 2.8 MPa so that the ethylene partial pressure was 2.5 MPa. After completion of pressure adjustment, 20 μmol of the transition metal complex prepared by the above method was injected with nitrogen to start copolymerization. During the reaction, the temperature was kept at 80 ° C., and ethylene was continuously supplied so as to maintain the pressure. After polymerization for 60 minutes, the reaction was stopped by cooling and depressurization. The reaction solution was poured into 1 liter of acetone to precipitate a polymer, and then collected by filtration, washing, and further dried under reduced pressure at 60 ° C. until a constant weight was obtained.
The polymerization conditions and polymerization results are shown in Table 1, and the physical property measurement results are shown in Table 2. In Table 2, “ND” means not measured. The polymerization activity was calculated on the assumption that the ligand and palladium bisdibenzylideneacetone reacted 1: 1 to form a palladium complex.

[Comparative Example 3]
Among the methods described in Example 3, the polar group-containing olefin copolymer of Comparative Example 3 was prepared by performing polymerization by changing the ligand amount, comonomer type, monomer concentration, polymerization temperature, and polymerization time, respectively. did. The polymerization conditions and polymerization results are shown in Table 1, and the physical property measurement results are shown in Table 2. In Table 2, “ND” means not measured.

[Comparative Example 4]
It is a copolymer of ethylene, propylene, and hexene, and is an olefin copolymer manufactured by a metallocene catalyst (Nippon Polyethylene Co., Ltd., brand: Kernel KF370). The results of physical property measurement are shown in Table 2.

[Comparative Example 5]
It is a copolymer of ethylene, methyl acrylate, and maleic anhydride, and is a polar group-containing olefin copolymer manufactured by a high-pressure process (brand name: Lexpearl ET ET220X manufactured by Nippon Polyethylene Co., Ltd.). The results of physical property measurement are shown in Table 2.

[Comparative Example 6]
It is a copolymer of ethylene, methyl acrylate, and maleic anhydride, and is a polar group-containing olefin copolymer manufactured by a high-pressure process (brand name: Lexper ET ET530H manufactured by Nippon Polyethylene Co., Ltd.). The results of physical property measurement are shown in Table 2.

[Comparative Example 7]
It is a copolymer of ethylene and glycidyl methacrylate, and is a polar group-containing olefin copolymer manufactured by a high-pressure process (brand name: Bond First E) manufactured by Sumitomo Chemical Co., Ltd. The results of physical property measurement are shown in Table 2.

[Comparative Example 8]
A copolymer of ethylene and glycidyl methacrylate, which is a polar group-containing olefin copolymer manufactured by a high-pressure process (brand name: Bondfast 2C, manufactured by Sumitomo Chemical Co., Ltd.). The results of physical property measurement are shown in Table 2.

[Consideration of results of Examples and Comparative Examples]
Examples 1 to 5 are multi-component polar group-containing olefin copolymers and show sufficient adhesiveness, but Comparative Example 4 of an olefin copolymer that does not contain a polar group shows no adhesiveness at all. It revealed that. This has shown that it is essential to contain a polar group in order to express adhesiveness.
The multi-component polar group-containing olefin copolymer of Examples 1 to 5 is more adhesive than the binary polar group-containing olefin copolymer of Comparative Examples 1 to 3 having the same polar group. It was clarified that it has improved dramatically. This indicates that the adhesiveness can be improved regardless of the type of the polar group or the third comonomer by making the copolymer flexible with an arbitrary third comonomer.
Examples 1 to 5 also show sufficient impact resistance while having high adhesion. On the other hand, Comparative Example 5 to Comparative Example 8 have sufficient adhesion performance but insufficient impact resistance. This is presumed to be due to the difference in molecular structure. Since Examples 1 to 5 are produced in the presence of a transition metal catalyst, the molecular structure is linear. However, it is known that Comparative Examples 5 to 8 are produced by a high-pressure method process, and the molecular structure is considered to be a structure having an excessive short chain branch and a long chain branch. Therefore, it is thought that impact resistance falls as a result.

  Significance and rationality of the multi-component polar group-containing olefin copolymer of the present invention capable of highly balancing adhesiveness and impact resistance by comparison with the good results of the above examples and comparative examples, and conventional The technical excellence is clarified.

  The multi-component polar olefin copolymer according to the present invention expresses high adhesiveness with other base materials, and makes it possible to produce industrially useful laminates. The multi-component polar olefin copolymer that can be produced according to the present invention is excellent not only in adhesiveness but also in mechanical and thermal properties, and can be applied as a useful multilayer molded product, and can be laminated on various substrates. Widely used in packaging materials, packaging containers, industrial materials such as fibers, pipes, fuel tanks, hollow containers and drums, civil engineering such as water-stopping materials, electronics such as electronics and household appliances, electric wires and cables, etc. Used in the electric wire field.

Claims (12)

One or two or more types selected from monomers having one or two or more nonpolar monomer (X1) units selected from ethylene and an α-olefin having 3 to 10 carbon atoms and an epoxy group, a carboxyl group or a dicarboxylic anhydride group A multi-component polar group-containing olefin copolymer (provided that each unit of X1, Z1, and Z2 is composed of an arbitrary acyclic or cyclic monomer (Z2) unit of Containing at least one of each of them)), which is obtained by copolymerization in the presence of a transition metal catalyst, containing a multi-component polar group characterized by a linear molecular structure and random copolymerization Olefin copolymer. The ratio of the weight average molecular weight (Mw) and the number average molecular weight (Mn) determined by gel permeation chromatography (GPC) is in the range of 1.5 to 3.5. Multi-component polar group-containing olefin copolymer. The multielement according to claim 1 or 2, wherein the amount of aluminum (Al) contained in the multi-component polar group-containing olefin copolymer is 0 to 100,000 µg per gram of the copolymer. Polar group-containing olefin copolymer. The melting point Tm (° C.) expressed by the temperature at the maximum peak position of the absorption curve measured by the differential scanning calorimetry (DSC) method is 50 <Tm <128-6.0 [Z1] (where Z1 The multi-component polar group-containing olefin copolymer according to any one of claims 1 to 3, wherein the monomer unit derived from is [Z1] (mol%)). . 5. The polar monomer (Z1) unit selected from monomers having an epoxy group, a carboxyl group or a dicarboxylic anhydride group is 0.001 to 19.999 mol%. The multi-component polar group-containing olefin copolymer described in item 1. The multipolar polar group-containing olefin copolymer according to any one of claims 1 to 5, wherein the nonpolar monomer (X1) unit is ethylene. The multi-component system polarity according to any one of claims 1 to 6, wherein the transition metal catalyst is a transition metal containing a chelating ligand and a Group 5-11 metal. Group-containing olefin copolymer. The multi-component polar group-containing olefin copolymer is a transition metal catalyst in which a triarylphosphine or a triarylarsine compound is coordinated to palladium or nickel metal, according to any one of claims 1 to 7. The multi-component polar group-containing olefin copolymer described in the item. The adhesive agent containing the multi-component polar group containing olefin copolymer described in any one of Claims 1-8. A multi-layered polar group-containing olefin copolymer according to any one of claims 1 to 9, or a laminate comprising at least a layer containing an adhesive and a base material layer. The base material layer according to claim 10, wherein the base material layer is selected from an olefin resin, a highly polar thermoplastic resin, a metal, a vapor deposition film of an inorganic oxide, paper, cellophane, a woven fabric, and a non-woven fabric. Laminated body.   The laminate according to claim 10 or claim 11, wherein the base material layer is a polyamide resin, a fluorine resin, or an ethylene-vinyl alcohol copolymer (EVOH).

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