JP6307321B2 - Polar group-containing olefin copolymer, adhesive material using the same, laminate and composite product - Google Patents

Description

  The present invention relates to a polar group-containing olefin copolymer, an adhesive using the same, a laminate using the same, and various composite products. More specifically, the present invention relates to a specific polar group and various groups. The present invention relates to a polar group-containing olefin copolymer having excellent adhesion performance to a material, and an adhesive, a laminate, and a composite product using the performance.

  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 polymers are generally non-polar, and when used in laminated materials, they have the disadvantage that their adhesive strength to other 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. 1 (b) and 1 (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 acrylates such as methyl acrylate and ethyl acrylate. The main focus is on a monomer containing a group and a copolymer of a specific polar group-containing monomer such as vinyl acetate and ethylene or α-olefin, and the polar group-containing olefin copolymer having these functional groups is highly polar. Adhesiveness with dissimilar materials 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, an epoxy group is generally known as a polar group capable of exhibiting excellent adhesiveness with a heterogeneous material having a high polarity. However, in an ordinary catalytic polymerization method, an epoxy group-containing comonomer is copolymerized. At present, polar olefin copolymers containing epoxy groups that are commercially available mainly are produced by a 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), a polar group-containing olefin copolymer obtained by copolymerizing 1,2-epoxy-9-decene, ethylene, and 1-butene 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 there is no mention of specific adhesion performance with different polar materials. Moreover, this patent document does not mention at all the resin physical properties necessary for the polar group-containing olefin copolymer to obtain sufficient adhesiveness with different polar materials, and the polarity is intended for high adhesive performance. Use as a group-containing olefin copolymer is not disclosed.

  In view of the above conventional methods, the method of introducing a polar group into an olefin copolymer, which includes respective problems such as graft modification, high pressure radical polymerization process, and a method using a large amount of organoaluminum, A polar group-containing olefin copolymer containing an epoxy group, which is produced without depending on the method of the above, and exhibits excellent adhesion performance to a highly polar different material, and The proposal of the laminated body using it was long-awaited.

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. It is an object of the present invention to develop a polar group-containing olefin copolymer exhibiting excellent adhesive performance, and to provide adhesives, laminates, various molded products, and various composite products using the same. It is.

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, the polar group-containing olefin copolymer having excellent adhesion performance with various different materials can be found, and the present invention has been made.
That is, the polymer of the present invention is a specific polar group-containing olefin copolymer polymerized using a transition metal catalyst. It is characterized by being excellent in various physical properties.

In the present invention, the structural unit amount derived from ethylene or an α-olefin having 3 to 20 carbon atoms is represented by 99.999 to 80 mol%, represented by the following structural formula (I) or the following structural formula (II). A polar group-containing olefin copolymer comprising 20 to 0.001 mol% of a structural unit derived from at least one of the polar group-containing monomers containing an epoxy group, and copolymerizing in the presence of a transition metal catalyst The basic structure (first invention) is a polar group-containing olefin copolymer obtained by 1), characterized in that the molecular structure is linear and random copolymerization.
Structural formula (I)

（構造式（Ｉ）中、Ｒ１は水素原子または炭素数１〜１０のアルキル基、Ｒ２、Ｒ３、Ｒ４はそれぞれ独立して、水素原子、炭化水素基、又はエポキシ基を含む下記の特定の官能基を示し、Ｒ２〜Ｒ４のいずれか１つはエポキシ基を含む特定の官能基である。
特定の官能基：エポキシ基を必須で含み、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), R1 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R2, R3, and R4 are each independently the following specific functions including a hydrogen atom, a hydrocarbon group, or an epoxy group. And any one of R2 to R4 is a specific functional group including an epoxy group.
Specific functional group: a group that contains an epoxy group as essential and has a molecular structure consisting of carbon, oxygen, and hydrogen)
Structural formula (II)

（構造式（ＩＩ）中、Ｒ５〜Ｒ８はそれぞれ独立して、水素原子、炭化水素基、又はエポキシ基を含む下記の特定の官能基を示し、Ｒ５〜Ｒ８のいずれか１つはエポキシ基を含む特定の官能基である。また、ｍは０〜２である。
特定の官能基：エポキシ基を必須で含み、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 the structural formula (II), R5 to R8 each independently represents a specific functional group including a hydrogen atom, a hydrocarbon group, or an epoxy group, and any one of R5 to R8 represents an epoxy group. In addition, m is 0-2.
Specific functional group: a group that contains an epoxy group as essential and has a molecular structure consisting of carbon, oxygen, and hydrogen)

  The subordinate inventions, which are embodiment inventions following the basic invention of the present invention, will be described in order. The second invention is a measurement of the polar group-containing olefin copolymer by the differential scanning calorimetry (DSC) method. The polar group-containing olefin copolymer according to the first aspect of the present invention is characterized in that the melting point is 50 ° C. to 140 ° C. represented by the temperature at the maximum peak position of the absorption curve.

  In a third aspect of the present invention, the polar group-containing olefin copolymer has a weight average molecular weight (Mw) determined by gel permeation chromatography (GPC) of 1,000 to 2,000,000. The polar group-containing olefin copolymer according to the first or second aspect of the invention.

  In the fourth invention of the present invention, the polar group-containing olefin copolymer has a weight average molecular weight (Mw) determined by gel permeation chromatography (GPC) of 33,000 to 2,000,000. This is a polar group-containing olefin copolymer according to the first to third inventions.

  In a fifth aspect of the present invention, the polar group-containing monomer containing an epoxy group is the structural formula (I), the specific functional group essentially contains an epoxy group, and further includes a hydrocarbon group, a carbonyl group, The polar group-containing olefin copolymer according to any one of the first to fourth inventions, characterized in that it is a group having a molecular structure consisting of a carbon atom, an oxygen atom and a hydrogen atom, which further contains any ether group It is.

  The sixth invention of the present invention is that the polar group-containing olefin copolymer is a copolymer polymerized in the presence of a transition metal catalyst of a Group 5-11 metal having a chelating ligand. The polar group-containing olefin copolymer according to any one of the first to fifth inventions.

  The seventh invention of the present invention is a copolymer obtained by polymerizing the polar group-containing olefin copolymer in the presence of a transition metal catalyst in which a triarylphosphine or a triarylarsine compound is coordinated to palladium or nickel metal. The polar group-containing olefin copolymer according to any one of the first to sixth inventions.

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

  A ninth invention of the present invention is a laminate including at least the polar group-containing olefin copolymer in the first to eighth inventions or a layer containing an adhesive and a base material layer.

  The tenth invention of the present invention is characterized in that the base material layer is selected from an olefin resin, a highly polar thermoplastic resin, a metal, a vapor-deposited film of inorganic oxide, paper, cellophane, woven fabric, and non-woven fabric. It is a laminated body in the ninth invention.

  The eleventh invention of the present invention is the tenth invention, wherein the base material layer is a polyamide resin, a fluorine resin, a polyester resin, or an ethylene-vinyl alcohol copolymer (EVOH). It is a laminate.

  In a twelfth aspect of the present invention, a triarylphosphine or a triarylarsine compound is coordinated to palladium or nickel metal with ethylene or an α-olefin having 3 to 20 carbon atoms and a polar group-containing monomer containing an epoxy group. It is a manufacturing method of the polar group containing olefin random copolymer in the 1st-7th invention characterized by copolymerizing in presence of a transition metal catalyst.

  In the thirteenth aspect of the present invention, the polar group-containing olefin copolymer in the first to eighth aspects or a laminate material containing an adhesive is used to laminate with one or more base layers. It is the laminated body characterized by having been laminated | stacked by.

  A fourteenth invention of the present invention is an extrusion-molded article comprising the polar group-containing olefin copolymer or the adhesive material in the first to eighth inventions.

  The fifteenth aspect of the present invention is a multilayer coextrusion molded article comprising at least the polar group-containing olefin copolymer in the first to eighth aspects, or a layer containing an adhesive and a base material layer. .

  A sixteenth aspect of the present invention is an injection-molded article comprising the polar group-containing olefin copolymer or the adhesive in the first to eighth aspects.

  The seventeenth invention of the present invention is characterized in that the polar group-containing olefin copolymer or the member containing an adhesive in the first to eighth inventions is combined with a base material by injection molding. This is a composite injection molded product.

  According to an eighteenth aspect of the present invention, there is provided the polar group-containing olefin copolymer-coated metal member, wherein the polar group-containing olefin copolymer or the adhesive material in the first to eighth inventions is coated with a metal. It is.

The polar group-containing olefin copolymer according to the present invention has a specific molecular structure and resin physical properties, so that it exhibits high adhesion to other substrates, and is an industrially useful laminate and composite material. Made it possible to manufacture. 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.
In addition, the polar group-containing olefin copolymer having a specific molecular structure and resin physical properties according to the present invention is excellent not only in adhesiveness but also in mechanical and thermal physical properties, and also has chemical resistance and is useful. It can be applied as a multilayer molded body, and can be formed into a multilayer film, a multilayer blow bottle, etc. by various uses, for example, extrusion molding and blow molding, and can be used for a wide range of applications.

Image diagram of molecular structure of olefin copolymer (a) polymerized by high pressure radical polymerization process, Image diagram of molecular structure of olefin copolymer polymerized using metal catalyst without long chain branching (b) It is an image figure of the molecular structure in the case of having a small amount of long chain branching in the olefin copolymer polymerized using a metal catalyst.

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

[I] About polar group-containing olefin copolymer (1) Polar group-containing olefin copolymer The polar group-containing olefin copolymer according to the present invention comprises ethylene or an α-olefin having 3 to 20 carbon atoms and an epoxy group. A copolymer with a monomer, which is a random copolymer obtained by random copolymerization of the monomer units, and a copolymer having a substantially linear molecular structure.

  The polar group-containing olefin copolymer obtained by copolymerizing ethylene or an α-olefin having 3 to 20 carbon atoms and an epoxy group-containing monomer may be graft-modified, high-pressure radical polymerization, or other polymerization methods described above. In the present invention, the known polar group-containing olefin copolymer is a random copolymer polymerized in the presence of a transition metal, and the molecular structure thereof is substantially It is characterized by being linear in nature, and as a range having a special adhesive effect, since it has the requirements for the structural unit amount described later, it is significantly different from known copolymers. is there.

  The polar group-containing olefin copolymer according to the present invention is obtained by polymerizing ethylene and / or an α-olefin having 3 to 20 carbon atoms and an epoxy group-containing monomer in the presence of a transition metal catalyst. Features. The ethylene or α-olefin having 3 to 20 carbon atoms to be used for polymerization is not particularly limited, but preferably contains ethylene in an essential manner and may further contain an α-olefin having 3 to 20 carbon atoms as necessary. Ethylene or α-olefin having 3 to 20 carbon atoms used for polymerization may be used alone, or two or more kinds may be used. Further, other monomers not containing a polar group may be further subjected to polymerization as long as they do not depart from the spirit of the present invention. The proportion of structural units derived from ethylene and / or α-olefin is usually 80 to 99.999 mol%, preferably 85 to 99.99 mol%, more preferably 90 to 99.98 mol%, more preferably 95. It is desirable to select from the range of -99.97 mol%.

(2) α-Olefin The α-olefin according to the present invention is an α-olefin having 3 to 20 carbon atoms represented by the structural formula: CH ₂ = CHR ¹⁸ (R ¹⁸ is a hydrocarbon having 1 to ¹⁸ carbon atoms). Group, which may have a straight chain structure or a branched structure). More preferably, it is an α-olefin having 3 to 12 carbon atoms, more preferably propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 3-methyl-1-butene, An α-olefin selected from 4-methyl-1-pentene, 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.

(3) Monomer not containing a polar group A monomer not containing a polar group according to the present invention is a monomer having one or more carbon-carbon double bonds in the molecular structure, and the element constituting the molecule is carbon. If it is only hydrogen, it will not be limited, for example, a diene, a triene, an aromatic vinyl monomer, a cyclic olefin etc. are mentioned, Preferably, it is butadiene, isoprene, styrene, vinylcyclohexane, cyclohexene, vinyl norbornene, and norbornene.

(4) Polar group-containing monomer The polar group-containing monomer according to the present invention needs to contain an epoxy group. If it is an olefin resin composition containing a polar group-containing olefin copolymer having an epoxy group, polarities such as polyamide resin, polyester resin, ethylene-vinyl alcohol copolymer (EVOH), and fluororesin imparted with adhesiveness It is possible to laminate and adhere to a high-temperature thermoplastic resin and a base material of a metal material such as aluminum or steel.

The polar group-containing monomer according to the present invention is preferably a monomer containing an epoxy group represented by the following structural formula (I) or structural formula (II).
Structural formula (I)

（構造式（Ｉ）中、Ｒ１は水素原子または炭素数１〜１０のアルキル基、Ｒ２、Ｒ３、Ｒ４はそれぞれ独立して、水素原子、炭化水素基、又はエポキシ基を含む下記の特定の官能基を示し、Ｒ２〜Ｒ４のいずれか１つはエポキシ基を含む特定の官能基である。
特定の官能基：エポキシ基を必須で含み、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), R1 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R2, R3, and R4 are each independently the following specific functions including a hydrogen atom, a hydrocarbon group, or an epoxy group. And any one of R2 to R4 is a specific functional group including an epoxy group.
Specific functional group: a group that contains an epoxy group as essential and has a molecular structure consisting of carbon, oxygen, and hydrogen)
Structural formula (II)

（構造式（ＩＩ）中、Ｒ５〜Ｒ８はそれぞれ独立して、水素原子、炭化水素基、又はエポキシ基を含む下記の特定の官能基を示し、Ｒ５〜Ｒ８のいずれか１つはエポキシ基を含む特定の官能基である。また、ｍは０〜２である。
特定の官能基：エポキシ基を必須で含み、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 the structural formula (II), R5 to R8 each independently represents a specific functional group including a hydrogen atom, a hydrocarbon group, or an epoxy group, and any one of R5 to R8 represents an epoxy group. In addition, m is 0-2.
Specific functional group: a group that contains an epoxy group as essential and has a molecular structure consisting of carbon, oxygen, and hydrogen)

The molecular structure of the epoxy 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 epoxy group-containing monomer, the epoxy group-containing monomer represented by the structural formula (I) is More preferred. Furthermore, among the epoxy 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 a hydrogen atom, a hydrocarbon group, Or it is either the following specific functional groups containing an epoxy group, and what is any one of R2-R4 is a specific functional group containing an epoxy group is more preferable. (Specific functional group: a group having a molecular structure composed of a carbon atom, an oxygen atom, and a hydrogen atom, which essentially includes an epoxy group and further includes any of a hydrocarbon group, a carbonyl group, and an ether group)
Examples of the polar group-containing monomer represented by the structural formula (I) or the structural formula (II) include 5-hexene epoxide, 6-heptene epoxide, 7-octene epoxide, 8-nonene epoxide, 9-decene epoxide, Ω-alkenyl epoxides such as 10-undecene epoxide, 11-dodecene epoxide, 2-methyl-6-heptene epoxide, 2-methyl-7-octene epoxide, 2-methyl-8-nonene epoxide, 2-methyl Ω-alkenyl epoxides having a branch in the molecular structure such as -9-decene epoxide, 2-methyl-10-undecene epoxide, allyl glycidyl ether, 2-methylallyl glycidyl ether, glycidyl ether of o-allylphenol, m -Unsaturated glycidyl ethers such as glycidyl ether of allylphenol and glycidyl ether of p-allylphenol Tellurium, 4-hydroxybutyl (meth) acrylate, acrylic acid, methacrylic acid, glycidyl p-styrylcarboxylate, endo-cis-bicyclo [2,2,1] hept-5-ene-2,3-dicarboxylic acid, Glycidyl ester of unsaturated carboxylic acid such as endo-cis-bicyclo [2,2,1] hept-5-ene-2-methyl-2,3-dicarboxylic acid, itaconic acid, citraconic acid, butenetricarboxylic acid, epoxy Cyclic olefins containing epoxy groups such as hexyl norbornene, epoxycyclohexane norbornene, methyl glycidyl ether norbornene, and others, 2- (o-vinylphenyl) ethylene oxide, 2- (p-vinylphenyl) ethylene oxide, 2- (o-allylphenyl) Ethylene oxide, 2- (p-allylpheny ) Ethylene oxide, 2- (o-vinylphenyl) propylene oxide, 2- (p-vinylphenyl) propylene oxide, 2- (o-allylphenyl) propylene oxide, 2- (p-allylphenyl) propylene oxide, p-glycidyl Styrene, 3,4-epoxy-1-butene, 3,4-epoxy-3-methyl-1-butene, 3,4-epoxy-1-pentene, 3,4-epoxy-3-methyl-1-pentene, Epoxy groups such as 5,6-epoxy-1-hexene, vinylcyclohexene monoxide, allyl-2,3-epoxycyclopentyl ether, 2,3-epoxy-5-vinylnorbornane, 1,2-epoxy-4-vinylcyclohexane The monomer containing can be mentioned. 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.
The epoxy group-containing monomer used for polymerization may be used alone or in combination of two or more.

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

(5) Structural unit of polar group-containing olefin copolymer The structural unit and the structural unit amount of the 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 having 3 to 20 carbon atoms and a polar group-containing monomer 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.

(6) Structural unit amount of polar group-containing monomer The structural unit amount derived from the epoxy group-containing monomer according to the present invention is usually in the range of 20 to 0.001 mol%, preferably in the range of 15 to 0.01 mol%, more preferably. Is selected from the range of 10 to 0.02 mol%, more preferably from the range of 5 to 0.03 mol%, and it is preferable that it is always present in the polar group-containing olefin copolymer of the present invention. 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.

(7) Measuring method of structural unit amount of polar group-containing monomer The structural unit amount of the polar group in the polar group-containing olefin copolymer according to the present invention is determined using a 1H-NMR spectrum. 1H-NMR spectrum was measured by the following method. 200-250 mg of a sample was placed in an NMR sample tube having an inner diameter of 10 mmφ together with 2.4 ml of o-dichlorobenzene / deuterated benzene bromide (C6D5Br) = 4/1 (volume ratio) and hexamethyldisiloxane which is a chemical shift reference material. The mixture was 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. 1H-NMR was measured with a pulse angle of 1 °, a pulse interval of 1.8 seconds, and the number of integrations 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.

Structural unit amount of polar group-containing monomer The comonomer content was determined from the 1H-NMR spectrum by the following method.
[Structural unit amount of 4-hydroxybutyl acrylate glycidyl ether (4-HBAGE)]
The peak integrated intensity sum of the polar group-containing olefin copolymer in the range of 0.3 to 3.1 ppm is IA1, and 2.4, 2.6, 3.0, 3.3, 3.4, 3.5 , And the sum of the integrated intensities of peaks due to protons of 4-HBAGE contained in the copolymer produced at 4.1 ppm was determined according to the following formula.
4-HBAGE content (mol%) = 40 × IX1 / (IA1−0.6 × IX1)

[Structural unit amount of 1,2-epoxy-9-decene (C8-EPO)]
The peak integrated intensity sum of the polar group-containing olefin copolymer in the range of 0.3 to 3.1 ppm is IA2, and C8- contained in the copolymer generated at 2.4, 2.6, and 2.8 ppm. When the sum of the integrated intensities of the peaks due to the protons of EPO was IX2, it was determined according to the following equation.
C8-EPO content (mol%)
= (400/3) x IX2 / (IA2-11 / 3 x IX2)

[Structural unit amount of 1,2-epoxy-4-vinylcyclohexane (EP-VCH)]
The integrated intensity of the peak due to the polar group-containing olefin copolymer in the range of 0.3 to 3.2 ppm is IA2, and the integrated intensity of the peak due to the proton of EP-VCH contained in the copolymer around 3.0 ppm. Was calculated according to the following equation.
EP-VCH content (mol%) = 100 × IX2 / (0.5 × IA2-2 × IX2)

[Structural unit amount of glycidyl methacrylate (GMA)]
IA3 is the peak integrated intensity sum of polar group-containing olefin copolymers in the range of 0.3 to 3.2 ppm, and occurs at 2.5, 2.6, 3.1, 3.9, and 4.3 ppm. When the sum of integrated intensities of peaks due to GMA protons contained in the copolymer was IX3, the sum was obtained according to the following equation.
GMA content (mol%) = 80 × IX3 / (IA3-0.8 × IX3)

(8) Molecular structure of polar group-containing olefin copolymer The polar group-containing olefin copolymer according to the present invention is a random copolymer of ethylene or a copolymer of an α-olefin having 3 to 20 carbon atoms and a polar group-containing monomer. It is a coalescence.
Examples of the molecular structure of the polar group-containing olefin copolymer according to the present invention are shown in the following paragraphs. The random copolymer means that the probability of finding each structural unit at a position in a given molecular chain of the A structural unit and the B structural unit in the molecular structure example shown below is the type of the adjacent structural unit. It is an unrelated copolymer. Moreover, the molecular chain terminal of the polar group-containing olefin copolymer may be ethylene, an α-olefin having 3 to 20 carbon atoms, or a polar group-containing monomer. As described below, in the molecular structure (example) of the polar group-containing olefin copolymer in the present invention, ethylene or an α-olefin having 3 to 20 carbon atoms and a monomer containing an epoxy group form a random copolymer. ing.

  In addition, when the molecular structure (example) of the olefin copolymer having a polar group introduced by graft modification is also referred to, a part of the olefin copolymer obtained by copolymerizing ethylene or an α-olefin having 3 to 20 carbon atoms is obtained. And graft-modified to an epoxy group-containing monomer.

  The 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. An image diagram of an olefin copolymer polymerized by a high-pressure radical polymerization process is illustrated in FIG. 1 (a), and an image diagram of an olefin copolymer polymerized using a metal catalyst is illustrated in FIGS. 1 (b) and 1 (c). As described above, 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 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 as shown in FIG. (B) A structure (b) containing no long-chain branches as shown in (c) or a structure (c) containing a small amount of long-chain branches that does not affect the mechanical strength 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 FIG. 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.

(9) Weight average molecular weight (Mw) of polar group-containing olefin copolymer
The weight average molecular weight (Mw) of the 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, and more preferably 20,000 to It is desirable that the range is 1,000,000, preferably 31,000 to 800,000, and more preferably 33,000 to 800,000. When Mw is less than 1,000, physical properties such as mechanical strength and impact resistance are not sufficient, and adhesion with a different material with high polarity is also inferior. When Mw exceeds 2,000,000, the melt viscosity becomes very high, and the molding process becomes difficult.

  The weight average molecular weight (Mw) of the polar group-containing olefin copolymer 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 formula [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 of polar group-containing olefin copolymer The melting point of the polar group-containing olefin copolymer according to the present invention is indicated by the maximum peak temperature of the endothermic curve measured by a differential scanning calorimeter (DSC). The maximum peak temperature is the height from the baseline when DSC measurement shows multiple peaks in the endothermic curve when the heat flow (mW) is taken on the vertical axis and the temperature (° C) is taken on the horizontal axis. Indicates the maximum peak temperature, and when there is one peak, it indicates the peak temperature.
Assuming polyethylene, the melting point is preferably 50 ° C to 140 ° C, more preferably 60 ° C to 138 ° C, and most preferably 70 ° C to 135 ° C. If it is lower than this range, the heat resistance is not sufficient, and if it is higher than this range, the adhesiveness is poor.

[II] Production of Polar Group-Containing Olefin Copolymer The method for producing a polar group-containing olefin copolymer according to the present invention comprises a transition metal catalyst and ethylene or an α-olefin having 3 to 20 carbon atoms and an epoxy group. It is obtained by copolymerizing with the containing monomer.

(1) Polymerization catalyst for polar group-containing olefin copolymer The type of the polymerization catalyst according to the present invention is a copolymer of ethylene or an α-olefin having 3 to 20 carbon atoms and a polar group-containing monomer containing an epoxy group. Although it will not specifically limit if it is possible, For example, there exists the method of superposing | polymerizing, using as a catalyst the 5-11 group transition metal compound which has a chelating ligand.
Specific examples of preferred transition metals include vanadium atom, niobium atom, tantalum atom, chromium atom, molybdenum atom, tungsten atom, manganese atom, iron atom, platinum atom, ruthenium atom, cobalt atom, rhodium atom, nickel atom, palladium atom, A copper atom etc. are mentioned.
Among these, vanadium atom, iron atom, platinum atom, cobalt atom, nickel atom, palladium atom and rhodium atom are preferable, and platinum atom, cobalt atom, nickel atom and palladium atom 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, and E1 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 heteroatom having 1 to 30 carbon atoms. Each of R ⁶ and R ⁷ independently represents hydrogen, halogen, a hydrocarbon group that may contain 1 to 30 carbon atoms, OR ² , CO ² ; _{^{2 R 2, CO 2 M '}} , C (O) N (R 1) 2, _{^{(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 from 0 It represents an integer up to 2. In addition, 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 hetero atom 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. R ¹ represents hydrogen or a hydrocarbon group having 1 to 20 carbon atoms, R ² 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.) More preferred is a transition metal complex represented by the following structural formula (C).

(In Structural Formula (C), M represents a transition metal belonging to any of Groups 5 to 11 of the periodic table of elements, that is, the above-described transition metal. X ¹ represents oxygen, sulfur, —SO ₃ —, Or —CO ₂ —, Y ¹ represents carbon or silicon, n represents an integer of 0 or 1, E ¹ represents phosphorus, arsenic, or antimony, and R ³ and R ⁴ are each independent. Represents a hydrogen atom or a hydrocarbon group which may contain a heteroatom having 1 to 30 carbon atoms, and R ⁵ may each independently contain hydrogen, halogen, or a heteroatom having 1 to 30 carbon atoms. R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ each independently represent 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 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 In addition, a plurality of groups appropriately selected from R8 to R11 are connected to each other, and 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 there is a substituent on the ring. R ¹ represents hydrogen or a hydrocarbon group having 1 to 20 carbon atoms, R ² represents a hydrocarbon group having 1 to 20 carbon atoms, L ¹ represents M Represents a coordinated ligand, and R ³ and L ¹ may be bonded to each other to form a ring.)

  Here, as the catalyst of the group 5-11 transition metal compound having a chelating ligand, there are typically known so-called “shop type” and “drent type” catalysts. 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 polar group-containing olefin copolymer according to the present invention, an epoxy group-containing monomer and a small amount of an organometallic compound are contacted, and then in the presence of the transition metal catalyst, ethylene and / or Alternatively, the polymerization activity can be further increased by copolymerizing an α-olefin having 3 to 20 carbon atoms and an epoxy group-containing monomer.
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 n M 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 polar group-containing olefin copolymer according to the remaining amount present invention aluminum (Al) is preferably not more than 100,000 micrograms _Al / g, more or less 70,000μg _Al / g preferably, 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 [mu] g _Al / g or less is most preferred. When more than this, the mechanical property fall of a polar group containing olefin copolymer (A), discoloration of a polymerization product, acceleration | stimulation of deterioration, etc. occur. 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 polar group-containing olefin copolymer is expressed in μg.

Aluminum (Al) amount The aluminum (Al) amount contained in the 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 coalescence.

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

<1> Fluorescent X-ray analysis 3-10 g of a measurement sample is weighed and heated and pressure-molded with a hot press machine 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 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 3 ml of measurement sample, 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 subjected to microwave decomposition. Using an apparatus (MLS-1200MEGA manufactured by Milestone General Co., Ltd.), 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 polar group-containing olefin copolymer The polymerization method of the polar group-containing olefin copolymer (A) 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. In addition, the polymerization format may be any of batch polymerization, semi-batch polymerization, and continuous polymerization. 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). For specific manufacturing processes and conditions, for example, JP 2010-260913 A and JP 2010-202647 A can be referred to.

[III] Additive The 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 a crosslinking agent within the scope not departing from the gist of the present invention. In addition, additives such as a foaming agent, a nucleating agent, a flame retardant, a conductive material, and a filler may be blended.

[IV] Adhesive The polar group-containing olefin copolymer of the present invention has a specific molecular structure and resin physical properties, so that it exhibits high adhesiveness with other substrates, and is an industrially useful laminate. Made it possible to manufacture. That is, the adhesion performance with various substrates is obtained by copolymerizing ethylene or an α-olefin having 3 to 20 carbon atoms and a polar group-containing monomer containing an epoxy group in the presence of a transition metal catalyst. In the group-containing olefin copolymer, the structural unit amount derived from the polar group-containing monomer in the polar group-containing olefin copolymer is usually in the range of 20 to 0.001 mol%, preferably in the range of 15 to 0.01 mol%. More preferably, it is sufficiently expressed in the range of 10 to 0.02 mol%, more preferably in the range of 5 to 0.03 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.

[V] Laminate (1) Material of Laminate The laminate according to the present invention is a laminate comprising a layer composed of a polar group-containing olefin copolymer according to the present invention and a substrate layer, and the substrate The layer is made of an olefin resin such as polyethylene or polypropylene, a polyamide resin, a polyester resin, a highly polar thermoplastic resin such as an ethylene-vinyl alcohol copolymer (EVOH), an adhesive fluorine resin, a metal such as aluminum or steel. A substrate such as a material can be exemplified.

  Specific examples of the substrate related to the present invention include high density polyethylene, medium density polyethylene, low density polyethylene, ethylene-vinyl acetate copolymer, ethylene-acrylic acid ester copolymer, ionomer, homopolypropylene resin, propylene and others. Copolymers with α-olefins, olefin resins such as poly-1-butene and poly-4-methyl-1-pentene, vinyl resins such as polyvinyl chloride, polyvinylidene chloride, polystyrene, polyacrylate and polyacrylonitrile Polymer, nylon 6, nylon 66, nylon 10, nylon 11, nylon 12, nylon 610, polyamide resin such as polymetaxylylene adipamide, polyethylene terephthalate, polyethylene terephthalate / isophthalate, polybutylene terephthalate, poly Heat having film-forming ability such as lactic acid, polybutylene succinate, polyester resins such as aromatic polyester, polyvinyl alcohol, ethylene / vinyl alcohol copolymer, polycarbonate resin, adhesive fluororesin, and cellophane Inorganic oxidation such as plastic resin film or sheet (and stretched or printed material thereof), metal foil or metal plate such as aluminum, iron, copper, or alloys based on these, silica-deposited plastic film, alumina-deposited plastic film Vapor deposition film, metal such as gold, silver and aluminum, or vapor deposition film such as compounds other than oxides of these metals, paper such as fine paper, kraft paper, paperboard, glassine paper, synthetic paper, cellophane, woven fabric, Nonwoven fabrics can be mentioned.

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 film according to the present invention is suitable, for example, as a food packaging material. 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.
Moreover, as a container, the ethylene-type copolymer layer surfaces of the said laminated body can be faced, and it can form by heat-sealing at least one part. Specifically, for example, water packaging, bags, liquid soup bags, liquid paper containers, lami raw fabrics, special shape liquid packaging bags (standing pouches, etc.), standard bags, heavy bags, semi-heavy bags, wrap films, sugar It is suitably used for bags, oil packaging bags, various packaging containers for food packaging, infusion bags and the like.

(3) Manufacture of laminates The processing methods include normal press molding, air-cooled inflation molding, air-cooled two-stage cooling inflation molding, high-speed inflation molding, flat die molding (T-die molding), and water-cooled inflation molding. Conventionally known methods such as laminating methods such as extrusion laminating, sand laminating, and dry laminating, 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 polar group-containing olefin copolymer of the present invention and at least one substrate layer. The laminate material in the present invention is a resin material containing the polar group-containing olefin copolymer of the present invention that can be used in 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, the polar group-containing olefin copolymer of the base material used in the present invention is formed on the side formed between the base material and the layer containing the polar group-containing olefin copolymer. In order to improve the barrier property, 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.

(5) Extrusion product The extrusion product according to the present invention is an extrusion product obtained by molding the polar group-containing olefin copolymer according to the present invention by extrusion molding. Extrusion products related to the present invention are known in various forms such as air-cooled inflation molding, air-cooled two-stage cooling inflation molding, high-speed inflation molding, water-cooled inflation molding, flat die molding, profile extrusion molding, tubular product molding, calendar molding, etc. It can be manufactured by extrusion. Further, it may be further shaped by various known methods such as sandwiching in a mold or the like, or applying deformation in a state where the extruded product obtained by extrusion molding is not completely solidified. Further, post-processing may be added by various known methods such as bending, cutting, and reheating after the obtained extrusion-molded product.

(6) Multi-layer co-extrusion molded product The multi-layer co-extrusion molded product related to the present invention is a multi-layer co-extrusion molded product that can be molded by a known multi-layer co-extrusion molding. It is a multilayer coextruded product including at least a layer containing a coalescence. Multi-layer co-extrusion products are multi-layer structures that can be manufactured by simultaneously extruding a plurality of thermoplastic materials into a plurality of layers and molding them by various shaping methods. It is a molded product with The method for producing a multilayer coextrusion molded product according to the present invention includes multilayer air-cooled inflation molding, multilayer air-cooled two-stage cooling inflation molding, multilayer high-speed inflation molding, multilayer water-cooled inflation molding, multilayer flat die molding (T-die molding), multilayer Well-known multilayer coextrusion molding, such as tubular product molding and multilayer corrugated pipe molding, can be mentioned. As the base material layer in the multilayer coextrusion molded product according to the present invention, various various materials as described above can be appropriately used. A multilayer coextrusion molded product according to the present invention is obtained by processing a layer containing the polar group-containing olefin copolymer according to the present invention and an appropriate base material by an appropriate molding method, so that a multilayer film, a multilayer sheet, a multilayer It can be manufactured as a known multilayer co-extrusion product such as a pipe, multilayer hose, multilayer tube, multilayer corrugated pipe and the like. Further, the multilayer coextrusion molded product obtained by the multilayer coextrusion molding may be further shaped by various known methods such as being sandwiched in a mold or the like or being deformed in a state where it is not solidified. Furthermore, post-processing may be added by various known methods such as bending, cutting, and re-heating after the obtained multilayer co-extruded product.

(7) Multilayer film The multilayer film according to the present invention is a multilayer film that can be produced by a known multilayer film molding method, and includes a layer and a base containing the polar group-containing olefin copolymer of the present invention. A multilayer film including at least a material layer. As a method for producing a multilayer film according to the present invention, a known multilayer such as multilayer air-cooled inflation molding, multilayer air-cooled two-stage cooling inflation molding, multilayer high-speed inflation molding, multilayer water-cooled inflation molding, multilayer flat die molding (T-die molding), etc. A film forming method can be used. As the base material layer of the multilayer film according to the present invention, various various materials as described above can be appropriately used.

(8) Multilayer Blow Molded Product A multilayer blow molded product related to the present invention is a multilayer blow molded product that can be manufactured by a known multilayer blow molding, and contains the polar group-containing olefin copolymer of the present invention. A multilayer blow-molded product including at least a layer and a base material layer. Examples of the method for producing a multilayer blow molded product according to the present invention include known blow molding methods such as multilayer direct blow molding, multidimensional multilayer blow molding, multilayer rotary blow molding and the like. As the base material layer of the multilayer blow molded product according to the present invention, various kinds of materials as described above can be appropriately used.

(9) Multilayer tubular molded article The multilayer tubular molded article related to the present invention is a multilayer tubular molded article that can be molded by a known multilayer tubular molding method, and contains the polar group-containing olefin copolymer of the present invention. A multilayer tubular molded article including at least a layer formed from the above and a base material layer. The multilayer tubular molding method according to the present invention is, for example, a composite of a plurality of materials in layers by simultaneously extruding a plurality of thermoplastic materials, and continuously discharging the shape from a circular or irregular discharge port. A tubular molded product having a shape conforming to the above can be molded, and a method of obtaining a tubular molded product by molding and cooling and solidifying by an appropriate shaping method and cooling method can be mentioned. The discharge port shape of the multilayer tubular molding method according to the present invention is not particularly limited, and a circular shape, an ellipse shape, a polygonal shape, and other known discharge port shapes can be selected. Further, the molding method of the multilayer tubular molding method according to the present invention is not particularly limited, and a sizing plate method, an internal pressure sizing method, an inner diameter sizing method, a vacuum sizing method, an extruded molten material is sandwiched between molds, and a compressed air from the mandrel side In addition, a known molding method such as a method of cooling while shaping by vacuuming from the mold side or the like can be used, and a cooling method can be appropriately used such as water cooling, air cooling, sandwiching in a mold, or the like. Furthermore, the multilayer tubular molded article once cooled and solidified can be reheated and further processed into another shape. As the base material layer of the multilayer tubular molded product according to the present invention, various kinds of materials as described above can be appropriately used.

(10) Multilayer sheet The multilayer sheet according to the present invention is a multilayer sheet that can be produced by known multilayer sheet molding, and a layer and a substrate comprising the polar group-containing olefin copolymer of the present invention. A multilayer sheet including at least a layer. Various known methods can be used as a method for producing a multilayer sheet according to the present invention. For example, a plurality of thermoplastic materials are simultaneously extruded to form a composite of a plurality of materials into a flat die, a circular die, etc. A method of forming a sheet by discharging from a known die can be mentioned. In these methods, the end of the sheet may be slit as necessary, or a process of opening a circular sheet may be added. Furthermore, in a state where it is not cooled and solidified after extrusion molding, or in a state where it is remelted by reheating the cooled and solidified multilayer sheet, various types such as vacuum forming, pressure forming, vacuum pressure forming, stamping forming, press forming, etc. It may be further shaped by a known molding method. As the base material layer of the multilayer sheet according to the present invention, various various materials as described above can be appropriately used.

(11) Injection molded product The injection molded product according to the present invention is an injection molded product obtained by molding the polar group-containing olefin copolymer according to the present invention by injection molding. A well-known method can be used for manufacture of the injection molded product concerning this invention.

(12) Multilayer injection-molded article The multilayer injection-molded article according to the present invention includes at least a layer containing the polar group-containing olefin copolymer of the present invention, and a plurality of layers are combined using injection molding. It is a multilayer injection-molded product that can be manufactured. The multilayer injection molded article only needs to be a composite of two or more types of materials, for example, two different types of layers containing the polar group-containing olefin copolymer of the present invention may be laminated, The layer comprising the polar group-containing olefin copolymer of the present invention and the layer comprising the substrate may be multilayered. Further, three or more layers may be multilayered. The multilayer injection molded product according to the present invention can be molded by a known injection molding method. It may be a multi-layer injection-molded product formed by multilayering two or more layers containing a polar group-containing olefin copolymer, but has a high adhesiveness with a different material that is a feature of the present invention. Considering this, it is preferable to use a composite injection-molded product in which a layer made of different materials is laminated. As an injection molding method capable of producing a multilayer injection molded product, a known method can be exemplified. For example, the polar group-containing olefin copolymer of the present invention is processed into a member in advance by a known method such as injection molding, extrusion molding, press molding, or cutting, and the base is further inserted in an injection mold. A method of multilayering by injecting a material material, processing a base material into a member in advance, and injecting the polar group-containing olefin copolymer according to the present invention with the base material member inserted in an injection mold In this method, a polar group-containing olefin copolymer and a base material according to the present invention are sequentially injected into a mold in an appropriate order using a multi-color injection molding machine having a plurality of injection units. The method of multilayering etc. can be mentioned. In the multilayer injection-molded article according to the present invention, various kinds of base materials as described above can be used as appropriate as the types of members to be combined with the polar group-containing olefin copolymer according to the present invention.

(13) Coated metal member The coated metal member according to the present invention is a coating that can be produced by coating a metal with a metal coating material using the polar group-containing olefin copolymer of the present invention as a metal coating material. It is a metal member. The coated metal member according to the present invention can be produced by a known metal coating method. Examples of the coated metal member include, for example, a coated steel pipe in which a coating material is coated on an outer surface or an inner surface of a steel pipe through an undercoat as necessary, a coated metal wire coated with a metal coating material, a metal coating material Electric wire coated with powder, coated metal coated with fluid-coated method using powder-coated metal material, coated metal coated with electrostatic coating using powder-coated metal material, sheets and films in advance Examples thereof include a coated metal coated by thermally welding a metal coating material processed into a metal material.

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

  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) Polar group-containing structural unit amount in polar group-containing olefin copolymer The polar group-containing structural unit amount in the polar group-containing olefin copolymer was determined using a 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). In addition, the molecular weight distribution parameter (Mw / Mn) was further calculated by the number average molecular weight (Mn) by gel permeation chromatography (GPC), and the Mw / Mn ratio, 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] Press plate adjustment method of measurement sample The measurement sample is put into 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-type three-layer multilayer film with EVOH as the central layer and LLDPE as both outer layers, the LLDPE of the outer layer is peeled off, A 100 μm thick EVOH monolayer 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 central layer is polyamide and both outer layers are LLDPE, the outer layer LLDPE is peeled off, A 100 μm thick polyamide 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] Adjustment method of polyester film Using a multi-layer T-die molding machine, after forming a two-layer three-layer film with polyester as the central layer and LLDPE as both outer layers, the LLDPE in the outer layer is peeled off, A polyester monolayer film having a thickness of 100 μm 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: Polyethylene terephthalate (Mitsubishi Chemical Corporation brand: Novapex IG229Z)

[5] Method for adjusting fluororesin film Using a multi-layer T-die molding machine, after forming a two-type three-layer multilayer film in which the central layer is fluororesin and both outer layers are LLDPE, the outer layer LLDPE is peeled off. A fluororesin single layer film having a thickness of 100 μm 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)

[6] Preparation method of laminate of EVOH film and polar group-containing olefin copolymer Press plate of measurement sample obtained by the above-mentioned press plate preparation method, and EVOH film obtained by the above-mentioned preparation method of EVOH film The cut pieces of 50 mm x 60 mm are superposed, put into a hot press mold with dimensions: 50 mm x 60 mm and thickness 0.5 mm, and heated at 4.9 MPa for 3 minutes using a hot press machine with a surface temperature of 200 ° C. Pressed. 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.

[7] Preparation method of laminate of polyamide film and polar group-containing olefin copolymer A press plate of a measurement sample obtained by the above press plate preparation method and a polyamide film obtained by the above polyamide film preparation method The cut pieces of 50 mm x 60 mm are superposed, put into a hot press mold with dimensions: 50 mm x 60 mm and thickness 0.5 mm, and heated at 4.9 MPa for 5 minutes using a hot press machine with a surface temperature of 250 ° C. Pressed. 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.

[8] Preparation method of laminate of polyester film and polar group-containing olefin copolymer Press plate of measurement sample obtained by the above press plate preparation method, and polyester film obtained by the above polyester film preparation method The cut pieces of 50 mm x 60 mm are superposed, put into a hot press mold with dimensions: 50 mm x 60 mm and thickness 0.5 mm, and heated at 4.9 MPa for 3 minutes using a hot press machine with a surface temperature of 200 ° C. Pressed. Then, it moved 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 of the measurement sample and the laminated body of polyester were prepared.

[9] Preparation method of laminate of fluororesin film and polar group-containing olefin copolymer Measured sample press plate obtained by the above press plate preparation method and fluorine obtained by the above fluororesin film preparation method A resin film cut to a size of 50 mm × 60 mm is overlaid, put into a mold for heating press with dimensions: 50 mm × 60 mm, thickness 0.5 mm, and 4.9 MPa using a hot press machine with a surface temperature of 200 ° C. Pressurized for 3 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 laminated body of the press board of a measurement sample and a fluororesin was prepared.

[10] Method for measuring adhesive strength of laminate The laminate obtained by the laminate preparation method was cut into a width of 10 mm, and a tensile tester of Tensilon (Toyo Seiki Co., Ltd.) was used. The adhesive strength was measured by T-peeling at a speed of minutes. The unit of adhesive strength is indicated by gf / 10 mm. Further, when the adhesive strength is very strong, the polar group-containing olefin copolymer 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 rupture strengths of the polar group-containing olefin copolymer layer or the base material layer. It can be judged that it is very expensive. 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) Chemical resistance [1] Method for preparing polar group-containing olefin copolymer resin plate A polar group-containing olefin copolymer is placed in a hot press mold having dimensions of 50 mm x 60 mm and a thickness of 1 mm, and a surface temperature of 180 mm. After preheating in a hot press machine at 5 ° C. 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 produced the polar group containing olefin copolymer resin board about 0.9 mm in thickness.

[2] Chemical resistance evaluation method A polar group-containing olefin copolymer resin plate prepared by a method for preparing a polar group-containing olefin copolymer resin plate is cut into a width of 10 mm to prepare a test piece for evaluating chemical resistance. did. This test piece for evaluation was placed in a pressure vessel, and a mixed solution of three kinds of isooctane 455 ml / toluene 455 ml / ethanol 90 ml was further added. The pressure vessel was placed in an oven adjusted to 60 ° C., and after 24 hours, the test specimen for evaluation was taken out and air-dried in a draft for another 24 hours.
When the test specimen for evaluation after air drying did not retain the original shape, the chemical resistance was judged as “X”, and when the original shape was maintained, the chemical resistance was judged as “◯”.

(6) The sample for measurement of the phase angle δ (G * = 0.1 MPa) at the absolute value G * = 0.1 MPa of the complex elastic modulus is put into a mold for heating press having a thickness of 1.0 mm, and 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) content The amount of aluminum (Al) contained in the polar group-containing olefin copolymer is the same as the amount of aluminum (Al) contained in the alkylaluminum subjected to the polymerization. It can be determined by a method of calculating as a value divided by the yield of the copolymer and a method of measuring by fluorescent X-ray analysis.

[1] Method of calculating from alkyl aluminum polymerization addition amount Specifically, the calculation was performed 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 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 polar group-containing olefin copolymer was determined using fluorescent X-ray analysis. Details are described above.

[Example 1]
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 into 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.

Copolymerization of ethylene and 1,2-epoxy-9-decene After replacing an autoclave with a stirring blade of 2.4 liters in internal volume with purified nitrogen, dry toluene (1.0 liter) and 1,2-epoxy- 36 ml (0.2 mol) of 9-decene was charged. The temperature of the autoclave was raised to 100 ° C. while stirring, nitrogen was supplied to 0.3 MPa, and then ethylene was supplied to 1.3 MPa so that the ethylene partial pressure became 1 MPa. After completion of pressure adjustment, 150 μmol of a transition metal complex (I-Pd complex) was injected with nitrogen to initiate copolymerization. During the reaction, the temperature was kept at 100 ° C., ethylene was continuously supplied so as to maintain the pressure, polymerized for 120 minutes, and then cooled and depressurized to stop the reaction. 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. In Table 1, the polymerization activity represents the copolymer yield (g) per 1 mol of the complex used for the polymerization. The polymerization activity was calculated on the assumption that the ligand and palladium bisdibenzylideneacetone reacted 1: 1 to form a palladium complex.

[Example 2]
Copolymerization of ethylene and 4-vinyl-1,2-epoxycyclohexane Using 20.9 ml (0.2 mol) of 4-vinyl-1,2-epoxycyclohexane as the epoxy group-containing monomer, the amount of transition metal complex Was performed in the same manner as in Example 1, except that the polymerization pressure was 2.3 MPa, the polymerization temperature was 100 ° C., and the polymerization time was 240 minutes. The polymerization conditions and polymerization results are shown in Table 1, and the physical property measurement results are shown in Table 2.

Example 3
Copolymerization of ethylene and 4-hydroxybutyl acrylate glycidyl ether (4-HBAGE) Using 54 ml (0.3 mol) of 4-HBAGE as an epoxy group-containing monomer, the amount of transition metal complex is 50 μmol, the polymerization temperature is 90 ° C., and the polymerization time is The procedure was the same as Example 1 except that the time was 70 minutes. The polymerization conditions and polymerization results are shown in Table 1, and the physical property measurement results are shown in Table 2.

Example 4
Synthesis of SHOP type ligand: B-27DM The following ligand B-27DM was obtained according to the method described in WO2010-050256 (Synthesis Example 4).

Formation of Complex 112 mg (200 μmol) of the following 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.

Copolymerization of ethylene and 4-hydroxybutyl acrylate glycidyl ether (4-HBAGE) In an autoclave with a stirring blade having an internal volume of 2.4 liters, 1000 ml of dry toluene, 36.6 mg of tri-n-octylaluminum (TNOA) ( 0.1 mmol) and 2.7 ml (15 mmol) of 4-HBAGE were charged. The temperature of the autoclave was raised to 100 ° 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 the temperature and pressure were stabilized, 2.4 ml (24 μmol) of the B-27DM-Ni complex solution prepared previously was injected with nitrogen to initiate copolymerization. During the reaction, the temperature was kept at 100 ° C., and ethylene was continuously supplied so that the pressure was maintained. After polymerization for 80 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 28 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 1, the polymerization activity represents the copolymer yield (g) per 1 mol of the complex used for the polymerization. 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.

[Examples 5 to 12]
Of the methods described in Example 4, the polar group-containing olefin copolymer of Examples 5 to 12 was polymerized by changing the ligand amount, the polar group-containing monomer concentration, the polymerization temperature, and the polymerization time, respectively. Was prepared. The polymerization conditions and polymerization results are shown in Table 1, and the physical property measurement results are shown in Table 2.

[Examples 13 to 15]
Based on the method described in Example 4, polymerization was carried out without replenishing ethylene after the start of polymerization. At that time, polar group-containing olefin copolymers of Examples 13 to 15 were prepared by performing polymerization while changing the ligand amount, the polar group-containing monomer concentration, the polymerization temperature, and the polymerization time, respectively. The polymerization conditions and polymerization results are shown in Table 1, and the physical property measurement results are shown in Table 2. Since ethylene is not replenished in this polymerization method, the ethylene partial pressure at the end of the polymerization is lower than that at the start of the polymerization. The ethylene partial pressure in Table 1 is expressed as “2.5 → 1.5” because the ethylene partial pressure at the start of polymerization is 2.5 MPa and the ethylene partial pressure at the end of polymerization is 1. .5 MPa.

Example 16
SHOP-based ligand: Synthesis of 2- (2,6-diphenoxyphenyl) (2-phenoxyphenyl) phosphanyl-6- (pentafluorophenyl) phenol (B-114) (1) 1,3-diphenoxybenzene To a solution of (B-114_1, 2.62 g, 10 mmol) in dehydrated tetrahydrofuran (100 mL) was added n-butyllithium (2.5 M, 4.0 mL, 10 mmol) at 0 ° C., and then the temperature was gradually raised to room temperature. . The mixture was stirred at room temperature for 1 hour to synthesize a tetrahydrofuran solution of 2,6-diphenoxyphenyllithium (B-114_2).
(2) Dehydrated tetrahydrofuran of 2-phenoxybromobenzene (B-114_3, 7.5 g, 40 mmol) to a dehydrated (50 mL) mixture of magnesium (1.0 g, 40 mmol) and 1,2-dibromoethane (0.2 mL) (50 mL) solution was added dropwise at room temperature. The mixture was stirred at room temperature for 3 hours and it was added to a solution of phosphorus trichloride (2.6 mL, 30 mmol) in dehydrated tetrahydrofuran (20 mL) at -78 ° C. After the addition, the solution temperature was gradually raised to room temperature, and further stirred at room temperature for 1 hour. The solvent and excess phosphorus trichloride were removed under reduced pressure and the residue was dissolved in dehydrated tetrahydrofuran (50 mL). The solution was cooled to −78 ° C., and a tetrahydrofuran solution of B-114_2 synthesized in (1) was added thereto. After completion of the addition, the solution temperature was gradually raised to room temperature, and the mixture was further stirred at room temperature for 2 hours, whereby (2,6-diphenoxyphenyl) (2-phenoxyphenyl) phosphanyl chloride (B-114_5) in tetrahydrofuran was added. A solution was obtained.
(3) n-Butyllithium (2.5 M, 12 mL, 30 mmol) was added dropwise at 0 ° C. to a dehydrated tetrahydrofuran (40 mL) solution of methoxymethyl phenyl ether (B-114 — 6, 4.2 g, 30 mmol). The mixture was gradually warmed to room temperature and further stirred at room temperature for 1 hour. Thereafter, the mixture was cooled to −30 ° C., and a tetrahydrofuran solution of B-114 — 5) obtained in (2) was added dropwise thereto. After the addition, the mixture was gradually warmed to room temperature and stirred at room temperature overnight. Water (50 mL) was added to the mixture, stirred for 10 minutes, and then the organic solvent was removed under reduced pressure. Then, after extracting with ethyl acetate (50 mL × 3), the extract was concentrated, and the resulting residue was purified by silica gel chromatography (petroleum ether: ethyl acetate = 50: 1) to give methoxymethyl (2- (2,6 -Diphenoxyphenyl) (2-phenoxyphenyl) phosphanylphenyl) ether was obtained (B-114_7, 2 g, purity 62%).
And by repeating (3), 8.1g (purity 75%) of B-114_7 was obtained. By recrystallizing it from diethyl ether, B-114_7 was obtained (5.5 g, purity 92%).
(4) n-Butyllithium (2.5 M, 3.2 mL, 9.2 mmol) was added dropwise at 0 ° C. to a dehydrated tetrahydrofuran (50 mL) solution of B-114_7 (5.5 g, 9.2 mmol). The mixture was gradually warmed to room temperature, and further stirred at room temperature for 2 hours. Thereafter, the mixture was cooled to 0 ° C., hexafluorobenzene (5.4 mL, 46 mmol) was slowly added dropwise thereto, and the mixture was gradually warmed to room temperature and then stirred at room temperature overnight. Methanol (20 mL) was added to the reaction solution, and after stirring for 10 minutes, the organic solvent was removed under reduced pressure. Then, after extracting with ethyl acetate (50 mL × 3), the extract was concentrated, and the resulting residue was purified by silica gel chromatography (petroleum ether: ethyl acetate = 100: 1) to give methoxymethyl (2- (2,6 -Diphenoxyphenyl) (2-phenoxyphenyl) phosphanyl-6- (pentafluorophenyl) phenyl) ether was obtained (B-114_8, 1.6 g, purity 94%).
And by repeating (4), B-114_8 (10 g, purity 85%) was obtained, and then B-114_8 was obtained by HPLC purification (6 g, 7.8 mmol).
(5) The compound (B-114_8, 6.0 g, 7.8 mmol) obtained in (4) was added to an ethyl acetate solution of hydrogen chloride (4M, 100 mL) at 0 ° C. The resulting mixture was gradually warmed to room temperature and then stirred at room temperature for 2 hours. The solvent was removed, and ethyl acetate (50 mL) and saturated aqueous sodium hydrogencarbonate (50 mL) were added to the residue, followed by stirring for 30 minutes. Then, extraction operation was performed with ethyl acetate, and the organic layer was washed with saturated brine. After dehydration with sodium sulfate, sodium sulfate was filtered off, and the solvent was distilled off under reduced pressure and concentrated. The obtained crude product was purified by silica gel chromatography (petroleum ether: ethyl acetate = 40: 1) to give 2- (2,6-diphenoxyphenyl) (2-phenoxyphenyl) phosphanyl-6- (pentafluorophenyl). ) Phenol was obtained (5.0 g, 6.9 mmol, 88%)
¹ H NMR (CDCl 3, δ, ppm): 6.55-6.65 (m, 2H), 6.70-6.74 (m, 1H), 6.75-6.82 (m, 4H), 6.82-6.87 (m, 2H), 6.87-6.95 (m, 1H), 6.95-7.30 (m, 15), 7.65-7.77 (m, 1H) ); ³¹ P NMR (CDCl 3, δ, ppm): −54.0 (s).

Formation of Complex 145 mg (200 μmol) of the following B-114 was weighed out 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-114 and stirred for 30 minutes in a hot water bath at 40 ° C., so that B-114 and Ni (COD 20 ml of a 10 mmol / l solution of the reaction product of 2) was obtained.

Copolymerization of ethylene and 4-hydroxybutyl acrylate glycidyl ether (4-HBAGE) In an autoclave with a stirring blade having an internal volume of 2.4 liters, 1000 ml of dry toluene, 36.6 mg of tri-n-octylaluminum (TNOA) ( 0.10 mmol) and 1.8 ml (10 mmol) of 4-HBAGE. The temperature of the autoclave was raised to 90 ° C. while stirring and nitrogen was supplied to 0.3 MPa. Then, ethylene was supplied to a pressure of 2.8 MPa so that the ethylene partial pressure was 2.5 MPa. After the temperature and pressure were stabilized, 2.0 ml (20 μmol) of the previously prepared B-114-Ni complex solution was injected with nitrogen to initiate copolymerization. The temperature was kept at 90 ° C. during the reaction. After polymerization for 46 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 residual polar group-containing monomer was removed, and finally 32 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. In Table 1, the polymerization activity represents the copolymer yield (g) per 1 mol of the complex used for the polymerization. Since ethylene is not replenished in this polymerization method, the ethylene partial pressure at the end of the polymerization is lower than that at the start of the polymerization. The ethylene partial pressure in Table 1 is expressed as “2.5 → 1.5” because the ethylene partial pressure at the start of polymerization is 2.5 MPa and the ethylene partial pressure at the end of polymerization is 1. .5 MPa.
The polymerization activity was calculated on the assumption that B-114 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.

[Comparative Example 1]
Ethylene homopolymerization polar group-containing comonomer and tri-n-octylaluminum (TNOA) were not used, the amount of transition metal complex was 0.2 μmol, the polymerization pressure was 3.0 MPa, the polymerization temperature was 100 ° C., and the polymerization time was 30 minutes. Except for this, the same procedure as in Example 4 was performed. The polymerization conditions and polymerization results are shown in Table 1, and the physical property measurement results are shown in Table 2.

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

[Comparative Example 3]
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]
In Examples 1 to 16, all polar group structural unit amounts are 0.001 mol% or more, and have practically sufficient adhesiveness with polyamide. Further, Examples 1 to 14 have a weight average molecular weight (Mw) of 33,000 or more, and show excellent adhesion with polyamide. In comparison, Comparative Example 1 does not contain polar groups and does not adhere to the polyamide at all. From this, it was shown that if the amount of the polar group structural unit contained in the polar group-containing olefin copolymer is 0.001 mol% or more, it has sufficient adhesion with a highly polar substrate.
Examples 1 to 3 and Examples 4 to 15 and Example 16 are polar group-containing olefin copolymers produced by different production methods. Even if it is the polar group containing olefin copolymer manufactured by any manufacturing method, each has shown sufficient adhesiveness. This fact is not particularly limited as long as it is a production that polymerizes in the presence of a specific transition metal catalyst in producing a polar group-containing olefin copolymer having sufficient adhesion performance with a highly polar material, It showed that the manufacturing method of the polar group containing olefin copolymer in connection with this invention is not limited.
Example 11 and Example 12 are not limited to polyamide resin, and EVOH, polyester, and fluororesin have practically sufficient adhesiveness. From this fact, it is clear that the polar group-containing olefin copolymer of the present invention has sufficient adhesiveness not only with specific polar materials but also with various polar materials. I made it.
Examples 1 to 16 also show sufficient chemical resistance while having high adhesiveness. On the other hand, Comparative Example 2 and Comparative Example 3 have sufficient adhesion performance but insufficient chemical resistance. This is presumed to be due to the difference in molecular structure. Since Examples 1 to 16 are produced in the presence of a transition metal catalyst, the molecular structure is linear. However, it is known that Comparative Example 2 and Comparative Example 3 are produced by a high-pressure method process, and the molecular structure is considered to be a structure having an excessive number of short chain branches and long chain branches. It is considered that this difference in structure gives a difference in the swelling property of the amorphous part due to the chemical, and the chemical resistance is also different. From this result, it is confirmed that the polar group-containing olefin copolymer according to the present invention is a polar group-containing olefin copolymer having excellent chemical resistance while having high adhesion to a highly polar base material. Indicated.
The significance and rationality of the configuration of the present invention (invention specific matter) and the superiority over the prior art are clarified by the good results of each of the above examples and the comparison with each comparative example.

  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, making it possible to produce industrially useful laminates. . In addition, the 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. Laminated on various base materials, 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, and electronics such as electronics and household appliances Used in the electric wire field such as electric wires and cables.

Claims (17)

A polar group containing an epoxy group represented by the following structural formula (I) or the following structural formula (II) having a structural unit amount derived from ethylene or an α-olefin having 3 to 20 carbon atoms of 99.999 to 80 mol% A polar group-containing olefin copolymer comprising 20 to 0.001 mol% of structural units derived from at least one monomer, and having a molecular structure directly obtained by copolymerization in the presence of a transition metal catalyst. A polar group-containing olefin copolymer, which is a chain-like and random copolymer, and the amount of aluminum (Al) remaining in 1 g is 10,000 μg _Al / g or less .
Structural formula (I)

(In the structural formula (I), R1 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R2, R3, and R4 are each independently the following specific functions including a hydrogen atom, a hydrocarbon group, or an epoxy group. And any one of R2 to R4 is a specific functional group including an epoxy group.
Specific functional group: a group that contains an epoxy group as essential and has a molecular structure consisting of carbon, oxygen, and hydrogen)
Structural formula (II)

(In the structural formula (II), R5 to R8 each independently represents a specific functional group including a hydrogen atom, a hydrocarbon group, or an epoxy group, and any one of R5 to R8 represents an epoxy group. In addition, m is 0-2.
Specific functional group: a group that contains an epoxy group as essential and has a molecular structure consisting of carbon, oxygen, and hydrogen) The polar group-containing olefin copolymer has a melting point of 50 ° C. to 140 ° C. expressed by the temperature at the maximum peak position of an absorption curve measured by a differential scanning calorimetry (DSC) method. The polar group-containing olefin copolymer according to claim 1. The weight average molecular weight (Mw) determined by gel permeation chromatography (GPC) of the polar group-containing olefin copolymer is 1,000 to 2,000,000. Alternatively, the polar group-containing olefin copolymer according to claim 2. The weight average molecular weight (Mw) determined by gel permeation chromatography (GPC) of the polar group-containing olefin copolymer is 33,000 to 2,000,000. The polar group-containing olefin copolymer described in any one of claims 3 to 4. The polar group-containing monomer containing the epoxy group is the above structural formula (I), the specific functional group essentially includes an epoxy group, and further includes any one of a hydrocarbon group, a carbonyl group, and an ether group. The polar group-containing olefin copolymer according to any one of claims 1 to 4, wherein the polar group-containing olefin copolymer is a group having a molecular structure composed of a carbon atom, an oxygen atom, and a hydrogen atom. The polar group-containing olefin copolymer is a copolymer polymerized in the presence of a group 5-11 metal transition metal catalyst having a chelating ligand. Item 6. The polar group-containing olefin copolymer described in Item 5. The polar group-containing olefin copolymer is a copolymer polymerized in the presence of a transition metal catalyst in which a triarylphosphine or a triarylarsine compound is coordinated to palladium or nickel metal. The polar group-containing olefin copolymer according to any one of claims 1 to 6. The adhesive material containing the polar group containing olefin copolymer described in any one of Claims 1-7. A laminate comprising at least the polar group-containing olefin copolymer described in any one of claims 1 to 8 or a layer containing an adhesive and a base material layer. The base material layer according to claim 9, 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, wherein the base material layer is a polyamide resin, a fluorine resin, a polyester resin, or an ethylene-vinyl alcohol copolymer (EVOH). By laminating with one or more substrate layers using the polar group-containing olefin copolymer according to any one of claims 1 to 8, or a laminate material containing an adhesive. A laminated laminate characterized by being laminated.   An extruded product comprising the polar group-containing olefin copolymer according to any one of claims 1 to 8, or an adhesive. A multilayer coextrusion molded article comprising at least the polar group-containing olefin copolymer described in any one of claims 1 to 8 or a layer containing an adhesive and a base material layer. An injection-molded product comprising the polar group-containing olefin copolymer according to any one of claims 1 to 8, or an adhesive. The polar group-containing olefin copolymer according to any one of claims 1 to 8, or a member containing an adhesive and a base material are combined by injection molding. Combined injection molded products A polar group-containing olefin copolymer-coated metal member, wherein the polar group-containing olefin copolymer or the adhesive according to any one of claims 1 to 8 is coated with a metal.

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