JP6316053B2 - Olefin resin composition - Google Patents

Description

The present invention relates to an olefin resin composition containing a polar group-containing olefin copolymer and an olefin resin, and a laminate using the same, and more specifically, a polar group-containing olefin copolymer containing a specific polar group. An olefinic resin composition containing a coalescence and an olefinic resin at a specific ratio, and has excellent adhesion performance to various base materials, an olefinic resin composition, a laminate, and a composite It relates to the product.

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

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

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

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

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

  On the other hand, when a conventional metallocene catalyst is used to copolymerize ethylene and a polar group-containing monomer, it has been said that catalytic polymerization activity is reduced and polymerization is difficult. A method of polymerizing a polar group-containing olefin copolymer in the presence of a catalyst coordinated to a transition metal has been proposed (see Patent Documents 5 to 8). According to these methods, although it has a high elastic modulus and mechanical strength compared with the polar group-containing olefin copolymer obtained by the high-pressure radical process, it is possible to increase the polar group content. 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.

Moreover, the polar group containing olefin copolymer proposed by patent document 2-patent document 9 is touched by the manufacturing method of the polar group containing olefin copolymer, and adhesiveness with a specific base material. However, there is no mention of a specific method when blended with other olefinic resins and various physical properties such as adhesiveness of the resin composition obtained thereby. Furthermore, when increasing the polar group content for the purpose of improving the adhesive performance, a decrease in crystallinity is inevitable, and as the content increases, heat resistance, mechanical properties, rigidity, etc. decrease. Cannot solve the problem.

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, An olefin-based resin composition containing an epoxy group-containing polar group-containing olefin copolymer, which is produced without depending on the method, and exhibits excellent adhesion performance to various kinds of highly polar different materials The proposal of the olefin resin composition containing a polar group containing olefin copolymer and the laminated body using the same was 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

  The object of the present invention is based on the conventional problems described above as the background art, and is produced by a simple and efficient polymerization method, regardless of any conventional method, including each problem. Proposing an olefin-based resin composition containing a polar group-containing olefin that has a linear molecular structure and is a random copolymer, and the adhesion performance that is characteristic of the polar group-containing olefin copolymer is Olefinic resin composition having various physical properties such as mechanical properties, impact resistance, long-term durability, heat resistance, moldability, etc. obtained by blending various olefinic resins while maintaining It is an object of the invention to provide the above.

In order to solve the above-mentioned problems, the present inventors aim to produce the copolymer by a simple and efficient production method in the production of the polar group-containing olefin copolymer. The selection was verified. As a result, the present inventors first copolymerize ethylene or an α-olefin having 3 to 20 carbon atoms and a specific polar group-containing monomer in the presence of a transition metal catalyst such as a so-called postmetallocene catalyst. A novel polar group-containing olefin copolymer satisfying a specific structural unit amount ratio is found in the application on the same day as the present application. . However, a monomer containing a polar group is generally economically disadvantageous as compared with ethylene and α-olefin, which are main constituent monomers of an olefin resin. Olefin-based resin material with excellent adhesiveness and excellent economic properties of polar group-containing olefin copolymer obtained by copolymerizing monomer containing polar group and monomer selected from ethylene and α-olefin Is required. Based on this, a resin material that contributes well to economic efficiency, has sufficient adhesion performance with highly polar substrates, etc., and also has the performance of an olefin resin with excellent physical properties. Further studies were conducted to obtain it.
After examining the composition ratio of the olefin resin mixed with the polar group-containing olefin copolymer and the type of base material to be adhered, etc., the polar group-containing olefin copolymer having a specific molecular chain structure was obtained. On the other hand, by blending other olefin-based resins at a specific blending ratio, the adhesiveness with various dissimilar materials is sufficiently maintained even though the total polar group content as the resin composition is reduced. It has been found that an olefin resin composition can be obtained. According to the present invention, various good physical properties can be added while having sufficient adhesiveness with various different materials, which could not be achieved with the polar group-containing olefin copolymer alone, and also economical. An excellent olefin resin composition can be obtained, leading to the creation of the present invention.

That is, the object of the present invention is to add the olefinic resin at a specific ratio to the polar group-containing olefin copolymer, thereby imparting the excellent physical properties of the olefinic resin while making the economy more advantageous, and polar An object of the present invention is to provide a resin composition that maintains sufficient adhesion performance of a group-containing olefin copolymer to a highly polar different material.
And as a component of the olefin-based resin composition, a copolymer obtained by polymerizing a specific polar group-containing monomer is essential as a main component, and a specific polar group-containing olefin copolymer and It is an olefin resin composition that can be mixed with an olefin resin in a specific ratio, thereby providing excellent economic efficiency, adhesiveness, and various other physical properties selected as required. It is characterized by its remarkable effect when applied to laminates and composite products.

  Specifically, the present invention provides a molecule obtained by copolymerizing ethylene and / 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. An olefin resin composition (C) comprising a polar group-containing olefin copolymer (A) having a linear structure and random copolymer, and an olefin resin (B), the olefin resin (B) ) Based on olefin-based olefin copolymer (A) (100 parts by weight), the basic invention (first invention) And

The subordinate inventions, which are embodiment inventions that follow the basic invention of the present invention, will be described in order. In the second invention of the present invention, the polar group-containing monomer containing the epoxy group is represented by the following structural formula (I) or A polar group-containing monomer containing an epoxy group represented by the following 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)

  3rd invention of this invention is 99.999-80 mol% of structural unit amounts derived from ethylene or a C3-C20 alpha olefin in this polar group containing olefin copolymer (A), epoxy group. The amount of structural units derived from the polar group-containing monomer to be contained is 20 to 0.001 mol%, which is the olefin-based resin composition in the first or second invention.

  According to a fourth aspect of the present invention, the olefin resin (B) is a homopolymer and / or a copolymer obtained by polymerizing a monomer selected from ethylene and / or an α-olefin having 3 to 20 carbon atoms. The olefin-based resin composition according to any one of the first to third inventions, which is a coalescence.

According to a fifth aspect of the present invention, the olefin resin (B) is an ethylene homopolymer or a copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms. It is an olefin resin composition in the 4th invention.

According to a sixth aspect of the present invention, the polar group-containing olefin copolymer (A) has a melting point represented by the temperature at the maximum peak position in the absorption curve measured by differential scanning calorimetry (DSC). It is the range of 50-140 degreeC, It is the olefin resin composition in the 1st-5th invention characterized by the above-mentioned.

  The seventh invention of the present invention is a copolymer obtained by polymerizing the polar group-containing olefin copolymer (A) in the presence of a transition metal catalyst of a Group 5-11 metal having a chelating ligand. The olefin-based resin composition according to any one of the first to sixth inventions.

In an eighth aspect of the present invention, the polar group-containing olefin copolymer (A) is polymerized in the presence of a transition metal catalyst in which a triarylphosphine or a triarylarsine compound is coordinated to palladium or nickel metal. It is an olefin resin composition in the 1st-7th invention characterized by being a polymer.

  According to a ninth aspect of the present invention, there is provided a laminate including at least the olefin-based resin composition according to the first to eighth aspects and a base material layer.

  The tenth invention of the present invention is characterized in that the base material layer is selected from olefin resins, highly polar thermoplastic resins, metals, vapor-deposited films of inorganic oxides, papers, cellophane, woven fabric, and non-woven fabric. It is a laminated body in the ninth invention.

An eleventh aspect of the present invention is the laminate according to the tenth aspect, wherein the base material layer is a polyamide resin or a fluorine resin.

  The twelfth invention of the present invention uses a laminate material comprising the olefin resin composition according to the first to eighth inventions, and is laminated by laminating with one or more base material layers. This is a laminate laminate.

  A thirteenth aspect of the present invention is an extrusion-molded product comprising the olefin resin composition according to the first to eighth aspects.

  A fourteenth invention of the present invention is a multilayer coextrusion molded article comprising at least a layer comprising the olefin resin composition in the first to eighth inventions and a base material layer.

  A fifteenth aspect of the present invention is an injection-molded article comprising the olefin resin composition according to the first to eighth aspects.

  According to a sixteenth aspect of the present invention, there is provided a composite injection molding characterized in that a member comprising the olefin resin composition according to the first to eighth aspects and a base material are combined by injection molding. It is a product.

  The seventeenth invention of the present invention is a polar group-containing olefin copolymer-coated metal member, characterized in that the olefin resin composition in the first to eighth inventions is coated with a metal.

  In addition, this invention makes a polar group containing olefin copolymer (A) by making a specific novel polar group containing olefin copolymer (A) into a resin composition (C) with an olefin resin (B). The olefin-based resin composition is provided with various other physical properties while sufficiently maintaining the excellent adhesive performance), and such a composition cannot be obtained from conventional patent documents.

  The olefin resin composition of the present invention comprises a polar group-containing olefin copolymer having a specific molecular structure, produced by a simple and efficient polymerization method, and a specific olefin resin in a specific range. By mixing, it has a high adhesiveness to other base materials, but is further accompanied by the physical properties of other olefinic resins selected as necessary, and is an economically advantageous resin composition. It has made it possible to produce industrially useful laminates and composite products. 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. The olefin-based resin composition obtained by mixing the polar group-containing olefin copolymer and the olefin-based resin according to the present invention in a specific range of blending ratio has excellent adhesiveness with various highly polar substrates, and various uses. For example, it is formed into a multilayer film, a multilayer blow bottle, etc. by extrusion molding, blow molding or the like, and can be used for a wide range of applications.

It is an image figure of the molecular structure of the olefin copolymer (a) polymerized by the high pressure radical method polymerization process, and the olefin copolymer (b) (c) polymerized using the metal catalyst. It is a graph which shows the mixture ratio of the polar group containing olefin copolymer (A-1) in an olefin resin composition, and the change of the adhesive strength with respect to polyamide. It is a graph which shows the compounding ratio of the polar group containing olefin copolymer (A-2) in an olefin resin composition, and the change of the adhesive strength with respect to polyamide. It is a graph which shows the compounding ratio of the polar group containing olefin copolymer (A-3) in an olefin resin composition, and the change of the adhesive strength with respect to polyamide. It is a graph which shows the mixture ratio of the polar group containing olefin copolymer (A-4) in an olefin resin composition, and the change of the adhesive strength with respect to a fluororesin. It is a graph which shows the compounding ratio of the polar group containing olefin copolymer (A-5) in an olefin resin composition, and the change of the adhesive strength with respect to polyamide. It is a graph which shows the mixture ratio of the polar group containing olefin copolymer (B-1) in an olefin resin composition, and the change of the adhesive strength with respect to polyamide. It is a graph which shows the compounding ratio of the polar group containing olefin copolymer (B-1) in an olefin resin composition, and the change of the adhesive strength with respect to a fluororesin.

  In the following, for the olefin resin composition (C) of the present invention, the polar group-containing olefin copolymer (A), and the olefin polymer (B), those production methods and compositions thereof are used. The layered product and the composite product which have been used will be described specifically and in detail for each item.

[I] Polar group-containing olefin copolymer (A)
(1) Basic features of polar group-containing olefin copolymer (A) The polar group-containing olefin copolymer (A), which is the main component in the present invention, is ethylene or an α-olefin having 3 to 20 carbon atoms. , A copolymer with an epoxy group-containing monomer, a random copolymer in which the monomer units are randomly copolymerized, and a copolymer having a substantially linear molecular structure. The molecular structure and production method of the polar group-containing olefin copolymer (A) are basically the same as those of the polar group-containing olefin copolymer described in Japanese Patent Application No. 2013-67402, which is a related invention of the present invention. It is.

  A 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 has already been used in graft modification, high-pressure radical polymerization and other polymerization methods described above. Although known, 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 is substantially the same. It is characterized by being linear, which is significantly different from known polar group-containing olefin copolymers.

The polar group-containing olefin copolymer (A) 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. It is characterized by being able to. 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 containing no polar group The monomer containing no polar group in the present invention is a monomer having one or more carbon-carbon double bonds in the molecular structure, and the elements constituting the molecule are carbon and hydrogen. If it is only, it will not limit, For example, a diene, a triene, an aromatic vinyl monomer, a cyclic olefin etc. are mentioned, Preferably, it is a butadiene, isoprene, styrene, vinylcyclohexane, cyclohexene, vinyl norbornene, 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 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 polar group-containing monomer is not particularly limited, but considering the ease of copolymerization in the presence of a transition metal catalyst and the handling of the polar group-containing monomer, the polar group-containing monomer represented by the structural formula (I) is More preferred.
Furthermore, among the polar 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 using the epoxy group-containing monomer, 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.

(4) Structural unit of polar group-containing olefin copolymer (A) The structural unit and the structural unit amount of the polar group-containing olefin copolymer (A) according to the present invention will be described.
A structure derived from one molecule of ethylene or an α-olefin having 3 to 20 carbon atoms and an epoxy group-containing monomer is defined as one structural unit in the polar group-containing olefin copolymer (A). And what represented the ratio of each structural unit in a polar group containing olefin copolymer (A) by mol% is a structural unit amount.

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

(6) Method for Measuring 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) × IX2 / (IA2-11 / 3 × 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)

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

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 (A) 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 phase angle δ (G * = 0.1 MPa) of the complex elastic modulus measured with a rotary rheometer at an absolute G * = 0.1 MPa is 40 degrees or more, the molecular structure is as shown in FIG. ) A linear structure as shown in (c) which has no long chain branching (b) or a structure having a small amount of long chain branching which does not affect the mechanical strength ( c). 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.

(8) Weight average molecular weight (Mw) of polar group-containing olefin copolymer (A)
The weight average molecular weight (Mw) of the polar group-containing olefin copolymer (A) according to the present invention is usually 1,000 to 2,000,000, preferably 5,000 to 1,000,000, and more preferably 8. , Preferably in the range of 8,000 to 800,000. If the Mw is less than 1,000, the physical properties such as mechanical strength and impact resistance are not sufficient, and if it exceeds 2,000,000, the melt viscosity becomes very high and the molding process becomes difficult.

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

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

(9) Melting point of polar group-containing olefin copolymer (A) The melting point of polar group-containing olefin copolymer (A) according to the present invention is the maximum peak temperature of the endothermic curve measured by a differential scanning calorimeter (DSC). Indicated by. 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] Method for Producing Polar Group-Containing Olefin Copolymer (A) The polar group-containing olefin copolymer (A) according to the present invention comprises ethylene and / or α having 3 to 20 carbon atoms in the presence of a transition metal catalyst. -Obtained by copolymerizing an olefin and an epoxy group-containing monomer.

(1) Polymerization catalyst of polar group-containing olefin copolymer (A) The type of polymerization catalyst used in the production of the polar group-containing olefin copolymer (A) according to the present invention is ethylene and / or 3 to 20 carbon atoms. Although it will not specifically limit if alpha-olefin and an epoxy-group-containing monomer can be copolymerized, For example, the 5-11 group transition metal compound which has a chelating ligand is mentioned.
Specific examples of preferred transition metals include vanadium atom, niobium atom, tantalum atom, chromium atom, molybdenum atom, tungsten atom, manganese atom, iron atom, platinum atom, ruthenium atom, cobalt atom, rhodium atom, nickel atom, palladium atom, A copper atom etc. are mentioned.
Among these, vanadium 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, the above-described transition metal. X ¹ represents oxygen, sulfur, − Represents SO ₃ — or —CO ₂ —, Y ¹ represents carbon or silicon, n represents an integer of 0 or 1, E ¹ represents phosphorus, arsenic, or antimony, R ³ and R ⁴ Each independently represents hydrogen or a hydrocarbon group that may contain a heteroatom having 1 to 30 carbon atoms, and R ⁵ each independently contains hydrogen, a halogen, or a heteroatom having 1 to 30 carbon atoms. R ⁶ and R ⁷ each independently represents hydrogen, halogen, a hydrocarbon group that may contain a heteroatom having 1 to 30 carbon atoms, OR ² , CO ₂ R ^{2 _{, CO 2 M ', C (}} O) N (R 1) 2, C (O) R 2 _{^{SR 2, SO 2 R 2,}} SOR 2, OSO 2 R 2, P (O) (OR 2) 2 -y (R 1) y, CN, NHR 2, N (R 2) 2, Si (OR 1) _3- x (R ¹ ) x, OSi (OR ¹ ) ₃ -x (R ¹ ) x, NO ₂ , SO ₃ M ′, PO ₃ M ′ ₂ , P (O) (OR ² ) ₂ M ′ or epoxy M ′ represents an alkali metal, alkaline earth metal, ammonium, quaternary ammonium, or phosphonium, x represents an integer from 0 to 3, and y represents an integer from 0 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. is 5-8, which may have a substituent on the ring may .R ¹ may not have the water Or .R ² C 1 -C representing a hydrocarbon group of 20, .L ¹ representing a hydrocarbon group having 1 to 20 carbon atoms, represents a ligand coordinated to M. Further, ^{R 3} and ^{L 1} is More preferably, they are transition metal complexes 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 (A) according to the present invention, after contacting the epoxy group-containing monomer and a small amount of the organometallic compound, in the presence of the transition metal catalyst, Polymerization activity can be further increased by copolymerizing ethylene and / or 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.

Residual amount of aluminum (Al) The amount of aluminum (Al) remaining in 1 g of the polar group-containing olefin copolymer (A) according to the present invention is preferably 100,000 µg _Al / g or less, more preferably not more than 000μg _Al / g, more preferably less 20,000 _Al / g, particularly preferably not more than 10,000 _[Al / g, a preferable less 5,000 micrograms _Al / g, or less 1,000 .mu.g _Al / g Is more preferable, and 500 μg _{Al 2} / g or less is most preferable. 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 (A) is expressed in μg.

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

The amount of aluminum (Al) contained in the polar group-containing olefin copolymer (A) is calculated from the amount of polymerization of alkylaluminum, and is measured by fluorescent X-ray analysis or inductively coupled plasma emission (ICP) analysis. May be. 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 (A) 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.

[II] Olefin resin (B)
(1) Basic Features of Olefin Resin (B) The olefin resin (B) according to the present invention is a high pressure radical polymerization method, a high, middle or low pressure method using a Ziegler type, Phillips type or single site catalyst and other known methods. Selected from the homopolymers obtained by polymerizing monomers selected from ethylene homopolymers and α-olefins having 3 to 20 carbon atoms, ethylene, and / or α-olefins having 3 to 20 carbon atoms. It can be selected from olefin copolymers containing at least one monomer.

(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) Homopolymer The homopolymer according to the present invention is obtained by polymerizing only one kind of monomer selected from ethylene or an α-olefin having 3 to 20 carbon atoms. More preferred homopolymers are ethylene homopolymers, propylene homopolymers, 1-butene homopolymers, 1-hexene homopolymers, 1-octene homopolymers, 1-dodecene homopolymers, and the like. Are ethylene homopolymer and propylene homopolymer.

(4) Olefin-based copolymer The olefin-based copolymer according to the present invention includes ethylene, a C3-C20 α-olefin, a cyclic olefin, a vinyl monomer that does not contain other polar groups, and a vinyl that contains polar groups. A copolymer obtained by polymerizing two or more monomers selected from monomers, containing at least one monomer selected from ethylene or an α-olefin having 3 to 20 carbon atoms This is an olefin copolymer. Two or more types of monomers may be used for the polymerization. Preferred as the olefin copolymer is a copolymer of ethylene and one or more α-olefins selected from C 3-20 α-olefins, one or more selected from ethylene and cyclic olefins. It is a copolymer with a cyclic olefin. More preferred is a copolymer of ethylene and one or more α-olefins selected from propylene, 1-butene, 1-hexene and 1-octene, and a copolymer of ethylene and norbornene. .

(5) Cyclic olefins Cyclic olefins related to the present invention include, for example, monocyclic olefins such as cyclohexene and cyclooctene, norbornene, norbornadiene, dicyclopentadiene, dihydrodicyclopentadiene, tetracyclododecene, tricyclopentadiene, dihydrotricyclo Examples thereof include polycyclic olefins such as pentadiene, tetracyclopentadiene, dihydrotetracyclopentadiene, and substituted products in which a functional group is bonded to these olefins. Especially, norbornene is mentioned as a preferable cyclic olefin. In general, an olefin copolymer obtained by copolymerization of norbornene has low hygroscopicity because the main chain skeleton has an alicyclic structure, and the addition polymer also has excellent heat resistance.

(6) Monomers that do not contain polar groups Monomers that do not contain polar groups according to the present invention have one or more carbon-carbon double bonds in the molecular structure, and the elements constituting the molecule are carbon and hydrogen. Monomer. Excluding the above ethylene and α-olefin, examples include diene, triene, aromatic vinyl monomer, and the like, preferably butadiene, isoprene, styrene, vinylcyclohexane, and vinylnorbornene.

(7) Monomers containing polar groups Monomers containing polar groups according to the present invention are not limited, but include, for example, carboxylic acid group or acid anhydride group-containing monomers (a), ester group-containing monomers (b), hydroxyl group-containing A monomer (c), an amino group-containing monomer (d), or a silane group-containing monomer (e) can be selected.

Examples of the carboxylic acid group or acid anhydride group-containing monomer (a) include α, β-unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid and itaconic acid, or anhydrides thereof, acrylic acid, methacrylic acid and furanic acid. , Unsaturated monocarboxylic acids such as crotonic acid, vinyl acetate and pentenoic acid. Examples of the ester group-containing monomer (b) include methyl (meth) acrylate, ethyl (meth) acrylate, (n-, iso-) propyl (meth) acrylate, (n-, iso-, tert-) butyl (meth) acrylate. Among them, methyl acrylate is particularly preferable. Examples of the hydroxyl group-containing monomer (c) include hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate. Examples of the amino group-containing monomer (d) include aminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, cyclohexylaminoethyl (meth) acrylate, and the like. Examples of the silane group-containing monomer (e) include unsaturated silane compounds such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetylsilane, and vinyltrichlorosilane.

(8) Method for Producing Olefin Resin (B) The method for producing the olefin resin (B) according to the present invention is not limited. For example, high-pressure radical polymerization, Ziegler-type, Phillips type or single-site catalyst is used. The low pressure method and other known methods can be exemplified. Examples of the olefin resin (B) include Japanese Patent Publication No. 55-14084, Japanese Patent Publication No. 58-1708, Japanese Patent Application Laid-Open No. 08-301933, Japanese Patent Application Laid-Open No. 09-286820, Japanese Patent Application Laid-Open No. 11-228635, JP 2003-064187, JP 2000-109521, JP 2003-51496, JP 2003-504442, JP 2003-53233, JP 8-325333, JP 9 -031263, JP-A-9-087440, JP-2006-265387, JP-2006-265388, JP-2006-282927, JP-A-2001-525457, JP-A-2004-531629. JP, 120-385, JP, 58-193, JP No. 9, No. 59-95292, No. 60-35005, No. 60-35006, No. 60-35007, No. 60-35008, Japanese Laid-Open Patent Publication No. 60-35209, Japanese Laid-Open Patent Publication No. 61-130314, Japanese Laid-Open Patent Publication No. 3-163088, European Patent Application Publication No. 420,436, US Pat. No. 5,055,438 And various manufacturing methods described in International Publication No. WO09 / 04257 and the like.

(9) Melt flow rate (MFR) of olefin resin (B)
The MFR of the olefin-based resin (B) is measured under the condition of a load of 2.16 kg at a temperature of 190 ° C. based on the condition D based on JIS K7120 (1999), and usually 0.01 to 100 g / 10 minutes, preferably It is desirable to be in the range of 0.1 to 80 g / 10 minutes, more preferably 0.3 to 50 g / 10 minutes. When the MFR exceeds 100 g / 10 min, the physical properties such as mechanical strength and impact resistance are not sufficient, and when it is less than 0.01 g / 10 min, the melt viscosity becomes very high and the molding process becomes difficult.

(10) Density of Olefin Resin (B) The density of the olefin resin (B) is measured in accordance with JIS K7112-A method (1999) and is usually 0.840 to 1.20 g / cm ³ , preferably 0.850~0.990g / cm ^3, more preferably 0.860~0.980g / cm ^3, it is desirable preferably in the range of 0.870~0.970g / cm ^3. When the density exceeds 1.20 g / cm ³ , physical properties such as impact resistance are not sufficient, and when it is less than 0.840 g / cm ³ , the heat resistance is inferior.

[III] Olefin resin composition (C)
(1) Basic Features of Olefin Resin Composition (C) The olefin resin composition (C) according to the present invention comprises an olefin resin (100 parts by weight) based on 100 parts by weight of the polar group-containing olefin copolymer (A). B) is blended in an amount of 1 to 99,900 parts by weight. The amount of the olefin resin (B) is preferably 1 to 99,000 parts by weight, more preferably 1 to 90,000 parts by weight, still more preferably 1 to 50,000 parts by weight, and particularly 1 to 19,900 parts by weight. Part is suitable. Even if the blending amount of the olefin resin (B) is less than 1 part by weight or more than 99,900 parts by weight, the adhesiveness of the olefin resin composition (C) becomes poor.

The polar group-containing olefin copolymer (A) contained in the olefin resin composition (C) may be used alone or in combination. Moreover, the olefin resin (B) contained in an olefin resin composition (C) may be individual, and plural may be used.

(2) Production Method of Resin Composition (C) The olefin resin composition (C) according to the present invention can be produced by a known method, for example, a polar group-containing olefin copolymer (A) and an olefin type. Resin (B) and other components added as desired are melt kneaded using a single screw extruder, twin screw extruder, kneader, Banbury mixer, reciprocating kneader (BUSS KNEADER), roll kneader, etc. A polar group-containing olefin copolymer (A), an olefin-based resin (B), and other components added as required, in a suitable good solvent (for example, carbonization of hexane, heptane, decane, cyclohexane, xylene, etc.) In a hydrogen solvent), and then the solvent is removed.

(3) Additives To add other functions to the olefin-based resin composition (C) according to the present invention without departing from the gist of the functions of the composition of the present invention, antioxidants, ultraviolet absorption Additives such as an agent, a lubricant, an antistatic agent, a colorant, a pigment, a crosslinking agent, a foaming agent, a nucleating agent, a flame retardant, a filler, and a conductive material may be blended.

(4) Other components The olefin resin composition (C) according to the present invention may be blended with various resin modifiers and the like without departing from the scope of the function of the composition of the present invention. Examples of the component include butadiene rubber, isobutylene rubber, isoprene rubber, natural rubber, nitrile rubber, petroleum resin, and the like, and these may be used alone or as a mixture.

[IV] Laminate (1) Material of Laminate The laminate of the present invention is a laminate comprising a layer composed of the olefin resin composition (C) related 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. In addition, the pouch container can be formed by facing the ethylene copolymer layer surfaces of the laminate and heat-sealing at least a part thereof. Specifically, for example, water packaging, general bags, liquid soup bags, liquid paper containers, lami raw fabrics, special shaped liquid packaging bags (standing pouches, etc.), standard bags, heavy bags, semi heavy bags, wrap films, It is suitably used for sugar bags, oil packaging bags, various packaging containers for food packaging, infusion bags and the like.

(3) Manufacture of laminates As processing methods, extrusion molding such as normal press molding, air-cooled inflation molding, air-cooled two-stage cooling inflation molding, high-speed inflation molding, flat die molding (T-die molding), water-cooled inflation molding, etc. 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 laminating, sand laminating, dry laminating, etc. A laminate that can be produced by laminating a laminate material containing the olefin resin composition (C) according to the present invention and at least one substrate layer. The laminate material in the present invention is a resin material containing the olefin resin composition (C) according to the present invention, which can be subjected to various known laminating methods. Extrusion laminating is a molding method in which a molten resin film extruded from a T-die is continuously coated and pressure-bonded on a substrate, and coating and adhesion are performed simultaneously. Sand laminating is a method in which a molten resin is poured between paper and a film to be laminated, and the molten resin acts as an adhesive to bond and laminate. Dehumidify the ambient humidity in the vicinity of the adhesive and / or adhesive application roll for laminating the film to be laminated with the material, warm the temperature of the adhesive and / or adhesive application roll, or apply a film sheet This is a method of drying the mating surface.
In the sand laminating process and the dry laminating process, the olefinic resin composition (C) related to the present invention is included, but on the side where it is formed, between the base material and the layer containing the olefinic resin composition (C). 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) Extruded product The extruded product according to the present invention is an extruded product obtained by molding the olefin resin composition (C) 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, the extrusion molded product obtained by extrusion 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 the extruded product is not completely melted and solidified. Further, post-processing may be added by various known methods such as bending, cutting, and reheating after the obtained extrusion-molded product.

(6) Multilayer coextrusion molded product The multilayer coextrusion molded product related to the present invention is a multilayer coextrusion molded product that can be molded by a known multilayer coextrusion molding, and the olefin resin composition related to the present invention. It is a multilayer coextrusion molded product including at least a layer containing (C). 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 olefin-based resin composition (C) according to the present invention and a suitable base material by a suitable molding method, thereby producing a multilayer film, a multilayer sheet, It can be manufactured as a known multilayer co-extrusion product such as a multilayer 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 is a layer containing the olefin-based resin composition (C) according to the present invention. And a base 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 produced 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 according to the present invention is a multilayer tubular molded article that can be molded by a known multilayer tubular molding method, and the olefin resin composition (C) according to the present invention. Is a multilayer tubular molded article including at least a layer containing a base material 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 includes a layer comprising the olefin resin composition (C) according to the present invention. A multilayer sheet including at least a base material 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 olefin resin composition (C) 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 member containing the olefin resin composition (C) according to the present invention, and a plurality of members are combined using injection molding. This is a composite injection-molded product that can be manufactured by making it. The composite injection molded article only needs to be composed of two or more kinds of materials. For example, even if two different kinds of members containing the olefin resin composition (C) of the present invention are composited. The member formed of the olefin resin composition (C) related to the present invention and the member formed of the base material may be combined. Further, three or more kinds of members may be combined. The compounded injection molded product according to the present invention can be molded by a known injection molding method capable of compounded injection molding. Although it may be a composite injection-molded product formed by combining two or more kinds of members containing the polar group-containing olefin copolymer olefin-based resin composition (C) related to the present invention, Considering the characteristic high adhesiveness with different materials, it is preferable to use a composite injection molded product that is combined with a member made of different materials. As an injection molding method capable of producing a composite injection molded product, a known method can be exemplified. For example, the olefin resin composition (C) according to the present invention is processed into a member in advance by a known method such as injection molding, extrusion molding, press molding, cutting, etc., and the member is inserted into the injection mold. Further, a method of compounding by injecting a base material, an olefin resin composition (C) according to the present invention in which the base material is processed into a member in advance and the base material member is inserted into an injection mold. And a multicolor injection molding machine having a plurality of injection units, the olefin resin composition (C) and the base material according to the present invention are sequentially placed in an appropriate order in the mold. The method of compounding by injecting into can be mentioned. In the composite injection-molded product 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 olefin resin composition (C) according to the present invention.

(13) Coated metal member The coated metal member according to the present invention can be produced by coating the metal with a metal coating material using the olefin resin composition (C) according to the present invention as a metal coating material. It is a covering 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.

[V] Other uses The olefin resin composition (C) according to the present invention is not only suitably used as the above adhesive resin material, but also polyolefin resins such as polypropylene resins, polyamide resins, polyester resins, polycarbonate resins. Various modifiers such as acrylic resin and polyvinyl chloride resin, or 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 compatibilizer.
Other applications include steel pipe coating, wire coating, wire coating, drum cans and tank inner wall coatings, or coupling materials used for flame retardants, filler dispersions such as talc and glass fiber. Etc. are suitably used.

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 according to the present invention, the production method of the olefin-based resin composition, 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 holding at 30 ° C. for 5 minutes, the absorption curve when the temperature was raised again at 10 ° C./min was measured, and the maximum peak temperature was taken as the melting point.

(4) Adhesive strength Adhesive strength is prepared by preparing a measurement sample processed into a press plate of an olefin-based resin composition and various substrate films, respectively, and laminating the two by hot pressing, It was measured by performing a peel test. 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 placed in a hot press mold having dimensions of 50 mm × 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 Polyamide Film Using a multi-layer T-die molding machine, after forming a two-layer, three-layer multilayer film in which the center layer is polyamide and both outer layers are LLDPE, the outer layer LLDPE is peeled off to form a polyamide having a thickness of 100 μm A single layer film was prepared. The film forming conditions are as follows.
Molding machine: 2 types, 3 layers T-die Molding temperature: 250 ° C. Layer structure: LLDPE / EVOH / LLDPE Film thickness: 300 μm (100 μm / 100 μm / 100 μm) Outer layer: LLDPE (manufactured by Nippon Polyethylene Co., Ltd. Brand: Novatec UF943) MFR = 2.0 g / 10 min, density = 0.937 / cm3 Intermediate layer: Polyamide (made by Toray Industries, Inc. Brand: Amilan CM1021FS)

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

[4] Preparation Method of Laminate of Polyamide Film and Olefin Resin Composition A measurement sample press plate obtained by the above press plate preparation method and a polyamide film obtained by the above polyamide film preparation method are 50 mm × The cut pieces of 60 mm were stacked, placed in a hot press mold with dimensions: 50 mm × 60 mm, thickness 0.5 mm, and pressed at 4.9 MPa for 5 minutes using a hot press machine with a surface temperature of 250 ° C. . Then, it transferred to the press machine with a surface temperature of 25 degreeC, it cooled by hold | maintaining for 3 minutes with the pressure of 4.9 Mpa, and the laminated body of the press board and polyamide of the measurement sample was prepared.

[5] Preparation method of laminate of fluororesin film and olefin resin composition Press plate of measurement sample obtained by the above press plate preparation method, and fluororesin film obtained by the above fluororesin film preparation method Are cut into a size of 50 mm × 60 mm, placed in a hot press mold having dimensions of 50 mm × 60 mm and a thickness of 0.5 mm, and using a hot press with a surface temperature of 200 ° C. for 3 minutes at 4.9 MPa. Pressurized. 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.

[6] Method for Measuring Adhesive Strength of Laminate The laminate obtained by the method for preparing a laminate is cut to a width of 10 mm, and using a Tensilon (Toyo Seiki Co., Ltd.) tensile tester, the speed is 50 mm / min. The adhesive strength was measured by T-peeling. The unit of adhesive strength is indicated by gf / 10 mm. Further, when the adhesive strength is very strong, the olefin resin composition 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 olefin resin composition layer or the base material layer, and the adhesiveness is very high. It can be judged that it is 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) The measurement sample 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.

(6) Aluminum (Al) amount 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 addition amount of alkylaluminum polymerization Specifically, the calculation was performed according to 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 measurement 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.

(7) Melt flow rate (MFR)
MFR was measured according to JIS K7120 (1999) at a temperature of 190 ° C. under a load of 2.16 kg. Details are described above.

(8) Density was measured according to JIS K7112-A method (1999). Details are described above.

[Production Example 1] Production of polar group-containing olefin copolymer (A-1)
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 and tri-n-octylaluminum (TNOA) were added. 54.9 mg (0.15 mmol) and 2.7 ml (15 mmol) of 4-HBAGE were charged. The temperature of the autoclave was raised to 105 ° C. while stirring, 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, 3.0 ml (30 μmol) of the previously prepared B-27DM-Ni complex solution was injected with nitrogen to initiate copolymerization. During the reaction, the temperature was maintained at 105 ° C., and ethylene was continuously supplied so that the pressure was maintained. After polymerization for 60 minutes, the reaction was stopped by cooling and depressurization. The reaction solution was poured into 1 liter of acetone to precipitate 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 38 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. 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.

[Production Examples 2 to 4] Production of polar group-containing olefin copolymer (A-2, A-3, A-4) Among the methods described in Production Example 1, the amount of ligand, the polar group-containing monomer concentration, The polar group-containing olefin copolymers of Production Examples 2 to 4 were prepared by changing the polymerization temperature and 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. In Table 2, “ND” means not measured.

[Production Example 5] Production of Polar Group-Containing Olefin Copolymer (A-5) Based on the method described in Production Example 1, polymerization was carried out without replenishing ethylene after the initiation of polymerization. At that time, the polar group-containing olefin copolymer of Production Example 5 was prepared by performing polymerization while changing the ligand amount, the polar group-containing monomer concentration, the polymerization temperature, and the polymerization time. 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. 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.

[Production Example 6] Production of polar group-containing olefin copolymer (A-6)
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 the 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 reaction product 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 and tri-n-octylaluminum (TNOA) were added. 36.6 mg (0.10 mmol) and 4-HBAGE 1.8 ml (10 mmol) were charged. 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.

[Production Example 7] Production of polar group-containing olefin copolymer (A-7)
Dren-based ligand: Synthesis of (2-isopropyl-phenyl) (2'-methoxy-phenyl) (2 '' -sulfonyl- phenyl) phosphine (I) Anhydrous benzenesulfonic acid (2 g, 12.6 mmol) ) Solution of normal butyl lithium hexane (2.5 M, 10 mL, 25.3 mmol) was slowly added dropwise at 0 ° C. and 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, 3H), 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.

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

Copolymerization of ethylene and 1,2-epoxy-9-decene After replacing an autoclave with a stirring blade having an internal volume of 2.4 liters with a stirring blade 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.

[Production Example 8] Production of polar group-containing olefin copolymer (A-8)
Copolymerization of ethylene and 4-hydroxybutyl acrylate glycidyl ether (4-HBAGE) Among the methods described in Preparation Example 7, 54 ml (0.3 mol) of 4-HBAGE was used as an epoxy group-containing monomer, and a transition metal was used. The same procedure as in Production Example 7 was carried out except that the amount of complex was 50 μmol, the polymerization temperature was 90 ° C., and the polymerization 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. In Table 2, “ND” means not measured.

Polar group-containing olefin copolymer (B-1)
A copolymer of ethylene and glycidyl methacrylate, and a polar group-containing olefin copolymer produced by a high-pressure process (brand name: BondFirst E) manufactured by Sumitomo Chemical Co., Ltd.
It is. Table 2 shows the physical properties of the polar group-containing olefin copolymer.

[Example 1]
Dry blend of 0.05 g of polar group-containing olefin copolymer (A-1) and 9.95 g of linear low density polyethylene (manufactured by Nippon Polyethylene Co., Ltd., trade name: F30FG, indicated as “LLDPE” in the table) Then, it was put into a small twin-screw kneader (model: MC15 manufactured by DSM Xplore) and melt-kneaded for 5 minutes. At that time, the barrel temperature was 180 ° C., and the screw rotation speed was 100 rpm. After 5 minutes, a rod-shaped olefin-based resin composition was extruded from a resin discharge port, placed on a stainless steel tray, and solidified by cooling at room temperature. The cooled olefin resin composition was cut into pellets to produce olefin resin composition pellets. The obtained pellets of the olefin-based resin composition were subjected to the above adhesive strength measurement, and the adhesive strength was measured. The adhesive strength measurement results are shown in Table 3.

[Examples 2-32]
Among the methods described in Example 1, the types of the polar group-containing olefin copolymer and the mixing ratios of the polar group-containing olefin copolymer and the linear low density polyethylene were changed to produce Examples 2-32. The olefin resin composition was manufactured. Tables 3 and 4 show the blending ratio of the raw material resins and the adhesion strength measurement results.

Example 33
3.0 g of polar group-containing olefin copolymer (A-7) and 7.0 g of linear low density polyethylene (manufactured by Nippon Polyethylene Co., Ltd., trade name: F30FG) are dry blended, and a small twin-screw kneader (DSM Xplore) Model type: MC15) and melt kneaded for 5 minutes. At that time, the barrel temperature was 180 ° C., and the screw rotation speed was 100 rpm. After 5 minutes, a rod-shaped olefin-based resin composition was extruded from a resin discharge port, placed on a stainless steel tray, and solidified by cooling at room temperature. The cooled olefin resin composition was cut into pellets to produce olefin resin composition pellets. The obtained pellets of the olefin-based resin composition were subjected to the above adhesive strength measurement, and the adhesive strength was measured. The adhesive strength measurement results are shown in Table 6.

Example 34
3.0 g of polar group-containing olefin copolymer (A-8) and 7.0 g of linear low density polyethylene (manufactured by Nippon Polyethylene Co., Ltd., trade name: F30FG) are dry blended, and a small twin-screw kneader (DSM Xplore) Model type: MC15) and melt kneaded for 5 minutes. At that time, the barrel temperature was 180 ° C., and the screw rotation speed was 100 rpm. After 5 minutes, a rod-shaped olefin-based resin composition was extruded from a resin discharge port, placed on a stainless steel tray, and solidified by cooling at room temperature. The cooled olefin resin composition was cut into pellets to produce olefin resin composition pellets. The obtained pellets of the olefin-based resin composition were subjected to the above adhesive strength measurement, and the adhesive strength was measured. The adhesive strength measurement results are shown in Table 6.

[Examples 35 to 39]
Except that the linear low density polyethylene of Example 34 was changed to the olefinic resin shown in Table 5, the olefinic resin compositions of Examples 35 to 39 were produced in the same manner as in Example 34, and the adhesive strength was measured. did. Table 5 shows the manufacturer, brand name, grade, monomer species used for polymerization, and physical properties of each olefin resin, and Table 6 shows the measurement results of adhesive strength. “LLDPE” in Table 5 represents linear low density polyethylene, respectively.

[Comparative Examples 1 to 10]
Of the methods described in Example 1, the type of polar group-containing olefin copolymer is the polar group-containing olefin copolymer (B-1), and the type of polar group-containing olefin copolymer is polar group-containing olefin copolymer. The olefin resin compositions of Comparative Examples 1 to 10 were manufactured by changing the blending ratio of the coalesced polymer and the linear low density polyethylene. Table 7 shows the blending ratio of the raw resin and the measurement results of the adhesive strength.

[Comparative Example 11]
10 g of linear low density polyethylene (manufactured by Nippon Polyethylene Co., Ltd., trade name: Novatec (F30FG), indicated as “LLDPE” in the table) is charged into a small twin-screw kneader (model: MC15, manufactured by DSM Xplore) Melt kneading for 5 minutes. At that time, the barrel temperature was 180 ° C., and the screw rotation speed was 100 rpm. After 5 minutes, a rod-shaped olefin-based resin composition was extruded from a resin discharge port, placed on a stainless steel tray, and solidified by cooling at room temperature. The cooled olefin resin composition was cut into pellets to produce olefin resin composition pellets. The obtained pellets of the olefin-based resin composition were subjected to the above adhesive strength measurement, and the adhesive strength was measured. The adhesive strength measurement results are shown in Table 7.

[Consideration of results of Examples and Comparative Examples]
Examples 1 to 7 are olefin resin compositions obtained by appropriately blending linear low density polyethylene (LLDPE) at a blending ratio of 1 to 99,900 parts by weight with respect to 100 parts by weight of the polar group-containing olefin copolymer (A-1). It is a thing. The blending ratio of the polar group-containing olefin copolymer (A-1) and the adhesive strength between the polyamides are summarized in FIG.
Comparative Examples 1, 2, 3, 5, 7, 9, and 10 were linear low density polyethylene (LLDPE) with respect to 100 parts by weight of the polar group-containing olefin copolymer (B-1) produced by the high pressure process. Is an olefin-based resin composition appropriately blended at a blending ratio of 1 to 99,900 parts by weight. The blending ratio of the polar group-containing olefin copolymer (B-1) and the adhesive strength with the polyamide are summarized in FIG. The olefin-based resin composition blended with the polar group-containing olefin copolymer (B-1) exhibits sufficient adhesiveness in a region where the blending ratio of the polar group-containing olefin copolymer (B-1) is large. As the ratio decreases, the adhesiveness decreases rapidly. On the other hand, the olefin resin composition in which the polar group-containing olefin copolymer (A-1) is blended maintains high adhesion regardless of the blending ratio of the polar group-containing olefin copolymer (A-1). As a result, if the olefin resin composition is a blend of a polar group-containing olefin copolymer produced in the presence of a transition metal catalyst and an olefin resin in a specific range, the blend ratio of the olefin resin Even if it was increased, it showed sufficient adhesion to highly polar materials.

Examples 1 to 23 and Examples 29 to 32 are polar group-containing olefin copolymers having different polar group contents (A-1, A-2, A-3, A-5, A- It is an olefin resin composition obtained by appropriately blending LLDPE at a blending ratio of 1 to 99,900 parts by weight with respect to 100 parts by weight of 6). The blending ratio of the polar group-containing olefin copolymer (A-2) and the adhesive strength with the polyamide are shown in FIG. 3, and the blending ratio of the polar group-containing olefin copolymer (A-3) and the adhesive strength with the polyamide are shown in FIG. FIG. 6 shows the blending ratio of the polar group-containing olefin copolymer (A-5) and the adhesive strength with the polyamide. These olefin-based resin compositions exhibit sufficient adhesiveness regardless of the blending ratio of the polar group-containing olefin copolymer. This fact clarified that the olefin resin composition according to the present invention exhibits sufficient adhesiveness regardless of the polar group structural unit amount of the polar group-containing olefin copolymer to be blended.

In Examples 33 to 39, 233 parts of various olefin resins are blended with 100 parts by weight of the polar group-containing olefin copolymer. Regardless of the MFR of the olefin resin, the density, and the monomer species subjected to the polymerization, the resulting olefin resin composition exhibits sufficient adhesion to the polyamide. This fact indicates that, regardless of the type and physical properties of the olefin resin, sufficient adhesion can be obtained if the polar group-containing olefin copolymer and the olefin resin are blended in a specific range of blending ratio. It is expressed.

Examples 24-28 are olefin-based resin compositions in which linear low-density polyethylene (LLDPE) is appropriately blended at a blending ratio of 1-99,900 parts by weight with respect to 100 parts by weight of the polar group-containing olefin copolymer (A-4). It is a thing. The blending ratio of the polar group-containing olefin copolymer (A-4) and the adhesive strength between the fluororesin are summarized in FIG. In Comparative Examples 2, 4, 6, 8, and 10, linear low density polyethylene (LLDPE) was added in an amount of 1 to 99 with respect to 100 parts by weight of the polar group-containing olefin copolymer (B-1) produced by a high pressure process. , An olefin resin composition appropriately blended at a blending ratio of 900 parts by weight. The blending ratio of the polar group-containing olefin copolymer (B-1) and the adhesive strength between the fluororesin are summarized in FIG. The resin composition in which the polar group-containing olefin copolymer (B-1) is blended exhibits sufficient adhesiveness in a region where the blending ratio of the polar group-containing olefin copolymer (B-1) is large. The adhesiveness decreases rapidly with the decrease. On the other hand, the resin composition containing the polar group-containing olefin copolymer (A-4) maintains high adhesion regardless of the blending ratio of the polar group-containing olefin copolymer (A-4). If the resin composition is a blend of a polar group-containing olefin copolymer and an olefin resin produced in the presence of a transition metal catalyst at a blending ratio in a specific range, the blending ratio of the olefin resin is increased. Also showed that it has sufficient adhesion to a highly polar material and that this trend is not limited to combinations with certain highly polar substrates.

The adhesion of the olefin resin composition obtained by blending an olefin resin with a polar group-containing olefin copolymer having a linear structure is maintained regardless of the blending ratio of the polar group-containing olefin copolymer and the olefin resin. The reason for this is not clear, but it is considered that the molecular structure of the polar group-containing olefin copolymer contained in the olefin-based resin composition should be a linear structure. Adhesion performance between a highly polar dissimilar material and an olefin copolymer is measured by a peel test as exemplified in JIS K6854-1-4 (1999) “Adhesive-Peel Adhesive Strength Test Method”. Although the numerical value is evaluated, the numerical value measured by this method is the sum of the chemical and physical bonding force at the interface between different materials and the cohesive force of the material or the stress at the time of deformation. Conceivable. The polar group-containing olefin copolymer produced by the high-pressure radical polymerization process has a highly branched molecular structure containing an excessive amount of short-chain branches and long-chain branches. Olefin resins having such a structure are known to have inferior mechanical properties, cohesive strength, impact resistance, etc., compared with olefin resins having a linear structure. It is inferred that the polymer also has this tendency. Even if the polar group-containing olefin copolymer produced by the high-pressure radical polymerization process has sufficient chemical bonds with different materials, the cohesive force is inferior to that of the polar group-containing olefin copolymer having a linear structure. As a result, the adhesiveness is considered to decrease.

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.

The polyolefin resin composition of the present invention is obtained by blending a polar group-containing olefin copolymer (A) having a specific molecular structure and resin physical properties with an olefin resin (B) in a specific range. High adhesiveness with the base material was developed, and industrially useful laminates could be produced. The resin composition that can be produced according to the present invention is excellent not only in adhesiveness but also in mechanical and thermal properties, and can be applied as a useful multilayer molded article. In the field of packaging materials, packaging containers, industrial materials such as fibers, pipes, fuel tanks, hollow containers and drums, civil engineering such as water-stopping materials, electronics such as electronics and household appliances, and electric wires such as electric wires and cables Be utilized.

Claims (17)

Ethylene and / or having 3 to 20 carbon atoms and α- olefin and a polar group-containing monomer containing an epoxy group, nickel (II), palladium (II) and platinum (II) of the element selected from Ranaru group Olefin containing a polar group-containing olefin copolymer (A) having a linear molecular structure and random copolymer obtained by copolymerization in the presence of a transition metal catalyst, and an olefin resin (B) The resin composition (C) is characterized in that the amount of the olefin resin (B) is 1 to 99,900 parts by weight with respect to 100 parts by weight of the polar group-containing olefin copolymer (A). An olefin-based resin composition. The olefin according to claim 1, wherein the polar group-containing monomer containing an epoxy group is a polar group-containing monomer containing an epoxy group represented by the following structural formula (I) or the following structural formula (II). -Based resin composition.
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)   In the polar group-containing olefin copolymer (A), the amount of structural units derived from ethylene or an α-olefin having 3 to 20 carbon atoms is 99.999 to 80 mol%, a structure derived from a polar group-containing monomer containing an epoxy group The olefin resin composition according to claim 1 or 2, wherein the unit amount is 20 to 0.001 mol%.   The olefin resin (B) is a homopolymer and / or copolymer obtained by polymerizing a monomer selected from ethylene and / or an α-olefin having 3 to 20 carbon atoms, The olefin resin composition described in any one of claims 1 to 3. The olefin-based resin (B) is an ethylene homopolymer or a copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms, according to any one of claims 1 to 4. 2. The olefin resin composition described in 1. Among the absorption curves measured by differential scanning calorimetry (DSC) of the polar group-containing olefin copolymer (A), the melting point represented by the temperature at the maximum peak position is in the range of 50 to 140 ° C. The olefin-based resin composition according to any one of claims 1 to 5, wherein Polar group-containing olefin copolymer (A), the presence of a chelating nickel having a ligand (II), palladium (II) and platinum (II) or Ranaru elemental transition metal catalyst selected from the group The olefin-based resin composition according to any one of claims 1 to 6, wherein the olefin-based resin composition is a copolymer that has been polymerized into an olefin resin. The polar group-containing olefin copolymer (A) 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 olefin resin composition described in any one of claims 1 to 7.   A laminate comprising at least the olefin resin composition according to any one of claims 1 to 8 and a base material layer.   The base material layer is selected from olefin resin, highly polar thermoplastic resin, metal, vapor-deposited film of inorganic oxide, paper, cellophane, woven fabric, and non-woven fabric, according to claim 9. Laminated body. The laminate according to claim 10, wherein the base material layer is a polyamide resin or a fluorine resin.   A laminate material comprising the olefin-based resin composition according to any one of claims 1 to 8 is used, and the laminate material is laminated by laminating with one or more base material layers. Laminated laminate.   The extrusion molded product formed by containing the olefin resin composition as described in any one of Claims 1-8.   A multilayer coextrusion molded article comprising at least a layer comprising the olefin-based resin composition described in any one of claims 1 to 8 and a base material layer.   An injection-molded article comprising the olefin-based resin composition according to any one of claims 1 to 8.   A composite injection-molded article, wherein a member comprising the olefin-based resin composition according to any one of claims 1 to 8 and a base material are combined by injection molding.   A polar group-containing olefin copolymer-coated metal member, wherein the olefin-based resin composition according to any one of claims 1 to 8 is coated with a metal.

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