JP6050270B2 - Olefin resin composition and laminate - 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 olefin resin composition containing a coalesced olefin resin having a melting point in a specific range at a specified ratio, and having an excellent adhesion performance to various base materials Moreover, it concerns a laminated body.

  Olefin 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, olefinic resins are non-polar, and when used in laminated materials, they have the disadvantage that their adhesion strength to other materials such as other synthetic resins, metals, and wood is extremely low or not bonded.

  Therefore, in order to improve adhesion with different materials, a method of grafting a polar group-containing monomer onto an olefin resin using an organic peroxide has been widely performed (for example, see Patent Document 1). However, this method causes intermolecular crosslinking between olefin resin molecular chains and molecular chain scission of olefin resin molecular chains in parallel with the grafting reaction. The problem that physical properties are not maintained 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.

  By increasing the polar group content in the polar group-containing olefin copolymer, the adhesiveness with different polar materials can be increased, but a large amount of polar group-containing monomer can be grafted onto the olefin resin by graft modification. Is not easy. 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 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 removing this leads to an increase in cost. 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.

  As a technique for improving the adhesiveness of the polar group-containing olefin copolymer that is polymerized in the presence of the transition metal catalyst, a method for increasing the epoxy group content contained in the polar group-containing olefin copolymer is conceivable. However, when the epoxy group content in the copolymer is increased by a method such as increasing the amount of the epoxy group-containing monomer to be used for polymerization, an improvement in adhesion is expected, but self-reaction between epoxy groups also occurs. It becomes easy. Due to self-reaction of the epoxy groups in the polar group-containing olefin copolymer, gelation by molecular chain crosslinking or excessive crosslinking proceeds, and the excellent physical properties possessed by the polar group-containing olefin copolymer In addition, the impact resistance, long-term durability, and the like are lowered, and the moldability is lowered due to an increase in melt viscosity. Therefore, the measure for improving the adhesion performance by increasing the epoxy group content in the polar group-containing olefin copolymer has a problem that it is difficult to achieve compatibility with mechanical properties and the like.

  By the way, in patent document 2-patent document 9, although polar group containing olefin copolymer, the manufacturing method of polar group containing olefin copolymer, and also adhesiveness with a specific base material are mentioned, polar No particular mention is made of physical properties such as adhesion when the olefin resin is blended with the group-containing olefin copolymer.

  In view of the above conventional methods, any method including a method of introducing a polar group into an olefin copolymer, such as graft modification, a high-pressure radical polymerization process, and a method using a large amount of organoaluminum, Adhesive performance without using a method to increase the epoxy group content in the polar group-containing olefin copolymer, including a polar group-containing olefin copolymer containing an epoxy group, which is produced regardless of the method. It can be said that development of a method for improving the quality is desired.

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

  In view of the conventional problems described above as the background art, the present invention incorporates the respective problems, and does not depend on any conventional method, and is produced by a simple and efficient polymerization method. Olefin-based resin composition comprising a polar group-containing olefin copolymer that has a molecular structure and a random copolymer, and has excellent mechanical properties possessed by the polar group-containing olefin copolymer It is an object of the invention to provide a resin composition containing a polar group-containing olefin copolymer for the purpose of achieving both improvement in impact resistance, long-term durability, moldability, etc. and improvement in adhesion with different materials. To do.

  As a result of intensive studies to solve the above problems, the present inventors have determined that the olefin resin having a specific range of melting point is a specified blending ratio with respect to a polar group-containing olefin copolymer having a specific molecular chain structure. It has been found that the adhesion performance is improved while maintaining the excellent mechanical properties, impact resistance, etc. of the polar group-containing olefin copolymer by blending with. According to the present invention, by blending an olefin resin having a melting point in a specific range with a polar group-containing olefin copolymer, compared with the case where the polar group-containing olefin copolymer is used alone, Adhesion performance can be dramatically improved and the epoxy group content in the olefin-based resin composition can be kept low. Crosslinking and gelation of molecular chains due to self-reaction of epoxy groups, resulting in mechanical properties and impact resistance. The possibility of impairing properties and moldability can also be avoided.

The object of the present invention is to blend an olefin resin having a melting point in a specific range with a polar group-containing olefin copolymer at a specified blending ratio, thereby adhering to different materials rather than using the polar group-containing olefin copolymer alone. It is to provide an olefin resin composition with improved performance.
As a constituent component of the olefin-based resin composition, an olefin-based resin that contains a specific polar group-containing olefin copolymer obtained by polymerizing an epoxy group-containing monomer as a main component and has a melting point in a specific range. Further, it is necessary that the resin is mixed in a specified composition ratio range. As a result, the adhesion with different materials is dramatically improved, and an olefin-based resin composition having excellent adhesion performance can be produced, and can exhibit remarkable effects when applied to a laminate.

  The present invention provides a polar group-containing olefin copolymer 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. Olefin resin (B), characterized in that the melting point represented by the temperature of the maximum peak position of the absorption curve measured by differential scanning calorimetry (DSC) is 30 to 124 ° C. 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). The olefin resin composition characterized by the above is defined as a basic invention (first invention).

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

（式中、Ｒ^１は水素原子または炭素数１〜１０のアルキル基、Ｒ^２、Ｒ^３、Ｒ^４はそれぞれ独立して、水素原子、炭化水素基、又はエポキシ基を含む下記の特定の官能基を示し、Ｒ^２〜Ｒ^４のいずれか１つ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 formula, R ¹ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R ² , R ³ , and R ⁴ are each independently the following specific functions including a hydrogen atom, a hydrocarbon group, or an epoxy group. And any one of R ^{2 to} R ⁴ 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)

（式中、Ｒ^５〜Ｒ^８はそれぞれ独立して、水素原子、炭化水素基、又はエポキシ基を含む下記の特定の官能基を示し、Ｒ^５〜Ｒ^８のいずれか１つはエポキシ基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）

(Wherein R ^{5 to} R ⁸ each independently represent a specific functional group including a hydrogen atom, a hydrocarbon group, or an epoxy group, and any one of R ^{5 to} R ⁸ 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 is 20 to 0.001 mol%, which is the olefin-based resin composition in the first or second invention.

  The fourth invention of the present invention 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 in the olefin resin (B). It is an olefin resin composition in the 1st-3rd invention characterized by being.

  According to a fifth 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 of an absorption curve measured by differential scanning calorimetry (DSC) of 50 ° C. It is the range of -140 degreeC, It is the olefin resin composition in the 1st-4th invention characterized by the above-mentioned.

  The sixth invention of the present invention is characterized in that the polar group-containing olefin copolymer (A) is polymerized in the presence of a transition metal catalyst of a Group 5-11 metal having a chelating ligand. The olefin-based resin composition in the first to fifth inventions.

  The seventh invention of the present invention is that 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. The olefin-based resin composition according to any one of the first to sixth inventions.

  The eighth invention of the present invention is a laminate including at least a layer made of the olefin-based resin composition in the first to seventh inventions and a base material layer.

  The ninth 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. This is the laminate in the eighth invention.

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

  In the present invention, the polar group-containing olefin copolymer (A) is blended at a specified composition ratio with an olefin resin (B) having a melting point in a specific range with respect to the polar group-containing olefin copolymer (A). (A) It provides an olefin resin composition (C) having improved adhesion performance and much better adhesion performance than the case where it is used alone. Absent.

  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 mixed at a specified blending ratio. By using the olefin-based resin composition, the adhesiveness is improved as compared with the case where the polar group-containing olefin copolymer is used alone, and the adhesive property is economically advantageous while having high adhesiveness with other base materials. And 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 at a specified blending ratio has excellent adhesiveness with various highly polar substrates, and various uses. For example, it can be formed into a multilayer film, a multilayer blow bottle or the like 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.

  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 laminated body 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 a copolymer with an epoxy group-containing monomer, which is a random copolymer obtained by random copolymerization of the monomer units, and a substantially linear copolymer having a molecular structure. is there. 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 has the requirement of being linear, and the like, which is significantly different from known polar group-containing olefin copolymers.

  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 (shown in the second to third inventions). It is obtained by polymerizing in the presence of 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%, and more preferably. It is desirable to select from the range of 95 to 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 to be used for polymerization may be used alone or in combination of two or more.

(3) Monomer not containing a polar group The monomer not containing a 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 becomes possible to laminate and adhere to a thermoplastic resin having a group and a metal material such as aluminum or steel.

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

（構造式（Ｉ）中、Ｒ^１は水素原子または炭素数１〜１０のアルキル基、Ｒ^２、Ｒ^３、Ｒ^４はそれぞれ独立して、水素原子、炭化水素基、又はエポキシ基を含む下記の特定の官能基を示し、Ｒ^２〜Ｒ^４のいずれか１つ以上がエポキシ基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), R ¹ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R ² , R ³ , and R ⁴ each independently include a hydrogen atom, a hydrocarbon group, or an epoxy group) And any one or more of R ^{2 to} R ⁴ are specific functional groups containing 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、Ｒ^５〜Ｒ^８はそれぞれ独立して、水素原子、炭化水素基、又はエポキシ基を含む下記の特定の官能基を示し、Ｒ^５〜Ｒ^８のいずれか１つはエポキシ基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 Structural Formula (II), R ^{5 to} R ⁸ each independently represent a specific functional group including a hydrogen atom, a hydrocarbon group, or an epoxy group, and any one of R ^{5 to} R ^8. Is a specific functional group including an epoxy group, and m is 0 to 2. Specific functional group: a group having an epoxy group as an essential component and having a molecular structure composed of a carbon atom, an oxygen atom, and a hydrogen atom )

The molecular structure of the epoxy group-containing monomer is not particularly limited, but considering the ease of copolymerization in the presence of a transition metal catalyst and the handling of the epoxy group-containing monomer, the epoxy group-containing monomer represented by the structural formula (I) is More preferred. Furthermore, among the epoxy group-containing monomers represented by the structural formula (I), R1 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R2, R3, and R4 are each independently a hydrogen atom, a hydrocarbon group, Or the monomer which is either the following specific functional groups containing an epoxy group, and any one or more 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 epoxy 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, 12-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 -Glycidyl ether of allylphenol, p -Unsaturated glycidyl ethers such as glycidyl ether of allylphenol, 4-hydroxybutyl (meth) acrylate, acrylic acid, methacrylic acid, glycidyl p-styrylcarboxylate, endo-cis-bicyclo [2,2,1] hept- 5-ene-2,3-dicarboxylic acid, endo-cis-bicyclo [2,2,1] hept-5-ene-2-methyl-2,3-dicarboxylic acid, itaconic acid, citraconic acid, butenetricarboxylic acid, Cyclic olefins containing epoxy groups such as glycidyl esters of unsaturated carboxylic acids such as epoxy hexyl norbornene, epoxy cyclohexane norbornene, methyl glycidyl ether norbornene, 2- (o-vinylphenyl) ethylene oxide, 2- (p-vinylphenyl) ) Ethylene oxide, 2- ( -Allylphenyl) ethylene oxide, 2- (p-allylphenyl) ethylene oxide, 2- (o-vinylphenyl) propylene oxide, 2- (p-vinylphenyl) propylene oxide, 2- (o-allylphenyl) propylene oxide, 2 -(P-allylphenyl) propylene oxide, p-glycidylstyrene, 3,4-epoxy-1-butene, 3,4-epoxy-3-methyl-1-butene, 3,4-epoxy-1-pentene, 3 , 4-epoxy-3-methyl-1-pentene, 5,6-epoxy-1-hexene, vinylcyclohexene monoxide, allyl-2,3-epoxycyclopentyl ether, 2,3-epoxy-5-vinylnorbornane, , 2-epoxy-4-vinylcyclohexane and other monomers containing an epoxy group It is possible to gel. Among these, 1,2-epoxy-9-decene, 4-hydroxybutyl acrylate glycidyl ether, glycidyl methacrylate, 1,2-epoxy-4-vinylcyclohexane and the like represented by the following structural formula are particularly preferable.
The epoxy group-containing monomer used for polymerization may be used alone or in combination of two or more.

１，２−ｅｐｏｘｙ−９−ｄｅｃｅｎｅ

1,2-epoxy-9-decene

４−ｈｙｄｒｏｘｙｂｕｔｙｌ ａｃｒｙｌａｔｅ ｇｌｙｃｉｄｙｌｅｔｈｅｒ

4-hydroxybutyryl glycidylether

ｇｌｙｃｉｄｙｌ ｍｅｔｈａｃｒｙｌａｔｅ

glycidyl methacrylate

１，２−ｅｐｏｘｙ−４−ｖｉｎｙｌｃｙｃｌｏｈｅｘａｎｅ

1,2-epoxy-4-vinylcyclohexane

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

(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 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. And what represented the ratio of each structural unit in a polar group containing olefin copolymer in mol% is a structural unit amount.

(5) Structural Unit Amount of Epoxy Group-Containing Monomer The amount of structural unit derived from these epoxy group-containing monomers is usually in the range of 20 to 0.001 mol%, preferably in the range of 15 to 0.01 mol%, more preferably 10. It is preferably selected from the range of -0.02 mol%, more preferably from the range of 5-0.03 mol%, and it is always present in the polar group-containing olefin copolymer of the present invention. If the amount of the structural unit derived from the epoxy group-containing monomer is less than this range, the adhesion with a different polar material is not sufficient, and if it exceeds this range, sufficient mechanical properties cannot be obtained.

(6) Measuring method of structural unit amount of epoxy group-containing monomer The structural unit amount of the epoxy group in the polar group-containing olefin copolymer according to the present invention is determined using a 1H-NMR spectrum. The 1H-NMR spectrum can be measured, for example, 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, and heated and dissolved to obtain a uniform solution for NMR measurement. 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 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-4-vinylcyclohexane (EP-VCH)]
The integrated intensity of the peak due to the polar group-containing olefin copolymer in the range of 0.3 to 3.2 ppm is IA2, and the integrated intensity of the peak due to the proton of EP-VCH contained in the copolymer around 3.0 ppm. Was calculated according to the following equation.
EP-VCH content (mol%) = 100 × IX2 / (0.5 × IA2-2 × IX2)

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

(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. A random copolymer of these copolymers is desirable.
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. Moreover, the molecular chain terminal of the polar group-containing olefin copolymer 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.

  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. Specifically, when the absolute value G * = 0.1 MPa of the complex elastic modulus measured with a rotary rheometer is 40 degrees or more, the molecular structure is as shown in FIG. b) A structure as shown in (c) containing no long-chain branch at all or a small amount of long-chain branch that does not affect the mechanical strength. 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), and molecular weight distribution parameter (Mw / Mn)
The weight average molecular weight (Mw) of the polar group-containing olefin copolymer (A) is usually 1,000 to 2,000,000, preferably 5,000 to 1,000,000, more preferably 8,000 to 800. Is desirably in the range of 1,000. 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 equation [η] = K × Mα used for conversion to molecular weight uses the following numerical values.
PS: K = 1.38 × 10 −4, α = 0.7
PE: K = 3.92 × 10 −4, α = 0.733
PP: K = 1.03 × 10−4, α = 0.78

(9) Melting | fusing point of polar group containing olefin copolymer (A) Melting | fusing point of the olefin resin (A) in connection with this invention is shown by the maximum peak temperature of the endothermic curve measured with the differential scanning calorimeter (DSC). The maximum peak temperature is the height from the baseline when DSC measurement shows multiple peaks in the endothermic curve when the heat flow (mW) is taken on the vertical axis and the temperature (° C) is taken on the horizontal axis. Indicates the maximum peak temperature, and when there is one peak, it indicates the peak temperature.
Assuming polyethylene, the melting point is preferably 50 ° C to 140 ° C, more preferably 60 ° C to 138 ° C, and most preferably 70 ° C to 135 ° C. If it is lower than this range, the heat resistance is not sufficient, and if it is higher than this range, the adhesiveness is poor.

(10) Method for Producing Polar Group-Containing Olefin Copolymer (A) The polar group-containing olefin copolymer (A) according to the present invention is an 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.

(11) Polymerization catalyst of polar group-containing olefin copolymer (A) The type of the polymerization catalyst used for the production of the polar group-containing olefin copolymer (A) according to the present invention is ethylene and / or C3-20. Although it will not be limited if it can copolymerize an alpha olefin and an epoxy-group-containing monomer, 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.
Of these, vanadium atom, iron atom, platinum atom, cobalt atom, nickel atom, palladium atom, 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 a catalyst comprising a Group 5-11 transition metal compound having a chelating ligand, there are typically known so-called SHOP-based and Drent-based 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).

(12) Organometallic compound In the production of the polar group-containing olefin copolymer (A) according to the present invention, after bringing the epoxy group-containing monomer and the organometallic compound into contact, in the presence of the transition metal catalyst, ethylene and Polymerization activity can be further enhanced by copolymerizing an α-olefin having 3 to 20 carbon atoms and an epoxy group-containing monomer.
The organometallic compound is an organometallic compound including a hydrocarbon group which may have a substituent, and can be represented by the following structural formula (H).
^{_{R 30 n M 30 X 30 m}} -n structure (H)
(In the formula, R ³⁰ represents a hydrocarbon group which may have a substituent having 1 to 12 carbon atoms, and M ³⁰ represents Group 1, Group 2, Group 12 and Group 13 of the periodic table. A metal selected from the group consisting of: X ³⁰ represents a halogen atom or a hydrogen atom, m is a valence of M ³⁰ and n is 1 to m.)

  Examples of the organometallic compound represented by the structural formula (H) include tri-n-butylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, tri-n-decylaluminum and other alkylaluminums, methylaluminum Examples include alkylaluminum halides such as dichloride, ethylaluminum dichloride, dimethylaluminum chloride, diethylaluminum chloride, and diethylaluminum ethoxide, and trialkylaluminum is preferably selected. More preferably, a trialkylaluminum having a hydrocarbon group having 4 or more carbon atoms, more preferably a trialkylaluminum having a hydrocarbon group having 6 or more carbon atoms, more preferably tri-n-hexylaluminum, -N-octylaluminum and tri-n-decylaluminum are selected, and tri-n-octylaluminum can be most preferably used.

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 2} / g or less, and 70,000 μg _{Al 2} / g. less, still more preferably less 20,000 _Al / g, or less and particularly preferably 10,000 _[Al / g, a preferable less _{5,000μg Al / g, 1,000μg Al /} g or less and more preferably Yes, 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 is expressed in μg.

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

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

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

(13) 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. As the polymerization format, any of batch polymerization, semi-batch polymerization, and continuous polymerization may be used. Moreover, living polymerization may be sufficient and it may superpose | polymerize, combining chain transfer. Furthermore, so-called chain shunting agent (CSA) may be used in combination to perform chain shunting reaction or coordinative chain transfer polymerization (CCTP). Specific manufacturing processes and conditions are disclosed in, for example, JP 2010-260913 A and JP 2010-202647 A.

[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 / medium / low pressure method using a Ziegler type, a Phillips type or a single site catalyst, and other publicly 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 to be 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 type of monomer selected from ethylene or an α-olefin having 3 to 20 carbon atoms. More preferable 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 related to the present invention includes ethylene, an α-olefin having 3 to 20 carbon atoms, a cyclic olefin, a monomer that does not contain other polar groups, a monomer that contains polar groups, A copolymer obtained by polymerizing two or more monomers selected from the group consisting of at least one monomer selected from ethylene or an α-olefin having 3 to 20 carbon atoms. It is an olefin copolymer. Two or more types of monomers may be used for the polymerization. Preferred as the olefin copolymer is a copolymer that essentially contains ethylene and further contains one or more α-olefins having 3 to 20 carbon atoms, and a copolymer that essentially contains ethylene and contains one or more cyclic olefins. It is. More preferred is a copolymer containing ethylene as essential, and a copolymer containing one or more selected from propylene, 1-butene, 1-hexene and 1-octene, and a copolymer of ethylene and norbornene. is there.

(5) Cyclic olefins Cyclic olefins according 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) Olefin-based copolymer containing a polar group As the olefin-based resin (B) according to the present invention, the polar group-containing olefin copolymer (A) contains a polar group having a molecular structure, a production method and a physical property range different from each other. The olefin copolymer thus prepared can be used as appropriate.
The olefin copolymer containing a polar group of the olefin resin (B) according to the present invention is a monomer selected from ethylene and / or an α-olefin having 3 to 20 carbon atoms, and a vinyl monomer containing a polar group. If it is a copolymer, it will not specifically limit. The monomer selected from ethylene and / or an α-olefin having 3 to 20 carbon atoms may be one type or two or more types, and the vinyl monomer containing a polar group may be one type or two or more types. But it ’s okay. Moreover, even if there are two monomers used for the polymerization of a copolymer of a monomer selected from ethylene and / or an α-olefin having 3 to 20 carbon atoms and a vinyl monomer containing a polar group, three types It may be above. A copolymer of a monomer selected from ethylene and / or an α-olefin having 3 to 20 carbon atoms and a vinyl monomer containing a polar group is preferably a copolymer of ethylene and a vinyl monomer containing a polar group It is.

  The vinyl monomer containing a polar group used for copolymerization of a monomer selected from ethylene and / or an α-olefin having 3 to 20 carbon atoms and a vinyl monomer containing a polar group is not limited. The acid group or acid anhydride group-containing monomer (a), ester group-containing monomer (b), hydroxyl group-containing monomer (c), amino group-containing monomer (d), or 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 The method for producing the olefin resin (B) according to the present invention is not limited. For example, a high-pressure radical polymerization method, a high-medium-low pressure method using a Ziegler-type, Phillips type or single-site catalyst, 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) Density of Olefin Resin (B) The density of the olefin resin (B) according to the present invention is measured according to JIS K7112. Assuming polyethylene, 0.840 to 0.932 g / cm ³ is preferable, 0.840 to 0.928 g / cm ³ is more preferable, 0.840 to 0.922 g / cm ³ is further preferable, and 0.840. ˜0.915 g / cm ³ is preferable, and 0.840 to 0.900 g / cm ³ is more preferable. If it is higher than this range, the adhesiveness is inferior. As the olefin resin (B) according to the present invention is more flexible, that is, the density is lower, the adhesion is improved. For the above reasons, the lower limit is not particularly limited. However, when polyethylene is assumed, it is difficult to produce an olefin resin having a density lower than 0.840 g / cm ³ .
On the other hand, density of the use of 0.890g ^/ cm ³ ~0.932g ^/ cm 3 of the olefin resin (B), it is possible to obtain a resin composition having both heat resistance as well as adhesion.

(10) Melting point of olefin resin (B) The melting point of the olefin resin (B) according to the present invention is indicated by the maximum peak temperature of the endothermic curve measured by a differential scanning calorimeter (DSC).
The melting point of the olefin resin used in the present invention is required to be 30 to 124 ° C, more preferably 30 to 120 ° C, still more preferably 40 to 115 ° C, and preferably 40 to 110 ° C, 40 to 100 ° C is more preferred. When it is higher than this range, the adhesiveness is poor. As the olefin resin (B) used in the present invention is more flexible, that is, the melting point is lower, the adhesion is improved. For the above reasons, the lower limit is not particularly limited, but when polyethylene is assumed, it is difficult to produce an olefin resin having a melting point lower than 30 ° C.
In addition, when olefin resin (B) whose melting | fusing point is 90 to 124 degreeC is used, the resin composition which has not only adhesiveness but heat resistance can be obtained.
In addition, the amount of heat of fusion ΔH (J / g) calculated from the peak area of the endothermic curve of DSC measurement depends on the crystallinity of the olefin resin. Therefore, as the crystallinity of the olefin resin decreases, ΔH Decreases and the endothermic curve peak becomes difficult to observe. That is, the melting point defined by the maximum peak temperature of the endothermic curve may not be measured with an olefin resin having a low crystallinity. The gist of the present invention is to blend flexible olefinic resins, and even if the melting point cannot be defined, such a resin may be used as long as it is a flexible resin with low crystallinity. (The heat of fusion ΔH (J / g) is a value calculated from the peak area of the endothermic curve obtained when the heat flow (mW) on the vertical axis and the temperature (° C.) on the horizontal axis in DSC measurement, (The amount of total heat energy absorbed when the crystals contained in 1 g of the sample are melted is expressed in J units.)

[III] Olefin resin composition (C)
(1) Basic features of olefin resin composition (C) The olefin resin composition (C) according to the present invention is an olefin resin (100 parts by weight) based on 100 parts by weight of the polar group-containing olefin copolymer (A). B) 1 to 99,900 parts by weight, more preferably 1 to 99,000 parts by weight, still more preferably 1 to 90,000 parts by weight, still more preferably 1 to 50,000 parts by weight, and particularly preferably 1 to It is an olefin resin composition containing 19,900 parts by weight. 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 olefin resin composition (C) The olefin resin composition (C) can be produced by a known method. For example, the polar group-containing olefin copolymer (A) and the olefin resin ( B) and a method of melt kneading the other components added as desired using a single screw extruder, a twin screw extruder, a kneader, a Banbury mixer, a reciprocating kneader (BUSS KNEADER), a roll kneader, etc. , Polar group-containing olefin copolymer (A), olefin-based resin (B), and other components to be added as required, suitable good solvents (for example, hydrocarbon solvents such as hexane, heptane, decane, cyclohexane, xylene, etc. ) And then the solvent is removed.

(3) Additives To add other functions to the olefin resin composition (C) without departing from the gist of the function of the composition of the present invention, antioxidants, ultraviolet absorbers, lubricants, You may mix | blend additives, such as an antistatic agent, a coloring agent, a pigment, a crosslinking agent, a foaming agent, a nucleating agent, a flame retardant, a filler, and a electrically conductive material.

(4) Other components In the range which does not deviate from the main point of the function of the composition of this invention, you may mix | blend various resin modifiers etc. with an olefin resin composition (C). 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 according to the present invention is a laminate comprising a layer composed of an olefin resin composition according to the present invention and a substrate layer, and the substrate layer is , Polyolefin resin such as polyethylene and polypropylene, polyamide resin, polyester resin, thermoplastic resin with high polarity such as ethylene-vinyl alcohol copolymer (EVOH), metal material such as adhesive fluorine resin, aluminum and steel, etc. The base material can be illustrated.

  Specific examples of the substrate according to the present invention include polyethylene resins such as high-density polyethylene, medium-density polyethylene, low-density polyethylene, ethylene-vinyl acetate copolymer, and ethylene-acrylic acid ester copolymer, ionomer, and homopolypropylene. Resins, polypropylene resins such as copolymers of propylene and other α-olefins, olefin resins such as poly-1-butene and poly-4-methyl-1-pentene, polyvinyl chloride, polyvinylidene chloride, polystyrene , Vinyl polymers such as polyacrylate and polyacrylonitrile, nylon resins such as nylon 6, nylon 66, nylon 10, nylon 11, nylon 12, nylon 610, polymethoxyrylene adipamide, polyethylene terephthalate, polyethylene terephthalate / Polyester resins such as isophthalate, polybutylene terephthalate, polylactic acid, polybutylene succinate, aromatic polyester, polyvinyl alcohol, ethylene / vinyl alcohol copolymer, polycarbonate resin, adhesive fluororesin, cellulosic polymer such as cellophane Thermoplastic resin film or sheet (and stretched or printed material thereof) having a film-forming ability such as, metal foil or metal plate such as aluminum, iron, copper, or an alloy containing these as a main component, silica-deposited plastic film , Inorganic oxide vapor-deposited film such as alumina vapor-deposited plastic film, metal such as gold, silver and aluminum, or vapor-deposited film such as compounds other than oxides of these metals, fine paper, kraft paper, paperboard, glassine paper, synthetic paper, etc. Paper, Serov Examples thereof include a fan, a woven fabric, and a non-woven fabric.

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

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

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

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

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

(6) 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 of the present invention is used. It is a multilayer coextrusion molded product including at least a layer formed. 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. The multilayer co-extrusion product according to the present invention is a multilayer film, a multilayer sheet, a multilayer pipe, a layer containing the olefin resin composition according to the present invention and an appropriate base material processed by an appropriate molding method. It can be produced as a known multilayer coextrusion molded product such as a multilayer hose, multilayer tube, multilayer corrugated pipe or 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. Further, 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 a layer comprising the olefinic resin composition of the present invention and a substrate layer Is a multilayer film containing at least. As a method for producing a multilayer film according to the present invention, a known multilayer such as multilayer air-cooled inflation molding, multilayer air-cooled two-stage cooling inflation molding, multilayer high-speed inflation molding, multilayer water-cooled inflation molding, multilayer flat die molding (T-die molding), etc. A film forming method can be used. As the base material layer of the multilayer film according to the present invention, various various materials as described above can be appropriately used.

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

(9) Multilayer tubular molded article The multilayer tubular molded article related to the present invention is a multilayer tubular molded article that can be molded by a known multilayer tubular molding method, and contains the olefinic resin composition of the present invention. A multilayer tubular molded article including at least a layer 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 of the present invention and a base material layer. Is a multilayer sheet containing at least 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 into a sheet by discharging from a known die can be mentioned. In these methods, if necessary, the edge of the sheet may be slit 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 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 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 A multilayer injection-molded article according to the present invention includes at least a layer containing the olefin-based resin composition of the present invention, and a plurality of layers are multilayered using injection molding. It is a multilayer injection molded product that can be manufactured. The multilayer injection molded article only needs to be multilayered with two or more kinds of materials. For example, a layer containing two different types of the olefin resin composition of the present invention may be multilayered. The layer comprising the olefin resin composition and the layer comprising the substrate may be multilayered. Further, three or more layers may be multilayered. The multilayer injection molded product according to the present invention can be molded by a known injection molding method capable of multilayer injection molding. Although it may be a multi-layer injection-molded product formed by multilayering two or more layers containing the olefin-based resin composition of the present invention, it has a high adhesiveness to different materials that are the characteristics of the present invention. In view of the above, it is more preferable to use a multilayer injection molded product in which a layer made of different materials and a multilayer are formed. As an injection molding method capable of producing a multilayer injection molded product, a known method can be exemplified. For example, the olefin-based resin composition of the present invention is processed into a layer by a known method such as injection molding, extrusion molding, press molding, or cutting in advance, and the base material is further inserted in a state in which the member is inserted into the injection mold. Multi-layered by injecting the olefin-based resin composition according to the present invention in a state where the base material is processed into a layer in advance and the base material layer is inserted into the injection mold. A multi-color injection molding machine having a plurality of injection units, and a method of multilayering by sequentially injecting the olefin-based resin composition and the base material according to the present invention into a mold in an appropriate order, etc. Can be mentioned. In the multilayer injection-molded article according to the present invention, various kinds of base materials as described above can be appropriately used as the type of member to be multilayered with the olefin resin composition according to the present invention.

(13) Coated metal member The coated metal member according to the present invention is a coated metal member that can be produced by coating a metal with a metal coating material using the olefin resin composition according to the present invention as a metal coating material. It is. 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 powdered coated metal material by flow dipping method, Coated metal coated with electrostatic coated method using coated metal material with powdered property, sheet or film 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-based resin composition (C) according to the present invention is not only suitably used as the 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.

  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

(1) Polar group-containing structural unit amount in polar group-containing olefin copolymer (A) 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). Further, the molecular weight distribution parameter (Mw / Mn) was further calculated by the number average molecular weight (Mn) by gel permeation chromatography (GPC), and calculated by the ratio of Mw to Mn, Mw / Mn. Details are described above.

(3) Melting | fusing point Melting | fusing point is shown by the peak temperature of the endothermic curve measured with the differential scanning calorimeter (DSC). DSC (DSC7020) manufactured by SII Nano Technology Co., Ltd. was used for measurement, and the measurement was performed under the following measurement conditions.
About 5.0 mg of the sample was packed in an aluminum pan, increased to 200 ° C. at 10 ° C./min, held at 200 ° C. for 5 minutes, and then cooled to 30 ° C. at 10 ° C./min. After maintaining at 30 ° C. for 5 minutes, the maximum peak temperature in the absorption curve when the temperature was raised again at 10 ° C./min was taken as the melting point.

(4) Adhesive strength Adhesive strength is prepared by preparing a measurement sample processed into a pressed plate and various substrate films, respectively, and laminating the two by hot pressing, and further performing a peel test. Was measured. The adjustment method / measurement method of each process will be described in order.

(1) Measurement Sample of Olefin Resin Composition Resin Plate Press Plate Preparation Method A measurement sample is placed in a hot press mold having dimensions of 50 mm × 60 mm and a thickness of 0.5 mm in a hot press machine having a surface temperature of 180 ° C. After preheating for 5 minutes, pressurization and pressure reduction were repeated to degas the residual gas in the molten resin, 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 olefin resin composition resin board about 0.5 mm thick.

(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 / cm ³ Intermediate layer: Polyamide (made by Toray Industries, Inc. Brand: Amilan CM1021FS)

(3) Fluorine resin film adjustment method Using a multi-layer T-die molding machine, after forming a two-layer, three-layer multilayer film in which the 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 / cm ³ 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-based resin composition Obtained by the press plate of the measurement sample obtained by the press plate preparation method, the plate, and the preparation method of the fluororesin film A fluororesin film cut to a size of 50 mm x 60 mm is overlaid, put into a hot press mold having dimensions of 50 mm x 60 mm and a thickness of 0.5 mm, and 4.9 MPa using a hot press with a surface temperature of 200 ° C. For 3 minutes. Then, it transferred to the press machine with a surface temperature of 25 degreeC, it cooled by hold | maintaining for 3 minutes with the pressure of 4.9 MPa, and the laminated body of the press board of a measurement sample and a fluororesin was prepared.

(6) Method for measuring adhesive strength of laminate The laminate obtained by the laminate preparation method was cut into a width of 10 mm, and the speed was 50 mm / min using a Tensilon (Toyo Seiki Co., Ltd.) tensile tester. 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) Adhesive strength ratio By the adhesive strength measurement method, the resin composition of each Example and Comparative Example, the polar group-containing olefin copolymer contained in these resin compositions, and the respective adhesive strengths were measured, and the resin composition The value obtained by dividing the adhesive strength by the adhesive strength of the polar group-containing olefin copolymer contained in these resin compositions was calculated as the adhesive strength ratio.
This value is an index of the effect of improving the adhesiveness by blending the olefin resin with the polar group-containing olefin copolymer. If this value is larger than “1”, the polar group-containing olefin copolymer has It shows that the adhesion was improved by blending olefin resin.

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

(7) Aluminum (Al) amount The amount of aluminum (Al) contained in the 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.

Method of calculating from alkyl aluminum polymerization addition amount Specifically, the calculation was performed by the following calculation 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)

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

[Production Example 1] Production of polar group-containing olefin copolymer (A-1)
Drent-based ligand: Synthesis of (2-isopropyl-phenyl) (2′-methoxy-phenyl) (2 ″ -sulfonyl-phenyl) phosphine (I) Tetrahydrofuran of benzenesulfonic anhydride (2 g, 12.6 mmol) 20 mL), normal butyllithium hexane solution (2.5 M, 10 mL, 25.3 mmol) was slowly added dropwise at 0 ° C., and the mixture was stirred for 1 hour while raising the temperature to room temperature. The reaction solution was cooled to −78 ° C., phosphorus trichloride (1.0 mL, 12.6 mmol) was added, and the mixture was stirred for 2 hours (reaction solution A).
Magnesium was dispersed in tetrahydrofuran (20 mL), 1-bromo-2-methoxybenzene (2.3 g, 12.6 mmol) was added, and the mixture was stirred at room temperature for 3 hours. This solution was added dropwise to the previous reaction solution A at −78 ° C. and stirred for 1 hour (reaction solution B).
To a solution of 1-bromo-2-isopropylbenzene (2.5 g, 12.6 mmol) in diethyl ether (20 mL), slowly add normal butyl lithium hexane solution (2.5 M, 5.0 mL, 12.6 mmol) at −30 ° C. And stirred at room temperature for 2 hours. This solution was added dropwise to the previous reaction solution B at −78 ° C. and stirred overnight at room temperature. LC-MS purity 60%.
Water (50 mL) was added, acidified with hydrochloric acid (PH <3), extracted with methylene chloride (100 mL), dried over sodium sulfate, and the solvent was evaporated. By recrystallization from methanol, 1.1 g of white target product (I) was obtained. Yield 22%.
1H NMR (CDCl ₃ , ppm): 8.34 (t, J = 6.0 Hz, 1 H), 7.7-7.6 (m, 3 H), 7.50 (t, J = 6. 4 Hz, 1 H), 7.39 (m, 1 H), 7.23 (m, 1 H), 7.1-6.9 (m, 5 H), 3.75 (s, 3 H) , 3.05, (m, 1 H), 1.15 (d, J = 6.8 Hz, 3 H), 1.04 (d, J = 6.4 Hz, 3 H). 31P NMR (CDCl ₃ , 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 4-vinyl-1,2-epoxycyclohexene After substituting an autoclave with a stirring blade having an internal volume of 2.4 liter with a stirring blade with purified nitrogen, dry toluene (1.0 liter) and 4-vinyl 20.9 ml (0.2 mol) of -1,2-epoxycyclohexene 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 a pressure of 2.3 MPa so that the ethylene partial pressure was 2 MPa. After completion of pressure adjustment, 50 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., and ethylene was continuously supplied so that the pressure was maintained. After 240 minutes of polymerization, the reaction was stopped by cooling and depressurization. The reaction solution was poured into 1 liter of acetone to precipitate a polymer, and then collected by filtration, washing, and further dried under reduced pressure at 60 ° C. until a constant weight was obtained.
The polymerization conditions and polymerization results are shown in Table 1, and the physical property measurement results are shown in Table 2. In Table 2, “ND” means not measured. 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 2] Production of polar group-containing olefin copolymer (A-2)
SHOP-based ligand: Synthesis of 2- (2,6-diphenoxyphenyl) (2-phenoxyphenyl) phosphanyl-6- (pentafluorophenyl) phenol (B-114) (1) 1,3-diphenoxybenzene N-Butyllithium (2.5 M, 4.0 mL, 10 mmol) was added to a dehydrated tetrahydrofuran (100 mL) solution of (B-114_1, 2.62 g, 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 stirred for an additional hour at room temperature. Thereafter, the mixture was cooled to −30 ° C., and a tetrahydrofuran solution of B-114 — 5) obtained in (2) was added dropwise thereto. After the addition, the mixture was gradually warmed to room temperature and stirred at room temperature overnight. Water (50 mL) was added to the mixture, stirred for 10 minutes, and then the organic solvent was removed under reduced pressure. Then, after extracting with ethyl acetate (50 mL × 3), the extract was concentrated, and the resulting residue was purified by silica gel chromatography (petroleum ether: ethyl acetate = 50: 1) to give methoxymethyl (2- (2,6 -Diphenoxyphenyl) (2-phenoxyphenyl) phosphanylphenyl) ether was obtained (B-114_7, 2 g, purity 62%).
And by repeating (3), 8.1g (purity 75%) of B-114_7 was obtained. By recrystallizing it from diethyl ether, B-114_7 was obtained (5.5 g, purity 92%).
(4) n-Butyllithium (2.5 M, 3.2 mL, 9.2 mmol) was added dropwise at 0 ° C. to a dehydrated tetrahydrofuran (50 mL) solution of B-114_7 (5.5 g, 9.2 mmol). The mixture was gradually warmed to room temperature, and further stirred at room temperature for 2 hours. Thereafter, the mixture was cooled to 0 ° C., hexafluorobenzene (5.4 mL, 46 mmol) was slowly added dropwise thereto, and the mixture was gradually warmed to room temperature and then stirred at room temperature overnight. Methanol (20 mL) was added to the reaction solution, and after stirring for 10 minutes, the organic solvent was removed under reduced pressure. Then, after extracting with ethyl acetate (50 mL × 3), the extract was concentrated, and the resulting residue was purified by silica gel chromatography (petroleum ether: ethyl acetate = 100: 1) to give methoxymethyl (2- (2,6 -Diphenoxyphenyl) (2-phenoxyphenyl) phosphanyl-6- (pentafluorophenyl) phenyl) ether was obtained (B-114_8, 1.6 g, purity 94%).
And by repeating (4), B-114_8 (10 g, purity 85%) was obtained, and then B-114_8 was obtained by HPLC purification (6 g, 7.8 mmol).
(5) The compound (B-114_8, 6.0 g, 7.8 mmol) obtained in (4) was added to an ethyl acetate solution of hydrogen chloride (4M, 100 mL) at 0 ° C. The resulting mixture was gradually warmed to room temperature and then stirred at room temperature for 2 hours. The solvent was removed, and ethyl acetate (50 mL) and saturated aqueous sodium hydrogencarbonate (50 mL) were added to the residue, followed by stirring for 30 minutes. Then, extraction operation was performed with ethyl acetate, and the organic layer was washed with saturated brine. After dehydration with sodium sulfate, sodium sulfate was filtered off, and the solvent was distilled off under reduced pressure and concentrated. The obtained crude product was purified by silica gel chromatography (petroleum ether: ethyl acetate = 40: 1) to give 2- (2,6-diphenoxyphenyl) (2-phenoxyphenyl) phosphanyl-6- (pentafluorophenyl). ) Phenol was obtained (5.0 g, 6.9 mmol, 88%)
¹ H NMR (CDCl ₃ , δ, ppm): 6.55-6.65 (m, 2H), 6.70-6.74 (m, 1H), 6.75-6.82 (m, 4H) 6.82-6.87 (m, 2H), 6.87-6.95 (m, 1H), 6.95-7.30 (m, 15), 7.65-7.77 (m, 1H); ³¹ P NMR (CDCl ₃ , δ, ppm): −54.0 (s).

Formation of complex 145 mg (200 μmol) of the following B-114 was weighed out into a 50 ml eggplant-shaped flask sufficiently purged with nitrogen. Next, 56 mg (200 μmol) of bis-1,5-cyclooctadiene nickel (0) (hereinafter referred to as Ni (COD) ₂ ) was weighed into a 50 ml eggplant type flask, dissolved in 20 ml of dry toluene, and 10 mmol / l. A Ni (COD) ₂ toluene solution was prepared. The total amount (20 ml) of Ni (COD) ₂ toluene solution obtained here was added to an eggplant-shaped flask containing B-114, and stirred for 30 minutes in a hot water bath at 40 ° C., so that B-114 and Ni (COD ) 20 ml of a 10 mmol / l solution of 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 3] Production of polar group-containing olefin copolymer (A-3)
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. 36.6 mg (0.10 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, 2.5 ml (25 μmol) of the previously prepared B-27DM-Ni complex solution was injected with nitrogen to initiate copolymerization. The temperature was kept at 105 ° C. during the reaction. After polymerization for 170 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 33 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 “2.0 → 1.0” because the ethylene partial pressure at the start of polymerization is 2.0 MPa, and the ethylene partial pressure at the end of polymerization is 1. This indicates that the pressure was 0.0 MPa.
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 Example 4] Production of polar group-containing olefin copolymer (A-4)
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 2.7 ml (15 mmol) of 4-HBAGE were charged. The temperature of the autoclave was raised to 50 ° C. while stirring and nitrogen was supplied to 0.3 MPa, and then ethylene was supplied to a pressure of 2.8 MPa so that the ethylene partial pressure was 2.5 MPa. After the temperature and pressure were stabilized, 2.0 ml (20 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 50 ° C., and ethylene was continuously supplied so that the pressure was maintained. After polymerization for 50 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 41 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 Example 5 to Production Example 7] Production of Polar Group-Containing Olefin Copolymer (A-5 to A-7) Among the methods described in Production Example 4, the amount of ligand, polar group-containing monomer concentration, polymerization temperature. The polar group-containing olefin copolymers of Production Examples 5 to 7 were prepared by changing the polymerization time and polymerization. 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 8] Production of Polar Group-Containing Olefin Copolymer (A-8) Among the methods described in Production Example 3, the ligand amount, the polar group-containing monomer concentration, the polymerization temperature, and the polymerization time were changed. Thus, the polar group-containing olefin copolymer of Production Example 8 was prepared. The polymerization conditions and polymerization results are shown in Table 1, and the physical property measurement results are shown in Table 2. In Table 2, “ND” means not measured.

Polar group-containing olefin copolymer (A-9)
It is a copolymer of ethylene and glycidyl methacrylate, and is a polar group-containing olefin copolymer produced by a high-pressure process (Sumitomo Chemical Co., Ltd. brand: Bond First E). The results of physical property measurement are shown in Table 2.

[Example 1]
7.0 g of polar group-containing olefin copolymer (A-1) and 3.0 g of ethylene-butene copolymer (manufactured by Mitsui Chemicals, trade name: Toughmer (A-4085S)) are dry-blended. The mixture was put into a kneader (DSM Xplore Model: MC15) and melt-kneaded for 5 minutes. The barrel temperature at that time was 180 ° C., and the screw rotation speed was 100 rpm. After 5 minutes, the rod-shaped resin composition was extruded from the resin discharge port, placed on a stainless steel tray, and cooled and solidified at room temperature. The cooled resin composition was cut into pellets to produce pellets of the olefin resin composition, and the obtained olefin resin composition was subjected to various physical property tests. Table 3 shows the manufacturer, grade, product name, resin classification, monomer type used for polymerization, and physical properties of the resin used, Table 4 shows the blending ratio in the olefinic resin composition, and the physical property evaluation results. Table 5 shows.
In Table 3, “LDPE” is a high pressure method low density polyethylene, “LLDPE” is a linear low density polyethylene, “EEA” is an ethylene-ethyl acrylate copolymer, “EVA” is an ethylene-vinyl acetate copolymer, “ "EPR" represents ethylene propylene rubber, respectively.

[Examples 2 to 12, Comparative Examples 1 to 3]
Of the methods described in Example 1, the polar group-containing olefin copolymer, the type of the olefin resin, and the production ratio of the polar group-containing olefin copolymer and the olefin resin were changed to produce Example 2 -The resin composition of Example 12, Comparative Example 1- Comparative Example 3 was manufactured. Table 3 shows the manufacturer, grade, product name, resin classification, monomer type used for polymerization, and physical properties of the resin used, Table 4 shows the blending ratio in the olefinic resin composition, and the physical property evaluation results. Table 5 shows.

[Consideration of results of Examples and Comparative Examples]
Example 1, Example 3 to Example 8, Example 10, and Example 11 are polar group-containing olefin copolymers (A-1, A-3, A-4, A-6, A-7) each 100. It is an olefin resin composition in which an olefin resin having a melting point of 124 ° C. or less is appropriately blended at a blending ratio of 1 to 99,900 parts by weight with respect to parts by weight, and exhibits sufficiently excellent adhesion to fluororesins. In addition, the adhesive strength ratio is 1.0 or more, which shows a sufficient adhesive improvement effect. Further, Example 1, Example 3 to Example 8, and Example 11 in which an olefin resin having a melting point of 110 ° C. or less is blended, the adhesive strength ratio to the fluororesin is 2.0 or more, and the adhesiveness is dramatically improved. Showed the effect.
Comparative Example 1 using an olefin-based resin having a melting point exceeding 124 ° C. was very weak in adhesion to the fluororesin, and the adhesion strength ratio was less than 1.0, so that the effect of improving adhesion was not seen. .
In Comparative Example 2 and Comparative Example 3, 1 to 99 olefin resins having a melting point in a specific range with respect to 100 parts by weight of the polar group-containing olefin copolymer (A-9) produced by the high-pressure radical process. The olefin resin composition was blended appropriately at a blending ratio of 900 parts by weight, but the adhesive strength to the fluororesin was very low and the adhesive strength ratio was also inferior. From this fact, when the polar group-containing olefin copolymer of the present invention is blended with an olefin resin having a melting point of 124 ° C. or lower, compared with the polar group-containing olefin copolymer produced by the high-pressure radical polymerization process. The adhesion performance of the olefin copolymer having a melting point of 124 ° C. or lower is blended with 1 to 99,900 parts by weight with respect to 100 parts by weight of the polar group-containing olefin copolymer according to the present invention. It was shown that an improvement effect can be obtained.

  Reason why the adhesiveness of an olefin resin composition obtained by blending an olefin resin having a melting point of 124 ° C. or less with a polar group-containing olefin copolymer having a linear structure is improved as compared with a polar group-containing olefin copolymer alone. Although it is not clear, it is considered that the molecular structure of the polar group-containing olefin copolymer contained in the olefin-based resin composition needs to be a linear structure. Adhesion performance between a highly polar dissimilar material and an olefin copolymer is evaluated by numerical values measured by a peel test as exemplified in JIS K6854-1-4 “Adhesive-Peel Adhesion Strength Test Method”. However, the numerical value measured by this method is considered to be the sum of the chemical and physical bonding forces at the interface between different materials and the cohesive force of the material or the stress at the time of deformation. 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.

  In Example 2, Example 9, and Example 12, each of the polar group-containing olefin copolymers (A-2, A-5, A-8) is blended with an olefin resin having a melting point of 124 ° C. or less in a specific range. It was an olefin resin composition blended at a ratio, exhibiting sufficient adhesiveness to polyamide, and showing a dramatic adhesive improvement effect with an adhesive strength ratio of 2.0 or more. From this fact, the adhesion improving effect of the olefin resin composition obtained by blending an olefin resin having a melting point of 124 ° C. or lower with a polar group-containing olefin copolymer having a linear structure is Shown not limited.

  In Examples 1 to 12, an olefin resin having a melting point of 124 ° C. or lower is blended with the polar group-containing olefin copolymer. It was shown that a sufficient adhesive improvement effect can be obtained for the olefin resin composition regardless of the MFR of the olefin resin, the monomer type used for polymerization, and the blending ratio.

  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 (9)

With ethylene and / or having 3 to 20 carbon atoms α- olefin, a polar group-containing monomer containing an epoxy group, obtained by copolymerizing in the presence of a transition metal catalyst, ethylene or C3-20 α -The amount of structural units derived from olefin is 99.999 to 85 mol%, the amount of structural units derived from a polar group-containing monomer containing an epoxy group is 15 to 0.001 mol%, the molecular structure is linear and random The polar group-containing olefin copolymer (A), which is a polymerization, and the melting point represented by the temperature at the maximum peak position of the absorption curve measured by differential scanning calorimetry (DSC) is 30 to 124 ° C. An olefin-based resin composition (C) containing the characteristic olefin-based resin (B), wherein the blending amount of the olefin-based resin (B) is a polar group-containing olefin copolymer (A) 10 Relative parts by weight, an olefin resin composition which is a 1～99,900 parts. 2. The olefin system 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). Resin composition.
Formula (I)

(In the formula, R1 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R2, R3, and R4 each independently represent a specific functional group described below including a hydrogen atom, a hydrocarbon group, or an epoxy group, Any one of R2 to R4 is a specific functional group containing 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 formula, R5 to R8 each independently represent a specific functional group including a hydrogen atom, a hydrocarbon group, or an epoxy group, and any one of R5 to R8 includes a specific functional group including 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 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 according to claim 1 or 2 . The polar group-containing olefin copolymer (A) has a melting point represented by the temperature at the maximum peak position of the absorption curve measured by differential scanning calorimetry (DSC) in the range of 50 to 140 ° C. The olefin resin composition according to any one of claims 1 to 3 , wherein the olefin resin composition is characterized. Polar group-containing olefin copolymer (A), characterized in that it is polymerized in the presence of a transition metal catalyst Group 5-11 metals with chelating ligand, claims 1 to 4 The olefin resin composition described in any one of the above. 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. The olefin resin composition according to claim 5 . A laminate comprising at least the olefin-based resin composition according to any one of claims 1 to 6 and a base material layer. Base material layer, wherein depositing the film of the olefin-based resin, highly polar thermoplastic resins, metals, inorganic oxides, paper, cellophane, fabric, to be selected from the non-woven fabric, according to claim 7 Laminated body. The laminate according to claim 7 or 8 , wherein the base material layer is a polyamide-based resin or a fluorine-based resin.

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