JP5882885B2 - Polar group-containing olefin copolymer, method for producing the same, adhesive material using the same, laminate and other products for use - Google Patents

Description

The present invention relates to a polar group-containing olefin copolymer, an adhesive using the same, and a laminate using the same, and more specifically, contains a specific polar group and is excellent for various base materials. The present invention relates to a polar group-containing olefin copolymer having adhesive performance, a production method thereof, an adhesive material using the same, a laminate, and other products for use.

In general, olefin polymers such as polyethylene and polypropylene have high mechanical strength, excellent chemical resistance and corrosion resistance, are inexpensive, have excellent moldability, and are suitable for environmental problems. It is used as a material and is formed into films, laminates, containers, blow bottles, 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 EVOH or aluminum foil, in addition to the above properties, properties such as gas barrier properties can be added. It becomes possible to do.

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

Therefore, in order to improve the adhesion with different polar materials, a method of grafting a polar group-containing monomer using an organic peroxide has been widely performed (for example, see Patent Document 1).
However, in this method, intermolecular crosslinking between the olefin polymers and molecular chain scission of the olefin polymer occur in parallel with the grafting reaction, so that the excellent physical properties of polyolefin are not maintained in the graft modified product. Will occur.
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 polyolefin due to molecular chain breakage presents the problem of causing eye strain and fuming during molding.

Furthermore, by increasing the polar group content during olefin copolymerization, it is possible to increase the adhesion with different polar materials, but it is not easy to graft a large amount of polar group-containing monomers onto the polyolefin by graft modification. . 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 polymer, and the physical properties of the polyolefin are impaired. In addition, the amount of unreacted polar group-containing monomers and organic peroxide decomposition products remaining in the resin increases, resulting in problems such as accelerated deterioration of the resin and unpleasant odor. Therefore, there is a limit to increase the content of the polar group-containing monomer in the resin.

As a method for solving these problems caused by graft modification, linear LDPE is used as the graft modification material, and the modified product with high grafting efficiency is obtained by reducing contamination of the graft modified product and intermolecular crosslinking generated during graft modification. Has been disclosed (see Patent Document 2).
However, the effect of preventing intermolecular crosslinking and the improvement of graft efficiency are limited, and the residue of unreacted polar group-containing monomers and organic peroxide decomposition products, which are fundamental adverse effects due to graft modification, is eliminated. It cannot be said that it is still a sufficient improvement method.

By the way, there is no intermolecular cross-linking or gelation and molecular chain breakage between olefin polymers, and as a means of incorporating polar group-containing monomers into the olefin polymer, ethylene and polar group-containing vinyl are used using a high-pressure radical polymerization process. A method of obtaining a polar group-containing olefin copolymer by copolymerizing with a monomer is also disclosed (see, for example, Patent Document 3 and Patent Document 4).
In addition, although the molecular structure example of the olefin copolymer which introduce | transduced the polar group using the high pressure radical polymerization process is shown in FIG. 1 (a), the problem generate | occur | produced by graft modification is solved according to this method, It is possible to increase the content of the polar group-containing monomer in the 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 polar group-containing olefin copolymers having a low elastic modulus and low mechanical properties can be obtained as compared with olefin copolymers polymerized using a metal catalyst, and the application to applications where high strength is required. The application range was limited.

On the other hand, in conventional polymerization methods using metallocene catalysts, ethylene and polar group-containing monomers are said to be difficult to copolymerize due to a decrease in catalytic polymerization activity, but in recent years they are called so-called post-metallocenes. A method of polymerizing a polar group-containing olefin copolymer in the presence of a late transition metal complex catalyst has been proposed (see Patent Documents 5 to 8).
According to these methods, although it has a high elastic modulus and mechanical strength as compared with the olefin copolymer obtained by the high-pressure radical process, it is possible to increase the polar group content (in addition, using a transition metal catalyst) 2 (b) and FIG. 3 (c) show image diagrams of the molecular structure of the polymerized olefin copolymer. The methods described in these documents mainly contain acrylate groups such as methyl acrylate and ethyl acrylate. It focuses on monomers and copolymers of specific polar group-containing monomers such as vinyl acetate and ethylene or α-olefins, and these functional group-containing polar group-containing polyolefins have high adhesion to different polar materials. Is not enough. 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.

Furthermore, a carboxyl group or a derivative thereof is known as a polar group capable of exhibiting excellent adhesiveness with a different polar material when introduced into an olefin copolymer. A polar group-containing olefin copolymer containing a carboxyl group or a derivative thereof, which is polymerized without using a high-pressure radical polymerization process, as a specific metallocene catalyst and a sufficient amount of organoaluminum. There has been proposed a polar group-containing olefin copolymer obtained by copolymerizing (2,7-octadiene-1-yl) succinic anhydride, ethylene, and α-olefin (see Patent Document 9).
However, according to the present invention, a large amount of organoaluminum is required for the copolymerization of polar group-containing olefin, and the production cost must be increased. In addition, a large amount of organoaluminum is present in the copolymer as an impurity, which leads to further cost increase for removal. 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. In addition, 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 is intended for high adhesion performance. Use as a copolymer is not disclosed.

As another polar group-containing olefin copolymer, an olefin copolymer having a functional group comprising a polar group-containing monomer having a specific structure and a structural unit derived from ethylene, α-olefin, and non-conjugated diene. Has been proposed (see Patent Document 10).
However, the method for producing a polar group-containing olefin copolymer proposed by the patent document requires that the polar group-containing cyclic olefin used in the polymerization is reacted with an organometallic compound to mask the polar group in advance. Since the masking process is also performed after the copolymerization process, the manufacturing process becomes complicated and the manufacturing cost must be increased. Furthermore, there is a concern that the organometallic compound used for masking remains in the copolymer and adversely affects various physical properties of the resin, and even if it is removed, the manufacturing cost is further increased.

As another method for producing a polar group-containing olefin copolymer, by modifying the double bond portion of the olefin copolymer having a double bond at one end, both ends, or inside the molecular chain of the polymer chain, A method for introducing a polar group into a molecular chain is disclosed (see Patent Documents 11 to 15). When a polar group-containing olefin copolymer is produced by these methods, an olefin polymer having a double bond in the molecular chain is polymerized in advance, and then a polar group is contained in the double bond portion in the olefin copolymer. Compared with the case where a polar group-containing vinyl monomer and ethylene or α-olefin are directly copolymerized to obtain a polar group-containing olefin copolymer, it is necessary to go through a process of reacting the compound. This leads to increased manufacturing costs. Furthermore, when a polar group-containing olefin copolymer is to be obtained by modifying an olefin copolymer having a double bond at one or both ends, the molecular weight of the polymer chain and the polar group are determined based on the principle of the method. It is impossible to control the contents separately, and the use of the obtained polar group-containing olefin copolymer is limited.

JP 50-004144 A Japanese Patent Publication No. 3-11290 Japanese Patent No. 2792982 JP-A-3-229713 JP 2010-202647 A JP 2010-150532 A JP 2010-150246 A JP 2010-260913 A Japanese Patent No. 4672214 Japanese Patent No. 3606035 JP 2005-97587 A Japanese Patent Laid-Open No. 2005-97588 JP 2006-131707 A JP 2009-155655 A JP 2009-155656 A

In view of the above conventional methods, the polar group introduction method to the olefin copolymer is a graft modification, a high pressure radical polymerization process, a method using a large amount of organoaluminum, and the polar group of the polar group-containing monomer is organically used in the polymerization. Any method that includes each problem, such as masking with an organometallic compound such as aluminum and copolymerizing, or modifying the double bond part of the olefin copolymer having a double bond in the molecular chain. A polar group-containing olefin copolymer containing a carboxyl group or a dicarboxylic anhydride group that is a derivative thereof, and having excellent adhesion performance to different polar materials The proposal of the containing olefin copolymer and the laminated body using the same was awaited.

The present invention is superior to dissimilar materials with high polarity that are manufactured by any of the conventional methods, including the respective problems, in view of the conventional problems described above as the background art. It is an object of the present invention to develop a polar group-containing olefin copolymer exhibiting adhesive performance, and also to provide adhesives, laminates, and various products (including molded products and various members) using the same. Is.

In order to solve the above problems, the present inventors have produced the copolymer by a simple and efficient production method in the production of a polar group-containing olefin copolymer, and the adhesion of the copolymer to a different material. In order to improve the performance, the method of introducing polar groups, the selection of polar groups and polymerization catalyst, and the correlation between the structure of the copolymer and the adhesion performance were examined and verified in various ways. A polar group-containing olefin copolymer having excellent adhesion performance could be found, leading to the creation of the present invention.
That is, the polymer of the present invention is a specific polar group-containing olefin copolymer polymerized using a transition metal catalyst, and has a specific range of weight average molecular weight (Mw) and a specific range of polar group-containing monomer. The copolymer is characterized by exhibiting exceptional adhesion.

Specifically, the present invention includes at least one nonpolar monomer selected from ethylene and an α-olefin having 3 to 20 carbon atoms, and at least one polar group-containing monomer containing a carboxyl group or a dicarboxylic anhydride group. A polar group-containing olefin copolymer obtained by copolymerization in the presence of a transition metal catalyst, the polar group-containing olefin copolymer being a random copolymer, and the following requirements 1) and 2) A polar group-containing olefin copolymer characterized by satisfying the above conditions is defined as a basic invention (first invention).
1) The amount of structural units derived from the polar group-containing monomer in the polar group-containing olefin copolymer is 0.001 to 10 mol%.
2) The weight average molecular weight (Mw) calculated | required by gel permeation chromatography (GPC) is 45,000-1,000,000.

The second invention of the present invention is a polar group-containing olefin copolymer which is a random copolymer of ethylene or an α-olefin having 3 to 20 carbon atoms and a polar group-containing monomer containing a carboxyl group or a dicarboxylic anhydride group. In the union, the amount of structural units derived from the polar group-containing monomer contained within the molecular chain is greater than the amount of structural units derived from the polar group-containing monomer contained at the molecular chain end. It is a polar group-containing olefin copolymer.

According to a third aspect of the present invention, in the polar group-containing olefin copolymer, the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) determined by GPC is 1.5 to 3.5. The polar group-containing olefin copolymer according to the first or second aspect of the present invention,

According to a fourth aspect of the present invention, in the polar group-containing olefin copolymer, the melting point represented by the temperature at the maximum peak position of the absorption curve measured by DSC is 50 ° C to 140 ° C. The polar group-containing olefin copolymer in the first to third inventions.

A fifth invention of the present invention is characterized in that the polar group-containing olefin copolymer is polymerized in the presence of a group 5-11 transition metal catalyst having a chelating ligand. It is a polar group containing olefin copolymer in 4th invention.

According to a sixth aspect of the present invention, the polar group-containing olefin copolymer 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 polar group-containing olefin copolymer in the first to fifth inventions.

The seventh invention of the present invention is characterized in that the polar group-containing monomer used for the polymerization of the polar group-containing olefin copolymer is a polar group-containing monomer containing a dicarboxylic anhydride group. 6 is a polar group-containing olefin copolymer according to the sixth invention.

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

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

According to a tenth aspect of the present invention, the base material layer is selected from olefin resins, highly polar thermoplastic resins, metals, vapor-deposited films of inorganic oxides, papers, cellophane, woven fabric, and non-woven fabric. The laminate in the ninth invention.

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

  The twelfth invention of the present invention uses the polar group-containing olefin copolymer described in the first to eighth inventions, or a laminate material containing an adhesive, and has at least one substrate layer and laminate A laminate laminate characterized by being laminated by processing.

  A thirteenth invention of the present invention is a multilayer coextrusion molding comprising at least the polar group-containing olefin copolymer described in the first to eighth inventions or a layer containing an adhesive and a base material layer. It is a product.

  A fourteenth invention of the present invention is a multilayer coextrusion molded product in which the multilayer coextrusion molded product described in the thirteenth invention is a multilayer film, a multilayer blow molded product, a multilayer tubular molded product, or a multilayer sheet.

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

In a sixteenth aspect of the present invention, the polar group-containing olefin copolymer described in the first to eighth aspects or a member containing an adhesive and a base material are combined by injection molding. This is a composite injection molded product characterized by this.

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

Since the polar group-containing olefin copolymer of the present invention has a specific molecular structure and resin physical properties, it exhibits high adhesiveness with other base materials, making it possible to produce industrially useful laminates. . Such remarkable effects are verified by the data of each example of the present invention described later and the comparison between each example and each comparative example.
In addition, the polar group-containing olefin copolymer having a specific molecular structure and resin properties according to the present invention is excellent not only in adhesiveness but also in mechanical and thermal properties, and can be applied as a useful multilayer molded article. It is formed into a multilayer film, a multilayer blow bottle, etc. by various uses, for example, extrusion molding, blow molding, etc., and can be used for a wide range of applications.

(A) is a conceptual diagram of the molecular structure of the olefin copolymer polymerized by the high-pressure radical polymerization process. (B) is a conceptual diagram of a molecular structure in the case of an olefin copolymer polymerized using a metal catalyst and having no long chain branching. (C) is a conceptual diagram of a molecular structure in the case of an olefin copolymer polymerized using a metal catalyst and having a small amount of long-chain branching.

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

[I] Polar group-containing olefin copolymer (1) Polar group-containing olefin copolymer The polar group-containing olefin copolymer according to the present invention is at least one selected from ethylene and an α-olefin having 3 to 20 carbon atoms. A nonpolar monomer and at least one polar group-containing monomer containing a carboxyl group or a dicarboxylic anhydride group.

The polar group-containing olefin copolymer is already known in graft polymerization, high-pressure radical polymerization and other polymerization methods described above. In the present invention, the polar group-containing olefin copolymer is compared with the known polar group-containing olefin copolymer. In order to satisfy the requirement that the copolymer is a random copolymer polymerized in the presence of a transition metal, the molecular structure of the polymer is different from that of a known graft polymer or radical polymer. In addition, as a range having a special adhesive effect, the requirement 1) of the structural unit amount and the requirement 2) of the weight average molecular weight, which will be described later, are also provided, so that it is significantly different from the known copolymer.

(2) Nonpolar monomer As the nonpolar monomer used in the copolymer of the present invention, ethylene and / or α-olefin is used, and the α-olefin has 3 to 20 carbon atoms, more preferably 3 to 12 carbon atoms. Specific examples thereof include propylene, butene-1, pentene-1, hexene-1, 4-methyl-1-pentene, octene-1, dodecene-1, and the like. Among ethylene and C3-C20 α-olefins, ethylene is particularly preferable.
In addition, the amount of structural units derived from these ethylene or α-olefin is usually 90 to 99.999 mol%, preferably 95 to 99.99 mol%.
Moreover, the ethylene or C3-C20 alpha-olefin used may be individual, and may use 2 or more types together.
Examples of the two combinations include ethylene-propylene, ethylene-1-butene, ethylene-1-hexene, ethylene-1-octene, propylene-1-butene, propylene-1-hexene, and propylene-1-octene. .
Examples of the three combinations include ethylene-propylene-1-butene, ethylene-propylene-1-hexene, ethylene-propylene-1-octene, propylene-1-butene-hexene, and propylene-1-butene-1-octene. It is done.

(3) Polar group-containing monomer The polar group-containing monomer used for the polymerization of the polar group-containing olefin copolymer in the present invention needs to contain a carboxyl group or a dicarboxylic anhydride group. If it is an olefin copolymer having a carboxyl group or a dicarboxylic anhydride group, a highly polar thermoplastic resin such as polyamide resin, polyester resin, saponified ethylene / vinyl acetate copolymer resin (EVOH), and aluminum, It becomes possible to laminate and adhere to a base material of a metal material such as steel.

The polar group-containing monomer according to the present invention has a cyclic skeleton in the monomer structure, and further has a double bond in the cyclic skeleton, and particularly preferably has a norbornene skeleton. Copolymerization is possible, and is more preferable.
When the functional group contained in the polar group-containing monomer is a dicarboxylic acid anhydride, it is more useful from the viewpoint of adhesiveness to a different polar material.

Examples of polar group-containing monomers according to the present invention include acrylic acid, methacrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, norbornene dicarboxylic acid, bicyclo [2,2,1 ] Unsaturated carboxylic acids such as hept-2-ene-5,6-dicarboxylic acid, maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, 3,6-epoxy-1,2,3,6-tetrahydrophthalic anhydride, tetracyclo [6. 2. 1. 1 ^{3 , 6} . 0 ^{2 , 7} ] unsaturated carboxylic acid anhydrides such as dodeca-9-ene-4,5-dicarboxylic acid anhydride and 2,7-octadien-1-ylsuccinic acid anhydride. Furthermore, the polar group-containing monomer used may be used singly or in combination of two or more.
Among these, 2,7-octadien-1-yl succinic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, 3,6-epoxy-1,2,3 represented by the following chemical formula 6-tetrahydrophthalic anhydride and the like are preferable.

２，７−オクタジエン−１−イルコハク酸無水物

2,7-octadiene-1-ylsuccinic anhydride

５−ノルボルネン−２，３−ジカルボン酸無水物

5-norbornene-2,3-dicarboxylic anhydride

３，６−エポキシ−１，２，３，６−テトラヒドロフタル酸無水物

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

A polar group-containing olefin copolymer using a monomer containing an unsaturated dicarboxylic acid anhydride as a polar group-containing monomer reacts with water or water vapor in which a part of the dicarboxylic acid anhydride group is present in the air. Ring opening to form a carboxylic acid group. The dicarboxylic anhydride group may be ring-opened as long as it does not depart from the gist of the present invention.

(4) Structural unit of polar group-containing olefin copolymer The structural unit and the structural unit amount of the polar group-containing olefin copolymer in 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 a polar group-containing monomer is defined as one structural unit in the polar group-containing olefin copolymer. And what represented the ratio of each structural unit in a polar group containing olefin copolymer in mol% is a structural unit amount. In the molecular structure example of the polar group-containing olefin copolymer, the structures derived from the polar group-containing monomers A1, A2 and A3 in the structure to be described later are structural units, and the respective abundance ratios are the structural unit amounts. Become.

(5) Structural unit amount of polar group-containing monomer The structural unit amount derived from these polar group-containing monomers is usually selected in the range of 10 to 0.001 mol%, preferably in the range of 5 to 0.01 mol%. Is desirable. If the amount of the structural unit derived from the polar group-containing monomer is less than this range, the adhesion with a different polar material is not sufficient, and if it is more than this range, sufficient mechanical properties cannot be obtained.

The molecular chain terminal in the polar group-containing olefin copolymer according to the present invention, the polar group-containing monomer structural unit amount in the molecular chain, and the total structural unit amount of the polar group are determined using a ¹³ C-NMR spectrum. ^{The 13} C-NMR spectrum can be measured by the following method.
100 mg of polar group-containing olefin copolymer (A) is o-dichlorobenzene / deuterated benzene bromobromide (C ₆ D ₅ Br) = 4/1 (volume ratio) 2.4 ml and is a standard substance for chemical shift. A sample temperature of 130 ° C., a pulse angle of 90 °, a pulse interval of 20 seconds using a Bruker BioSpin Corporation AV400M NMR apparatus equipped with a cryoprobe and dissolved in a 10 mmφ NMR sample tube together with hexamethyldisiloxane, The number of integration is 500 times or more, and measurement is performed by the proton complete decoupling method. The chemical shift is set such that the methyl carbon peak of hexamethyldisiloxane is set to 1.98 ppm, and the chemical shift of the peak due to other carbon is based on this.

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

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

When the polar group-containing monomer species is (2,7-octadien-1-yl) succinic anhydride, when the polar group-containing monomer is introduced into the main chain of the molecular chain, the structure of A3 (hereinafter referred to as structure A3) ). In this case, a peak of methine carbon A3 _br of structure A3 bonded to the main chain is detected around 38.0 ppm. Moreover, even if the polar group-containing monomer is introduced into the main chain or at the end of the molecular chain, a peak of the methine carbon A3 _CH of the succinic anhydride group is generated around 41.0 ppm. When the integrated intensity of the peak of carbon A3 _br near 38.0 ppm is expressed as I _38.0 , and the peak integrated intensity of carbon A3 _CH near _41.0 ppm is expressed as I _41.0 etc., the total structural unit amount of the polar group Content of structure A3 is calculated | required from Formula-3, 4.

Total amount of polar group structural units (mol%)
= 2 x I _41.0 x 100 / (2 x I _41.0 + I _29.9 ) Formula 3

Structure A3 content (mol%)
= 2 × I _38.0 × 100 / (2 × I _41.0 + I _29.9 ) ... Formula-4

In the polar group-containing olefin copolymer of the present invention, the amount of structural units derived from the polar group-containing monomer contained in the molecular chain is greater than the amount of structural units derived from the polar group-containing monomer contained in the molecular chain terminal. However, it is essential for introducing a sufficient amount of polar groups into the polar group-containing olefin copolymer without reducing the molecular weight. When the amount of structural units derived from the polar group-containing monomer contained in the molecular chain is less than the amount of structural units derived from the polar group-containing monomer contained at the molecular chain end, most of the polar groups must be present at the molecular chain end. It becomes. As the molecular weight increases, the polar group content in the molecular chain relatively decreases, and sufficient adhesion cannot be obtained. Moreover, in order to increase the polar group content in the molecular chain, it is necessary to reduce the molecular weight, but as described below, in order to have sufficient adhesion with different polar materials, a specific range is required. Therefore, it is impossible to achieve both a sufficiently large molecular weight and a polar group content.

The amount of the structural unit derived from the polar group-containing monomer contained in the molecular chain is selected from the range of 10 to 0.001 mol%, preferably 5 to 0.01 mol%, more preferably 2 to 0.03 mol%. The polar group-containing olefin copolymer of the present invention is preferably present.
On the other hand, the structural unit amount derived from the polar group-containing monomer contained at the molecular chain terminal is selected from the range of 10 mol% or less, preferably 5 mol% or less, more preferably 0.1 mol% or less, and about 0.001 mol%. It may be present in very small amounts or 0 mol%.

The polar group-containing olefin copolymer in the present invention is desirably a random copolymer of ethylene or a copolymer of an α-olefin having 3 to 20 carbon atoms and a polar group-containing monomer.
An example of the molecular structure of the polar group-containing olefin copolymer in the present invention is shown in the following formula (i). Random copolymer is the probability that an A structural unit and a B structural unit of the molecular structure example shown in formula (i) will find each structural unit at a position in a given molecular chain, and its adjacent structural units. It is a copolymer unrelated to the type of Moreover, the molecular chain terminal of the polar group-containing olefin copolymer may be ethylene, an α-olefin having 3 to 20 carbon atoms, or a polar group-containing monomer.
As described below, in the molecular structure (example) of the polar group-containing olefin copolymer in the present invention, ethylene or an α-olefin having 3 to 20 carbon atoms and a monomer containing a carboxyl group or a derivative thereof are random copolymers. Is forming.

（ｉ）

(I)

In the formula (i), A is ethylene or an α-olefin having 3 to 20 carbon atoms, and B is a monomer containing a carboxyl group or a derivative thereof.

For reference, when the molecular structure (example) of an olefin copolymer having a polar group introduced by graft modification is listed in the following formula (ii), ethylene or an α-olefin having 3 to 20 carbon atoms was copolymerized. A part of the olefin copolymer is graft-modified to a monomer containing a carboxyl group or a derivative thereof.

（ｉｉ）

(Ii)

  In formula (ii), A is ethylene or an α-olefin having 3 to 20 carbon atoms, and B is a monomer containing a carboxyl group or a derivative thereof.

(6) Weight average molecular weight (Mw) of polar group-containing olefin copolymer
The weight average molecular weight (Mw) of the polar group-containing olefin copolymer is usually in the range of 45,000 to 1,000,000, preferably 45,500 to 500,000, more preferably 46,000 to 300,000. It is desirable to be.
If the Mw is less than 45,000, the adhesiveness with a highly polar dissimilar material is not sufficient, and if it exceeds 1,000,000, the melt viscosity becomes very high and the molding process becomes difficult.

The reason why the adhesiveness with a different polar material is insufficient when the weight average molecular weight (Mw) of the polar group-containing olefin copolymer is lower than 45,000 will be described below.
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”. The
When the adhesive evaluation result shown in the Example is seen, when the weight average molecular weight (Mw) of a polar group containing olefin copolymer becomes larger than 45,000, it will be understood that the measured adhesive strength increases. This is probably because the adhesion performance of the polar group-containing olefin copolymer is related to the cohesive strength of the resin. If the molecular chain of the polar group-containing olefin copolymer is longer than a certain degree, the polymer has sufficient cohesive strength to develop adhesive performance. As a result, if the weight average molecular weight (Mw) is larger than 45,000, sufficient adhesion is achieved. It is presumed to show sex.

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

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

The GPC measurement method according to the present invention is as follows. A weight average molecular weight (Mw) and a number average molecular weight (Mn) were obtained by performing measurement under the following conditions using a 150C type manufactured by Waters.
Column: ShowdexHT-G and HT-806M × 2 Solvent: Orthodichlorobenzene (ODCB) Temperature: 140 ° C. Flow rate: 1.0 ml / min The column was calibrated with monodisperse polystyrene manufactured by Showa Denko (S-7300). , S-3900, S-1950, S-1460, S-1010, S-565, S-152, S-66.0, S-28.5, S-5. ).
n-eicosane and n-tetracontane were measured, and the logarithmic values of elution time and molecular weight were approximated by a quartic equation. In addition, the following formula was used for conversion of the molecular weight of polystyrene and polyethylene. M _PE = 0.468 × M _PS

(7) Melting | fusing point of polar group containing olefin copolymer Melting | fusing point of the polar group containing olefin copolymer in this invention is shown by the peak temperature of the endothermic curve measured with the differential scanning calorimeter (DSC).
Assuming polyethylene, the melting point is preferably 50 ° C to 140 ° C, more preferably 60 ° C to 138 ° C, and most preferably 70 ° C to 135 ° C.
If it is lower than this range, the heat resistance is not sufficient, and if it is higher than this range, the adhesiveness is poor.

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

(1) Polymerization catalyst The type of polymerization catalyst according to the present invention is a copolymerization of ethylene or an α-olefin having 3 to 20 carbon atoms with a polar group-containing monomer containing a carboxyl group or a dicarboxylic anhydride group. Although it will not specifically limit if possible, For example, there exists the method of superposing | polymerizing using the transition metal compound which belongs to any of the 5-11 groups which have a chelating ligand as a catalyst.
Specific examples of preferred transition metals include vanadium atom, niobium atom, tantalum atom, chromium atom, molybdenum atom, tungsten atom, manganese atom, iron atom, platinum atom, ruthenium atom, cobalt atom, rhodium atom, nickel atom, palladium atom, A copper atom etc. are mentioned.
Among these, vanadium atom, iron atom, platinum atom, cobalt atom, nickel atom, palladium atom, rhodium atom are preferable, and platinum atom, cobalt atom, nickel atom, palladium atom, rhodium atom are particularly preferable. is there.
In particular, an element belonging to Group 10 is preferable from the viewpoint of polymerization activity, and preferably a nickel atom or a palladium atom. In particular, nickel (II) is preferable from the viewpoint of price and the like. These metals may be single or plural.

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.

In particular, the structure of the metal complex suitable for obtaining the polar group-containing olefin copolymer of the present invention is an arylphosphine compound, arylarsine compound or arylantimony compound which may have a substituent as a chelating ligand. And a transition metal catalyst in which a triarylphosphine or a triarylarsine compound which may have a substituent is coordinated to palladium or nickel metal.
Furthermore, at least one of the aryl groups in the triarylphosphine compound or triarylarsine compound is preferably a phenyl group substituted with a secondary or tertiary alkyl group.
In particular, transition metal complexes represented by the following structural formulas (A) and / or (B) are preferred from the viewpoint of polymerization activity.

（構造式（Ａ）、（Ｂ）において、Ｍは、上述の遷移金属を表す。Ｘ^１は、酸素、硫黄、−ＳＯ_３−、又は−ＣＯ_２−を表す。Ｙ^１は、炭素又はケイ素を表す。ｎは、０又は１の整数を表す。Ｅ^１は、リン、砒素又はアンチモンを表す。Ｒ^３及びＲ^４は、それぞれ独立に、水素原子又は炭素数１ないし３０のヘテロ原子を含有してもよい炭化水素基を表す。Ｒ^５は、それぞれ独立に、水素原子、ハロゲン原子、炭素数１ないし３０のヘテロ原子を含有してもよい炭化水素基を表す。Ｒ^６及びＲ^７は、それぞれ独立に、水素原子、ハロゲン原子、炭素数１ないし３０のヘテロ原子を含有してもよい炭化水素基、ＯＲ^２、ＣＯ_２Ｒ^２、ＣＯ_２Ｍ’、Ｃ（Ｏ）Ｎ（Ｒ^１）_２、Ｃ（Ｏ）Ｒ^２、ＳＲ^２、ＳＯ_２Ｒ^２、ＳＯＲ^２、ＯＳＯ_２Ｒ^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_３Ｍ’、ＰＯ_３Ｍ’_２、Ｐ（Ｏ）（ＯＲ^２）_２Ｍ’又はエポキシ含有基を表す。Ｍ’は、アルカリ金属、アルカリ土類金属、アンモニウム、４級アンモニウム又はフォスフォニウムを表し、ｘは、０から３までの整数、ｙは、０から２までの整数を表す。なお、Ｒ^６とＲ^７が互いに連結し、脂環式環、芳香族環、又は酸素、窒素、硫黄から選ばれるヘテロ原子を含有する複素環を形成してもよい。この時、環員数は５〜８であり、該環上に置換基を有していても、有していなくてもよい。Ｒ^１は、水素又は炭素数１ないし２０の炭化水素基を表す。Ｒ^２は、炭素数１ないし２０の炭化水素基を表す。Ｌ^１は、Ｍに配位したリガンドを表す。また、Ｒ^３とＬ^１が互いに結合して環を形成してもよい。）


より好ましくは、下記構造式（Ｃ）で表される遷移金属錯体である。

(In Structural Formulas (A) and (B), M represents 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 R ³ and R ⁴ each independently contains a hydrogen atom or a heteroatom having 1 to 30 carbon atoms R ⁵ represents a hydrocarbon group that may independently contain a hydrogen atom, a halogen atom, or a hetero atom having 1 to 30 carbon atoms, wherein R ⁶ and R ⁷ are , Each independently a hydrogen atom, a halogen atom, a hydrocarbon group that may contain a C 1-30 hetero atom, 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, _{^{SO 2 R 2, P (O}} ) (OR 2) 2-y (R 1) y, CN, NHR 2, N (R 2) 2, Si (OR 1) 3-x (R 1) x, OSi ( OR ¹ ) _3-x (R ¹ ) _x , NO ₂ , SO ₃ M ′, PO ₃ M ′ ₂ , P (O) (OR ² ) ₂ M ′ or an epoxy-containing group, where M ′ represents an alkali metal Represents 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 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, wherein the number of ring members is 5 to 8, and may have a substituent, may .R ¹ may not have a hydrogen or a hydrocarbon of from 20 C 1 -C .R ² representing a is .L ¹ representing a hydrocarbon group having 1 to 20 carbon atoms, represents a ligand coordinated to M. Further, even if bonded to form a ring R ³ and L ¹ are each other Good.)


More preferably, it is a transition metal complex represented by the following structural formula (C).

（構造式（Ｃ）において、Ｍは、上述の遷移金属を表す。Ｘ^１は、酸素原子、硫黄、−ＳＯ_３−、又は−ＣＯ_２−を表す。Ｙ^１は、炭素又はケイ素を表す。ｎは、０又は１の整数を表す。Ｅ^１は、リン、砒素又はアンチモンを表す。Ｒ^３及びＲ^４は、それぞれ独立に、水素原子又は炭素数１ないし３０のヘテロ原子を含有してもよい炭化水素基を表す。Ｒ^５は、それぞれ独立に、水素原子、ハロゲン原子、炭素数１ないし３０のヘテロ原子を含有してもよい炭化水素基を表す。Ｒ^８、Ｒ^９、Ｒ^１０及びＲ^１１は、それぞれ独立に、水素原子、ハロゲン原子、炭素数１ないし３０のヘテロ原子を含有してもよい炭化水素基、ＯＲ^２、ＣＯ_２Ｒ^２、ＣＯ_２Ｍ’、Ｃ（Ｏ）Ｎ（Ｒ^１）_２、Ｃ（Ｏ）Ｒ^２、ＳＲ^２、ＳＯ_２Ｒ^２、ＳＯＲ^２、ＯＳＯ_２Ｒ^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_３Ｍ’、ＰＯ_３Ｍ’_２、Ｐ（Ｏ）（ＯＲ^２）_２Ｍ’又はエポキシ含有基を表す。Ｍ’は、アルカリ金属、アルカリ土類金属、アンモニウム、４級アンモニウム又はフォスフォニウムを表し、ｘは、０から３までの整数、ｙは、０から２までの整数を表す。なお、Ｒ^８〜Ｒ^１１から適宜選択された複数の基が互いに連結し、脂環式環、芳香族環、又は酸素、窒素、硫黄から選ばれるヘテロ原子を含有する複素環を形成してもよい。この時、環員数は５〜８であり、該環上に置換基を有していても、有していなくてもよい。Ｒ^１は、水素又は炭素数１ないし２０の炭化水素基を表す。Ｒ^２は、炭素数１ないし２０の炭化水素基を表す。Ｌ^１は、Ｍに配位したリガンドを表す。また、Ｒ^３とＬ^１が互いに結合して環を形成してもよい。）

(In Structural Formula (C), M represents the above-described transition metal. X ¹ represents an oxygen atom, 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 each independently contain a hydrogen atom or a hetero atom having 1 to 30 carbon atoms. R ⁵ represents a hydrocarbon group that may independently contain a hydrogen atom, a halogen atom, or a hetero atom having 1 to 30 carbon atoms, R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group which 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 an epoxy-containing group. Represents an alkali metal, an 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 ^{8 to} R A plurality of groups appropriately selected from ¹¹ may be connected to each other to form an alicyclic ring, an aromatic ring, or a heterocyclic ring containing a heteroatom selected from oxygen, nitrogen, and sulfur. The number of members is 5 to 8, and it may or may not have a substituent on the ring. ¹ represents hydrogen or a hydrocarbon group having 1 to 20 carbon atoms, R ² represents a hydrocarbon group having 1 to 20 carbon atoms, L ¹ represents a ligand coordinated to M, and R ³ And L ¹ may be bonded to each other to form a ring.)

Here, as a catalyst of the Group 5-10 transition metal compound having a chelating ligand, catalysts called a so-called shop type and a drent type are typically known.
The Shop-based catalyst is a catalyst in which a phosphorus-based ligand having an aryl group which may have a substituent is coordinated to a transition metal of Groups 9 to 11, preferably nickel metal (for example, WO 2010-050256). See the publication). The Drent system is a catalyst in which a phosphorus-based ligand having an aryl group having a SO ₃ group is coordinated to a transition metal of group 8 to 10, preferably palladium metal (see, for example, JP 2010-202647 A). reference).

(2) Use Mode of Polymerization Catalyst The polymerization catalyst of the present invention may be used alone or may be used by being supported on a carrier. As a usable carrier, any carrier can be used as long as the gist of the present invention is not impaired.
In general, inorganic oxides and polymer carriers can be preferably used. Specific examples include SiO ₂ , Al ₂ O ₃ , MgO, ZrO ₂ , TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, ThO ₂ , or a mixture thereof, and SiO ₂ —Al ₂ O _3. , SiO ₂ —V ₂ O ₅ , SiO ₂ —TiO ₂ , SiO ₂ —MgO, SiO ₂ —Cr ₂ O ₃ and other mixed oxides can also be used, inorganic silicate, polyethylene carrier, polypropylene carrier, A polystyrene carrier, polyacrylic acid carrier, polymethacrylic acid carrier, polyacrylic acid ester carrier, polyester carrier, polyamide carrier, polyimide carrier and the like can be used.
These carriers are not particularly limited in particle size, particle size distribution, pore volume, specific surface area, etc., and any one can be used.

  The catalyst component may be prepolymerized in the presence of olefin in the polymerization tank or outside the polymerization tank. Olefin means a hydrocarbon containing at least one carbon-carbon double bond, and examples thereof include ethylene, propylene, 1-butene, 1-hexene, 3-methylbutene-1, styrene, divinylbenzene, and the like. There is no restriction | limiting, You may use the mixture of these and another olefin. Preferred are olefins having 2 or 3 carbon atoms. The olefin can be supplied by any method, such as a supply method for maintaining the olefin at a constant speed or in a constant pressure state, a combination thereof, or a stepwise change.

(3) Copolymerization reaction The copolymerization reaction in the present invention may be carried out using hydrocarbon solvents such as propane, n-butane, isobutane, n-hexane, n-heptane, toluene, xylene, cyclohexane, methylcyclohexane, and liquefied α-olefins. Liquid or in the presence or absence of polar solvents such as diethyl ether, ethylene glycol dimethyl ether, tetrahydrofuran, dioxane, ethyl acetate, methyl benzoate, acetone, methyl ethyl ketone, formylamide, acetonitrile, methanol, isopropyl alcohol, ethylene glycol, etc. Done below. Moreover, you may use the mixture of the liquid compound described here as a solvent. In addition, in order to obtain high polymerization activity and high molecular weight, the above-mentioned hydrocarbon solvent is more preferable.

In the copolymerization in the present invention, the copolymerization can be carried out in the presence or absence of a known additive. As the additive, a radical polymerization inhibitor or an additive having an action of stabilizing the produced copolymer is preferable. Examples of preferable additives include quinone derivatives and hindered phenol derivatives.
Specifically, monomethyl ether hydroquinone, 2,6-di-t-butyl 4-methylphenol (BHT), reaction product of trimethylaluminum and BHT, reaction product of alkoxide of tetravalent titanium and BHT, etc. Can be used.
Further, as an additive, inorganic and / or organic fillers may be used and polymerization may be performed in the presence of these fillers.

(4) Polymerization method In the present invention, the polymerization method is not particularly limited. Slurry polymerization in which at least a part of the produced polymer becomes a slurry in the medium, bulk polymerization using the liquefied monomer itself as a medium, gas phase polymerization performed in the vaporized monomer, or a polymer produced in the monomer liquefied at high temperature and high pressure High-pressure ionic polymerization in which at least a part of the polymer is dissolved is preferably used.
In addition, the polymerization format may be any of batch polymerization, semi-batch polymerization, and continuous polymerization. Moreover, living polymerization may be sufficient and it may superpose | polymerize, combining chain transfer. Furthermore, so-called chain shunting agent (CSA) may be used in combination to perform chain shunting reaction or coordinative chain transfer polymerization (CCTP).
For specific manufacturing processes and conditions, for example, JP 2010-260913 A and JP 2010-202647 A can be referred to.

There are no particular restrictions on the copolymerization temperature, copolymerization pressure, and copolymerization time, but usually optimum settings can be made in consideration of productivity and process capability from the following ranges.
That is, the copolymerization temperature is usually −20 ° C. to 290 ° C., preferably 0 ° C. to 250 ° C., the copolymerization pressure is 0.1 MPa to 100 MPa, preferably 0.3 MPa to 90 MPa, and the copolymerization time is 0.00. It can be selected from the range of 1 minute to 10 hours, preferably 0.5 minutes to 7 hours, more preferably 1 minute to 6 hours.
In the present invention, the copolymerization is generally performed in an inert gas atmosphere. For example, a nitrogen or argon atmosphere can be used, and a nitrogen atmosphere is preferably used. A small amount of oxygen or air may be mixed.

  There are no particular limitations on the supply of catalyst and monomer to the copolymerization reactor, and various supply methods can be employed depending on the purpose. For example, in the case of batch polymerization, it is possible to take a technique in which a predetermined amount of monomer is supplied to a copolymerization reactor in advance and a catalyst is supplied thereto. In this case, an additional monomer or an additional catalyst may be supplied to the copolymerization reactor. In the case of continuous polymerization, a method in which a predetermined amount of monomer and catalyst are continuously or intermittently supplied to the copolymerization reactor to carry out the copolymerization reaction continuously can be employed.

  Regarding the control of the copolymer composition, a method of controlling a copolymer by supplying a plurality of monomers to a reactor and changing the supply ratio thereof can be generally used. Other methods include controlling the copolymer composition using the difference in monomer reactivity ratio due to the difference in catalyst structure, and controlling the copolymer composition using the polymerization temperature dependence of the monomer reactivity ratio. .

A conventionally known method can be used for controlling the molecular weight of the copolymer. That is, a method for controlling the molecular weight by controlling the polymerization temperature, a method for controlling the molecular weight by controlling the monomer concentration, a method for controlling the molecular weight by using a chain transfer agent, and a control of the ligand structure in the transition metal complex. For example, controlling the molecular weight.
When a chain transfer agent is used, a conventionally known chain transfer agent can be used. For example, hydrogen, metal alkyl, etc. can be used.

[III] Additive The polar group-containing olefin copolymer according to the present invention includes an antioxidant, an ultraviolet absorber, a lubricant, an antistatic agent, a colorant, a pigment, and a crosslinking agent within the range not departing from the gist of the present invention. Additives such as a foaming agent, a nucleating agent, a flame retardant, and a filler may be blended.

[IV] Adhesive Material The polar group-containing olefin copolymer of the present invention has a specific molecular structure and resin physical properties, so that it exhibits high adhesiveness with other substrates, and is an industrially useful laminate. Made it possible to manufacture.
That is, the adhesion performance is obtained by copolymerizing ethylene or an α-olefin having 3 to 20 carbon atoms and a polar group-containing monomer containing a carboxyl group or a dicarboxylic anhydride group in the presence of a transition metal catalyst. The polar group-containing olefin copolymer to be produced is expressed by satisfying the following requirements 1) and 2).
1) The amount of structural units derived from the polar group-containing monomer in the polar group-containing olefin copolymer is 0.001 to 10 mol%.
2) The weight average molecular weight (Mw) calculated | required by gel permeation chromatography (GPC) is 45,000-1,000,000.
Its superiority as an adhesive is demonstrated by the data of the examples described later and the comparison between the examples and the comparative examples.

[IV] Laminate (1) Material of Laminate The laminate of the present invention is a laminate comprising a layer composed of the polar group-containing olefin copolymer of the present invention and a substrate layer, and the substrate layer comprises Polyolefin resin such as polyethylene and polypropylene, polyamide resin, polyester resin, highly polar thermoplastic resin such as saponified ethylene / vinyl acetate copolymer resin (EVOH), metal material such as aluminum and steel, etc. The material can be exemplified.
Specific examples of the substrate include high-density polyethylene, medium-density polyethylene, low-density polyethylene, ethylene-vinyl acetate copolymer, ethylene-acrylic acid ester copolymer, and other polyethylene resins, ionomers, homopolypropylene resins, and propylene. And other α-olefin copolymers such as polypropylene resins, poly-1-butene, olefin resins such as poly-4-methyl-1-pentene, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyacrylate , Vinyl polymers such as polyacrylonitrile, nylon 6, nylon 66, nylon 10, nylon 11, nylon 12, nylon 610, polyamide resins such as polymethaxylylene adipamide, polyethylene terephthalate, polyethylene terephthalate / isoform Rate, a thermoplastic resin film or sheet having a film-forming ability such as a polyester-based resin such as polybutylene terephthalate, polyvinyl alcohol, ethylene / vinyl alcohol copolymer, polycarbonate resin, cellophane, or the like (stretched products thereof) Printed matter), metal foils or metal plates such as aluminum, iron, copper, or alloys based on these, vapor deposited films of inorganic oxides such as silica vapor deposited plastic films, alumina vapor deposited plastic films, metals such as gold, silver, and aluminum Or vapor deposition films of compounds other than these metal oxides, paper such as high-quality paper, kraft paper, paperboard, glassine paper, and synthetic paper, cellophane, woven fabric, and non-woven fabric.

These base material layers can be appropriately selected depending on the use and the type of the object to be packaged. For example, if the package is a perishable food, a resin having excellent transparency, rigidity, and gas permeation resistance, such as polyamide, polyvinylidene chloride, ethylene / vinyl alcohol copolymer, polyvinyl alcohol, and polyester. 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.
As the barrier resin, polyamide resin, polyester resin, saponified ethylene-vinyl acetate copolymer (EVOH), polyvinylidene chloride resin, polycarbonate resin, expanded polypropylene (OPP), expanded polyester (OPET), stretched Examples thereof include metals such as polyamide, alumina vapor-deposited film and silica vapor-deposited film, vapor-deposited films of inorganic oxides, metal vapor-deposited films such as aluminum vapor-deposited, and metal foils.

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

(3) Manufacture of laminates As processing methods, extrusion molding such as normal press molding, air-cooled inflation molding, air-cooled two-stage cooling inflation molding, high-speed inflation molding, flat die molding (T-die molding), water-cooled inflation molding, etc. And conventionally known methods such as laminating methods such as extrusion laminating, sand laminating, and dry laminating, hollow blow molding, pressure forming, injection molding, and rotational molding.

(4) Laminate Laminate The laminate laminate in the present invention is a laminate that can be produced by a known laminating method such as extrusion laminating, sand laminating, or dry laminating. It is a laminate which can be produced by laminating a laminate material containing the polar group-containing olefin copolymer of the invention and at least one substrate layer.
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, on the side where the layer containing the polar group-containing olefin copolymer of the base material used in the present invention is formed, between the base material and the layer containing the polar group-containing olefin copolymer. Moreover, in order to improve the barrier property, it is easy to laminate the aluminum foil, polyester film, various barrier films and the like.
As the base material layer to be laminated with the laminating material according to the present invention, various materials described as the base material layer in the laminate of the present invention described above can be appropriately used.

(5) Multilayer coextrusion molded product The multilayer coextrusion molded product in the present invention is a multilayer coextrusion molded product that can be molded by a known multilayer coextrusion molding, and the polar group-containing olefin copolymer of the present invention Is a multilayer coextrusion molded article including at least a layer containing 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 in 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), and multilayer tubular. Well-known multilayer coextrusion molding, such as product molding and multilayer corrugated pipe molding, can be mentioned. As the base material layer in the multilayer coextrusion molded product in the present invention, various materials described as the base material layer in the laminate of the present invention described above can be appropriately used. The multilayer coextrusion molded product according to the present invention is obtained by processing the layer containing the polar group-containing olefin copolymer according to the present invention and an appropriate base material by an appropriate molding method, thereby producing a multilayer film, multilayer blow molded product, multilayer It can be manufactured as a known multilayer coextrusion product such as a tubular prize, a multilayer sheet, other multilayer pipes, multilayer hoses, multilayer tubes, multilayer corrugated pipes and the like.

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

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

(8) Multilayer tubular molded article The multilayer tubular molded article in the present invention is a multilayer tubular molded article that can be molded by a known multilayer tubular molding method, and contains the polar group-containing olefin copolymer of the present invention. A multilayer tubular molded article including at least a layer and a base material layer. In the multilayer tubular molding method of the present invention, for example, a plurality of materials are combined into a layer by extruding a plurality of thermoplastic materials at the same time, and continuously discharged into a discharge port shape by discharging from a circular or irregular discharge port. Examples thereof include a method of obtaining a tubular molded product by forming a tubular molded product having a similar shape, and molding and cooling and solidifying by an appropriate shaping method and a cooling method. The discharge port shape of the multilayer tubular molding method in 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 forming method of the multilayer tubular forming method in 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, sandwiching an extruded molten material with a mold, A known molding method such as a method of cooling while shaping by evacuation or the like from the mold side 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 article in the present invention, various materials described as the base material layer in the above-described laminate of the present invention can be appropriately used.

(9) Multilayer sheet The multilayer sheet in this invention is a multilayer sheet which can be manufactured by well-known multilayer sheet molding, and the layer and base material layer which contain the polar group containing olefin copolymer of this invention A multilayer sheet containing at least Various known methods can be used as a method for producing a multilayer sheet in the present invention. For example, a plurality of materials are compounded into layers by simultaneously extruding a plurality of thermoplastic materials, and a flat die, a circular die, or the like is known. A method of forming into a sheet by discharging from the die can be mentioned. In these methods, the end of the sheet may be slit as necessary, or a process of opening a circular sheet may be added. As the base material layer of the multilayer sheet in the present invention, various materials described as the base material layer in the laminate of the present invention described above can be appropriately used.

(10) Extruded product The extruded product in the present invention is an extruded product obtained by molding the polar group-containing olefin copolymer according to the present invention by extrusion molding. Extrusion products in the present invention include various types of inflation molding 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, and other known extrusions. Can be manufactured by molding.

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

(12) Compound Injection Molded Product The compound injection molded product in the present invention includes at least a member containing the polar group-containing olefin copolymer of the present invention, and a plurality of members are compounded using injection molding. This is a composite injection-molded product that can be manufactured. The composite injection-molded product may be composed of two or more kinds of materials, for example, two different kinds of members containing the polar group-containing olefin copolymer of the present invention may be composited. The member comprising the polar group-containing olefin copolymer of the present invention and the member comprising the substrate may be combined. Further, three or more kinds of members may be combined. The composite injection-molded article in the present invention can be molded by a known injection molding method capable of composite injection molding. Although it may be a composite injection-molded product formed by combining two or more types of members containing the polar group-containing olefin copolymer of the present invention, it has high adhesion to different materials that are the characteristics of the present invention. In view of the above, it is preferable that the composite injection molded product is combined with a member made of different materials. As an injection molding method capable of producing a composite injection molded product, a known method can be exemplified. For example, the polar group-containing olefin copolymer of the present invention is processed into a member in advance by a known method such as injection molding, extrusion molding, press molding, or cutting, and the base is further inserted in an injection mold. A method of compounding by injecting a material material, processing a base material into a member in advance, and injecting the polar group-containing olefin copolymer of the present invention with the base material member inserted in an injection mold A composite method by using a multicolor injection molding machine having a plurality of injection units, and sequentially injecting the polar group-containing olefin copolymer and the base material in the present invention into a mold in an appropriate order. Can be mentioned.
In the composite injection-molded article of the present invention, as the kind of the member to be composited with the polar group-containing olefin copolymer of the present invention, various materials described as the base material layer in the laminate of the present invention described above are appropriately used. I can do things.

(13) Coated metal member The coated metal member in the present invention is a coated metal member that can be produced by coating a metal with a metal coating material using the polar group-containing olefin copolymer of the present invention as a metal coating material. It is. The coated metal member in 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 Wire coated with, coated metal coated by fluid dipping method using coated metal material processed into powder, coated metal coated by electrostatic coating method using coated metal material processed into powder, etc. I can list them.

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

(1) Polar group-containing structural unit amount in polar group-containing olefin copolymer The polar group-containing structural unit amount in the polar group-containing olefin copolymer was determined using a ¹³ C-NMR spectrum. Details are described in the column “(5) Structural unit amount of polar group-containing monomer” in the present specification.

(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. These calculation methods are described in detail in the column “(6) Weight average molecular weight (Mw) of polar group-containing olefin copolymer” in the present specification.

(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, an absorption curve when the temperature was raised again at 10 ° C./min was measured, and the peak temperature was taken as the melting point.

(4) Adhesive strength Adhesive strength is prepared by preparing a laminate by pressing a polar group-containing olefin copolymer press plate, an EVOH film, and a polyamide film, and superposing and hot pressing the two types. It was measured by performing the test. The adjustment method / measurement method of each process will be described in order.

Method for preparing polar group-containing olefin copolymer resin plate Polar group-containing olefin copolymer is placed in a hot press mold having dimensions of 50 mm x 60 mm and a thickness of 1 mm, and a heat press machine having a surface temperature of 180C. After preheating for 5 minutes, residual gas in the molten resin was degassed by repeating pressurization and decompression, and further pressurized at 4.9 MPa and held for 5 minutes. Then, it transferred to the press machine with a surface temperature of 25 degreeC, it cooled by hold | maintaining for 3 minutes with the pressure of 4.9 Mpa, and produced the polar group containing olefin copolymer resin board about 0.9 mm in thickness.

Method for preparing EVOH film Using a multi-layer T-die molding machine, after forming a two-layer three-layer multilayer film with EVOH as the central layer and LLDPE as both outer layers, the LLDPE in the outer layer was peeled off, and the thickness was 150 μm. An EVOH monolayer film was prepared. The film forming conditions are as follows.
Molding machine: 2 types, 3 layers T die Molding temperature: 200 ° C. Layer structure: LLDPE / EVOH / LLDPE Film thickness: 350 μm (100 μm / 150 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: EVOH (Kuraray Co., Ltd. Brand: EVAL F101B)

Method for preparing 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 give a thickness of 150 μm. A polyamide monolayer 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: 350 μm (100 μm / 150 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)

Method for preparing laminate of EVOH film and polar group-containing olefin copolymer By resin plate of polar group-containing olefin copolymer obtained by the above resin plate preparation method, and by the above-mentioned method for preparing EVOH film The obtained EVOH film was cut to a size of 50 mm × 60 mm, placed in a hot press mold with dimensions: 50 mm × 60 mm, thickness 1 mm, and 4.9 MPa using a hot press with a surface temperature of 200 ° C. For 4 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 polar group containing olefin copolymer and EVOH was prepared.

Method for preparing laminate of polyamide film and polar group-containing olefin copolymer According to the method for preparing the polyamide film and the resin plate of the polar group-containing olefin copolymer obtained by the resin plate preparation method described above The obtained polyamide film cut into a size of 50 mm × 60 mm is superposed, put into a mold for heating press with dimensions: 50 mm × 60 mm, thickness 1 mm, and 4.9 MPa using a hot press machine with a surface temperature of 250 ° 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 polar group containing olefin copolymer and polyamide was prepared.

Method for measuring adhesive strength of laminate The laminate obtained by the laminate preparation method was cut into a width of 10 mm, and a speed tester of 50 mm / min was used using a Tensilon (Toyo Seiki Co., Ltd.) tensile tester. Now, the adhesive strength was measured by T-peeling. The unit of adhesive strength is indicated by gf / 10 mm. When the adhesive strength is very strong, the polar group-containing olefin copolymer 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 tensile breaking strength of the polar group-containing olefin copolymer layer, and it can be determined that the adhesiveness is very high. 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.

[Example 1]
Production and polymerization of the Drent catalyst 100 μmol of palladium bisdibenzylideneacetone and phosphorus sulfonic acid ligand (I) were weighed in a 30 mL flask sufficiently purged with nitrogen, and dehydrated toluene (10 mL) was added. The catalyst slurry was prepared by processing for 10 minutes with an ultrasonic vibrator.
Next, the inside of a stainless steel autoclave with an induction stirrer with an internal volume of 2.4 liters was replaced with purified nitrogen, and purified toluene, 5-norbornene-2,3-, so that the concentration of the polar monomer was 0.1 mol / L. Dicarboxylic anhydride was introduced into the autoclave under a purified nitrogen atmosphere.
The previously prepared catalyst solution was added, and polymerization was started at 100 ° C. and an ethylene pressure of 1 MPa. During the reaction, the temperature was kept at 100 ° C., and ethylene was continuously supplied so that the pressure was maintained.
After completion of the polymerization, ethylene was purged, the autoclave was cooled to room temperature, the obtained polar group-containing olefin copolymer was reprecipitated with acetone (1 L), and the precipitated copolymer was filtered. The solid polar group-containing olefin copolymer obtained by filtration was washed with acetone, dried under reduced pressure at 60 ° C. for 3 hours, and finally the polar group-containing olefin copolymer was recovered. The polymerization conditions and activity are shown in Table 1.

[Examples 2-11, 14 Comparative Examples 1-6]
Among the methods described in Example 1, polymerization is performed by changing the ligand species, the ligand amount, the polar group-containing monomer species, the polar group-containing monomer concentration, the polymerization pressure amount, the polymerization temperature, and the polymerization time, respectively. Thus, polar group-containing olefin copolymers of Examples 2 to 11, Example 14, and Comparative Examples 1 to 6 were prepared. The polymerization conditions and activity are shown in Table 1. Further, the ligand types (I) to (IV) in Table 1 are shown in the following chemical formula. Table 2 shows the analytical data of the polar group-containing olefin copolymer obtained in each Example and each Comparative Example, and the adhesive strength between the EVOH film. In Table 2, the terminal introduction is the amount of the polar group-containing structural unit of the polar group-containing monomer introduced at the terminal, and the main chain introduction is the polarity of the polar group-containing monomer introduced into the molecular chain (in the main chain). The group-containing structural unit amount and the total structural unit indicate the total amount of the introduced polar group-containing structural unit, respectively. In Table 2, “ND” means unmeasured.

Example 12
Synthesis of SHOP ligand: The following ligand B-27DM was obtained according to the method described in International Publication 2010-050256 (Synthesis Example 4).

Complex formation:
First, 112 mg (200 μmol) of the following B-27DM was weighed into a 50 ml eggplant-shaped flask. 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.
Next, the inside of a stainless steel autoclave with an induction stirrer with an internal volume of 2.4 liters was replaced with purified nitrogen, and purified toluene (1.0 L) and 5-norbornene so that the concentration of the polar-containing monomer was 0.05 mol / L. -2,3-dicarboxylic anhydride (8.2 g) was introduced into the autoclave under a purified nitrogen atmosphere. After setting the temperature of the autoclave to 100 ° C., 1 ml of a toluene solution of tri-normal octyl aluminum diluted to 0.1 mol / l was added. Thereafter, nitrogen was introduced to 0.3 MPa, and ethylene was further introduced to 2.8 MPa. After the temperature and pressure were stabilized, 2 ml (20 μmol) of the previously prepared complex solution was injected with nitrogen to initiate the reaction. During the reaction, the temperature was kept at 100 ° C., and polymerization was carried out for 30 minutes by continuously supplying ethylene so that the pressure was maintained.
After the polymerization was completed, ethylene was purged, the autoclave was cooled to room temperature, and the obtained polar group-containing olefin copolymer was precipitated using acetone (1 L), and the precipitated copolymer was filtered. The solid polar group-containing olefin copolymer obtained by filtration was washed with acetone, dried under reduced pressure at 60 ° C. for 3 hours, and finally the polar group-containing olefin copolymer was recovered. The polymerization conditions and activity are shown in Table 1.

Example 13
Among the methods described in Example 12, the concentration of 5-norbornene-2,3-dicarboxylic acid anhydride was changed to 0.02 mol / l, and the amount of complex solution was changed to 0.5 ml (5 μmol as a complex). For 20 minutes to obtain the polar group-containing olefin copolymer of Example 14. Table 2 shows the analytical data of the polar group-containing olefin copolymer obtained in each example and the adhesive strength between the EVOH film and the polyamide film.

[Consideration of results of Examples and Comparative Examples]
The polar group-containing olefin copolymers of Examples 1 to 14 have a weight average molecular weight (Mw) of 45,000 or more, and the adhesive strength is a value that is considered practically sufficient.
Compared with them, the weight average molecular weight (Mw) of Comparative Examples 1-4 and Comparative Example 6 is less than 45,000, and adhesiveness is inadequate.
In general, in order for a polar group-containing polyolefin to have a strong adhesive strength with a highly polar material, it is considered that a higher polar group content is advantageous. However, in Comparative Examples 1-4 and 6 compared with Examples 1-15, the fact that the adhesiveness was insufficient despite the sufficiently large amount of structural units derived from the polar group monomer is polar The group content does not uniquely determine the adhesiveness, but shows that the weight average molecular weight (Mw) of the polar group-containing olefin copolymer has a strong influence. That is, it has been clarified that adhesiveness is exhibited when the weight average molecular weight (Mw) is 45,000 or more and the structural unit derived from the polar group-containing monomer is 0.001 mol% or more.
Examples 1 to 10, and Examples 12 and 13 are 5-norbornene-2,3-dicarboxylic acid anhydride as a polar group-containing monomer, and Example 11 is 3,6-epoxy-1, as a polar group-containing monomer. Although 2,3,6-tetrahydrophthalic anhydride and Example 14 is a polar group-containing olefin copolymer each containing 2,7-octadien-1-ylsuccinic anhydride as a polar group-containing monomer, Each polar group-containing olefin copolymer containing any polar group-containing monomer exhibits sufficient adhesion. This fact is that the polar group-containing monomer species necessary for obtaining a polar group-containing olefin copolymer having sufficient adhesion performance with a highly polar material is not specified, and a polar group containing a carboxyl group or a dicarboxylic anhydride group If it is a containing monomer, it has shown that it will not be limited.
The olefin copolymer of Comparative Example 5 has a weight average molecular weight (Mw) of 45,000 or more, but the polar group species contained is ethyl acrylate. It was clarified that it is necessary to copolymerize a monomer containing a carboxyl group or a dicarboxylic anhydride group in order to have sufficient adhesiveness with a material having high polarity such as EVOH or polyamide.
Examples 12 and 13 are polar group-containing olefin copolymers produced by a production method different from those in Examples 1 to 10. Even if it is the polar group containing olefin copolymer manufactured by any manufacturing method, each has shown sufficient adhesiveness. This fact indicates that there is no need for a specific production method to obtain a polar group-containing olefin copolymer having sufficient adhesion performance with a highly polar material, and the production method is not limited.
In addition, Examples 12 and 13 show sufficient adhesion performance with polyamide in addition to EVOH. From this fact, it is clear that the polar group-containing olefin copolymer of the present invention has sufficient adhesiveness not only with specific polar materials but also with various polar materials. I made it.
The significance and rationality of the configuration of the present invention (invention specific matter) and the superiority over the prior art are clarified by the good results of each of the above examples and the comparison with each comparative example.

Since the polar group-containing olefin copolymer of the present invention has a specific molecular structure and resin physical properties, it exhibits high adhesiveness with other base materials, making it possible to produce industrially useful laminates. . In addition, the polar group-containing olefin copolymer having a specific molecular structure and resin properties according to the present invention is excellent not only in adhesiveness but also in mechanical and thermal properties, and can be applied as a useful multilayer molded article. Laminated on various base materials, widely used in packaging materials, packaging containers, industrial materials such as fibers, pipes, fuel tanks, hollow containers and drums, civil engineering such as water-stopping materials, and electronics such as electronics and household appliances Used in the electric wire field such as electric wires and cables.

Claims (14)

At least one nonpolar monomer selected from ethylene and an α-olefin having 3 to 20 carbon atoms, and at least one polar group-containing monomer containing a carboxyl group or a dicarboxylic anhydride group, a chelating ligand and a fifth A polar group-containing olefin copolymer obtained by copolymerization in the presence of a transition metal catalyst containing a group 11 metal , wherein the polar group-containing olefin copolymer is a random copolymer, ), 2) and 3) . The method for producing a polar group-containing olefin copolymer characterized by satisfying the above requirements.
1) The amount of structural units derived from the polar group-containing monomer in the polar group-containing olefin copolymer is 0.001 to 10 mol%.
2) The weight average molecular weight (Mw) calculated | required by gel permeation chromatography (GPC) is 45,000-1,000,000.
3) Melting | fusing point represented by the temperature of the maximum peak position of the absorption curve measured with a differential scanning calorimeter is 50 to 140 degreeC. In the polar group-containing olefin copolymer, the structural unit amount derived from the polar group-containing monomer contained in the molecular chain is larger than the structural unit amount derived from the polar group-containing monomer contained in the molecular chain terminal. The manufacturing method of the polar group containing olefin copolymer of Claim 1. The ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) determined by gel permeation chromatography is in the range of 1.5 to 3.5. Or the manufacturing method of the polar group containing olefin copolymer described in Claim 2. The transition metal catalyst according to any one of claims 1 to 3 , wherein the transition metal catalyst is a transition metal catalyst in which a triarylphosphine or a triarylarsine compound is coordinated to palladium or nickel metal. A method for producing a polar group-containing olefin copolymer. Wherein the polar group-containing monomer is a polar group-containing monomer containing a dicarboxylic acid anhydride group, the production of the polar group-containing olefin copolymer according to any one of claims 1 to 4 Way . Method for manufacturing a bonding material containing claim 1 polar group-containing olefin copolymer obtained by the production method described in any one of claims 5. A polar group-containing olefin copolymer obtained by the production method described in any one of claims 1 to 5 , or an adhesive obtained by the production method described in claim 6. A method for producing a laminate comprising at least a layer and a base material layer. The base layer is deposited film of an olefin resin, highly polar thermoplastic resins, metals, inorganic oxides, paper, characterized cellophane, fabric, to be selected from the non-woven fabric, according to claim 7 A method for manufacturing a laminated body. A laminate comprising a polar group-containing olefin copolymer obtained by the production method according to any one of claims 1 to 5 , or an adhesive obtained by the production method according to claim 6. A method for producing a laminated laminate, characterized by being laminated by laminating with one or more base material layers using a material. A layer comprising a polar group-containing olefin copolymer obtained by the production method according to any one of claims 1 to 5 , or an adhesive obtained by the production method according to claim 6. And a method for producing a multilayer coextruded product comprising at least a base material layer. The method for producing a multilayer coextrusion molded product according to claim 10, wherein the multilayer coextrusion molded product is a multilayer film, a multilayer blow molded product, a multilayer tubular molded product, or a multilayer sheet. The injection which contains the adhesive obtained by the polar group containing olefin copolymer obtained by the manufacturing method described in any one of Claims 1-5 , or the manufacturing method described in Claim 6. Manufacturing method of molded products. A member comprising the polar group-containing olefin copolymer obtained by the production method according to any one of claims 1 to 5 , or the adhesive obtained by the production method according to claim 6. And a base material are combined by injection molding, and a method for producing a composite injection molded product The polar group-containing olefin copolymer obtained by the production method described in any one of claims 1 to 5 or the adhesive obtained by the production method described in claim 6 is coated with a metal. A method for producing a polar group-containing olefin copolymer-coated metal member , characterized in that :

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