JP2018039880A - Olefinic resin composition and method for producing the same, molded body and laminated body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an olefinic resin composition excellent in adhesive force retention under high temperature environment.SOLUTION: An olefinic resin composition contains 10-99 pts.mass of an olefinic resin (β) and 1-90 pts.mass of a modified olefinic resin (α), where the olefinic resin (β) contains a graft type polymer [GP] satisfying requirements (i) and (ii), and the modified olefinic resin (α) contains a polar group. (i) an ethylenic copolymer constituting a main chain is formed of a repeating unit derived from ethylene and at least one C3-20 α-olefin of 10-50 mol% with respect to the total repeating unit contained in the main chain. (ii) the side chain is composed of a side chain constituted by an ethylenic polymer and/or a propylene polymer.SELECTED DRAWING: None

Description

  The present invention relates to an olefin-based resin composition, a method for producing the same, and a molded body. More specifically, the present invention relates to a resin composition containing an olefin-based resin containing a specific graft polymer, a method for producing the same, a molded body, and a laminate. About the body.

  Olefin-based resins are excellent in processability, chemical resistance, electrical properties, mechanical properties, etc., so they are processed into extrusion molded products, injection molded products, hollow molded products, films, sheets, fibers, etc. It is used in various fields such as kitchen utensils, packaging films, home appliances, machine parts, electrical parts, and automobile parts.

  Generally, polyolefin resins do not contain polar groups in their molecules, so they have poor affinity and adhesion to polar resins such as nylon, polyester, acrylic resin, ethylene-vinyl alcohol copolymer resin (EVOH), glass, or metals. . Therefore, in order to use them in combination with these materials, conventionally, a method for improving affinity by grafting a polyolefin with a polar group-containing monomer and modifying it is widely performed. (Patent Documents 1 to 5)

  However, even when the polyolefin resin modified in this way is used, there is a problem that the adhesive strength with a polar resin or the like decreases under a high temperature atmosphere. As means for improving the heat-resistant adhesiveness, for example, Patent Documents 6 and 7 propose a resin composition containing a specific long-chain branched ethylene / α-olefin copolymer. Even when these resin compositions are used, the adhesive strength tends to decrease under a high temperature environment, and further improvement has been desired.

  Attempts have also been made to improve the balance of physical properties by blending modified polyolefin and unmodified polyolefin. For example, Patent Document 8 discloses a method of blending resins having different densities. Patent Document 9 proposes a composition having a crystalline component produced by a single-site catalyst for improving heat resistance. However, these methods cannot be said to be sufficient in terms of the balance between the mechanical properties related to adhesiveness and heat resistance depending on applications, and further improvement has been desired.

JP 50-4144 A JP 52-49289 A WO07 / 114134 JP2015-137343A JP 2010-116498 A Japanese Patent Laid-Open No. 9-77923 JP-A-9-77924 JP 09-087603 A JP 2010-248409 A

  In view of the above problems, an object of the present invention is to provide an olefin-based resin composition having excellent adhesive strength retention under a high temperature environment.

As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by using an olefin resin containing a specific graft polymer. That is, the present invention relates to the following [1] to [12].
[1] 10 to 99 parts by mass of an olefin resin (β);
1 to 90 parts by mass of the modified olefin resin (α) (however, the total of the modified olefin resin (α) and the olefin resin (β) is 100 parts by mass),
The olefin resin (β) includes a graft polymer [GP], and the graft polymer [GP] includes a main chain (MC) composed of an ethylene copolymer and an olefin polymer. The graft polymer [GP] satisfies the following requirements (i) and (ii):
The olefin resin (β) satisfies the following requirement (β-1),
The modified olefin resin (α) satisfies the following requirement (α-1): an olefin resin composition.
(I) The ethylene-based copolymer constituting the main chain (MC) is a repeat derived from at least one α-olefin selected from a repeating unit derived from ethylene and an α-olefin having 3 to 20 carbon atoms. The content ratio of the repeating unit derived from the α-olefin is in the range of 10 to 50 mol% with respect to all the repeating units contained in the main chain (MC).
(Ii) The side chain (SC) is a side chain (SE) composed of an ethylene polymer and / or a side chain (SP) composed of a propylene polymer.
(Β-1) The melting point (Tm) measured by differential scanning calorimetry (DSC) is in the range of 80 ° C. to 170 ° C., and the glass transition temperature (Tg) is in the range of −80 to −30 ° C.
(Α-1) 0.01 to 10% by mass of a repeating unit containing a polar group selected from the group consisting of a carboxy group, an amino group, an imino group, a hydroxyl group and a silanol group [2] The graft polymer [GP] ] The olefin resin composition according to [1], further satisfying the following requirements (iii) and (iv):
(Iii) The side chain (SC) is a side chain (SE) composed of an ethylene polymer, and is selected from repeating units derived from ethylene, and optionally an α-olefin having 3 to 20 carbon atoms. It consists of a repeating unit derived from at least one kind, and the content ratio of the unit derived from ethylene is in the range of 95 to 100 mol% with respect to all repeating units contained in the side chain (SE).
(Iv) The weight average molecular weight of the ethylene polymer constituting the side chain (SE) is in the range of 1000 to 30000.
[3] The olefin resin composition according to [1], wherein the graft polymer [GP] further satisfies the following requirements (v) and (vi).
(V) The side chain (SC) is a side chain (SP) composed of a propylene polymer, and is composed of a repeating unit derived from propylene, and, if necessary, ethylene and an α-olefin having 4 to 20 carbon atoms. It is composed of at least one selected repeating unit, and the content ratio of the units derived from propylene is in the range of 95 to 100 mol% with respect to all repeating units contained in the side chain (SP).
(Vi) The weight average molecular weight of the propylene polymer constituting the side chain (SP) is in the range of 5,000 to 100,000.
[4] The olefin resin composition according to any one of [1] to [3], wherein the polar group in the requirement (α-1) is a carboxy group.
[5] The olefin resin according to any one of [1] to [4], wherein the repeating unit containing a polar group in the requirement (α-1) is a repeating unit derived from an unsaturated carboxylic acid or a derivative thereof. Composition.
[6] The olefin resin composition according to any one of [1] to [5], wherein the modified olefin resin (α) is a modified polyethylene or a modified polypropylene.
[7] The olefin resin composition according to [6], which further satisfies the following requirement (α-2) when the modified olefin resin (α) is a modified polyethylene.
(Α-2) Melt flow rate (measured at 190 ° C. under a load of 2.16 kg according to ASTM D1238) is in the range of 0.01 to 50 g / 10 min.
[8] The olefin resin composition according to [6], which further satisfies the following requirement (α-3) when the modified olefin resin (α) is a modified polypropylene.
(Α-3) The intrinsic viscosity [η] in decalin at 135 ° C. is in the range of 0.01 to 5 dl / g.
[9] Further, the pressure-sensitive adhesive (γ) is contained in an amount of 1 to 20 parts by mass with respect to a total of 100 parts by mass of the modified olefin resin (α) and the olefin resin (β). The olefin resin composition in any one.
[10] The following steps (A) and / or (B) and (C), and a step of mixing the olefin resin (β) and modified olefin resin (α) produced in the step (C): The manufacturing method of the olefin resin composition as described in [1]-[9] containing.
(A) Propylene is polymerized in the presence of an olefin polymerization catalyst containing a transition metal compound [A] belonging to Group 4 of the periodic table containing a ligand having a dimethylsilylbisindenyl skeleton to produce terminally unsaturated polypropylene. (B) The terminal unsaturated polyethylene is produced by polymerizing ethylene in the presence of an olefin polymerization catalyst containing a transition metal compound [B] of Group 4 or Group 5 of the periodic table having a phenoxyimine ligand. In the presence of a catalyst for olefin polymerization containing a transition metal compound [C] belonging to Group 4 of the periodic table, and (C) terminal unsaturated polypropylene produced in step (A) and / or produced in step (B). A process for producing an olefin-based resin (β) containing a graft polymer [GP] by copolymerizing terminal unsaturated polyethylene, ethylene and at least one α-olefin [11] A molded article comprising the olefin resin composition according to any one of [1] to [9].
[12] A laminate comprising at least one layer containing the olefin resin composition according to any one of [1] to [9].

  ADVANTAGE OF THE INVENTION According to this invention, the olefin resin composition which is excellent in the adhesive force retention property in a high temperature environment can be provided.

Hereinafter, the olefin resin composition according to the present invention, the production method thereof, and the molded body will be described in detail.
<Olefin resin composition>
The olefin resin composition according to the present invention includes an olefin resin (β) and a modified olefin resin (α), and the ratio is the sum of the modified olefin resin (α) and the olefin resin (β). Is 100 parts by mass of olefin resin (β) 10 to 99 parts by mass, modified olefin resin (α) 1 to 90 parts by mass, preferably 50 to 98 parts by mass of olefin resin (β), The modified olefinic resin (α) is 2 to 50 parts by mass, more preferably 60 to 97 parts by mass of the olefinic resin (β) and 3 to 40 parts by mass of (α). When the content ratio of the modified olefin resin (α) and the olefin resin (β) is in the above range, the olefin resin composition of the present invention has an excellent balance between adhesive force and heat resistance.

  Moreover, the olefin resin composition which concerns on this invention contains 1-20 mass parts of adhesives ((gamma)) with respect to a total of 100 mass parts of modified olefin resin ((alpha)) and olefin resin ((beta)). Is preferable, and it is more preferable to contain 5-15 mass parts.

<Olefin resin (β)>
The olefin resin (β) includes a graft polymer [GP]. The graft polymer [GP] has a main chain (MC) composed of an ethylene copolymer and a side chain (SC) composed of an olefin polymer, and the following requirements (i) and (ii) Meet. The olefin resin (β) further satisfies the following requirement (β-1), preferably further satisfies any one or more of the following requirements (β-2) to (β-5). The olefin resin (β) may be composed of only one olefin polymer or may be composed of two or more olefin polymers. Hereinafter, the graft polymer [GP] and the above requirements will be described in detail.

[Graft type polymer [GP]]
The olefin resin (β) contains the graft polymer [GP] as an essential component. The graft polymer [GP] has a main chain (MC) composed of an ethylene copolymer and a side chain (SC) composed of an olefin polymer, and the requirements (i) to (ii) Meet.

  The olefin resin (β) has moderate tackiness and flexibility due to the fact that the ethylene copolymer constituting the main chain of the graft polymer [GP] is substantially amorphous. And having excellent heat resistance and mechanical strength due to the fact that the olefin polymer constituting the side chain is substantially crystalline. Therefore, the olefin resin composition of the present invention containing the olefin resin (β) has a feature that it has excellent adhesion retention in a high temperature environment.

In the present invention, the term “graft polymer” means a polymer in which one or more side chains are bonded to the main chain.
The olefin resin (β) may contain components other than the graft polymer [GP]. According to the production method described later, a part of the terminal unsaturated polypropylene produced in the step (A) and the terminal unsaturated polyethylene produced in the step (B) are copolymerized in the step (C) to be graft type. Although it becomes a side chain of the polymer [GP], a part does not contribute to the copolymerization in the step (C), that is, it does not become a side chain of the graft polymer [GP], but becomes an olefin resin (β). May be included.

The proportion of the graft polymer [GP] in the entire olefin resin (β) is preferably 5 to 99 mass%, more preferably 10 to 99 mass%. The graft polymer [GP] satisfies the requirements (i) and (ii). The graft polymer [GP] includes the following embodiments (1) and (2) as a preferred embodiment.
(1) A mode in which the side chain (SC) is a side chain (SE) composed of an ethylene polymer, and the graft polymer [GP] further satisfies the requirements (iii) and (iv).
(2) A mode in which the side chain (SC) is a side chain (SP) composed of a propylene polymer, and the graft polymer [GP] further satisfies the requirements (v) and (vi).
Hereinafter, these requirements and preferred embodiments will be specifically described.

[Requirement (i)]
The ethylene polymer constituting the main chain (MC) comprises a repeating unit derived from ethylene and a repeating unit derived from at least one α-olefin selected from α-olefins having 3 to 20 carbon atoms. The content of the repeating unit derived from the α-olefin is in the range of 10 to 50 mol% with respect to all the repeating units contained in the main chain (MC).

  In the graft polymer [GP], the main chain (MC) composed of the ethylene-based copolymer is a part responsible for flexibility and tackiness for reducing stress concentration at the adhesive interface required as an adhesive. It becomes. In order to ensure such characteristics, the main chain of the graft polymer [GP] is at least one α-olefin selected from a repeating unit derived from ethylene and an α-olefin having 3 to 20 carbon atoms. It consists of repeating units derived from Here, in the ethylene copolymer constituting the main chain (MC), specific examples of the α-olefin having 3 to 20 carbon atoms copolymerized with ethylene include propylene, 1-butene, 2-methyl- 1-propene, 2-methyl-1-butene, 3-methyl-1-butene, 1-hexene, 2-ethyl-1-butene, 2,3-dimethyl-1-butene, 2-methyl-1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 3,3-dimethyl-1-butene, 1-heptene, methyl-1-hexene, dimethyl-1-pentene, ethyl-1-pentene, trimethyl- 1-butene, methylethyl-1-butene, 1-octene, methyl-1-pentene, ethyl-1-hexene, dimethyl-1-hexene, propyl-1-heptene, methylethyl-1-hept Emissions, trimethyl-1-pentene, propyl-1-pentene, diethyl-1-butene, 1-nonene, 1-decene, 1-undecene, 1-dodecene and the like. An α-olefin having 3 to 10 carbon atoms is more preferable, and an α-olefin having 3 to 8 carbon atoms is still more preferable. Specifically, linear olefins such as propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, and 4-methyl-1-pentene, 3-methyl-1-pentene, Examples thereof include branched olefins such as 3-methyl-1-butene, among which propylene, 1-butene, 1-pentene, 1-hexene and 1-octene are preferable, and 1-butene, 1-pentene and 1-hexene are preferable. 1-octene is more preferable.

  The ratio of repeating units derived from ethylene contained in the main chain (MC) of the graft polymer [GP] is preferably 50 to 90 mol%, more preferably 60 to 90%, based on all repeating units contained in the main chain. It is in the range of 90 mol%, more preferably 65 to 90 mol%. Moreover, the ratio of the repeating unit derived | led-out from the alpha olefin contained in a principal chain (MC) is 10-50 mol% with respect to all the repeating units contained in a principal chain, Preferably it is 10-40 mol%, More preferably, it is 10 The range is ˜35 mol%. In addition, the ratio of the repeating unit contained in the said principal chain (MC) means the ratio when all the repeating units contained in a principal chain (MC) are 100 mol%.

  The ratio of the repeating unit derived from ethylene and the repeating unit derived from α-olefin contained in the main chain (MC) is in the above range, whereby the olefin resin composition containing the olefin resin (β) is an adhesive resin. As a suitable flexibility.

  The molar ratio of the repeating unit derived from ethylene and the repeating unit derived from α-olefin in the main chain (MC) is the ethylene and α-olefin present in the polymerization reaction system in the process of producing the main chain (MC). It can be adjusted by controlling the concentration ratio. The process for producing the main chain (MC) is the process (C) in the production method described later.

  The molar ratio (mol%) of repeating units derived from the α-olefin contained in the main chain (MC), that is, the α-olefin composition in the main chain is, for example, terminal unsaturated polypropylene or terminal unsaturated polyethylene described later. The α-olefin composition of the ethylene copolymer obtained under the conditions containing no olefin is obtained by a conventional method, or from the α-olefin composition of the olefin resin (β), terminal unsaturated polypropylene, terminal unsaturated polyethylene, side chain This is obtained by subtracting the influence derived from (SC).

[Requirement (ii)]
The side chain (SC) is a side chain (SE) composed of an ethylene polymer and / or a side chain (SP) composed of a propylene polymer.

[Requirements (iii)]
The side chain (SC) is a side chain (SE) composed of an ethylene polymer, and is at least one selected from repeating units derived from ethylene, and optionally an α-olefin having 3 to 20 carbon atoms. The content ratio of the units derived from ethylene is in the range of 95 to 100 mol% with respect to all the repeating units contained in the side chain (SE). The content ratio of the units derived from ethylene is more preferably 98 to 100 mol%, and more preferably 99.5 to 100 mol%.

Examples of the α-olefin having 3 to 20 carbon atoms include the same α-olefin as the α-olefin mentioned in the item of requirement (i).
When the content ratio of the units derived from ethylene is in the above range, the side chain (SE) becomes a crystalline ethylene polymer chain. Since the side chain (SE) is crystalline, the olefin resin composition of the present invention containing the olefin resin (β) has excellent heat resistance and mechanical strength as an adhesive resin. It is presumed that the reason why such a feature is manifested is that the crystal component based on the side chain (SE) forms a physical crosslinking point (constrained phase).

[Requirement (iv)]
The weight average molecular weight of the ethylene polymer constituting the side chain (SE) is in the range of 1000 to 30000. Preferably it is the range of 1000-10000.

  When the weight average molecular weight of the ethylene polymer constituting the side chain (SE) is less than 1000, the melting point derived from the side chain (SE) decreases, and the heat resistance of the olefin resin composition containing the olefin resin (β). When the olefin-based resin composition containing the olefin-based resin (β) is used as an adhesive layer due to weakening of the physical crosslinking point formed by the crystal component based on the side chain (SE) May not be secured.

  On the other hand, when the weight average molecular weight of the ethylene polymer constituting the side chain (SE) exceeds 30000, the relative amount of the amorphous or low crystalline component consisting of the ethylene copolymer portion corresponding to the main chain (MC) decreases. There exists a possibility that a softness | flexibility cannot be ensured as the whole olefin resin composition containing an olefin resin ((beta)).

  The weight average molecular weight of the ethylene polymer constituting the side chain (SE) is the ethylene polymer (macromonomer) corresponding to the side chain (SE) separated as an elution component on the low side in GPC, or synthesized in advance. The GPC analysis of the ethylene polymer (macromonomer) corresponding to the side chain (SE), that is, the weight average molecular weight of the terminal unsaturated polyethylene produced in the following step (B) is obtained by GPC measurement. .

  Examples of the adjustment of the weight average molecular weight of the ethylene polymer constituting the side chain (SE) include a method of changing the type of the transition metal compound used in the terminal unsaturated polyethylene production catalyst described later and a method of adjusting the polymerization conditions. It is done.

[Requirement (v)]
The side chain (SC) is a side chain (SP) composed of a propylene polymer, and is at least selected from repeating units derived from propylene, and optionally ethylene and an α-olefin having 4 to 20 carbon atoms. It consists of a repeating unit derived from one kind, and the content ratio of the unit derived from propylene is in the range of 95 to 100 mol% with respect to all repeating units contained in the side chain (SP). The content ratio of units derived from propylene is preferably 99.5 to 100 mol%. That is, in the side chain (SP), a small amount of α-olefin other than ethylene and propylene may be copolymerized as long as the role and characteristics thereof are not impaired. Examples of the α-olefin having 4 to 20 carbon atoms include those other than propylene among the α-olefin having 3 to 20 carbon atoms mentioned in the section of requirement (i).

  When the content ratio of the unit derived from propylene is in the above range, the side chain (SP) becomes a crystalline propylene polymer chain. Since the side chain (SP) is crystalline, the olefin resin composition containing the olefin resin (β) exhibits excellent heat resistance and mechanical strength.

[Requirement (vi)]
The weight average molecular weight of the propylene polymer which comprises a side chain (SP) is the range of 5000-100000. Preferably it is 5000-60000, More preferably, it is the range of 5000-25000.

  Since the weight average molecular weight of the propylene polymer constituting the side chain (SP) of the graft polymer [GP] is in the above range, the olefin resin (β) is flexible as an adhesive and has high heat resistance.

  When the weight average molecular weight of the propylene polymer constituting the side chain (SP) of the graft polymer [GP] is smaller than 5000, the heat resistance may be lowered in the olefin resin (β).

  When the weight average molecular weight of the propylene polymer constituting the side chain (SP) of the graft polymer [GP] is larger than 100,000, the fluidity at the time of molding is deteriorated in the olefin resin (β), and the workability is deteriorated. It may cause. Moreover, since the relative amount of an amorphous or low crystalline component is lowered, flexibility may be lowered.

In addition, the weight average molecular weight of the propylene polymer which comprises a side chain (SP) can be calculated | required by measuring the weight average molecular weight of the terminal unsaturated polypropylene produced | generated at the following process (A) by a conventional method. For example, the weight average molecular weight in terms of polypropylene of the terminal unsaturated polypropylene determined by gel permeation chromatography (GPC) can be used as the weight average molecular weight of the propylene polymer constituting the side chain.
Examples of the method for adjusting the weight average molecular weight of the propylene polymer constituting the side chain (SP) include a method of adjusting the polymerization temperature and the polymerization pressure in the production step (A) described later.

[Requirement (β-1)]
The olefin resin (β) has a melting point (Tm) in the range of 80 to 170 ° C. in differential scanning calorimetry (DSC). That is, the olefin resin (β) has a melting peak measured by differential scanning calorimetry (DSC) in the range of 80 to 170 ° C. Further, the glass transition temperature (Tg) is in the range of −80 to −30 ° C.

  The temperature at which the melting peak appears, that is, the melting point (Tm), is obtained by melting the sample once by DSC in the heating step and then crystallizing it by the cooling step to 30 ° C. This is an analysis of the endothermic peak that appears at (° C./min).

  In the preferred embodiment (1) described above, the melting point due to the side chain (SE) is usually observed in the range of 80 to 130 ° C. Since the main chain (MC) is amorphous and the melting point due to the side chain (SE) is in this range, the olefin resin (β) is heat resistant while maintaining heat sealability (adhesion strength, etc.) at low temperatures. Adhesive resin with excellent properties. When the melting point is lower than 80 ° C., there is a possibility that sufficient heat resistance cannot be imparted. Moreover, it is thought that the effect which suppresses stickiness of resin is acquired because an olefin resin ((beta)) has the said property derived from the side chain (SE) of graft type polymer [GP]. Examples of a method for adjusting the melting point due to the side chain (SE) to the above range include a method for adjusting the polymerization temperature and the polymerization pressure in the production step (B) described later.

  In the preferred embodiment (2) described above, the melting point due to the side chain (SP) is usually observed in the range of 100 to 170 ° C. When the melting point due to the side chain (SE) is in the range, the olefin resin (β) becomes an adhesive resin excellent in heat resistance while maintaining heat sealability (adhesion strength, etc.) at low temperatures. When the melting point is lower than 100 ° C., there is a possibility that sufficient heat resistance cannot be imparted. As a method of adjusting the melting point due to the side chain (SP) to the above range, a method of adjusting the polymerization temperature and polymerization pressure in the production step (A) described later can be mentioned.

The glass transition temperature (Tg) is −80 to −30 ° C., more preferably −80 to −50 ° C., particularly preferably −75 ° C. to −55 ° C.
The glass transition temperature (Tg) is mainly attributed to the properties of the ethylene polymer constituting the main chain (MC) of the graft polymer [GP]. When the glass transition temperature (Tg) is in the range of −80 ° C. to −30 ° C., the olefin resin composition containing the olefin resin (β) has appropriate flexibility as the adhesive resin.
The glass transition temperature (Tg) in the above range can be obtained by controlling the type and composition of the α-olefin structural unit contained in the ethylene polymer constituting the main chain (MC).

[Requirement (β-2)]
The olefin resin (β) has an intrinsic viscosity [η] measured in decalin at 135 ° C. in the range of 0.5 to 5.0 dl / g. The intrinsic viscosity [η] is preferably 1.0 to 4.0 dl / g, more preferably 1.0 to 3.0 dl / g. When the intrinsic viscosity [η] is in the above range, the olefin resin composition containing the olefin resin (β) has an appropriate resin strength and processability, and thus is excellent as an adhesive resin.

[Requirement (β-3)]
The ratio of the ethylene polymer contained in the olefin resin (β) is 2 to 60% by mass, preferably 3 to 40% by mass, more preferably 5 to 30% by mass with respect to the entire olefin resin (β). %. Since the ratio of the ethylene polymer is within the above range, the olefin resin composition containing the olefin resin (β) has an appropriate flexibility as an adhesive resin while maintaining excellent mechanical strength and heat resistance. I can do it. Here, the ethylene polymer contained in the olefin resin (β) corresponds to a polymer or a side chain derived from the terminal unsaturated polyethylene produced in the step (B) according to the production method described later. That is, it is a polyethylene linear polymer not incorporated into the side chain (SE) and main chain copolymerized in the step (C).

  The ratio of the ethylene polymer contained in the olefin resin (β) is, for example, from the ratio of the weight of the terminal unsaturated polyethylene used in the polymerization step (B) described later and the weight of the obtained olefin resin (β). Desired.

[Requirements (β-4)]
The proportion of the propylene polymer contained in the olefin resin (β) is 2 to 60% by mass, preferably 5 to 55% by mass, more preferably 5 to 50% by mass with respect to the entire olefin resin (β). %. Here, the propylene polymer contained in the olefin resin (β) corresponds to a polymer or a side chain derived from the terminal unsaturated polypropylene produced in the step (A) according to the production method described later. The polypropylene linear polymer not incorporated into the side chain (SP) and main chain copolymerized in step (C).

  The proportion of the propylene polymer contained in the olefin resin (β) is determined from, for example, the ratio of the weight of the terminal unsaturated polypropylene used in the polymerization step (A) described later and the weight of the obtained olefin resin (β). It is done.

[Requirements (β-5)]
In the olefin resin (β), the content of a repeating unit containing a polar group selected from the group consisting of a carboxy group, an amino group, an imino group, a hydroxyl group and a silanol group is less than 0.01% by mass.

  When the side chain (SC) is a side chain (SE) composed of an ethylene polymer, in addition to the requirement (β-1), one or more of the following requirements (β-6) and (β-7) are satisfied. It is preferable.

[Requirements (β-6)]
The olefin resin (β) has a proportion (E value) of an orthodichlorobenzene-soluble component of 20 ° C. or less measured by a cross fractionation chromatograph (CFC) of 45 wt% or less, preferably 35% or less. More preferably, it is 30% or less.

  Usually, commercially available ethylene / α-olefin copolymers such as ethylene / propylene copolymer, ethylene / butene copolymer, and ethylene / octene copolymer are α- such as propylene, 1-butene or 1-octene. It is a polymer adjusted to have an olefin composition of about 10 to 50 mol%, exhibits amorphous or low crystallinity, and dissolves well in a specific organic solvent even at a temperature below room temperature. For example, commercially available ethylene / butene copolymer resins such as Tafmer A-0550S are mostly soluble in orthodichlorobenzene at 20 ° C. or lower, and the E value is usually 93% or higher.

  On the other hand, the graft polymer [GP] constituting the olefin resin (β) according to the present invention is a crystalline ethylene polymer having a side chain that is an ethylene copolymer as described above and a side chain that is a crystalline ethylene polymer. Therefore, it becomes hardly soluble in orthodichlorobenzene at room temperature or lower. Therefore, the olefin resin (β) has a feature that the E value is small.

  The fact that the olefin resin (β) has a small E value is indirect evidence that the main chain structure and the side chain structure of the graft polymer [GP] are chemically bonded. It shows that a considerable amount of graft polymer [GP] is contained in the resin (β). By containing a considerable amount of the graft polymer [GP], as described above, the crystalline component based on the side chain (SE) forms a physical crosslinking point (constrained phase), so that the olefin resin (β) of the present invention is added. The olefin resin composition to be included is considered to have excellent heat resistance and resin mechanical strength.

Further, it is preferable that the heat of fusion ΔH and the E value at the melting peak obtained in the differential scanning calorimetry (DSC) of the olefin resin (β) satisfy any one of the following a), b) and c). .
a) When ΔH is 5 J / g or more and less than 15 J / g, E is 45 wt% or less, preferably 40 wt% or less, more preferably 10 to 35 wt%.
b) When ΔH is 15 J / g or more and less than 30 J / g, E is 40 wt% or less, preferably 35 wt% or less, more preferably 5 to 30 wt%.
c) When ΔH is 30 J / g or more, E is 30 wt% or less, preferably 25 wt% or less.

  Satisfying the relationship shown above indicates that the amount of the graft polymer [GP] contained in the olefin resin (β) according to the present invention is sufficiently large to obtain the effects of the present invention. ing.

  In the olefin resin (β), when the side chain (SC) is a side chain (SE) composed of an ethylene polymer, a crystalline ethylene polymer site is chemically bonded to the ethylene copolymer. This component can be satisfied because it contains a considerable amount of ingredients. In order to obtain such a resin, it is important to select a catalyst to be used in the step of copolymerizing ethylene with an α-olefin and a terminal vinylethylene polymer, and a crosslinked metallocene compound represented by the general formula [C] described later This can be achieved by using

[Requirements (β-7)]
Intrinsic viscosity measured in decalin at 135 ° C. with a melt flow rate (MFR) at 190 ° C. and a load of 2.16 kg obtained in accordance with ASTM D1238E of olefin resin (β) as Mg / 10 min [ When η] is H g / dl, the value A represented by the following relational expression (Eq-1) is in the range of 30 to 280, preferably in the range of 60 to 250, more preferably in the range of 70 to 200. .

The fact that the olefin resin (β) has an A value in such a range indicates that the macromonomer introduction rate is high, and the present invention includes the olefin resin (β) that satisfies the requirement (β-7). The olefin-based resin composition is excellent in adhesion retention in a high temperature environment.
When the side chain (SC) is a side chain (SP) composed of a propylene polymer, it is preferable that the following requirement (β-8) is satisfied in addition to the requirement (β-1).

[Requirement (β-8)]
The olefin-based resin (β) is a ratio (hereinafter also referred to as a ratio E) of a component having a peak temperature of a differential elution curve of less than 65 ° C. measured by a cross-fractionation chromatograph (CFC) using orthodichlorobenzene as a solvent. When Ewt% and the proportion of the propylene polymer contained in the olefin resin (β) (hereinafter also referred to as the ratio P) is Pwt%, the value a represented by the following relational expression (Eq-2) (hereinafter, a value) is 1.4 or more, preferably 1.6 or more, more preferably 2.2 or more.

  The differential elution curve is obtained by differentiating a cumulative elution curve obtained at an elution temperature in the range of −20 ° C. to 140 ° C. Furthermore, the component ratio of each elution peak can be obtained by separating each elution peak appearing in the differential elution curve into a normal distribution curve. Here, the ratio of soluble components below −20 ° C. (the proportion of components not coated in the temperature rising elution fractionation (TREF) column even at −20 ° C. in the cooling step of CFC measurement) is E (<−20 ° C.) wt. %, The sum of the proportions of the eluted components having a peak at −20 ° C. or more and less than 65 ° C. E (<65 ° C.) wt%, and the sum of the proportions of the eluted components having a peak at 65 ° C. or more and 140 ° C. or less E (≧ 65 ° C) wt%, E (> 140 ° C) + E (<-20 ° C) + E (<65 ° C) + E (≧ 65 ° C) + E (> 140 ° C) = 100 Is defined as E = E (<−20 ° C.) + E (<65 ° C.).

  Usually, the olefin resin (β) is completely soluble in orthodichlorobenzene at 140 ° C. and can detect a clear peak that is easily separated at 65 ° C. or higher, so that E (> 140 ° C.) = 0. The case is defined as E = 100−E (≧ 65 ° C.).

As a detector in the CFC measurement, an infrared spectrophotometer (detection wavelength 3.42 μm) is preferably used.
In the above-mentioned ratio E and ratio P with respect to the total amount of the olefin resin (β), the total amount is only for the resin obtained through the polymerization step described later, and the separately added resin, additive, etc. It is not included in the total amount.

  The a value being in the above range indicates that the olefin resin (β) contains a considerable amount of a graft polymer [GP], that is, an ethylene copolymer having a propylene polymer moiety as a side chain. Yes.

  The relationship between E and P at a = 1 indicates a case where the graft polymer [GP] is not included, that is, a mixture of an ethylene copolymer and a propylene polymer. On the other hand, as the production efficiency of the graft polymer [GP] increases, the value of the ratio E with respect to the ratio P decreases, and a large value of a indicates that the production efficiency of the graft polymer [GP] is high. Indicates.

  Usually, commercially available olefin elastomers used for polypropylene resin modifiers and the like are composed of ethylene / α-olefin copolymers (for example, ethylene / butene copolymers and ethylene / octene copolymers), and the composition of ethylene. Is a polymer adjusted to about 90 mol% to 50 mol%. Therefore, the elution component ratio E of the normal ethylene / α-olefin copolymer is substantially 100%.

The olefin resin (β) contains a high content of a graft polymer [GP] in which a crystalline propylene polymer is chemically bonded to an ethylene copolymer. And E is small.
This requirement is also disclosed in WO2015 / 147187.

<Method for producing olefin resin (β)>
The olefin resin (β) is produced, for example, by a production method including the following steps (A) and / or (B) and (C).

(A) Propylene is polymerized in the presence of an olefin polymerization catalyst containing a transition metal compound [A] belonging to Group 4 of the periodic table containing a ligand having a dimethylsilylbisindenyl skeleton to produce terminally unsaturated polypropylene. (B) a terminal unsaturated polyethylene is produced by polymerizing ethylene in the presence of an olefin polymerization catalyst containing a transition metal compound [B] of Group 4 or Group 5 of the periodic table having a phenoxyimine ligand. In the presence of a catalyst for olefin polymerization containing a transition metal compound [C] belonging to Group 4 of the periodic table, and (C) terminal unsaturated polypropylene produced in step (A) and / or produced in step (B). A step of copolymerizing at least one α-olefin selected from terminal unsaturated polyethylene, ethylene, and an α-olefin having 3 to 20 carbon atoms. And step (C) may be performed simultaneously. This is because an olefin polymerization catalyst containing a compound [B] of a transition metal belonging to Group 4 or Group 5 of the periodic table having a phenoxyimine ligand can be used even under conditions where comonomers such as ethylene and α-olefin coexist. This is because ethylene can be selectively polymerized to produce a terminal unsaturated polyethylene, and it is preferable to perform the step (B) and the step (C) simultaneously in terms of simplifying the production process.
Hereinafter, the steps (A), (B), and (C) will be described in order.

[Process (A)]
Step (A) is a step of producing terminally unsaturated polypropylene that is a raw material for a side chain (SP) composed of a propylene polymer of a graft polymer [GP].

  In this step, propylene is polymerized in the presence of a transition metal compound [A] (hereinafter also referred to as a transition metal compound [A]) containing a ligand having a dimethylsilylbisindenyl skeleton. And a process for producing terminally unsaturated polypropylene.

  The terminal unsaturated polypropylene means a polypropylene having an unsaturated terminal represented by the following terminal structures (I) to (IV). “Poly” in the terminal structures (I) to (IV) indicates a bonding position between the terminal structure and a propylene polymer molecular chain other than the terminal structure.

前記末端不飽和ポリプロピレンにおける不飽和末端の割合は１０００炭素原子あたり通常０．１〜１０であるが、より好ましくは０．４〜５.０である。さらに、一般的に末端ビニルと呼ばれる末端構造（Ｉ）で表される不飽和末端割合は炭素原子１０００個あたり、通常０．１〜２．０個であるが、好ましくは、０．２〜２．０個の範囲にある。

The ratio of unsaturated ends in the terminal unsaturated polypropylene is usually 0.1 to 10 per 1000 carbon atoms, more preferably 0.4 to 5.0. Furthermore, the unsaturated terminal ratio represented by the terminal structure (I) generally called terminal vinyl is usually 0.1 to 2.0 per 1000 carbon atoms, preferably 0.2 to 2 In the range of 0.

The quantification of the unsaturated terminal is determined by determining the terminal structure of the terminal unsaturated polypropylene by ¹ H-NMR. ¹ H-NMR may be measured according to a conventional method. The end structure can be assigned according to the method described in Macromolecular Rapid Communications 2000, 1103 and the like.

For example, in the case of the terminal structure (I), when the integral value A of δ4.9 to 5.1 (2H) and the total integral value derived from the propylene polymer are B, the terminal structure (I) per 1000 carbon atoms The ratio is obtained by the formula of 1000 × (A / 2) / (B / 2). When determining the ratio of other terminal structures, it should be replaced with the integrated value of the peak attributed to each structure while paying attention to the ratio of hydrogen.
The proportion of the terminal structure (I) in the unsaturated terminal is usually 30% or more, preferably 50% or more, more preferably 60% or more. In addition, the ratio for which terminal structure (I) accounts among the above-mentioned unsaturated terminal is the sum of the number of each said terminal structure (I)-(IV) which exists per 1000 carbon atoms contained in terminal unsaturated polypropylene. The ratio of the number of terminal structures (I) present per 1000 carbon atoms is expressed as a percentage.

The transition metal compound [A] functions as a polymerization catalyst for producing terminally unsaturated polypropylene in combination with the compound [D] described later.
As an olefin polymerization catalyst for producing terminally unsaturated polypropylene, Resconi, L .; J. et al. Am. Chem. Soc. 1992, 114, 1025-1032, etc., but the side chain of the olefin copolymer [GP] is isotactic or syndiotactic terminal unsaturated polypropylene, more preferably isotactic. Suitable terminally unsaturated polypropylene is preferred.

  As the transition metal compound [A] contained in the olefin polymerization catalyst used for producing such a highly stereoregular polypropylene having a terminal structure (I) and a high content of terminal unsaturated polypropylene, a transition metal compound [A] can be used. The compounds disclosed in JP-A No. 1000579, JP-T-2001-525461, JP-A-2005-336091, JP-A-2009-299046, JP-A-11-130807, JP-A-2008-285443 and the like can be suitably used.

  More specifically, examples of the transition metal compound [A] include compounds selected from the group consisting of bridged bis (indenyl) zirconocenes or hafnocenes. More preferred is dimethylsilyl bridged bis (indenyl) zirconocene or hafnocene. More preferably, it is dimethylsilyl-bridged bis (indenyl) zirconocene, and by selecting zirconocene, the production of a long-chain branched polymer caused by the insertion reaction of terminal unsaturated polypropylene is suppressed, and the olefin resin (β) is an adhesive resin. The balance of physical properties when blended with heat resistance and a thermoplastic resin as a material. On the other hand, when a large amount of the long-chain branched polymer is produced in the step (A), the olefin-based resin (β) may deteriorate in heat resistance or may lose rigidity when blended with a thermoplastic resin. .

  More specifically, dimethylsilylbis (2-methyl-4-phenylindenyl) zirconium dichloride or dimethylsilylbis (2-methyl-4-phenylindenyl) zirconium dimethyl can be used as a suitable compound.

Step (A) can be carried out by any method of gas phase polymerization, slurry polymerization, bulk polymerization, and solution (dissolution) polymerization, and the polymerization form is not particularly limited.
When the step (A) is performed by solution polymerization, examples of the polymerization solvent include aliphatic hydrocarbons and aromatic hydrocarbons. Specifically, aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, kerosene, alicyclic hydrocarbons such as cyclopentane, cyclohexane, methylcyclopentane, benzene, toluene, xylene And aromatic hydrocarbons such as ethylene chloride, chlorobenzene, and dichloromethane. These polymerization solvents may be used alone or in combination of two or more. Of these, hexane is preferred from the viewpoint of reducing the load of the post-treatment process.

  In addition, the polymerization temperature in the step (A) is usually 50 ° C. to 200 ° C., preferably in the range of 80 ° C. to 150 ° C., more preferably in the range of 80 ° C. to 130 ° C., and the polymerization temperature is appropriately controlled. Thus, it becomes possible to obtain a terminally unsaturated polypropylene having a desired molecular weight and stereoregularity.

  The polymerization pressure in the step (A) is usually a normal pressure to 10 MPa gauge pressure, preferably a normal pressure to 5 MPa gauge pressure, and the polymerization reaction can be performed in any of batch, semi-continuous and continuous methods. It can be carried out. In the present invention, among these, it is preferable to employ a method in which a monomer is continuously supplied to a reactor to perform polymerization.

  The reaction time (average residence time when copolymerization is carried out in a continuous process) varies depending on conditions such as catalyst concentration and polymerization temperature, but is usually 0.5 minutes to 5 hours, preferably 5 minutes to 3 hours. It is.

  In the step (A), the polymer concentration is 5 to 50 wt%, preferably 10 to 40 wt% during steady operation. From the viewpoint of viscosity limitation in the polymerization ability, load of the post-treatment process (desolvation) and productivity, it is preferably 15 to 50 wt%.

  It is preferable that the weight average molecular weight of the terminal unsaturated polypropylene manufactured at a process (A) is the range of 5000-100000, More preferably, it is 5000-60000, More preferably, it is the range of 5000-25000. By being a terminal unsaturated polypropylene having a weight average molecular weight within the above range, in the step (C) described later, the molar concentration of the terminal unsaturated polypropylene can be relatively increased with respect to ethylene or α-olefin. The efficiency of introduction into the chain is increased. On the other hand, when exceeding the said range, the molar concentration of terminal unsaturated polypropylene will become relatively low, and the introduction | transduction efficiency to a principal chain will become low. Moreover, when it is less than the above range, there are practical problems such as a decrease in melting point.

  The molecular weight distribution (Mw / Mn) of the terminal unsaturated polypropylene produced in the step (A) is 1.5 to 3.0, typically about 1.7 to 2.5. In some cases, a mixture of side chains having different molecular weights may be used.

The ratio of the unsaturated terminal measured by ¹ H-NMR of the terminal unsaturated polypropylene produced in the step (A) is usually from 0.1 to 10 per 1000 carbon atoms, more preferably from 0.4 to 5.0. Furthermore, the ratio of the unsaturated terminal having the terminal structure (I), the so-called terminal vinyl amount, is usually 0.1 to 2.0 per 1000 carbon atoms, preferably 0.4 to 2.0. It is in the range. When the amount of terminal vinyl is small, the amount of introduction of the terminal unsaturated polypropylene into the main chain in the subsequent step (B) is low, and the amount of graft-type olefin polymer produced is small, so the desired effect may not be obtained. .

As described above, the amount of the unsaturated terminal and the ratio of each terminal structure by ¹ H-NMR measurement can be calculated according to the method described in, for example, Macromolecular Rapid Communications 2000, 1103.

[Process (B)]
Step (B) is a step of producing terminally unsaturated polyethylene as a raw material for the side chain (SE) composed of an ethylene polymer of graft type polymer [GP].

  This step is conducted in the presence of a catalyst for olefin polymerization containing a compound [B] (hereinafter also referred to as complex [B]) of a transition metal of Group 4 or Group 5 of the periodic table having a phenoxyimine ligand. Is a step of producing terminally unsaturated polyethylene.

  Here, the terminal unsaturated polyethylene includes polyethylene having a vinyl group at one end of the polymer chain, and the terminal unsaturated polyethylene is polyethylene having a vinyl group at one end, usually 60% or more, Preferably 70%, more preferably 80% or more, still more preferably 90% or more. The terminal unsaturated polyethylene may include polyethylene having an unsaturated carbon-carbon bond such as vinylene group or vinylidene group or both-end saturated polyethylene, in addition to polyethylene having a vinyl group at one end of the polymer chain. The terminal vinyl ratio (ratio of the number of vinyl groups to the total unsaturated carbon-carbon bonds) is usually 60% or more, preferably 70%, more preferably 80% or more, and even more preferably 90% or more.

The ratio of terminal vinyl groups in the terminal unsaturated polyethylene is usually 0.1 to 30 per 1000 carbon atoms, preferably in the range of 0.5 to 20, more preferably 1.0 to 10 Is in range. The vinyl group ratio and the terminal vinyl group ratio in the terminal unsaturated polyethylene can be calculated by a conventional method by polymer structure analysis by ¹ H-NMR measurement.

More specifically, the complex [B] includes complexes represented by the following general formulas [B0], [B1], and [B2].
Complex [B] functions as a polymerization catalyst for producing terminal unsaturated polyethylene in combination with compound [D] described below.

（一般式［Ｂ０］中、Ｍは周期表第４または５族の遷移金属の原子を示し、ｍは１〜４の整数を示し、Ｒ¹は、炭素原子数１〜２０の非環式炭化水素基（Ｃ_n'Ｈ_2n'+1，ｎ'＝１〜２０）または水素原子を示し、Ｒ²〜Ｒ⁶は、互いに同一でも異なっていてもよく、水素原子、ハロゲン原子、炭化水素基、ヘテロ環式化合物残基、酸素含有基、窒素含有基、ホウ素含有基、イオウ含有基、リン含有基、ケイ素含有基、ゲルマニウム含有基、またはスズ含有基を示し、これらのうちの２個以上が互いに連結して環を形成していてもよく、また、ｍが２以上の場合にはＲ²〜Ｒ⁶で示される基のうち２個の基が連結されていてもよく、ｎは、Ｍの価数を満たす数であり、Ｘは、水素原子、ハロゲン原子、炭化水素基、酸素含有基、イオウ含有基、窒素含有基、ホウ素含有基、アルミニウム含有基、リン含有基、ハロゲン含有基、ヘテロ環式化合物残基、ケイ素含有基、ゲルマニウム含有基、またはスズ含有基を示し、ｎが２以上の場合には、互いに同一であっても、異なっていてもよく、また、Ｘで示される複数の基は互いに結合して環を形成してもよい。）

(In General Formula [B0], M represents a transition metal atom of Group 4 or 5 of the periodic table, m represents an integer of 1 to 4, and R ¹ represents an acyclic carbon atom having 1 to 20 carbon atoms. Represents a hydrogen group (C _{n ′} H _{2n ′ + 1} , n ′ = 1 to 20) or a hydrogen atom, and R ^{2 to} R ⁶ may be the same as or different from each other, and represent a hydrogen atom, a halogen atom, or a hydrocarbon group. , A heterocyclic compound residue, oxygen-containing group, nitrogen-containing group, boron-containing group, sulfur-containing group, phosphorus-containing group, silicon-containing group, germanium-containing group, or tin-containing group, two or more of these May be linked to each other to form a ring, and when m is 2 or more, ^two groups represented by R ^{2 to} R ⁶ may be linked, and n is X is a number satisfying the valence of M, and X is a hydrogen atom, halogen atom, hydrocarbon group, oxygen-containing group, sulfur-containing group, nitrogen A group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, a heterocyclic compound residue, a silicon-containing group, a germanium-containing group, or a tin-containing group, and when n is 2 or more, And may be the same or different from each other, and a plurality of groups represented by X may be bonded to each other to form a ring.)

（一般式［Ｂ１］中、Ｍは周期表第４〜５族の遷移金属の原子を示し、ｍは１〜４の整数を示し、Ｒ¹は、１つまたは複数の置換基を有していてもよい３〜１０員環の脂環式炭化水素基を示し、Ｒ²〜Ｒ⁶は、互いに同一でも異なっていてもよく、水素原子、ハロゲン原子、炭化水素基、ヘテロ環式化合物残基、酸素含有基、窒素含有基、ホウ素含有基、イオウ含有基、リン含有基、ケイ素含有基、ゲルマニウム含有基、またはスズ含有基を示し、これらのうちの２個以上が互いに連結して環を形成していてもよく、また、ｍが２以上の場合にはＲ²〜Ｒ⁶で示される基のうち２個の基が連結されていてもよく、ｎは、Ｍの価数を満たす数であり、Ｘは、水素原子、ハロゲン原子、炭化水素基、酸素含有基、イオウ含有基、窒素含有基、ホウ素含有基、アルミニウム含有基、リン含有基、ハロゲン含有基、ヘテロ環式化合物残基、ケイ素含有基、ゲルマニウム含有基、またはスズ含有基を示す。なお、ｎが２以上の場合には、互いに同一であっても、異なっていてもよく、またＸで示される複数の基は互いに結合して環を形成してもよい。）

(In the general formula [B1], M represents an atom of a transition metal of Groups 4 to 5 of the periodic table, m represents an integer of 1 to 4, and R ¹ has one or more substituents. 3 to 10-membered alicyclic hydrocarbon group which may be the same, R ^{2 to} R ⁶ may be the same or different from each other, and may be a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue; , An oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group. And when m is 2 or more, two of the groups represented by R ^{2 to} R ⁶ may be linked, and n is a number that satisfies the valence of M. X is a hydrogen atom, halogen atom, hydrocarbon group, oxygen-containing group, sulfur-containing group, nitrogen-containing group, boron An organic group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, a heterocyclic compound residue, a silicon-containing group, a germanium-containing group, or a tin-containing group. Or a plurality of groups represented by X may be bonded to each other to form a ring.)

（一般式［Ｂ２］中、Ｍは周期表第４〜５族の遷移金属の原子を示し、ｍは１〜４の整数を示し、Ｒ¹は、１つまたは複数の置換基を有していてもよい炭素原子数４〜２０の少なくとも１つ以上の炭素を共有する２環性脂肪族炭化水素基であり、Ｒ²〜Ｒ⁶は、互いに同一でも異なっていてもよく、水素原子、ハロゲン原子、炭化水素基、ヘテロ環式化合物残基、酸素含有基、窒素含有基、ホウ素含有基、イオウ含有基、リン含有基、ケイ素含有基、ゲルマニウム含有基、またはスズ含有基を示し、これらのうちの２個以上が互いに連結して環を形成していてもよく、また、ｍが２以上の場合にはＲ²〜Ｒ⁶で示される基のうち２個の基が連結されていてもよく、ｎは、Ｍの価数を満たす数であり、Ｘは、水素原子、ハロゲン原子、炭化水素基、酸素含有基、イオウ含有基、窒素含有基、ホウ素含有基、アルミニウム含有基、リン含有基、ハロゲン含有基、ヘテロ環式化合物残基、ケイ素含有基、ゲルマニウム含有基、またはスズ含有基を示し、ｎが２以上の場合には、互いに同一であっても、異なっていてもよく、またＸで示される複数の基は互いに結合して環を形成してもよい。）

(In General Formula [B2], M represents an atom of a transition metal of Groups 4 to 5 of the periodic table, m represents an integer of 1 to 4, and R ¹ has one or more substituents. And a bicyclic aliphatic hydrocarbon group sharing at least one carbon having 4 to 20 carbon atoms, and R ^{2 to} R ⁶ may be the same as or different from each other, and may be a hydrogen atom, halogen, Atom, hydrocarbon group, heterocyclic compound residue, oxygen-containing group, nitrogen-containing group, boron-containing group, sulfur-containing group, phosphorus-containing group, silicon-containing group, germanium-containing group, or tin-containing group Two or more of them may be connected to each other to form a ring, and when m is 2 or more, two of the groups represented by R ^{2 to} R ⁶ may be connected. Well, n is a number that satisfies the valence of M, and X is a hydrogen atom, a halogen atom, or a hydrocarbon group An oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, a heterocyclic compound residue, a silicon-containing group, a germanium-containing group, or a tin-containing group, When n is 2 or more, they may be the same or different from each other, and a plurality of groups represented by X may be bonded to each other to form a ring.)

Examples of preferable compound structures of the complexes represented by the above general formulas [B0], [B1], and [B2] include transition metal compounds disclosed in JP-A-2003-73412.
Complexes [B] represented by the above general formulas [B0], [B1], and [B2] can be used singly or in combination of two or more.

[Preferred embodiment of complex [B]]
The complex [B] is preferably a compound having a structure represented by the above general formula [B0]. Particularly preferred embodiments of the general formula [B0] are as follows.

In general formula [B0], M represents a transition metal atom of Group 4 of the periodic table,
m represents an integer of 1 to 4,
R ¹ is a linear hydrocarbon group having 1 to 10 carbon atoms,
R ^{2 to} R ⁵ may be the same or different from each other, and are a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, phosphorus A containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group, and two or more of these may be linked to each other to form a ring,
R ⁶ is a branched alkyl group having 3 to 20 carbon atoms, wherein at least one hydrogen atom is substituted with an aryl group having 6 to 20 carbon atoms,
n is a number that satisfies the valence of M, and X is a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, A halogen-containing group, a heterocyclic compound residue, a silicon-containing group, a germanium-containing group, or a tin-containing group, and when n is an integer of 2 or more, a plurality of Xs may be the same or different And a plurality of groups represented by X may be bonded to each other to form a ring.

[Process (C)]
In the step (C), the terminal unsaturated polypropylene produced in the step (A) and / or the step (B) is produced in the presence of an olefin polymerization catalyst containing a transition metal compound [C] belonging to Group 4 of the periodic table. This is a step of copolymerizing the terminal unsaturated polyethylene, ethylene, and at least one α-olefin selected from α-olefins having 3 to 20 carbon atoms. The olefin polymerization catalyst used in step (C) may be the same as or different from the olefin polymerization catalyst used in step (A). When it is the same as the olefin polymerization catalyst used in the step (A), it is preferable in that the catalyst used in the step (A) can be used also in the step (C). As described above, the step (C) may be performed simultaneously with the step (B).

In addition, the transition metal compound [C] of Group 4 of the periodic table is a superordinate concept of the transition metal compound [A] of Group 4 of the periodic table including a ligand having a dimethylsilylbisindenyl skeleton.
The transition metal compound [C] of Group 4 of the periodic table is preferably a Group 4 transition metal compound containing a ligand having a cyclopentadienyl skeleton. The cyclopentadienyl skeleton is recognized as a superordinate concept of the indenyl skeleton and the fluorenyl skeleton. When using a catalyst different from the olefin polymerization catalyst used in the step (A), the step (C) is preferably performed in the presence of an olefin polymerization catalyst containing a crosslinked metallocene compound represented by the following general formula [C]. At least one α selected from terminal unsaturated polypropylene produced in step (A) and / or terminal unsaturated polyethylene produced in step (B), ethylene, and an α-olefin having 3 to 20 carbon atoms. -A step of copolymerizing with olefin.

（式［Ｃ］中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁸、Ｒ⁹およびＲ¹²はそれぞれ独立に水素原子、炭化水素基、ケイ素含有基またはケイ素含有基以外のヘテロ原子含有基を示し、Ｒ¹〜Ｒ⁴のうち相互に隣り合う二つの基同士は互いに結合して環を形成していてもよい。

(In the formula [C], R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁸ , R ⁹ and R ¹² are each independently hydrogen atom, hydrocarbon group, silicon-containing group or silicon-containing group. A hetero atom-containing group is shown, and two groups adjacent to each other among R ^{1 to} R ⁴ may be bonded to each other to form a ring.

R ⁶ and R ¹¹ are the same atom or the same group selected from a hydrogen atom, a hydrocarbon group, a silicon-containing group and a heteroatom-containing group other than a silicon-containing group, and R ⁷ and R ¹⁰ are a hydrogen atom, a hydrocarbon group, are the same atoms or the same group selected from heteroatom-containing groups other than silicon-containing group and a silicon-containing group, R ⁶ and R ⁷ may bond to each other to form a ring, R ¹⁰ and R ¹¹ may be bonded to each other to form a ring; provided that R ⁶ , R ⁷ , R ¹⁰ and R ¹¹ are not all hydrogen atoms.

R ¹³ and R ¹⁴ each independently represents an aryl group.
M ¹ represents a zirconium atom or a hafnium atom.
Y ¹ represents a carbon atom or a silicon atom.

  Q represents a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a neutral conjugated or nonconjugated diene having 4 to 10 carbon atoms, an anionic ligand, or a neutral ligand capable of coordinating with a lone electron pair. J represents an integer of 1 to 4, and when j is an integer of 2 or more, a plurality of Qs may be the same or different. )

  In the step (C), it is important to select a catalyst that exhibits sufficient activity at a high temperature, can be highly copolymerized, and can have a high molecular weight. Since the terminal vinyl polypropylene (the terminal structure (I)) has a methyl branch at the 4-position and has a sterically bulky structure, it is difficult to polymerize compared to a linear vinyl monomer. Moreover, terminal vinyl polypropylene is difficult to be copolymerized under low temperature conditions where the polymer is precipitated. For this reason, the catalyst is preferably required to exhibit a sufficient activity at a polymerization temperature of 90 ° C. or higher and to make the main chain have a desired molecular weight.

From such a viewpoint, in order to obtain the olefin resin (β) containing a high content of polypropylene, the bridged metallocene compound [C] is preferably used in the step (C).
The bridged metallocene compound [C] is combined with the compound [D] described later, the terminal unsaturated polypropylene produced in the step (A) and / or the terminal unsaturated polyethylene produced in the step (B), ethylene, It functions as an olefin polymerization catalyst that is copolymerized with at least one α-olefin selected from α-olefins having 3 to 20 carbon atoms.

Hereinafter, characteristics of the chemical structure of the bridged metallocene compound [C] used in the present invention will be described.
The bridged metallocene compound [C] is structurally provided with the following features [m1] and [m2].

  [M1] Of the two ligands, one is a cyclopentadienyl group which may have a substituent, and the other is a fluorenyl group having a substituent (hereinafter referred to as “substituted fluorenyl group”). Say.)

[M2] The two ligands are bonded by an aryl group-containing covalently bonded bridge portion (hereinafter also referred to as “bridge portion”) composed of a carbon atom or a silicon atom having an aryl group.
Hereinafter, the cyclopentadienyl group which may have a substituent, the substituted fluorenyl group, the bridge | crosslinking part, and other characteristics which bridge | crosslinking metallocene compound [C] has are demonstrated sequentially.

(Cyclopentadienyl group which may have a substituent)
In the formula [C], R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom, a hydrocarbon group, a silicon-containing group or a heteroatom-containing group other than a silicon-containing group. As a structure for taking in pyrene well, R ¹ , R ² , R ³ and R ⁴ are all hydrogen atoms, or ^one or more of R ¹ , R ² , R ³ and R ⁴ are methyl groups. The structure is particularly preferred.

(Substituted fluorenyl group)
In the formula [C], R ⁵ , R ⁸ , R ⁹ and R ¹² each independently represent a hydrogen atom, a hydrocarbon group, a silicon-containing group or a heteroatom-containing group other than a silicon-containing group. Or a silicon-containing group is preferable. R ⁶ and R ¹¹ are the same atom or the same group selected from a hydrogen atom, a hydrocarbon group, a silicon-containing group and a heteroatom-containing group other than a silicon-containing group, and the hydrogen atom, the hydrocarbon group, and the silicon-containing group are preferably; R ⁷ and R ¹⁰ are a hydrogen atom, a hydrocarbon group, are the same atoms or the same group selected from heteroatom-containing groups other than silicon-containing group and a silicon-containing group, a hydrogen atom, a hydrocarbon group and a silicon-containing R ⁶ and R ⁷ may be bonded to each other to form a ring, and R ¹⁰ and R ¹¹ may be bonded to each other to form a ring; provided that “R ⁶ , R ⁷ , R ¹⁰ and R ¹¹ are not all hydrogen atoms.

From the viewpoint of polymerization activity, R ⁶ and R ¹¹ are preferably not both hydrogen atoms; R ⁶ , R ⁷ , R ¹⁰ and R ¹¹ are all preferably not hydrogen atoms; R ⁶ and R ¹¹ Are preferably the same group selected from a hydrocarbon group and a silicon-containing group, and R ⁷ and R ¹⁰ are particularly preferably the same group selected from a hydrocarbon group and a silicon-containing group. It is also preferable that R ⁶ and R ⁷ are bonded to each other to form an alicyclic ring or an aromatic ring, and R ¹⁰ and R ¹¹ are bonded to each other to form an alicyclic ring or an aromatic ring.

Examples and preferred groups of hydrocarbon groups in R ^{5 to} R ¹² include, for example, a hydrocarbon group (preferably a hydrocarbon group having 1 to 20 carbon atoms, hereinafter referred to as “hydrocarbon group (f1)”). Or a silicon-containing group (preferably a silicon-containing group having 1 to 20 carbon atoms, hereinafter sometimes referred to as “silicon-containing group (f2)”). In addition, examples of the substituent in the substituted cyclopentadienyl group include heteroatom-containing groups (excluding silicon-containing groups (f2)) such as halogenated hydrocarbon groups, oxygen-containing groups, and nitrogen-containing groups. Specific examples of the hydrocarbon group (f1) include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, linear hydrocarbon group such as n-nonyl group, n-decanyl group, allyl group; isopropyl group, isobutyl group, sec-butyl group, t-butyl group, amyl group, 3-methylpentyl group, neopentyl group Group, 1,1-diethylpropyl group, 1,1-dimethylbutyl group, 1-methyl-1-propylbutyl group, 1,1-propylbutyl group, 1,1-dimethyl-2-methylpropyl group, 1- Branched hydrocarbon groups such as methyl-1-isopropyl-2-methylpropyl group; cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, norbornyl group, adamanty group A cyclic saturated hydrocarbon group such as a group; a cyclic unsaturated hydrocarbon group such as a phenyl group, a naphthyl group, a biphenyl group, a phenanthryl group, and an anthracenyl group, and a nuclear alkyl substituent thereof; a saturated hydrocarbon such as a benzyl group and a cumyl group And a group in which at least one hydrogen atom of the group is substituted with an aryl group. The silicon-containing group (f2) in R ^{5 to} R ¹² is preferably a silicon-containing group having 1 to 20 carbon atoms. For example, the silicon atom is directly covalently bonded to the ring carbon of the cyclopentadienyl group. Specific examples include an alkylsilyl group (eg, trimethylsilyl group) and an arylsilyl group (eg, triphenylsilyl group).

  Specific examples of the hetero atom-containing group (excluding the silicon-containing group (f2)) include a methoxy group, an ethoxy group, a phenoxy group, an N-methylamino group, a trifluoromethyl group, a tribromomethyl group, and a pentafluoroethyl group. And pentafluorophenyl group.

  Among the hydrocarbon groups (f1), linear or branched aliphatic hydrocarbon groups having 1 to 20 carbon atoms, specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n- Suitable examples include butyl, isobutyl, sec-butyl, t-butyl, neopentyl, n-hexyl and the like.

Examples of the substituted fluorenyl group in the case where R ⁶ and R ⁷ (R ¹⁰ and R ¹¹ ) are bonded to each other to form an alicyclic ring or an aromatic ring include compounds represented by general formulas [II] to [VI] described later. The group derived from it is mentioned as a suitable example.

(Bridged part)
In the formula [C], R ¹³ and R ¹⁴ each independently represents an aryl group, and Y ¹ represents a carbon atom or a silicon atom. The important point in the method for producing an olefin polymer is that the bridging atom Y ¹ of the bridging portion has R ¹³ and R ¹⁴ which are aryl groups which may be the same or different from each other. From the viewpoint of ease of production, it is preferable that R ¹³ and R ¹⁴ are the same.

  Examples of the aryl group include a phenyl group, a naphthyl group, an anthracenyl group, and a group in which one or more of aromatic hydrogen (sp2-type hydrogen) contained in the aryl group is substituted with a substituent. Examples of the substituent include the hydrocarbon group (f1) and the silicon-containing group (f2), a halogen atom, and a halogenated hydrocarbon group.

  Specific examples of the aryl group include unsubstituted aryl groups having 6 to 14 carbon atoms, preferably 6 to 10 carbon atoms such as phenyl, naphthyl, anthracenyl, and biphenyl groups; tolyl, isopropylphenyl, and n-butylphenyl Group, alkyl group-substituted aryl group such as t-butylphenyl group, dimethylphenyl group; cycloalkyl group-substituted aryl group such as cyclohexylphenyl group; halogenated aryl group such as chlorophenyl group, bromophenyl group, dichlorophenyl group, dibromophenyl group A halogenated alkyl group-substituted aryl group such as (trifluoromethyl) phenyl group and bis (trifluoromethyl) phenyl group; The position of the substituent is preferably a meta position and / or a para position. Among these, a substituted phenyl group in which the substituent is located at the meta position and / or the para position is more preferable.

(Other features of bridged metallocene compound [C])
In the formula [C], Q can be coordinated by a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a neutral conjugated or nonconjugated diene having 4 to 10 carbon atoms, an anionic ligand, or a lone electron pair. Represents a neutral ligand, j represents an integer of 1 to 4, and when j is an integer of 2 or more, a plurality of Qs may be the same or different.

  Examples of the hydrocarbon group for Q include a linear or branched aliphatic hydrocarbon group having 1 to 10 carbon atoms and an alicyclic hydrocarbon group having 3 to 10 carbon atoms. Examples of the aliphatic hydrocarbon group include methyl group, ethyl group, n-propyl group, isopropyl group, 2-methylpropyl group, 1,1-dimethylpropyl group, 2,2-dimethylpropyl group, 1,1- Diethylpropyl group, 1-ethyl-1-methylpropyl group, 1,1,2,2-tetramethylpropyl group, sec-butyl group, tert-butyl group, 1,1-dimethylbutyl group, 1,1,3 -A trimethylbutyl group and a neopentyl group are mentioned. Examples of the alicyclic hydrocarbon group include a cyclohexyl group, a cyclohexylmethyl group, and a 1-methyl-1-cyclohexyl group.

Examples of the halogenated hydrocarbon group for Q include groups in which at least one hydrogen atom of the hydrocarbon group for Q is substituted with a halogen atom.
In the formula [C], M ¹ represents a zirconium atom or a hafnium atom, which is preferable in that the hafnium atom copolymerizes terminal unsaturated polypropylene with high efficiency and can be controlled to have a high molecular weight. The use of a catalyst having a performance capable of copolymerizing terminally unsaturated polypropylene with high efficiency and controllable to a high molecular weight is important for ensuring high productivity. This is because it is desirable to carry out the reaction under high temperature conditions in order to ensure high productivity, but the molecular weight produced tends to decrease under high temperature conditions.

  The above bridged metallocene compound [C] can be produced by a known method, and the production method is not particularly limited. Known methods include, for example, the methods described in WO 01/27124 pamphlet and WO 04/029062 pamphlet.

The above bridged metallocene compound [C] is used singly or in combination of two or more.
The step (C) can be carried out in solution (dissolution) polymerization, and the polymerization conditions are not particularly limited as long as a solution polymerization process for producing an olefin polymer is used, but it has a step of obtaining the following polymerization reaction solution. Is preferred.

The step of obtaining a polymerization reaction liquid is a method in which an aliphatic hydrocarbon is used as a polymerization solvent and R ¹³ and R ¹⁴ bonded to the bridged metallocene compound [C], preferably Y ¹ in the general formula [C] are In the presence of a metallocene catalyst, which is a phenyl group or a phenyl group substituted by an alkyl group or a halogen group, and R ⁷ and R ¹⁰ include a transition metal compound having an alkyl substituent, ethylene, 3 to 3 carbon atoms This is a step of obtaining a polymerization reaction solution of a copolymer of 20 α-olefins and terminal unsaturated polypropylene produced in step (A) and / or terminal unsaturated polyethylene produced in step (B).

  In step (C), the terminal unsaturated polypropylene produced in step (A) and the terminal unsaturated polyethylene produced in step (B) are fed to the reactor in step (C) in the form of a solution or slurry. Is done. The feed method is not particularly limited, and even if the polymerization liquid obtained in step (A) is continuously fed to the reactor in step (C), the steps (A) and (B) After the polymerization solution is once stored in the buffer tank, it may be fed to the step (C).

  Examples of the polymerization solvent in the step (C) include aliphatic hydrocarbons and aromatic hydrocarbons. Specifically, aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, kerosene, alicyclic hydrocarbons such as cyclopentane, cyclohexane, methylcyclopentane, benzene, toluene, xylene And aromatic hydrocarbons such as ethylene chloride, chlorobenzene, and dichloromethane. These may be used alone or in combination of two or more. Further, the polymerization solvent in step (C) may be the same as or different from the polymerization solvent in step (A). Of these, aliphatic hydrocarbons such as hexane and heptane are preferable from the industrial viewpoint, and hexane is preferable from the viewpoint of separation and purification from the olefin resin (β).

  Moreover, the range of 90 degreeC-200 degreeC is preferable, and, as for the polymerization temperature of a process (C), More preferably, it is the range of 100 degreeC-200 degreeC. Such a temperature is preferable because the temperature at which the terminal unsaturated polypropylene is satisfactorily dissolved in aliphatic hydrocarbons such as hexane and heptane, which are preferably used industrially as the polymerization solvent, is 90 ° C. or higher. is there. A higher temperature is preferable for improving the amount of polypropylene side chain introduced. Furthermore, it is preferable that it is higher temperature also from a viewpoint of productivity improvement.

  The polymerization pressure in the step (C) is usually a normal pressure to 10 MPa gauge pressure, preferably a normal pressure to 5 MPa gauge pressure, and the polymerization reaction may be performed in any of batch, semi-continuous and continuous methods. It can be carried out. Furthermore, the polymerization can be performed in two or more stages having different reaction conditions. In the present invention, among these, it is preferable to employ a method in which a monomer is continuously supplied to a reactor to carry out copolymerization.

  The reaction time of step (C) (average residence time when copolymerization is carried out in a continuous process) varies depending on conditions such as catalyst concentration and polymerization temperature, but is usually 0.5 minutes to 5 hours, preferably 5 minutes to 3 hours.

  In the step (C), the polymer concentration is 5 to 50 wt%, preferably 10 to 40 wt% during steady operation. From the viewpoints of viscosity limitation in polymerization ability, post-treatment process (desolvation) load, and productivity, the content is preferably 15 to 35 wt%.

  The molecular weight of the resulting copolymer can be adjusted by allowing hydrogen to be present in the polymerization system or by changing the polymerization temperature or polymerization pressure. Furthermore, it can also adjust with the usage-amount of the below-mentioned compound [D1]. Specific examples include triisobutylaluminum, methylaluminoxane, diethylzinc and the like. When hydrogen is added, the amount is suitably about 0.001 to 100 NL per kg of olefin.

[Compound [D]]
In the method for producing the olefin resin (β) according to the present invention, the transition metal compound [A], the complex [B] and the cross-linking used as the olefin polymerization catalyst in the steps (A), (B) and (C) described above. It is preferable to use the compound [D] together with the metallocene compound [C].

  Compound [D] reacts with transition metal compound [A], complex [B] and bridged metallocene compound [C] to function as a catalyst for olefin polymerization. Specifically, [D1] organometallic The compound, [D2] an organoaluminum oxy compound, and [D3] a compound that reacts with the transition metal compound [A] or the bridged metallocene compound [C] to form an ion pair. About compound [D], the thing similar to compound [C] of WO2015 / 147187 is illustrated.

[Process (E)]
The method for producing the olefin-based resin (β) may include a step (E) of recovering a polymer produced in each step, if necessary, after the steps (A), (B), and (C). This step is a step of separating the organic solvent used in steps (A), (B) and (C), taking out the polymer and converting it to a product form, and existing polyolefins such as solvent concentration, extrusion degassing, pelletizing, etc. There is no particular limitation as long as it is a process for producing a resin.

[Other ingredients]
The olefin resin (β) of the present invention can be blended with other resins, rubbers, inorganic fillers, etc. within the range not impairing the object of the present invention, and also has a weather resistance stabilizer, heat resistance stabilizer, antistatic agent. Additives such as crystal nucleating agents such as anti-slip agents, anti-blocking agents, anti-fogging agents, lubricants, pigments, dyes, plasticizers, anti-aging agents, hydrochloric acid absorbents and antioxidants can be blended. In the olefin resin according to the present invention, the addition amount of the other resin, other rubber, inorganic filler, additive and the like is not particularly limited as long as the object of the present invention is not impaired. For example, the aspect contained so that it may become 50 mass% or less of the olefin resin ((beta)), Preferably it is 30 mass% or less, More preferably, it is 10 mass% or less can be illustrated.

<Modified olefin resin (α)>
It is a modified polymer containing a structural unit derived from one or more selected from ethylene and an α-olefin having 3 to 20 carbon atoms. Examples of the α-olefin having 3 to 20 carbon atoms are the same as those exemplified in the section of the olefin resin (β). Hereinafter, the resin before modification may be referred to as unmodified olefin resin (α ′). The unmodified olefin-based resin (α ′) includes, for example, vinyl acetate, methyl acrylate, ethyl acrylate, butyl acrylate as structural units that may be included in addition to ethylene and an α-olefin having 3 to 20 carbon atoms. And structural units derived from methyl methacrylate and the like.

  The modified olefin resin (α) is most preferably modified polyethylene and modified polypropylene. That is, the unmodified olefin resin (α ′) is most preferably polyethylene and polypropylene. Here, polyethylene means a polymer containing 80 mol% or more of a repeating unit derived from ethylene, and is preferably a copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms. It means a polymer containing 80 mol% or more of repeating units derived from propylene, and a copolymer of propylene, ethylene and an α-olefin having 4 to 20 carbon atoms is preferable.

  Further, as described above, as the unmodified olefin resin (α ′), a resin containing a structural unit derived from vinyl acetate, methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, or the like, that is, EVA ( Polar resins such as ethylene / vinyl acetate copolymer), EMA (ethylene-methyl acrylate copolymer), and EEA (ethylene-ethyl acrylate copolymer) can be used. ), The content M of the repeating unit containing a polar group is easily adjusted to a relatively high range.

  The modified olefin resin (α) satisfies the following requirement (α-1). When the modified olefin resin (α) is a modified polyethylene, it preferably satisfies the requirement (α-2) in addition to the requirement (α-1). Further, when the modified olefin resin (α) is a modified polypropylene, it preferably satisfies the requirement (α-3) in addition to the requirement (α-1). The resin corresponding to both the olefin resin (β) and the modified olefin resin (α) is assumed to be an olefin resin (β).

Requirement (α-1)
It contains 0.01 to 10% by mass of a repeating unit containing a polar group selected from the group consisting of a carboxy group, an amino group, an imino group, a hydroxyl group and a silanol group (hereinafter also referred to as polar group (P)). Preferably, the repeating unit containing the polar group is contained in an amount of 0.05 to 5% by mass.

  It is preferable in terms of the balance between adhesiveness and moldability that the content M of the repeating unit containing the polar group (hereinafter also simply referred to as content M) is within the above range. The content M can be obtained from a separately prepared calibration curve based on the peak intensity of the wave number attributed to the carbonyl group by FT-IR as described later.

Requirement (α-2)
The melt flow rate (measured at 190 ° C. under a load of 2.16 kg according to ASTM D1238) is in the range of 0.01 to 50 g / 10 min. Preferably, the melt flow rate is in the range of 0.1-10 g / 10 min.
Requirements (α-3)
The intrinsic viscosity [η] in decalin at 135 ° C. is in the range of 0.01 to 5 dl / g. The method for measuring the intrinsic viscosity [η] is the same as the method for measuring the intrinsic viscosity [η] of the olefin resin (β), and is described in detail in the Examples section.

[Polar group (P)]
The polar group (P) is preferably at least one selected from the group consisting of a carboxy group, an amino group, an imino group, a hydroxyl group and a silanol group. Among these, a carboxy group and a hydroxyl group are preferable, and a carboxy group is most preferable.

Specific examples of the repeating unit containing a polar group (P) include a repeating unit derived from a “compound imparting a repeating unit containing a polar group (P)” described later.
Content of the repeating unit containing a polar group (P) is 0.1-50 mass% with respect to the sum total of all the repeating units contained in modified olefin resin ((alpha)), Preferably 0.1-10 mass%, More preferably, it is 0.1-5 mass%, More preferably, it is 0.2-3 mass%. If the content of the repeating unit containing the polar group (P) is less than 0.1% by mass, the adhesive strength of the laminated base material and the affinity with the thermoplastic resin are inferior. Is not economical.

The content of the repeating unit containing the polar group (P) can be generally evaluated by ¹ H-NMR or IR (infrared absorption spectrum) as described in the Examples section. Alternatively, evaluation by elemental analysis or titration by acid or base is possible. In order to make the content of the repeating unit containing the polar group (P) in such a range, a method of carrying out the reaction in the presence of a radical initiator in the method for producing the modified olefin resin (α) described later can be mentioned. .

[Compound imparting repeating unit containing polar group (P)]
Examples of the compound imparting a repeating unit containing a polar group (P) include unsaturated carboxylic acids and derivatives thereof, hydroxyl group-containing ethylenically unsaturated compounds, amino group-containing ethylenically unsaturated compounds, vinyl group-containing organosilicon compounds, and the like. These compounds, epoxy group-containing ethylenically unsaturated compounds, vinyl chloride, aromatic vinyl compounds, vinyl ester compounds, carbodiimide compounds, mercapto group-containing compounds, and the like.

  Of these, unsaturated carboxylic acids and derivatives thereof, vinyl group-containing organosilicon compounds, and hydroxyl group-containing ethylenically unsaturated compounds are preferred, and unsaturated carboxylic acids and derivatives thereof are most preferred.

  Examples of unsaturated carboxylic acids and derivatives thereof include unsaturated compounds having one or more carboxylic acid groups, esters of compounds having carboxylic acid groups and alkyl alcohols, unsaturated compounds having one or more carboxylic anhydride groups, and the like. Examples of the unsaturated group include a vinyl group, a vinylene group, and an unsaturated cyclic hydrocarbon group. Conventionally known compounds can be used for these compounds and are not particularly limited. Specific examples include (meth) acrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, nadic acid [trademark] (endocis-bicyclo [2.2.1] hept Unsaturated carboxylic acids such as -5-ene-2,3-dicarboxylic acid), and derivatives thereof, such as acid halides, amides, imides, anhydrides, esters, and the like. Specific examples of such derivatives include methyl acrylate, methyl methacrylate, dimethyl maleate, monomethyl maleate, dimethyl fumarate, dimethyl itaconate, diethyl citraconic acid, dimethyl tetrahydrophthalate, dimethyl nadic acid (endocis-bicyclo [2 , 2,1] hept-5-ene-2,3-dicarboxylate), maleenyl chloride, maleimide, maleic anhydride, citraconic anhydride, monomethyl maleate, dimethyl maleate, glycidyl maleate and the like. These unsaturated carboxylic acids and derivatives thereof can be used singly or in combination of two or more. Of these, unsaturated dicarboxylic acids or acid anhydrides thereof are preferred, and maleic acid, nadic acid [trademark] or acid anhydrides thereof are particularly preferably used. Maleic anhydride is particularly preferred because of its high reactivity.

  A conventionally well-known thing can be used as a vinyl group containing organosilicon compound, and it does not restrict | limit in particular. Specifically, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris (β-methoxy-ethoxysilane), γ-glycidoxypropyl-tripril trimethoxysilane, γ-aminopropyltriethoxysilane, γ-methacryloxy Propyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethylethoxysilane, p-styryltrimethoxysilane, 3-meta Cloxypropylmethyldimethylmethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyl Dimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-triethoxysilyl -N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-isocyanatopropyltriethoxysilane and the like can be used. Preferably, γ-glycidoxypropyltripyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane More preferably, vinyltriethoxysilane, vinyltrimethoxysilane, and 3-acryloxypropyltrimethoxysilane having small steric hindrance and high graft modification efficiency can be used.

<Production Method of Modified Olefin Resin (α)>
A typical method for producing a modified olefinic resin (α) by introducing a repeating unit containing a polar group (P) is graft modification. Graft modification is exemplified by unmodified olefinic resin (α ′). ) Is dissolved in an organic solvent, and then a compound (such as maleic anhydride) that gives a repeating unit containing a polar group (such as maleic anhydride) and a radical initiator are added to the solution, preferably at 70 to 200 ° C, more preferably at 80 to 190 ° C. The reaction can be carried out at a temperature, preferably for 0.5 to 15 hours, more preferably for 1 to 10 hours.

  In addition, using an extruder or the like, the unmodified olefin resin (α ′) can be reacted with the compound imparting a repeating unit containing a polar group without solvent. This reaction is usually preferably carried out at a temperature equal to or higher than the melting point of the unmodified olefin resin (α ′), specifically 120 to 300 ° C., usually for 0.5 to 10 minutes. In particular, the kneading is preferably performed at 300 ° C. or lower, more preferably 280 ° C. or lower.

  This graft polymerization is usually carried out in the presence of a radical initiator. Examples of the radical initiator include organic peroxides and azo compounds. Specifically, for example, dicumyl peroxide, di-t-butyl peroxide, di-t-butylperoxy-3,3,5-trimethylcyclohexane, t-butylcumyl peroxide, di-t-amyl peroxide , T-butyl hydroperoxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3,2,5-dimethyl-2,5-di (benzoylperoxy) hexane, 2, 5-dimethyl-2,5-di (t-butylperoxy) hexane, α, α′-bis (t-butylperoxy-m-isopropyl) benzene, 2,5-dimethyl-2,5-bis (t -Dibutyl peroxides such as -3-hexyne; t-butyl peroxyacetate, t-butylperoxyisobutyrate, t-butylperper Peroxyesters such as xypivalate, t-butylperoxymaleic acid, t-butylperoxyneodecanoate, t-butylperoxybenzoate, di-t-butylperoxyphthalate; ketone perper such as dicyclohexanone peroxide Oxides; and mixtures thereof.

  The radical initiator can be used as it is by mixing it with the unmodified olefin resin (α ′) and the compound to which a repeating unit containing a polar group is added, but it can also be used after being dissolved in a small amount of an organic solvent. it can. Any organic solvent that can dissolve the radical initiator can be used without particular limitation.

A reducing substance may be used for graft modification. When a reducing substance is used, the amount of grafting of the compound imparting a repeating unit containing a polar group can be improved.
The compound which gives the repeating unit containing the polar group (P) is usually 0.1 to 100 parts by weight, preferably 0.5 to 80 parts by weight, with respect to 100 parts by weight of the unmodified olefin resin (α ′). More preferably, it is used in an amount of 1 to 50 parts by mass.
The compound which provides the repeating unit containing a polar group (P) can also be used individually by 1 type, and can also be used in combination of 2 or more type.

<Adhesive (γ)>
The pressure-sensitive adhesive (γ) is a resin different from the modified olefin resin (α) and the olefin resin (β). For example, the alicyclic hydrogenated tackifier, natural rosin, modified rosin, or esters thereof Synthetic petroleum resins such as chemical compounds, polyterpene resins, aliphatic petroleum resins, alicyclic petroleum resins, aromatic petroleum resins, copolymerized petroleum resins of aliphatic and aromatic components, coumarone resins, phenolic resins And xylene resins, styrene resins, low molecular weight styrene resins, isoprene resins, terpene resins, coumarone-indene resins, and the like. These pressure-sensitive adhesives can be used alone or in combination of two or more.

Among these, rosin resins, polyterpene resins, and synthetic petroleum resins are preferable, and those having an aliphatic and / or alicyclic structure are more preferable.
Particularly preferred as petroleum resins having an aliphatic and / or alicyclic structure are partially and fully hydrogenated rosins and their derivatives for rosin resins, and homopolymers or copolymers of cyclic terpenes for polyterpene resins. Examples of coal and synthetic petroleum resins include aliphatic petroleum resins, alicyclic petroleum resins, aliphatic-alicyclic copolymer resins, and hydrogenated products of copolymers of naphtha cracked oil and various terpenes.

  In the present invention, a pressure-sensitive adhesive having a softening point in the range of 25 to 160 ° C. is preferable, and a pressure-sensitive adhesive having a softening point of less than 25 ° C. may bleed on the surface. There is a possibility that the viscosity at the time of melting becomes high and the workability becomes poor. Specific examples of the pressure-sensitive adhesive having a softening point in the range of 25 to 160 ° C. include Alcon P-70, Alcon P-90, Alcon P-100, Alcon P-115, and Alcon P-125 manufactured by Arakawa Chemical Industries, Ltd. Alcon P-140 (all are trade names) is preferably used. These pressure-sensitive adhesives can be used alone or in admixture of two or more.

<Other components (additives, etc.)>
The composition of the present invention can contain the following flow modifiers as required.
As flow modifiers, for example, paraffinic process oil, naphthenic oil, liquid polybutene, phthalic acid esters, adipic acid esters, fatty acid esters, glycols, epoxy polymer plasticizer, etc. Any known one can be used. In particular, a flow modifier having a melt viscosity at 190 ° C. of 1 to 15,000 mPa · s, preferably 10 to 12,000 mPa · s, more preferably 25 to 10,000 mPa · s can be suitably used. The flow modifier can be used in an amount of 10 to 150 parts by weight based on 100 parts by weight of the olefin resin composition of the present invention. These flow modifiers may be used alone or in admixture of two or more.

  Further, as necessary, conventionally known nucleating agents, antioxidants, heat stabilizers, UV absorbers, light stabilizers, pigments, dyes, antibacterial agents, antifungal agents, antistatic agents, foaming agents, foaming aids. A filler or the like can be added within a range not impairing the object of the present invention. Usually, when adding these arbitrary additives, it is the range of 0.05 part-0.5 weight part per 100 weight part of resin compositions.

<Method for producing olefin resin composition>
The resin composition of the present invention can be obtained by mixing each component and, if necessary, other additives using a Henschel mixer, a Banbury mixer, a V-type blender, a tumbler blender, a ribbon blender, or the like. As the resin composition of the present invention, the mixture is melt kneaded at 180 to 300 ° C., preferably 190 to 260 ° C. using a single screw extruder, a multi screw extruder, a roll, a kneader, etc. A composition in which additives used as necessary are uniformly dispersed and mixed is desirable.

<Molded body>
The olefin resin composition of the present invention can be produced by various known molding methods such as injection molding, extrusion molding, inflation molding, blow molding, extrusion blow molding, injection blow molding, press molding, vacuum molding, calendar molding, and foam molding. It can be molded into a molded body, and can be applied to various known uses such as automobile parts, containers for food use and medical use, and packaging materials for food use and electronic materials.

<Adhesive>
The olefin resin composition of the present invention can be used as a hot melt adhesive. As a method for use as a hot-melt adhesive, a pellet-shaped resin composition is preferably formed into a sheet or film by a screw-type extruder having a die portion called a T-die method, an inflation method, a calendar method, or a spinning method. Or in a non-woven fabric, fixed in the middle of the adherend to be laminated and bonded, or by heat-bonding, or a sheet-formed adhesive is heated and melted on one of the adherends and bonded as it is There is a method in which the other adherend is bonded onto the agent while cooling.

  In addition, a method in which the pellet is melted by the screw type extruder described above and inserted between the substrates to be directly laminated and thermally bonded, or if one of the substrates is a thermoplastic, is it directly bonded by coextrusion? There is a method in which it is directly applied to one of the adherends and is again heat-bonded.

<Laminate>
The laminate of the present invention includes at least one layer containing the olefin resin composition of the present invention.
Since the olefin resin composition is excellent in adhesiveness, it can be used in combination with various materials. For example, it can be used as a laminate of various resins, carbon fibers, glass, and various metals. The present invention can also be applied to lamination with a foam layer, lamination with a fiber layer, honeycomb lamination, tubular lamination, perforated layer, network layer, uneven layer, deformation sheet lamination, and the like. Further, it can be used as a surface layer of a laminate, and can also be used as an intermediate layer or an adhesive layer. There is no restriction | limiting in the whole as a laminated body and each layer thickness, A film form, a sheet form, a block form etc. are mentioned. A known method can be applied as a method of laminating.

  Examples of the various resins include polyester resins, polycarbonate resins and polyvinylidene chloride resins, polystyrene resins, ABS resins and polyacrylonitrile resins, ethylene / vinyl acetate copolymer saponified resins (EVOH), and the like. Olefin resins such as polyethylene and polypropylene, polyamide and the like can also be used.

  Especially, it is preferable that the molded object of this invention contains the layer which consists of polyester resins. The polyester resin is composed of aliphatic glycols such as ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol and hexamethylene glycol, alicyclic glycols such as cyclohexanedimethanol, and aromatic dihydroxy compounds such as bisphenol. Or a component unit derived from a dihydroxy compound selected from two or more of these and an aromatic dicarboxylic acid such as terephthalic acid, isophthalic acid or 2,6-naphthalenedicarboxylic acid, oxalic acid, succinic acid, adipic acid, Thermoplastic composed of an aliphatic dicarboxylic acid such as sebacic acid or undecane dicarboxylic acid, an alicyclic dicarboxylic acid such as hexahydroterephthalic acid, or a component unit derived from a dicarboxylic acid selected from two or more of these. Polyester, thermoplastic Unless indicated, it may be modified in such trivalent or higher polyhydroxy compound or a polycarboxylic acid, such as a small amount of a triol or tricarboxylic acid.

  Specific examples of such thermoplastic polyesters include polyethylene terephthalate, polybutylene terephthalate, and polyethylene isophthalate / terephthalate copolymer.

The polycarbonate resin is various polycarbonates obtained by reacting a dihydroxy compound with phosgene or diphenyl carbonate by a known method.
Specific examples of the polyvinylidene chloride resin include a copolymer of 50% by weight or more of vinylidene chloride and acrylonitrile, vinyl chloride, acrylic acid ester, or methacrylic acid ester.

  Examples of the polystyrene-based resin include polystyrene, impact-resistant polystyrene (rubber-containing polystyrene), AS resin (styrene / acrylonitrile copolymer (SAN)), and the like.

  As the ethylene / vinyl acetate copolymer saponified resin (EVOH), an ethylene / vinyl acetate copolymer having an ethylene content of 15 to 60 mol%, preferably 25 to 50 mol%, has a saponification degree of 50%. For example, a resin saponified so as to be 90% or more is preferable.

In the laminate according to the present invention, the thickness of the layer containing the resin composition of the present invention is usually in the range of 0.1 to 80%, preferably 0.5 to 50%, more preferably 1 to 30% of the total thickness. It is in.
When the laminate is a multilayer film, the total thickness is usually in the range of 10 to 500 μm, preferably 10 to 300 μm, more preferably 10 to 100 μm, and the layer containing the resin composition of the present invention contained in the multilayer film. The thickness is usually in the range of 1 to 100 μm, preferably 3 to 50 μm, more preferably 5 to 20 μm.

Any of these laminates or any of the layers constituting the laminate may be uniaxially or biaxially oriented.
As a laminating method for producing these laminates, a conventionally known laminating method such as a co-extrusion laminating method or a so-called sandwich laminating method in which a resin composition layer is melt-extruded between previously formed layers is used. In view of interlayer adhesion, a coextrusion molding method is preferable.

  There are a T-die method using a flat die and an inflation method using a circular die. The flat die may be either a single manifold type using a black box or a multi-manifold type. Any known die can be used as the die used for the inflation method.

  Among the laminates of the present invention, the sheet-like laminate is formed by vacuum forming, pressure forming, plug assist forming, or the like, thereby obtaining cup-shaped or tray-shaped containers. Also, by hollow-molding the parison formed by extruding the olefin resin composition of the present invention and other resins for forming a layer other than the layer containing the resin composition through a circular die Laminated containers such as bottles, tanks and tubes are obtained.

EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated further more concretely, this invention is not restrict | limited at all to these Examples, unless the summary is exceeded.
(Various measurement methods)
In this example and the like, measurement was performed according to the following method.
≪Method for measuring physical properties of olefin resin (β) ≫
[Measurement of melting point (Tm), heat of fusion (ΔH), glass transition temperature (Tg)]
The melting point (Tm), the heat of fusion (ΔH) and the glass transition temperature (Tg) were determined by DSC measurement under the following conditions.

  Using a differential scanning calorimeter [SII DSC220], a sample of about 5.0 mg was heated from 30 ° C. to 200 ° C. at a heating rate of 10 ° C./min in a nitrogen atmosphere and held at that temperature for 10 minutes. Further, after cooling to 30 ° C. at a temperature lowering rate of 10 ° C./min and holding at that temperature for 5 minutes, the temperature was raised to 200 ° C. at a temperature rising rate of 10 ° C./min. The endothermic peak observed during the second temperature increase was taken as the melting peak, and the temperature at which the melting peak appears was determined as the melting point (Tm). The heat of fusion (ΔH) was determined by calculating the area of the melting peak. When the melting peak was multimodal, the area of the entire melting peak was calculated and determined. The glass transition temperature (Tg) is sensed in such a manner that the DSC curve is bent due to the change in specific heat and the base line moves in parallel during the second temperature increase. The glass transition temperature (Tg) was defined as the temperature at the intersection of the tangent to the base line, which is lower than the bending, and the tangent at the point where the inclination is maximum at the bent portion.

[Intrinsic viscosity measurement]
Intrinsic viscosity [η] was measured in decalin at 135 ° C.
Specifically, about 20 mg of resin was dissolved in 25 ml of decalin, and then the specific viscosity ηsp was measured in an oil bath at 135 ° C. using an Ubbelohde viscometer. After 5 ml of decalin was added to the decalin solution for dilution, the specific viscosity ηsp was measured in the same manner as described above.
This dilution operation was further repeated twice, and the value of ηsp / C when the concentration (C) was extrapolated to 0 was determined as the intrinsic viscosity [η] (unit: dl / g) (see the following formula 1).
[Η] = lim (ηsp / C) (C → 0) Equation 1

[GPC analysis]
For molecular weight analysis, GPC analysis was performed under the following conditions. Apparatus: Waters Alliance GPC 2000 type, column: TSKgel GMH6-HTx2 TSKgel GMH6-HTLx2 (both manufactured by Tosoh Corporation, inner diameter 7.5 mm × length 30 cm), column temperature: 140 ° C., mobile phase: orthodichlorobenzene (0 0.025% dibutylhydroxytoluene), detector: differential refractometer, flow rate: 1.0 mL / min, sample concentration: 0.15% (w / v), injection volume: 0.5 mL, sampling time interval: 1 second Column calibration: monodisperse polystyrene (manufactured by Tosoh Corporation)
The average molecular weight in terms of polystyrene obtained by the above measurement was converted to the average molecular weight of polyethylene.

[ ¹³ C-NMR measurement]
For the purpose of composition ratio analysis of ethylene and α-olefin of the polymer, ¹³ C-NMR measurement was performed under the following conditions. Apparatus: AVANCE III500 CryoProbe Prodigy type nuclear magnetic resonance apparatus manufactured by Bruker Biospin Co., Ltd., measurement nucleus: ¹³ C (125 MHz), measurement mode: single pulse proton broadband decoupling, pulse width: 45 ° (5.00 μsec), number of points: 64 k , Measurement range: 250 ppm (−55 to 195 ppm), repetition time: 5.5 seconds, number of integrations: 512 times, measurement solvent: orthodichlorobenzene / benzene-d ₆ (4/1 v / v), sample concentration: ca . 60 mg / 0.6 mL, measurement temperature: 120 ° C., window function: exponential (BF: 1.0 Hz), chemical shift standard: benzene-d ₆ (128.0 ppm).

[Calculation of composition ratio of α-olefin]
The composition ratio of the α-olefin of the ethylene copolymer constituting the main chain (MC) of the graft polymer [GP] was calculated by the following method.

  Regarding the olefin resin β-1 described later, from the calibration curve based on the correlation between the composition ratio (mmol%) of 1-butene of the ethylene-1-butene copolymer and the glass transition temperature [Tg] (° C.), α- The composition ratio of olefin was calculated. A calibration curve was prepared by performing polymerization in the same manner as in Production Example 1 described later except that the compound (1) was not used, and further changing the supply ratio of ethylene and 1-butene to be continuously supplied. A plurality of ethylene-1-butene copolymer resins having different composition ratios were obtained. About the obtained ethylene-1-butene copolymer resin, the composition ratio and glass transition temperature of 1-butene were measured by the above-mentioned method, and the analytical curve was created.

[Ratio of ethylene polymer]
The ratio of the ethylene polymer contained in the olefin resin was calculated by the following method.
That is, the ratio of the ethylene polymer was calculated by a calibration curve based on the correlation between the heat of fusion ΔH (J / g) derived from the ethylene polymer and the ethylene polymer content (wt%).

  Preparation method of calibration curve: In Production Example 1 to be described later, a terminal unsaturated polyethylene was obtained in the same manner except that the compound (2) was not used. The obtained terminal unsaturated polyethylene, ethylene and 1-butene were copolymerized by a batch polymerization method using a polymerization catalyst containing the compound (2). Here, by changing the amount of terminal unsaturated polyethylene charged, a plurality of types of olefin resins with different proportions of the ethylene polymer contained were collected. The ethylene polymer content (wt%) of the obtained plurality of olefin resins is determined from the ratio of the amount of terminal unsaturated polyethylene charged and the amount of olefin resin produced, and the heat of fusion ΔH (J / g) is calculated as described above. A calibration curve was created from the correlation between the two values.

[density]
The density was measured with a density gradient tube after heat treating the obtained resin strand according to JIS-K6922 at 120 ° C. for 1 hour and gradually cooling to room temperature over 1 hour.

[Melt flow rate (MFR: [g / 10 min])]
The melt flow rate was measured with a 2.16 kg load according to ASTM D1238. The measurement temperature was 190 ° C.

[Production Example 1] Olefin resin (β-1)
The compound (1) represented by the following formula (1) and the compound (2) represented by the following formula (2) used as the catalyst were synthesized by a known method. In a 100 L stainless steel polymerization vessel (stirring rotation speed 250 rpm, internal temperature 110 ° C., polymerization pressure 1.0 MPa · G) equipped with stirring blades, 23 L / hr of dehydrated and purified hexane and 0.02 of compound (2) were added. 0090 mmol / hr, Compound (1) at 0.0029 mmol / hr, triphenylcarbenium tetrakis (pentafluorophenyl) borate at 0.049 mmol / hr, and triisobutylaluminum at 5.0 mmol / hr were continuously fed. . Butene, ethylene, and hydrogen were continuously supplied so that the gas composition in the gas phase polymerization reactor was 0.33 (molar ratio) as butene / ethylene and 0.040 (molar ratio) as hydrogen / ethylene. The produced polymerization solution was continuously discharged through the discharge port provided in the side wall of the polymerization vessel while adjusting the opening of the liquid level control valve so as to maintain the amount of solution in the polymerization vessel 28L. The obtained polymerization solution is led to a heater, heated to 180 ° C., methanol is added at 80 mL / h as a catalyst deactivator, polymerization is stopped, and it is continuously transferred to a devolatilization step under reduced pressure and dried. As a result, an olefin resin (β-1) was obtained at a production rate of 4.1 kg / hr. Table 1 shows the analysis results of the resulting olefin resin (β-1).

[Production Example 2] Olefin resin (b-1)
In a 100 L stainless steel polymerization vessel equipped with stirring blades (stirring speed = 250 rpm, internal temperature 110 ° C., polymerization pressure 1.0 MPa · G), dehydrated and purified hexane was 23 L / hr, and compound (2) was 0. .0078 mmol / hr, triphenylcarbenium tetrakis (pentafluorophenyl) borate was continuously supplied at a rate of 0.031 mmol / hr, and triisobutylaluminum was continuously supplied at a rate of 2.3 mmol / hr. Butene, ethylene, and hydrogen were continuously supplied so that the gas composition in the gas phase polymerization reactor was 0.23 (molar ratio) as butene / ethylene and 0.040 (molar ratio) as hydrogen / ethylene. The produced polymerization solution was continuously discharged through the discharge port provided in the side wall of the polymerization vessel while adjusting the opening of the liquid level control valve so as to maintain the amount of solution in the polymerization vessel 28L. The obtained polymerization solution is led to a heater, heated to 180 ° C., methanol is added at 80 mL / h as a catalyst deactivator, polymerization is stopped, and it is continuously transferred to a devolatilization step under reduced pressure and dried. Thus, an olefin polymer (b-1) was obtained at a production rate of 3.1 kg / hr.
The analysis result of the obtained olefin polymer (b-1) is shown in Table 1.

[Production Example 3] Olefin resin (b-2)
In a 100 L stainless steel polymerization vessel equipped with stirring blades (stirring speed = 250 rpm, internal temperature 110 ° C., polymerization pressure 1.0 MPa · G), dehydrated and purified hexane was 23 L / hr, and compound (2) was 0. .0045 mmol / hr, 0.018 mmol / hr of triphenylcarbenium tetrakis (pentafluorophenyl) borate, and 2.3 mmol / hr of triisobutylaluminum were continuously supplied. Butene, ethylene, and hydrogen were continuously supplied so that the gas composition in the gas phase polymerization reactor was 0.14 (molar ratio) as butene / ethylene and 0.16 (molar ratio) as hydrogen / ethylene. The produced polymerization solution was continuously discharged through the discharge port provided in the side wall of the polymerization vessel while adjusting the opening of the liquid level control valve so as to maintain the amount of solution in the polymerization vessel 28L. The obtained polymerization solution is led to a heater, heated to 180 ° C., methanol is added at 80 mL / h as a catalyst deactivator, polymerization is stopped, and it is continuously transferred to a devolatilization step under reduced pressure and dried. As a result, an olefin polymer (b-2) was obtained at a production rate of 4.0 kg / hr.
Table 1 shows the analysis results of the obtained olefin polymer (b-2).

[Ethylene polymer]
In Comparative Example 2 to be described later, as an ethylene-based polymer, Neozex (trademark) 65150 Prime Polymer polyethylene (ethylene-1-butene copolymer, density 961 kg / m ³ , MFR (2.16 kg load, 190 ° C.) ) 16 g / 10 min).

[Other olefin resins]
In Comparative Example 3 which will be described later, an olefin crystal / ethylene butylene / olefin crystal block polymer (CEBC) manufactured by Dynaron (trademark) 6200 JSR Co., Ltd. was used.

[Modified olefin resin (α)]
As modified olefin resin (α), modified polyethylene (α-1) obtained by modifying polyethylene with maleic anhydride (maleic anhydride graft amount (content M) 2.2 mass%, MFR (2.16 kg)) Load) 5.0 g / 10 min) was used.

<Content M of Repeating Unit Containing Polar Group>
The content M (mass%) was determined from a separately prepared calibration curve based on the peak intensity of the wave number attributed to the carbonyl group in FT-IR. More specifically, it was determined by calculating the average ratio of the CH ₂ group peak intensity (1470 cm ⁻¹ ) and the carboxy group peak intensity (sum of the intensity of 1710 cm ⁻¹ and 1790 cm ⁻¹ ). The peak intensity was calculated in a state where a spectrum free from interference fringes and noise was obtained. For the CH ₂ group peak intensity, the inflection point in the range of 1400 cm ⁻¹ to 1410 cm ⁻¹ is set as the start point, the inflection point in the range of 1510 cm ⁻¹ to 1520 cm ⁻¹ is set as the end point, and the peak intensity is measured from these areas. did. As for the carboxyl group peak intensity, the peak intensity at around 1710 cm ^-1 is the starting point of the inflection point in the range of 1670 cm ^-1 in 1680 cm ^-1, and the end point of the inflection point in the range of 1755 cm ^-1 from 1745 cm ^-1 determined, the peak intensity at around 1790 cm ^-1 is determined from 1760 cm ^-1 starting from the inflection point in the range of 1770 cm ^-1, and ending the inflection point in the range from 1810 cm ^-1 to 1820 cm ^-1, from their area Peak intensity was measured.

[Adhesive (γ)]
As an adhesive (γ-1), Alcon (trademark) (P-125, Arakawa Chemical Industries, Ltd., aliphatic saturated hydrocarbon resin) was used.

[Example 1]
A 65 mmφ single screw extruder (Dalmage) in which olefin resin (β-1), modified polyethylene (α-1) and pressure-sensitive adhesive (γ-1) were mixed with a tumbler at a mass ratio shown in Table 2 and set to 200 ° C. The mixture was kneaded and granulated with a screw to obtain an adhesive resin composition (X) which was an olefin resin composition.

<Multilayer film (laminate) molding>
Adhesive resin composition (X) and polyethylene terephthalate resin [Mitsui Chemicals, Mitsui PET (trademark) J125, intrinsic viscosity (IV) 0.76 dl / g], LLDPE [2021L; manufactured by Prime Polymer Co., Ltd.] Were used to form two types of three-layer co-extruded films having a thickness of 50 μm and 200 μm, that is, multilayer films, under the following conditions.

<Molding conditions>
Extruder Die diameter 40 mmφ: Molding temperature 270 ° C (for PET)
Die diameter 40 mmφ: Molding temperature 220 ° C (for LLDPE, adhesive resin)
・ Die temperature 270 ℃
Film structure and film thickness of each layer, molding speed 50 μm Thick film: molding speed 20 m / min PET / adhesive resin composition (X) / LLDPE = 20/10/20 (μm)
200 μm thickness film: molding speed 5 m / min PET / adhesive resin composition (X) / LLDPE = 80/40/80 (μm)

<Evaluation of multilayer film>
A test piece having a width of 15 mm and a length of 100 mm was cut from the obtained multilayer film, and the PET layer on one end and the adhesive resin composition (X) layer were peeled off, and then the temperature was measured using an Instron tensile tester. Evaluation was performed by a T-type peeling method at a peeling speed of 300 mm / min in an atmosphere of 23 ° C., 80 ° C., 90 ° C. and 100 ° C.

[Comparative Examples 1-3]
A multilayer film was molded and evaluated in the same manner as in Example 1 except that the composition in Example 1 was changed to the composition shown in Table 2. The results are shown in Table 2.

[Contrast between Example and Comparative Example]
Comparative Example 1 is an example using an olefin resin that does not contain the graft polymer [GP], and it can be seen that the adhesion amount at a high temperature of 90 ° C. or more is lower than that of Example 1.

The side chain (SC) of the graft polymer [GP] included in Example 1 is a side chain (SC) composed of an ethylene polymer, but in contrast to that, only the ethylene polymer was blended. In Comparative Example 2, which is an example that does not contain the graft polymer [GP], it can be seen that although the adhesive strength is observed at 23 ° C., the adhesive strength is significantly low at a high temperature of 80 ° C. or higher.
Further, it can be seen that Comparative Example 3 using olefin crystal / ethylene butylene / olefin crystal block polymer (CEBC) has lower adhesive force than Example 1.

Claims (12)

10 to 99 parts by mass of an olefin resin (β),
1 to 90 parts by mass of the modified olefin resin (α) (however, the total of the modified olefin resin (α) and the olefin resin (β) is 100 parts by mass),
The olefin resin (β) includes a graft polymer [GP], and the graft polymer [GP] includes a main chain (MC) composed of an ethylene copolymer and an olefin polymer. The graft polymer [GP] satisfies the following requirements (i) and (ii):
The olefin resin (β) satisfies the following requirement (β-1),
The modified olefin resin (α) satisfies the following requirement (α-1): an olefin resin composition.
(I) The ethylene-based copolymer constituting the main chain (MC) is a repeat derived from at least one α-olefin selected from a repeating unit derived from ethylene and an α-olefin having 3 to 20 carbon atoms. The content ratio of the repeating unit derived from the α-olefin is in the range of 10 to 50 mol% with respect to all the repeating units contained in the main chain (MC).
(Ii) The side chain (SC) is a side chain (SE) composed of an ethylene polymer and / or a side chain (SP) composed of a propylene polymer.
(Β-1) The melting point (Tm) measured by differential scanning calorimetry (DSC) is in the range of 80 ° C. to 170 ° C., and the glass transition temperature (Tg) is in the range of −80 to −30 ° C.
(Α-1) 0.01 to 10% by mass of a repeating unit containing a polar group selected from the group consisting of carboxy group, amino group, imino group, hydroxyl group and silanol group The olefin resin composition according to claim 1, wherein the graft polymer [GP] further satisfies the following requirements (iii) and (iv).
(Iii) The side chain (SC) is a side chain (SE) composed of an ethylene polymer, and is selected from repeating units derived from ethylene, and optionally an α-olefin having 3 to 20 carbon atoms. It consists of a repeating unit derived from at least one kind, and the content ratio of the unit derived from ethylene is in the range of 95 to 100 mol% with respect to all repeating units contained in the side chain (SE).
(Iv) The weight average molecular weight of the ethylene polymer constituting the side chain (SE) is in the range of 1000 to 30000. The olefin resin composition according to claim 1, wherein the graft polymer [GP] further satisfies the following requirements (v) and (vi).
(V) The side chain (SC) is a side chain (SP) composed of a propylene polymer, and is composed of a repeating unit derived from propylene, and, if necessary, ethylene and an α-olefin having 4 to 20 carbon atoms. It is composed of at least one selected repeating unit, and the content ratio of the units derived from propylene is in the range of 95 to 100 mol% with respect to all repeating units contained in the side chain (SP).
(Vi) The weight average molecular weight of the propylene polymer constituting the side chain (SP) is in the range of 5,000 to 100,000.   The olefin resin composition according to any one of claims 1 to 3, wherein the polar group in the requirement (α-1) is a carboxy group.   The olefin resin composition according to any one of claims 1 to 4, wherein the repeating unit containing a polar group in the requirement (α-1) is a repeating unit derived from an unsaturated carboxylic acid or a derivative thereof.   The olefin resin composition according to any one of claims 1 to 5, wherein the modified olefin resin (α) is a modified polyethylene or a modified polypropylene. The olefin resin composition according to claim 6, further satisfying the following requirement (α-2) when the modified olefin resin (α) is a modified polyethylene.
(Α-2) Melt flow rate (measured at 190 ° C. under a load of 2.16 kg according to ASTM D1238) is in the range of 0.01 to 50 g / 10 min. The olefin resin composition according to claim 6, further satisfying the following requirement (α-3) when the modified olefin resin (α) is a modified polypropylene.
(Α-3) The intrinsic viscosity [η] in decalin at 135 ° C. is in the range of 0.01 to 5 dl / g.   Furthermore, 1-20 mass parts is included in adhesive agent ((gamma)) with respect to a total of 100 mass parts of modified olefin resin ((alpha)) and olefin resin ((beta)). The olefin resin composition described. The following steps (A) and / or (B) and (C), and the step of mixing the olefin resin (β) and modified olefin resin (α) produced in the step (C), The manufacturing method of the olefin resin composition of Claims 1-9.
(A) Propylene is polymerized in the presence of an olefin polymerization catalyst containing a transition metal compound [A] belonging to Group 4 of the periodic table containing a ligand having a dimethylsilylbisindenyl skeleton to produce terminally unsaturated polypropylene. (B) The terminal unsaturated polyethylene is produced by polymerizing ethylene in the presence of an olefin polymerization catalyst containing a transition metal compound [B] of Group 4 or Group 5 of the periodic table having a phenoxyimine ligand. In the presence of a catalyst for olefin polymerization containing a transition metal compound [C] belonging to Group 4 of the periodic table, and (C) terminal unsaturated polypropylene produced in step (A) and / or produced in step (B). A process for producing an olefin-based resin (β) containing a graft polymer [GP] by copolymerizing terminal unsaturated polyethylene, ethylene and at least one α-olefin   The molded object which comprises the olefin resin composition as described in any one of Claims 1-9.   The laminated body containing at least 1 layer containing the olefin resin composition as described in any one of Claims 1-9.