JP2021109946A - Dynamically crosslinked olefin polymer composition, molded article made of the same, and parts for automobiles - Google Patents

Abstract

The present invention provides a dynamically crosslinked olefin polymer composition that has both adhesion to polar resins and resistance to settling, as well as molded articles and automobile parts made of the same. SOLUTION: A dynamically crosslinked olefin polymer composition containing the following components (A) to (E). Component (A): Polypropylene polymer component (B): Ethylene/α-olefin/non-conjugated diene copolymer component (C): Phenol resin crosslinking agent component (D): Softener component for hydrocarbon rubber (E ): Diene polymer with hydroxyl group and/or its hydrogenated product [Selection diagram] None

Description

The present invention relates to a dynamically crosslinked olefin polymer composition, a molded product comprising the dynamically crosslinked olefin polymer composition, and parts for automobiles.

Dynamically crosslinked olefin-based polymers have good mechanical properties, heat resistance, solvent resistance, oil resistance, chemical resistance, and other properties. Therefore, they are raw materials for manufacturing industrial parts such as automobiles and electrical equipment, and daily necessities. It is widely used as.

In such applications, it is required to have excellent adhesion (adhesiveness) with other members. For example, in automobile interior / exterior members such as window moldings, adhesive strength with a urethane-based adhesive when flocking is required. However, olefin-based polymers such as polypropylene do not have a polar group in the molecule and are chemically inert, so that the adhesive strength with other resins is not good. Therefore, a proposal has been made for improving the adhesive strength of the olefin polymer.

For example, Patent Document 1 contains modified thermoplastics obtained by dynamically heat-treating in the presence of an organic peroxide containing an olefin rubber, a polyolefin-based polymer resin, a diene polymer having a hydroxyl group, or a hydrogenated product thereof. A synthetic resin molded body in which an elastomer and a urethane-based rubber are bonded is described.

JP-A-2002-187209

Among the interior and exterior parts of automobiles, movable and deformable parts such as window moldings exhibit a sealing function and a holding function by bending the shape. Therefore, the conventional dynamically crosslinked olefin polymer composition and its molded product used for these parts have the property of rapidly deforming according to the movement of the moving part and maintaining the deformation return even after long-term use (resistance). It is also required to have settling property). When the so-called settling (permanent strain) occurs due to long-term exposure to the bent state and the reaction force value gradually decreases, the glass flutters in the window molding and the drainage property in the seal. As a result, deterioration of the above occurs.

Under such circumstances, the modified thermoplastic elastomer of Patent Document 1 has room for improvement in terms of both adhesion (adhesive strength) with the polar resin and settling resistance.

The present invention focuses on the above-mentioned problems in the prior art, and provides a dynamically crosslinked olefin polymer composition having both adhesion to a polar resin and settling resistance, a molded product and parts for automobiles. The purpose is to do.

As a result of diligent studies to solve the above problems, the present inventor has made a polypropylene-based polymer, an ethylene / α-olefin / non-conjugated diene copolymer, a phenol resin cross-linking agent, a hydrocarbon-based rubber softener, and a diene having a hydroxyl group. The present invention has been completed by finding that a dynamically crosslinked olefin polymer composition containing a polymer and / or a hydrocarbon thereof can achieve both adhesion to a polar resin and settling resistance.

That is, the gist of the present invention lies in the following [1] to [6].

[1] A dynamically crosslinked olefin polymer composition containing the following components (A) to (E).
Component (A): Polypropylene-based polymer Component (B): Ethylene / α-olefin / non-conjugated diene copolymer Component (C): Phenol formaldehyde cross-linking agent Component (D): Hydrocarbon-based rubber softener component (E) ): Diene polymer having a hydroxyl group and / or its hydrocarbon additive

[2] The dynamically crosslinked olefin polymer composition according to [1], wherein the phenol resin crosslinking agent is an alkylphenol formaldehyde resin.

[3] The dynamically crosslinked olefin polymer composition according to [1] or [2], wherein the diene polymer having a hydroxyl group and / or a hydrogenated product thereof has a terminal hydroxyl group.

[4] The dynamically crosslinked olefin polymer composition according to any one of [1] to [3], which further contains the following component (F).
Component (F): Organometallic compound

[5] A molded product of the dynamically crosslinked olefin polymer composition according to any one of [1] to [4].

[6] An automobile part including the molded product according to [5].

According to the present invention, it is possible to provide a dynamically crosslinked olefin polymer composition having both adhesion to a polar resin and settling resistance, a molded product made of the same, and an automobile part.

Hereinafter, embodiments of the present invention will be described in detail, but the present invention is not limited to the following description, and can be arbitrarily modified and carried out without departing from the gist of the present invention. In addition, in this specification, when a numerical value or a physical property value is put before and after using "~", it is used as including the value before and after that.

In the present invention, the "unit" in the polypropylene-based polymer or ethylene / α-olefin / non-conjugated diene copolymer is the polypropylene-based polymer or ethylene obtained as a result of polymerization of the raw material olefin or non-conjugated diene. It refers to a structural unit derived from the olefin or non-conjugated diene formed in an α-olefin / non-conjugated diene copolymer. For example, the "propylene unit" is a unit per propylene produced as a result of the polymerization of propylene.
The content of each unit in the polypropylene-based polymer or the ethylene / α-olefin / non-conjugated diene copolymer can be determined by infrared spectroscopy.

[Dynamic crosslinked olefin polymer composition]
The dynamically crosslinked olefin polymer composition of the present invention contains the following components (A) to (E), and more preferably contains the following components (F).
Component (A): Polypropylene polymer Component (B): Ethylene / α-olefin / non-conjugated diene copolymer Component (C): Phenolic resin cross-linking agent Component (D): Hydrocarbon-based rubber softener component (E) ): Diene polymer having a hydroxyl group and / or its hydrocarbon component (F): Organic metal compound

<Component (A): Polypropylene polymer>
The dynamically crosslinked olefin polymer composition of the present invention contains the component (A): polypropylene polymer.
The polypropylene-based polymer is not particularly limited, and any of propylene homopolymers, block copolymers of propylene and other copolymerization components, and propylene-based copolymers such as random copolymers can be used. be able to. As the component (A): polypropylene-based polymer, one type may be used alone, or two or more types may be used in combination.

Here, the propylene-based copolymer means a copolymer having a content of propylene units of more than 50% by mass. From the viewpoint of heat resistance, rigidity, crystallinity, chemical resistance, etc., the content of the propylene unit in the propylene-based copolymer is preferably 60% by mass or more, more preferably 75% by mass or more, still more preferably 90% by mass. % Or more. On the other hand, the upper limit of the content of the propylene unit of the propylene-based copolymer is not particularly limited, but is usually less than 100% by mass.

When the polypropylene-based copolymer of the component (A) is a propylene-based copolymer (propylene-based block copolymer or random copolymer), other copolymerization components that copolymerize with propylene include ethylene and 1-butene. , 2-Methylpropylene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene and the like α-olefin having 2 or 4 to 12 carbon atoms. Cyclic olefins such as cyclopentene, norbornene, tetracyclo [6,2,11,8,13,6] -4-dodecene; norbornene such as 5-methylene-2-norbornene, 5-ethylidene-2-norbornene; 1,4 Dienes such as −hexadiene, methyl-1,4-hexadiene, 7-methyl-1,6-octadien; vinyl chloride, vinylidene chloride, acrylonitrile, vinyl acetate, acrylic acid, methacrylic acid, maleic acid, ethyl acrylate, acrylic acid. Examples thereof include vinyl monomers such as butyl, methyl methacrylate, maleic anhydride, styrene, methylstyrene, vinyltoluene and divinylbenzene, but the present invention is not particularly limited thereto. One of these other copolymerization components may be used alone, or two or more thereof may be used in combination. Among these, ethylene and 1-butene are preferable.

The polypropylene-based polymer of the component (A) preferably has a melt flow rate (MFR; ASTM D 1238, 230 ° C., load 21.2 N) of 0.05 to 200 g / 10 minutes, more preferably 0.10. ~ 100 g / 10 minutes, more preferably 0.5-60 g / 10 minutes. By using the polypropylene-based polymer of the component (A) having such MFR, good moldability can be ensured.

Further, the polypropylene-based polymer of the component (A) preferably has a density (ISO 1183: 1987) in the range of ^{0.85 to 0.92 g / cm 3.}

The polypropylene-based polymer of the component (A) can be obtained by a known production method. The manufacturing method thereof is, for example, JP-A-50-108385, JP-A-50-126590, JP-A-51-20297, JP-A-51-28189, JP-A-52-151691. The techniques described in these are also available in the present invention.

Further, as the polypropylene-based polymer of the component (A), a commercially available one may be used. Commercially available products of component (A) include, for example, PRIME Polypro (registered trademark) manufactured by Prime Polymer Co., Ltd., Sumitomo Noblen (registered trademark) manufactured by Sumitomo Chemical Corporation, polypropylene block copolymer manufactured by SunAllomer Ltd., and Novatec manufactured by Japan Polypropylene Corporation. (Registered Trademarks) PP, Waymax (WAYMAX (Registered Trademarks)), Moplen (Registered Trademarks) manufactured by Lyondell Basell, ExxonMobile PP manufactured by ExxonMobile, Versify (Registered Trademarks) manufactured by Dow Chemical Co., Ltd., and Formosa Plastics Co., Ltd. Formolene®, Borealis PP from Borealis, SEETEC PP from LG Chemical, A.M. Schulman Inc. of ASI POLYPROPYLENE, INEOS Olefins & Polymers, Inc. of INEOS PP, Braskem manufactured by Braskem PP, SAMSUNG TOTAL PETROCHEMICALS Co., Ltd. of Sumsung Total, Sabic manufactured by Sabic (registered trademark) PP, TOTAL PETROCHEMICALS Co., Ltd. TOTAL PETROCHEMICALS Polypropylene , SK manufactured by YUPLENE (registered trademark). One of these may be used alone, or two or more thereof may be used in combination.

<Component (B): ethylene / α-olefin / non-conjugated diene copolymer>
The ethylene / α-olefin / non-conjugated diene copolymer of the component (B) is a copolymer containing ethylene, an α-olefin, and a non-conjugated diene (also referred to as a “non-conjugated diene compound”) as copolymerizing components. It is a polymer.
The ethylene / α-olefin / non-conjugated diene copolymer is a mixture of an ethylene / α-olefin / non-conjugated diene copolymer and a hydrocarbon softener (hereinafter, “oil-extended ethylene / α-olefin /”. There are oil-expandable types that are "non-conjugated diene copolymers") and non-oil-extended types that do not contain hydrocarbon-based rubber softeners. In this embodiment, the oil-extended type is used. Although a copolymer is intended, a low oil-extending type or a non-oil-extending type can also be preferably used.
That is, in the present invention, the ethylene / α-olefin / non-conjugated diene copolymer of the component (B) can be used in either an oil-expanding type or a non-oil-expanding type, and is a non-oil-expanding type or an oil-expanding type. One of the types may be used alone, or two or more of them may be used in combination. Further, one or more oil-extending types and one or two or more non-oil-extending types can be used in any combination and ratio.
Here, when the component (B) is an oil-extended ethylene / α-olefin / non-conjugated diene copolymer, the hydrocarbon-based rubber contained in the oil-extended ethylene / α-olefin / non-conjugated diene copolymer is used. The softener for softening is contained in the softening agent for hydrocarbon rubber as the component (D).

Examples of the α-olefin in the component (B) include propylene, 1-butene, 3-methyl-1-butene, 1-pentene, 4-methyl-1-pentene, 4,4-dimethyl-1-pentene, and 1-. Examples thereof include α-olefins having 3 to 20 carbon atoms such as hexene, 4-methyl-1-hexene, 1-hexene, 1-octene, 1-decene and 1-octadecene, but the present invention is not particularly limited thereto. Among these, α-olefins having 3 to 8 carbon atoms are preferable, and propylene, 1-butene, 3-methyl-1-butene, 1 -Pentene is more preferred, more preferably propylene, 1-butene. As the α-olefin, one type may be used alone, or two or more types may be used in combination.

Examples of the non-conjugated diene in the component (B) include dicyclopentadiene, 1,4-hexadiene, cyclohexadiene, cyclooctadiene, dicyclooctadiene, 1,6-octadien, 5-methyl-1,4-hexadiene. , 3,7-Dimethyl-1,6-octadien, 1,3-cyclopentadiene, 1,4-cyclohexadiene, 2-methyl-1,5-hexadiene, 6-methyl-1,5-heptadiene, 7-methyl Echiliden norbornene such as -1,6-octadien, tetrahydroinden, methyltetrahydroinden, 5-isopropyriden-2-norbornene, 5-vinyl-2-norbornene, vinylidene norbornene, 5-ethylidene-2-norbornene (ENB), 5 Examples thereof include methylenenorbornene such as −methylene-2-norbornene (MNB), but the present invention is not particularly limited thereto. Among these, dicyclopentadiene, etylidene norbornene and vinylidene norbornene are preferable, and dicyclopentadiene, 5-ethylidene-2-norbornene and vinylidene norbornene are more preferable from the viewpoint of cross-linking property by a cross-linking agent at the time of dynamic cross-linking. .. As the non-conjugated diene, one type may be used alone, or two or more types may be used in combination.

Specific examples of the ethylene / α-olefin / non-conjugated diene copolymer include ethylene / propylene / 5-ethylidene-2-norbornene copolymer, ethylene / propylene / dicyclopentadiene copolymer, and ethylene / propylene / 1, Ethylene propylene / non-conjugated diene copolymer (EPDM) such as 4-hexadiene copolymer, ethylene / propylene / 5-vinyl-2-norbornene copolymer, ethylene / 1-butene / 5-ethylidene-2- Examples thereof include norbornene copolymers, but the present invention is not particularly limited thereto. Among these, ethylene / propylene / non-conjugated diene copolymer (EPDM) is preferable from the viewpoint of crosslinkability by the cross-linking agent at the time of dynamic cross-linking and suppression of bloom-out. The ethylene / α-olefin / non-conjugated diene copolymer may be used alone or in combination of two or more.

The content of ethylene units in the ethylene / α-olefin / non-conjugated diene copolymer is not particularly limited, but is preferably 50 to 80% by mass, more preferably 55 to 80% by mass, and further preferably 60 to 60 to 80% by mass. It is 80% by mass. When the content of ethylene units is within the above preferable range, a dynamically crosslinked olefin polymer composition having excellent mechanical strength and rubber elasticity tends to be easily obtained.

The content of the α-olefin unit in the ethylene / α-olefin / non-conjugated diene copolymer is not particularly limited, but is preferably 10 to 49.5% by mass, more preferably 10 to 44% by mass, and further. It is preferably 10 to 38% by mass. When the content of the α-olefin unit is within the above preferable range, a dynamically crosslinked olefin polymer composition having excellent mechanical strength, appropriate flexibility, and rubber elasticity tends to be easily obtained.

Further, the content of the non-conjugated diene unit in the ethylene / α-olefin / non-conjugated diene copolymer is not particularly limited, but is preferably 0.5 to 10% by mass, more preferably 1 to 10% by mass. , More preferably 2 to 10% by mass. When the content of the non-conjugated diene unit is within the above preferable range, the crosslinkability and moldability can be easily adjusted, and a dynamically crosslinked olefin polymer composition having excellent mechanical strength and rubber elasticity tends to be easily obtained. be.

In the present invention, as the component (B), in particular, the content of ethylene unit is 55 to 75% by mass, the content of propylene unit is 15 to 40% by mass, and dicyclopentadiene, 5-ethylidene-2. An ethylene / propylene / non-conjugated diene copolymer having a content of at least one non-conjugated diene unit selected from the group consisting of -norbornene and vinylidene norbornene having a content of 1 to 10% by mass is preferable.

As a method for producing the component (B) such as ethylene / propylene / non-conjugated diene copolymer (EPDM), a known polymerization method using a known catalyst for olefin polymerization can be applied. For example, a component (B) such as EPDM by a slurry polymerization method, a solution polymerization method, a massive polymerization method, a gas phase polymerization method or the like using a Ziegler-Natta catalyst, a complex catalyst such as a metallocene complex or a non-metallocene complex. Can be manufactured.

Ethylene / α-olefin / non-conjugated diene copolymer (non-oil-extended ethylene / α-olefin / non-conjugated diene copolymer, that is, non-oil-expanded ethylene / α-olefin) of the component (B) used in the present invention. _{The Mooney viscosity (ML 1 + 4} , 125 ° C.) of the non-conjugated diene copolymer) is preferably 45 or more, more preferably 50 or more. _{The Mooney viscosity (ML 1 + 4} , 125 ° C.) of the non-oil-extended ethylene / α-olefin / non-conjugated diene copolymer is particularly preferably 50 to 400, and particularly preferably 50 to 300. _{The Mooney viscosity (ML 1 + 4} , 125 ° C.) of the oil-extended ethylene / α-olefin / conjugated diene copolymer is not particularly limited, but is preferably 30 to 100, more preferably 35 to 80.
When the Mooney viscosity of the component (B) is at least the above lower limit value, the compression set becomes good, which is preferable from the viewpoint of improving the appearance of the obtained molded product, and when it is at least the above upper limit value, from the viewpoint of moldability. Is preferable.

_{In the present invention, the Mooney viscosity (ML 1 + 4} , 125 ° C.) of the pre-oil-extended ethylene / α-olefin / non-conjugated diene copolymer and the oil-extended ethylene / α-olefin / non-conjugated diene copolymer of the component (B). The relationship is expressed by the following formula as described in Japanese Patent Application Laid-Open No. 1-103369.
Calculation formula: log (ML ₁ / ML ₂ ) = 0.0066 (ΔPHR)
ML ₁ : Mooney viscosity of pre-oil- _{extended ethylene / α-olefin / non-conjugated diene copolymer ML 2} : Mooney viscosity of oil-extended ethylene / α-olefin / non-conjugated diene copolymer ΔPHR: Ethylene / α-olefin / non-coated Amount of oil spread per 100 parts by mass of conjugated diene copolymer

The density of the ethylene / α-olefin / non-conjugated diene copolymer of the component (B) is not particularly limited ^{, but is preferably 0.850 g / cm 3} or more, and more preferably 0.860 g / cm ^3. On the other hand, ^{it is preferably 0.900 g / cm 3} or less, and more preferably 0.890 g / cm ³ or less. When the density of the ethylene / α-olefin / non-conjugated diene copolymer of the component (B) is within the above preferable number range, a dynamically crosslinked olefin polymer composition having excellent processability, moldability, flexibility and the like can be obtained. It tends to be easy to obtain. Here, the density of the component (B) can be measured based on ISO 1183: 1987.

As described above, an oil-extended ethylene / α-olefin / conjugated diene copolymer can also be used as the component (B). In oil-developed ethylene / α-olefin / conjugated diene copolymers, hydrocarbon-based rubber softeners soften ethylene / α-olefin / non-conjugated diene copolymers, increase flexibility and elasticity, and obtain them. It is used for the purpose of improving the processability and fluidity of the dynamically crosslinked olefin polymer composition.

Examples of the softening agent for hydrocarbon-based rubber used for the oil-extended ethylene / α-olefin / conjugated diene copolymer include a softening agent for mineral oil-based rubber and a softening agent for synthetic resin-based rubber. From the viewpoint of affinity with the components of the above, a softening agent for mineral oil-based rubber is preferable. The softener for mineral oil-based rubber is generally a mixture of aromatic hydrocarbons, naphthenic hydrocarbons and paraffinic hydrocarbons, and the ratio of carbon of the paraffinic hydrocarbon to the total carbon atom is 50% by mass. The above are paraffin oils, naphthenic hydrocarbons with a carbon content of 30 to 45% by mass are naphthenic oils, and aromatic hydrocarbons with a carbon content of 35% by mass or more are aromatic oils. It is called. Among these, as the softener for hydrocarbon rubber of the oil-extended ethylene / α-olefin / conjugated diene copolymer of the component (B), a softening agent for paraffin-based rubber (paraffin-based oil) is preferable. As the hydrocarbon softener for rubber, one type may be used alone, or two or more types may be used in combination.

The paraffin-based oil used for the oil-extended ethylene / α-olefin / non-conjugated diene copolymer of the component (B) is not particularly limited, but has a kinematic viscosity at 40 ° C. of usually 20 cSt (centistokes) or more, preferably 50 cSt or more. It is usually 800 cSt or less, preferably 600 cSt or less. The pour point is usually −40 ° C. or higher, preferably −30 ° C. or higher, and 0 ° C. or lower is preferably used. Further, a flash point (COC) of usually 200 ° C. or higher, preferably 250 ° C. or higher, and usually 400 ° C. or lower, preferably 350 ° C. or lower is preferably used.

When an oil-developed ethylene / α-olefin / non-conjugated diene copolymer is used as the component (B), the content ratio of the ethylene / α-olefin / non-conjugated diene copolymer and the softening agent for hydrocarbon rubber is as follows. Although not particularly limited, the content of the hydrocarbon-based rubber softener is usually 10 parts by mass or more, preferably 20 parts by mass or more, based on 100 parts by mass of the ethylene / α-olefin / non-conjugated diene copolymer. On the other hand, it is usually 200 parts by mass or less, preferably 160 parts by mass or less, and more preferably 120 parts by mass or less.

The method for preparing the oil-extended ethylene / α-olefin / non-conjugated diene copolymer (oil-expanding method) is not particularly limited, and a known method can be used. As an oil spreading method, for example, a method of mechanically kneading an ethylene / α-olefin / non-conjugated diene copolymer and a softening agent for a hydrocarbon-based rubber using a mixing roll or a Banbury mixer to oil-expand the ethylene / α-olefin / non-conjugated diene copolymer. A method in which a predetermined amount of a softening agent for hydrocarbon-based rubber is added to a solution of an α-olefin / non-conjugated diene copolymer and then desolvated by a method such as steam stripping, a crumb-like ethylene / α-olefin / non- Examples thereof include a method of impregnating a mixture of a conjugated diene copolymer and a softening agent for hydrocarbon rubber by stirring with a Henchel mixer or the like. From the viewpoint of preparing a high-molecular-weight oil-developed ethylene / α-olefin / non-conjugated diene copolymer, in a polymerization reaction solution or suspension of the ethylene / α-olefin / non-conjugated diene copolymer of the component (B). A method in which a predetermined amount of a softening agent for hydrocarbon rubber is added and then the solvent is removed is preferable.

As the ethylene / α-olefin / non-conjugated diene copolymer of the component (B), many grades of various grades are commercially available from domestic and overseas manufacturers, and the commercially available products can be used. Examples of commercially available products include JSR EP manufactured by JSR Corporation, Mitsui EPT (registered trademark) manufactured by Mitsui Chemicals, Esplen (registered trademark) manufactured by Sumitomo Chemical Co., Ltd., and Keltan (registered trademark) manufactured by ARLANXEO.

<Component (C): Phenol resin cross-linking agent>
Examples of the phenol resin cross-linking agent of the component (C) include alkylphenol formaldehyde and alkylphenol formaldehyde bromide. One of these phenol resins may be used alone, or two or more thereof may be used in combination.

As the phenol resin cross-linking agent of the component (C), a non-halogen-based alkylphenol formaldehyde is particularly preferable, and specifically, one represented by the following formula (I) is preferable.

(In the formula, Q is _{selected from the -divalent linking group -CH 2-} or -CH _2- O-CH _2- , n is an integer of 0 to 20, and R is preferably less than 20 carbon atoms. Is an alkyl group having 1 to 12 carbon atoms.)

Examples of the above non-halogen alkylphenol formaldehyde products include TACKIROL 201 and 202 (trade name) manufactured by Taoka Chemical Industry Co., Ltd., PR-4507 (trade name) manufactured by Gunei Chemical Industry Co., Ltd., and Hoechst Co., Ltd. Vulkarest 510E, 532E, Vulkaresen E, 105E, 130E, Vulkeresol 315E (trade name), Rohm & Haas Amberol ST 137X (trade name), Sumitomo Durez Co., Ltd. Sumilite Resin PR-22193 (trade name) Anchor Chem. Symphon-C-100, C-1001 (trade name) manufactured by Arakawa Chemical Industry Co., Ltd., Tamanor 531 (trade name) manufactured by Arakawa Chemical Industry Co., Ltd., Schenectady Chem. Schenectady SP1045, SP1055, SP1056, SP1059 (trade name) manufactured by Schenectady, U.S.A. C. Examples thereof include CRR-0803 (trade name) manufactured by C company, CRM-0803 (trade name) manufactured by Showa Union Synthetic Co., Ltd., and Vulkadur A (trade name) manufactured by Bayer.

As the non-halogen alkylphenol formaldehyde component (C), a p-octylphenol formaldehyde resin represented by the following formula (II) is particularly preferably used, and among them, those having a mass average molecular weight of 2,500 to 4,000 are used. Most preferably used. As the non-halogen phenol resin, those commercially available as the above-mentioned TACKIROL 201, 202 (trade name) can be used.

In addition, the phenol resin cross-linking agent is usually used together with an activator. Examples of the activator that can be used here include halogen donors such as stannous chloride, ferric chloride, chlorinated paraffin, chlorinated polyethylene, and chlorosulphonized polyethylene, and iron oxide and titanium oxide. Acid receiving agents such as magnesium oxide, silicon dioxide and zinc oxide are used. When the phenolic resin is halogenated, the halogen donor may not be used.

Commercially available phenolic resin cross-linking agents include hydrocarbon-based rubber softeners and fillers corresponding to the component (D) described later, but the phenolic resin cross-linking agent used is carbonized. When the softening agent for hydrogen-based rubber is contained, the softening agent for hydrocarbon-based rubber is included in the softening agent for hydrocarbon-based rubber as the component (D). The same applies to the filler.

<Component (D): Hydrocarbon-based rubber softener>
The dynamically crosslinked thermoplastic elastomer composition of the present invention contains a hydrocarbon-based rubber softener as a component (D) from the viewpoint of increasing flexibility and elasticity and improving processability and fluidity. When an oil-extended ethylene / α-olefin / non-conjugated diene copolymer is used as the above-mentioned component (B), this component (D) contains a hydrocarbon-based rubber softening agent contained therein. However, even when an oil-extended ethylene / α-olefin / non-conjugated diene copolymer is used as the component (B), it is used as a component (D) separately from the oil-extended ethylene / α-olefin / non-conjugated diene copolymer. It is preferable to add a hydrocarbon softener for rubber separately. In this case, the hydrocarbon-based rubber softener to be added separately is the same, the same type, or different from the hydrocarbon-based rubber softener in the oil-extended ethylene / α-olefin / non-conjugated diene copolymer of the component (B). Any of the hydrocarbon softeners for rubber can be used. The same applies to the case where the phenol resin cross-linking agent of the component (C) contains a softening agent for hydrocarbon rubber.

Examples of the hydrocarbon-based rubber softener to be added separately from the component (B) include mineral oil-based rubber softeners, synthetic resin-based rubber softeners, and the like, and among these, affinity with other components. From the viewpoint of properties and the like, a softening agent for mineral oil-based rubber is preferable. As described above, the softener for mineral oil-based rubber is generally a mixture of aromatic hydrocarbons, naphthenic hydrocarbons and paraffinic hydrocarbons, and the ratio of carbon of the paraffinic hydrocarbon to the total carbon atoms. Those with a carbon content of 50% by mass or more are paraffin oils, those with a carbon content of naphthenic hydrocarbons of 30 to 45% by mass are naphthenic oils, and those with a carbon content of aromatic hydrocarbons of 35% by mass or more. It is called an aromatic oil. Among these, as the hydrocarbon-based rubber softener, a liquid hydrocarbon-based rubber softener that is liquid at room temperature (23 ± 2 ° C.) is preferable, and a liquid paraffin-based oil that is liquid at room temperature is more preferable. By using a liquid hydrocarbon softener as a hydrocarbon softener, the flexibility and elasticity of the dynamically crosslinked thermoplastic elastomer composition of the present invention can be increased, and workability and fluidity can be increased. Tends to improve dramatically. As the softener for hydrocarbon rubber, one type may be used alone, or two or more types may be used in combination.

The paraffin-based oil is not particularly limited, but has a kinematic viscosity at 40 ° C. of usually 20 cSt or more, preferably 50 cSt or more, and usually 800 cSt or less, preferably 600 cSt or less. The pour point is usually −40 ° C. or higher, preferably −30 ° C. or higher, and 0 ° C. or lower is preferably used. Further, the flash point is usually 200 ° C. or higher, preferably 250 ° C. or higher, and usually 400 ° C. or lower, preferably 350 ° C. or lower is preferably used.

Even when an oil-extended ethylene / α-olefin / non-conjugated diene copolymer is used as the component (B), the component (D) is provided by attaching a hydrocarbon softener as the component (D). ), The content of the hydrocarbon-based rubber softener should be adjusted arbitrarily without depending on the content of the hydrocarbon-based rubber softener in the oil-developed ethylene / α-olefin / non-conjugated diene copolymer. Is possible.

Examples of the above-mentioned hydrocarbon-based rubber softeners include NA solvent (isoparaffin-based hydrocarbon oil, trade name) manufactured by Nippon Oil & Fats Co., Ltd. and PW-90 (n-paraffin-based) manufactured by Idemitsu Kosan Co., Ltd. Process oil (trade name), IP-solvent 2835 (synthetic isoparaffin hydrocarbon, 99.8% by mass or more isoparaffin, trade name) manufactured by Idemitsu Petrochemical Co., Ltd., neothiozole (n) manufactured by Sanko Chemical Industry Co., Ltd. -Paraffin-based process oil, trade name). These may be used alone or in combination of two or more.

<Component (E): Diene polymer having a hydroxyl group and / or its hydrogenated agent>
Examples of the hydroxyl group-containing diene polymer and / or its hydrogenated additive used in the present invention include polyhydroxypolyolefin and / or its hydrogenated additive. Specifically, it has at least one hydroxyl group (preferably a terminal hydroxyl group) and has a number average molecular weight of usually 200 to 100,000, preferably 500 to 50,000, more preferably 800 to 10,000, at room temperature. Examples include liquid, semi-solid, or solid polymers. The average number of hydroxyl groups per molecule is usually 1 to 10, preferably 1.5 to 5. The hydroxyl value is usually 15 to 250, preferably 25 to 125 KOHmg / g.

The hydrogenated diene polymer can be obtained, for example, by hydrogenating by the method described in JP-A-51-7391. Hydrogenation is performed on all or part of the double bonds contained in the polymer. The iodine value of the hydrogenated product is usually 0 to 20 g / 100 g, preferably 0 to 5 g / 100 g.

Examples of products of the diene polymer having a hydroxyl group and / or a hydrogenated product thereof include liquid polybutadiene containing hydroxyl groups at both ends (manufactured by Nippon Soda Co., Ltd .: G-1000) and polyhydroxy polyolefin (manufactured by Mitsubishi Chemical Co., Ltd .: Polytail H) and polycaprolactone polyol (manufactured by Daicel Chemical Co., Ltd .: PLACCEL320) can be mentioned.

As the diene polymer having a hydroxyl group of the component (E) and / or its hydrogenated additive, one type may be used alone or two or more types may be used in combination.

<Component (F): Organometallic compound>
The dynamically crosslinked olefin polymer composition of the present invention may further contain an organometallic compound.
By containing the organometallic compound, the organometallic compound acts as a catalyst for the reaction between the hydroxyl group of the diene polymer of the component (E) and / or its hydrogenated product and the adhesive, and can exhibit an excellent adhesive effect even at room temperature. can.

Examples of the organic metal compound used include an organic tin compound, an organic titanium compound, an organic nickel compound, an organic zirconium compound, an organic cobalt compound, an organic copper compound, an organic iron compound, and an organic manganese compound. These organometallic compounds may be used alone or in combination of two or more.

Of these, an organotin compound is preferable from the viewpoint of high catalytic action, and specific examples of the organotin compound include dibutyltin dichloride, dibutyltin dilaurate, dibutyltin malate, dibutyltin oxide, dibutyltin diacetate, and dibutyltinbis (dibutyltin diacetate). 2-Ethylhexyl mercaptoacetate), dibutyltinbis (isooctyl mercaptoacetate), dioctyltindilaurate.

<Mixing ratio>
In the dynamically crosslinked thermoplastic elastomer composition of the present invention, the contents of the component (A) and the component (B) are 5 to 50 parts by mass for the component (A) and 50 to 95 parts by mass for the component (B). It is preferable (however, the total of the component (A) and the component (B) is 100 parts by mass). By setting the contents of the component (A) and the component (B) within the above ranges, the desired hardness and rubber elasticity can be maintained, the molded appearance can be improved, and the oil resistance can be maintained. From this point of view, the content of the component (A) in the total of 100 parts by mass of the component (A) and the component (B) is 10 to 50 parts by mass, and the content of the component (B) is 50 to 90 parts by mass. It is preferable that the content of the component (A) is 10 to 45 parts by mass and the content of the component (B) is 55 to 90 parts by mass.
Here, the content of the component (B) refers to ethylene that does not contain a hydrocarbon-based rubber softener when an oil-extended ethylene / α-olefin / non-conjugated diene copolymer is used as the component (B). -Content as an α-olefin / non-conjugated diene copolymer.

The content of the component (C) with respect to a total of 100 parts by mass of the component (A) and the component (B) is preferably 0.1 part by mass or more, more preferably 0.1 part by mass or more, from the viewpoint of sufficiently advancing the crosslinking reaction. It is 0.2 parts by mass or more, more preferably 0.4 parts by mass or more. On the other hand, the content of the component (C) is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, with respect to a total of 100 parts by mass of the component (A) and the component (B) from the viewpoint of controlling the cross-linking reaction. It is more preferably 8 parts by mass or less, particularly preferably 6 parts by mass or less, and particularly preferably 4 parts by mass or less.
As described above, when the component (C) contains a hydrocarbon-based rubber softener or a filler, these are not included in the content of the component (C).

Further, the content of the hydrocarbon-based rubber softener of the component (D) is preferably 10 to 300 parts by mass with respect to a total of 100 parts by mass of the component (A) and the component (B). By setting the content of the hydrocarbon-based rubber softener of the component (D) in the above range, the effect of improving the elasticity, oil resistance, and workability of the component (D) can be obtained, and bleeding out from the surface can be suppressed. .. From this viewpoint, the content of the component (D) with respect to a total of 100 parts by mass of the component (A) and the component (B) is preferably 20 to 200 parts by mass, and more preferably 25 to 150 parts by mass. ..
Here, the content of the component (D) is used for the hydrocarbon rubber in the component (B) when an oil-extended ethylene / α-olefin / non-conjugated diene copolymer is used as the component (B). It is the total content of the softening agent and the hydrocarbon-based rubber softening agent as the component (D) attached to the component (B), and the hydrocarbon-based rubber softening agent is contained in the component (C). When it is contained, it is the total content including the softening agent for hydrocarbon rubber.

Further, the content of the component (E) tends to be 1 to 20 parts by mass per 100 parts by mass of the total of the components (A) and (B), so that the desired adhesive strength tends to be easily obtained. By setting the content of E) in the above range, it is possible to obtain excellent adhesiveness to the polar resin, suppress bleeding out from the surface of itself, and prevent deterioration of adhesive strength due to bleeding out. The content of the component (E) with respect to a total of 100 parts by mass of the component (A) and the component (B) is more preferably 2 to 10 parts by mass.

When the dynamically crosslinked olefin polymer composition of the present invention contains the component (F), the content of the component (F) is preferably 0.1 per 100 parts by mass of the total of the components (A) and (B). ~ 5 parts by mass, more preferably 0.1 to 4 parts by mass, still more preferably 0.1 to 3 parts by mass. By setting the content of the component (F) in the above range, the adhesive, for example, the adhesive for flocking to the molded body is excellent in adhesion, the flocking strength is sufficiently high, and the bloom of itself is suppressed. However, it is possible to prevent a decrease in flocking strength due to bleed-out.

<Other ingredients>
The dynamically crosslinked olefin polymer composition of the present invention contains, if necessary, other components (in the present specification) other than the above components (A) to (F), as long as the object of the present invention is not impaired. It may simply contain "other components"). Examples of other components include resins and elastomers other than the components (A) and (B) (these may be collectively referred to as "other resins" in the present specification) and various additives.

Other resins that can be contained in the dynamically crosslinked olefin polymer composition of the present invention include polyolefin resins (excluding those corresponding to the component (A)), polyester resins, polyamide resins, and styrene resins. Resins such as acrylic resin, polycarbonate resin, and polyvinyl chloride resin, and olefin elastomers such as ethylene / propylene copolymer rubber (EPM), ethylene / butene copolymer rubber (EBM), and ethylene / propylene / butene copolymer rubber (however) (Excluding those corresponding to the component (B)); Polyamide-based elastomers such as polyamide / polyol copolymers; Polyvinyl chloride-based elastomers and polybutadiene-based elastomers, modified with hydrogenated products thereof, acid anhydrides, etc. Examples thereof include those in which a polar functional group has been introduced, and those in which other monomers are grafted, random and / or block copolymerized. The other resins listed above may contain only one type or two or more types.

Among these, examples of the polyolefin resin include a single α-olefin having 2 to 4 carbon atoms such as ethylene, propylene, and 1-butene, or a copolymer containing these as main components. Specifically, these polyolefin resins are not limited to copolymers such as polyethylene and poly-1-butene, and other polyolefin resins having 5 to 20 carbon atoms as long as the main component is an α-olefin having 2 to 4 carbon atoms. Also contains a copolymer of α-olefin or a vinyl compound such as vinyl acetate, vinyl chloride, acrylic acid, methacrylic acid and styrene. Further, a graft copolymer modified by grafting with an unsaturated carboxylic acid such as maleic anhydride, maleic acid or acrylic acid or a derivative thereof may be used. Further, these polyolefin resins may be a mixture.

When the dynamically crosslinked olefin polymer composition of the present invention contains other resins, the total content of the other resins in the dynamically crosslinked olefin polymer composition of the present invention is the component (A). It is preferably 40 parts by mass or less, and more preferably 30 parts by mass or less, per 100 parts by mass of the total of the component (B) and the component (B).

Further, as the additive that can be contained in the dynamically crosslinked olefin polymer composition of the present invention, in addition to the activator used together with the phenol resin crosslinking agent, an antioxidant, a crystal nucleating agent, a lubricant and the like are assisted in molding processing. Agents, UV absorbers, light stabilizers such as hindered amine compounds, hydrolysis resistance improvers, pigments, colorants such as dyes, antistatic agents, conductive agents, flame retardants, reinforcing agents, fillers, plasticizers, mold release Agents, foaming agents and the like can be mentioned.

For example, in the dynamically crosslinked olefin polymer composition of the present invention, as antioxidants, dithiocarbamate-based antioxidants, hindered phenol-based antioxidants, sulfur-based antioxidants, phosphorus-based antioxidants, etc. Can be blended.
These antioxidants may be used alone or in combination of two or more.

When the dynamically crosslinked olefin polymer composition of the present invention contains an antioxidant, the content of the antioxidant is preferably 0.01 per 100 parts by mass of the total of the component (A) and the component (B). ~ 5 parts by mass. When the content of the antioxidant is 0.01 parts by mass or more, it is preferable from the viewpoint of improving the heat resistance deterioration effect, while when it is 5 parts by mass or less, problems such as bleeding are less likely to occur, and the composition. It is preferable from the viewpoint of mechanical strength and the like.

Further, the dynamically crosslinked olefin polymer composition of the present invention preferably contains a colorant such as carbon black in order to improve designability and weather resistance. In this case, the colorant is a component (A). ) And the component (B) in total of 100 parts by mass, preferably 0.1 to 5 parts by mass, particularly 0.3 to 3 parts by mass. It is preferable that a trace amount of a component such as a colorant such as carbon black is blended as a masterbatch of a resin such as a polyolefin resin in terms of uniform dispersibility in the dynamically crosslinked olefin polymer composition.

Further, the dynamically crosslinked olefin polymer composition of the present invention may contain a filler in order to improve production stability, dimensional stability and flame retardancy. In this case, the filler is glass. Fibers, hollow glass spheres, carbon fibers, talc, calcium carbonate, mica, clay, potassium titanate fibers, silica, metal soap, titanium dioxide, carbon black and the like can be mentioned (carbon black can be used as a colorant and a filler). Can also be used.). When the filler is blended, the filler is usually used in an amount of 0.1 to 200 parts by mass with respect to a total of 100 parts by mass of the component (A) and the component (B).

[Method for Producing Dynamically Crosslinked Olefin Polymer Composition]
The dynamically crosslinked olefin polymer composition of the present invention comprises the above components (A), (B), (C), (D), and component (E), and further, a component (F) to be blended as needed. , Other resin components and various additives are mixed, kneaded or melt-kneaded by a conventional method using a normal extruder, Banbury mixer, mixing roll, roll, lavender plastograph, kneader lavender, etc. can do. Among these, it is preferable to use an extruder, particularly a twin-screw extruder. At this time, the component (E) may be added after the components (A), (B), (C), and (D) are kneaded.
When the dynamically crosslinked olefin polymer composition of the present invention is kneaded and produced by an extruder or the like, it is preferably melt-kneaded in a state of being heated to usually 80 to 300 ° C., preferably 100 to 230 ° C. The treatment time for performing the dynamic heat treatment is not particularly limited, but is usually 0.1 to 30 minutes in consideration of productivity and the like.

Here, "dynamic heat treatment" means kneading in a molten state or a semi-melted state in the presence of the component (C). This dynamic heat treatment is preferably performed by melt-kneading, and when a twin-screw extruder is used, each component is supplied to a raw material supply port (hopper) of a twin-screw extruder having a plurality of raw material supply ports. It is more preferable to perform a specific heat treatment. By performing the dynamic heat treatment of melt-kneading in the presence of the above component (C) in this way, a dynamically crosslinked olefin polymer composition can be obtained.

[Forming method of dynamically crosslinked olefin polymer composition]
The molding method of the dynamically crosslinked olefin polymer composition of the present invention is not particularly limited, and a molded product can be obtained by, for example, various molding methods such as injection molding, extrusion molding, hollow molding, and compression molding. Of these, extrusion molding is preferable. Further, it is also possible to obtain a molded product obtained by performing secondary processing such as laminating molding and thermoforming after performing these moldings.

[Molded parts and composite molded parts]
The molded product of the present invention is obtained by molding the dynamically crosslinked olefin polymer composition of the present invention by extrusion molding or the like.

In particular, the dynamically crosslinked olefin polymer composition of the present invention is excellent in adhesion to the polar resin, and therefore can be suitably used for use as a composite molded product with the polar resin. For example, by molding a polar resin on a molded product made of the dynamically crosslinked olefin polymer composition of the present invention, the crosslinked olefin weight in which the dynamically crosslinked olefin polymer composition and the polar resin are firmly adhered to each other. A combined composition / polar resin composite molded product can be easily obtained. In this case, the molded product made of the dynamically crosslinked olefin polymer composition is subjected to electrical treatment such as corona discharge, mechanical roughening, flame treatment, oxygen treatment or surface treatment such as ozone treatment to perform a polar resin. By directly bonding to the polar resin without performing pretreatment such as pretreatment or primer treatment for improving the affinity for the resin, a composite molded product having excellent adhesion to the polar resin can be obtained. As a method for producing such a composite molded product, for example, a molded product made of a dynamically crosslinked olefin polymer composition is placed in a mold for manufacturing parts, and then a polar resin stock solution is poured into the mold to close the mold. Examples thereof include a method of simultaneously molding and adhering a polar resin.

Examples of the polar resin applied to such a composite molded body include urethane resin, urethane foam, melamine resin, benzoguanamine resin, urea resin, alkyd resin, acrylic resin, epoxy resin, epoxy ester resin, polyester resin, polyamide, and chloroprene rubber. , Nitrile rubber and the like. Among these, urethane resin, urethane foam, melamine resin, and alkyd resin are preferable.

The molded product made of the dynamically crosslinked olefin polymer composition of the present invention is a polar resin-based paint or adhesive, for example, a paint such as a urethane resin-based paint or an amino resin-based paint, a urethane resin-based adhesive, or an amino resin. Since it has excellent adhesion to system adhesives and the like, it is also suitable for painting with such a paint and for adhering parts to each other using the above-mentioned adhesive.

In either case, primer treatment and surface treatment to improve adhesion to polar resin-based paints and adhesives can be eliminated, reducing treatment equipment and manufacturing processes, and reducing manufacturing costs. be able to.

[Use]
The molded product of the present invention made of the dynamically crosslinked olefin polymer composition of the present invention or the composite molded product obtained by directly bonding the molded product to a polar resin is described by various industrial parts such as automobile parts and motorcycle parts. It can be widely used for electrical equipment parts, daily necessities, building materials, office equipment, packaging materials, sporting goods, medical supplies, etc.
Of these, it is particularly suitable as an automobile part, and specifically, an automobile interior part such as an instrument panel, a center panel, a center console box, a door trim, a pillar, an assist grip, a steering wheel, and an airbag cover; Such as automobile exterior parts; automobile functional parts such as rack and pinion boots, suspension boots, constant velocity joint boots, etc.;

Since the molded product of the present invention has excellent settling resistance, it can be suitably used for the window molding structure for fixing the elevating door glass of an automobile among the above. By applying the molded product of the present invention to a window molding, it can be quickly deformed according to the ascent and descent of the door glass, and can be kept deformed even after long-term use, and the dustproof and water-wiping roles of the molding are effective. Can be demonstrated.

Hereinafter, specific embodiments of the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples as long as the gist of the present invention is not exceeded. The values of various production conditions and evaluation results in the following examples have meanings as preferable values of the upper limit or the lower limit in the embodiment of the present invention, and the preferable range is the above-mentioned upper limit or lower limit value. , The range specified by the combination of the values of the following examples or the values of the examples may be used.

[raw materials]
The raw materials used in the following examples and comparative examples are as follows.

<Component (A): Polypropylene polymer>
(A-1): Novatec (registered trademark) PP manufactured by Japan Polypropylene Corporation
Propene unit content: 100 mol%
MFR (230 ° C, 21.2N): 2.5g / 10 minutes
Density (ISO 1183: 1987): 0.90 g / cm ³

<Component (B): ethylene / α-olefin / non-conjugated diene copolymer>
(B-1) + (D-1) mixture: Ethylene / propylene / 5-ethylidene-2-norbornene copolymer (component (B-1)) 100 parts by mass of the following component (D-1) per 100 parts by mass oil-extended ethylene-alpha-olefin-non-conjugated diene copolymer oil-extended before Mooney viscosity containing _{(ML 1 + 4, 125 ℃} ): 292
Mooney viscosity after oil spreading (ML _{1 + 4} , 125 ° C): 64
Ethylene unit content of component (B-1): 67 mol%
Propylene unit content of component (B-1): 28.5 mol%
5-Etylidene-2-norbornene unit content of component (B-1): 4.5 mol%
Density (ISO 1183: 1987): 0.86 g / cm ³

<Component (C): Phenol resin cross-linking agent>
(C-1) + (D-1) mixture: 30 parts by mass of the following component (C-1) and 70 parts by mass of the following component (D-1) (C-1): Methylol groups at both ends Alkylphenol formaldehyde resin
TACKIROL 201 manufactured by Taoka Chemical Industry Co., Ltd.

<Crosslinking agent other than component (C)>
(C-2): Organic peroxide
Kayaku Akzo Corporation Kayahexa AD40C
(2,5-dimethyl-2,5-di (t-butylperoxy) hexane 40% by mass
And 60% by mass of calcium carbonate)

<Component (D): Hydrocarbon-based rubber softener>
(D-1): Paraffinic oil
Idemitsu Kosan Co., Ltd. Diana Process Oil PW-90
Viscosity at 40 ° C: 95.54 cSt
Pour point: -15 ° C
Flash point: 272 ° C

<Component (E): Diene polymer having a hydroxyl group and / or its hydrogenated agent>
(E-1): Polyhydroxy polyolefin
Polytail H manufactured by Mitsubishi Chemical Corporation
Number average molecular weight: 2800
Average number of hydroxyl groups per molecule: 2
Hydroxy group value: 50 mgKOH / g

<Component (F): Organometallic compound>
(F-1): Dioctyl tin dilaurate (DOTDL)
TVS8501 manufactured by Nitto Kasei Co., Ltd.

<Other ingredients>
<X-1>: Filler / Talc PHSH manufactured by Takehara Chemical Industry Co., Ltd.
<X-2>: Antioxidant / BASF Japan Co., Ltd. Ilganox 1010
<X-3>: Acid receiving agent / manufactured by Wako Pure Chemical Industries, Ltd. Zinc oxide <X-4>: Halogen donor / manufactured by Wako Pure Chemical Industries, Ltd. Stannous chloride <X-5>: Crosslinking aid / TMPMA manufactured by Mitsubishi Chemical Industries, Ltd. (purity 98.4%)
Trimethylolpropane methacrylic acid

[Evaluation method]
The evaluation method of the dynamically crosslinked olefin polymer composition in the following Examples and Comparative Examples is as follows.
In the following measurements, each dynamically crosslinked olefin polymer composition was used in an in-line screw type injection molding machine (“IS130” manufactured by Toshiba Machine Co., Ltd.) at an injection pressure of 50 MPa, a cylinder temperature of 220 ° C., and gold. Under the condition of the mold temperature of 40 ° C., each dynamically crosslinked olefin polymer composition was injection-molded to obtain a sheet having a thickness of 2 mm, a width of 120 mm and a length of 80 mm.

<Peeling strength>
Solvent-based one-component moisture-curable urethane resin adhesive (solvent: toluene + methyl ethyl ketone + butyl acetate, non-volatile content: 47%, constituents: diphenylmethane diisocyanate / liquid polybutadiene polyol / polypropylene glycol / 2-ethyl Apply -1,3-hexanediol = 33/39/19/8 (mass ratio)) with a bar coater to a thickness of about 7 μm, and while the adhesive is wet, urethane tape (manufactured by Okuda Sangyo Co., Ltd.) Polycotape, width 1.5 cm) was layered. Then, it was dried in an oven at 80 ° C. for 2 minutes, and then air-dried at room temperature for 48 hours.
With respect to the obtained test piece, the peel strength between the tape and the sheet was measured with reference to the standard of ISO 8510-2: 1990.
The adhesion between the dynamically crosslinked olefin polymer composition and the urethane resin was evaluated from this peel strength. The larger this value is, the better the adhesion is.

<Compressive permanent strain>
The injection-molded sheet was subjected to compression permanent strain measurement at 70 ° C. for 22 hours under 25% compression conditions with reference to the ISO 815: 1: 2008 standard. The smaller this value is, the smaller the so-called settling (permanent strain) due to long-term exposure to the deformed state, and the better the settling resistance.

[Examples 1 and 2, Comparative Examples 1 and 3]
Each component is blended in the ratio shown in Table 1 (the total of components (A) and (B) is 100 parts by mass), and the mixture is mixed in the same direction twin-screw extruder (Japan Steel Works "TEX30", L / D = 52.5, number of cylinder blocks: 14). The temperature of the upstream portion to the downstream portion was raised in the range of 120 to 210 ° C., melt kneading was performed, and pelletization was performed to produce a dynamically crosslinked olefin polymer composition.
The peel strength and compression set were evaluated for this dynamically crosslinked olefin polymer composition. The evaluation results are shown in Table-1.

As shown in Table 1, it can be seen that Examples 1 and 2 corresponding to the dynamically crosslinked olefin polymer composition of the present invention all have good adhesion and settling resistance.
On the other hand, Comparative Example 1 did not contain a diene polymer having a hydroxyl group of the component (E) and / or a hydrogenated additive thereof, and the adhesion was insufficient. In Comparative Example 2 and Comparative Example 3, a peroxide cross-linking agent was used instead of the phenol resin cross-linking agent of the component (C), but in each case, the adhesion was insufficient and the settling resistance was also deteriorated.

Claims (6)

A dynamically crosslinked olefin polymer composition containing the following components (A) to (E).
Component (A): Polypropylene-based polymer Component (B): Ethylene / α-olefin / non-conjugated diene copolymer Component (C): Phenol formaldehyde cross-linking agent Component (D): Hydrocarbon-based rubber softener component (E) ): Diene polymer having a hydroxyl group and / or its hydrocarbon additive The dynamically crosslinked olefin polymer composition according to claim 1, wherein the phenol resin crosslinking agent is an alkylphenol formaldehyde resin. The dynamically crosslinked olefin polymer composition according to claim 1 or 2, wherein the diene polymer having a hydroxyl group and / or a hydrogenated product thereof has a terminal hydroxyl group. The dynamically crosslinked olefin polymer composition according to any one of claims 1 to 3, further containing the following component (F).
Component (F): Organometallic compound A molded product of the dynamically crosslinked olefin polymer composition according to any one of claims 1 to 4. An automobile part including the molded product according to claim 5.