JP2018135415A - Method for producing thermoplastic elastomer composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a thermoplastic elastomer composition which has excellent permanent compression set (settling resistance) and vibration-proof property, and has good extrusion moldability.SOLUTION: A method for producing a thermoplastic elastomer composition by kneading at least the following components (A) to (C) and component (D) includes at least a step (1) of kneading at least components (A) to (C), and a step (2) of mixing or reacting the component (D) after the step (1), where an amount of the component (D) is 0.1-100 pts.mass with respect to 100 pts.mass of the total amount of the components (A) to (C). Component (A): polypropylene-based resin. Component (B): ethylene-α-olefin copolymer rubber. Component (C): crosslinking agent. Component (D): 4-methyl-1-pentene-ethylene and/or α-olefin copolymer.SELECTED DRAWING: None

Description

  The present invention relates to a method for producing a thermoplastic elastomer composition and a method for producing a molded product, which are excellent in vibration-proofing property and compression set (sagging property) when molded, and have good moldability. The thermoplastic elastomer composition and molded product produced by the present invention are useful as a sealing material for automobiles, a sealing material for building materials, and the like.

  A thermoplastic elastomer composition obtained by dynamically heat-treating a mixture containing a polypropylene resin and an ethylene / α-olefin copolymer in the presence of a crosslinking agent is vulcanized while exhibiting properties as a rubber-like soft material. A process is unnecessary and it has the same moldability as a thermoplastic resin. For this reason, such a thermoplastic elastomer composition is attracting attention from the viewpoint of rationalization of the manufacturing process and recyclability, and is widely used in the fields of automobile parts, household appliances, medical equipment parts, electric wires, miscellaneous goods, and the like. .

However, a molded product obtained by molding a thermoplastic elastomer composition obtained by performing a widely used dynamic heat treatment has been particularly demanded in recent years as a sealing material for automobiles or a sealing material for building materials. In addition, there was a problem in terms of achieving both compression set (sagging) and vibration isolation.
That is, the compression set is a performance that becomes better if the rubber elasticity is high, and is inherently contrary to the vibration-proofing property that becomes better if the viscosity of the rubber is high.

  Conventionally, as a technique for obtaining a good compression set, an olefin thermoplastic elastomer obtained by dynamic heat treatment has an elastic modulus of bending (JIS K7203) of 500 MPa or less and has no crosslinked structure. A technique for mixing a thermoplastic elastomer component is disclosed in Patent Document 1. In addition, Patent Document 2 discloses that the vibration-proof property is high when a 4-methyl-1-pentene / α-olefin copolymer is contained.

JP 2006-36813 A Japanese Patent Laid-Open No. 2006-56954

As a result of detailed studies by the present inventors, the thermoplastic elastomer composition as described in Patent Document 1 has good compression set (sagging property), but the vibration-proof property is not sufficient. I understood. In addition, the technique disclosed in Patent Document 2 provides high vibration proofing properties. However, since the study on the combination with the ethylene / α-olefin copolymer rubber and the crosslinking technique is not sufficient, a good compression permanent property is obtained. It is presumed that no distortion can be obtained, and there is still a problem in terms of achieving both vibration proofing and compression set.
Thus, the present situation is that the thermoplastic elastomer composition which optimized the material and the process, and was able to make compression set, vibration proof, and extrudability all good simultaneously is not provided yet.

  The present invention solves the above-mentioned problems of the prior art, can form a molded article having excellent compression set (sagging property) and vibration proofing property, and is a thermoplastic elastomer composition having good extrusion moldability. It is an object to provide a manufacturing method.

As a result of repeated studies to solve the above-mentioned problems, the present inventor solved a conventional problem by using a specific propylene resin and a rubber polymer as a raw material in combination and producing them by a specific method. I found out that I could do it.
That is, the gist of the present invention is as follows.

[1] A method for producing a thermoplastic elastomer composition by kneading at least the following components (A) to (C) and a component (D) as raw materials, comprising step (1); at least components (A) to ( A step of kneading C) and step (2): at least a step of mixing or reacting component (D) after step (1), and with respect to 100 parts by mass of the total amount of components (A) to (C) The manufacturing method of the thermoplastic elastomer composition which makes the ratio of a component (D) 0.1-100 mass parts.
Component (A): Polypropylene resin component (B): Ethylene / α-olefin copolymer rubber component (C): Crosslinker component (D): 4-methyl-1-pentene / ethylene and / or α-olefin Copolymer

[2] The method for producing a thermoplastic elastomer composition according to [1], wherein the component (B) is an ethylene / α-olefin / non-conjugated diene copolymer.

[3] The method for producing a thermoplastic elastomer composition according to [1] or [2], wherein the component (A) is a polypropylene resin containing the following component (A1) and component (A2).
Component (A1): Propylene polymer having a melting peak temperature of 157 ° C. or higher and 175 ° C. or lower Component (A2): Propylene random copolymer having a melting peak temperature of 100 ° C. or higher and lower than 157 ° C.

[4] The ratio of the component (A) is 40 to 70 parts by mass and the ratio of the component (B) is 30 to 60 parts by mass with respect to 100 parts by mass of the total amount of the components (A) and (B). ] The manufacturing method of the thermoplastic-elastomer composition in any one of [3].

[5] Furthermore, the following component (E) is used as a raw material, and the use amount thereof is 80 to 160 parts by mass with respect to 100 parts by mass of the component (B), according to any one of [1] to [4] A method for producing a thermoplastic elastomer composition.
Component (E): Hydrocarbon softener

[6] A method for producing a molded body using the thermoplastic elastomer composition produced by the method for producing a thermoplastic elastomer composition according to any one of [1] to [5].

[7] The method for producing a molded article according to [6], which is a method for producing a member for an automobile.

[8] The method for producing a molded article according to [7], which is a method for producing a glass run channel for automobiles.

According to the present invention, it is possible to produce a thermoplastic elastomer composition excellent in vibration-proofing property and compression set (sagability) of a molded body when molded, and having good extrusion moldability (fluidity), Using the produced thermoplastic elastomer composition, it is possible to obtain a molded article excellent in both vibration proofing property and compression set (sagging property) with good productivity.
The thermoplastic elastomer composition and molded article produced by the present invention have an anti-vibration property, a compression set (sagging property) and an extrusion property (fluidity), so that it is a sealing material for automobiles and a sealing material for building materials. It is useful as a glass run channel for automobiles.

  Hereinafter, 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 implemented without departing from the gist of the present invention. In addition, in this specification, when expressing by putting a numerical value or a physical-property value before and behind using "-", it shall use as what includes the value before and behind.

[Method for producing thermoplastic elastomer composition]
The method for producing a thermoplastic elastomer composition of the present invention is a method for producing a thermoplastic elastomer composition by kneading at least the following components (A) to (C) and a component (D) as raw materials, comprising the steps ( 1); including at least a step of kneading components (A) to (C), and a step (2): mixing or reacting component (D) after step (1), and components (A) to (C) The ratio of the component (D) to 100 parts by mass of the total amount of (C) is 0.1 to 100 parts by mass.
Component (A): Polypropylene resin component (B): Ethylene / α-olefin copolymer rubber component (C): Crosslinker component (D): 4-methyl-1-pentene / ethylene and / or α-olefin Copolymer

  In the following, the thermoplastic elastomer composition produced by the method for producing a thermoplastic elastomer composition of the present invention will be referred to as “the thermoplastic elastomer composition of the present invention” and will be described later by the method for producing a molded article of the present invention. The manufactured molded body may be referred to as “the molded body of the present invention”.

[mechanism]
According to the method for producing a thermoplastic elastomer composition of the present invention, a thermoplastic elastomer composition having an excellent vibration-proof property and compression set (sagability) and good moldability (fluidity) is obtained. The effect that it can be manufactured is produced.
Although the details of the reason why the method for producing the thermoplastic elastomer composition of the present invention has such an effect is not clear, component (D) as a vibration-proof component: 4-methyl-1-pentene / ethylene and / or By adding the α-olefin copolymer as the step (2) (post-step), the component (B), which is a compression set imparting component that could not be achieved by the conventional batch addition, and the component for imparting vibration resistance This is considered to be due to the excellent effect of the uniform dispersion of each component (D). That is, by adding the component (D) in the subsequent step, the shearing force in the step (1) is mainly used for dispersion of the component (B): ethylene / α-olefin copolymer rubber, and in this state, crosslinking is performed. Since the reaction proceeds to the middle, the composition obtained in the step (1) has a matrix domain structure in which the domain of the component (B) is uniformly dispersed in the matrix phase of the component (A). By adding the component (D) here, the shear force of the step (2) is mainly used for the dispersion of the component (D), and the component (D) is favorably on the matrix side of the matrix domain structure. Since the dynamic heat treatment is completed in a dispersed state, finally, a composition in which each of the component (B) and the component (D) is uniformly dispersed in the component (A) is obtained. Since the composition of the component (D) is closer to the component (A), the fluidity provided by the component (A) is not impaired, and this maintains the compression set (sagability), and the component (D) It is presumed that this is a mechanism that can provide a thermoplastic elastomer composition that can effectively exhibit the vibration-proofing property and has excellent fluidity.
In the conventional batch addition method in which the component (B) and the component (D) are added simultaneously, not only the shearing force is distributed to the dispersion of the component (B) and the component (D), but also the crosslinking reaction proceeds simultaneously. It is difficult to obtain uniform dispersion of each component as described above, and it is difficult to achieve both vibration isolation and compression set (sagging).

[Component (A)]
The component (A) used in the thermoplastic elastomer composition of the present invention is preferably a polypropylene resin containing the following component (A1) and component (A2), and other polypropylene resins can be used as long as these are included. It may be included. In the present invention, the “polypropylene resin” means a propylene unit content of 50% by mass or more. In the present invention, the component (A) mainly contributes to extrusion moldability.
Component (A1): Propylene polymer having a melting peak temperature of 157 ° C. or higher and 175 ° C. or lower Component (A2): Propylene random copolymer having a melting peak temperature of 100 ° C. or higher and lower than 157 ° C.

In addition, the melting peak temperature of a component (A1) and a component (A2) can be measured with the following method according to JISK7121.
That is, using a differential scanning calorimeter (DSC 6220 manufactured by SSI Nanotechnology Inc.), the following steps (1) to (3) are sequentially performed to measure the melting behavior of the polypropylene resin.
In each step, time is plotted on the horizontal axis and heat of fusion is plotted on the vertical axis to obtain a melting curve, and the peak top of the peak observed in step (3) is taken as the melting peak temperature.
Step (1): A sample of 5 mg is heated from room temperature at a rate of 100 ° C./min from 40 ° C. to 200 ° C., and held for 3 minutes after the temperature increase is completed.
Step (2): The temperature is lowered from 200 ° C. to 40 ° C. at a rate of 10 ° C./min, and held for 3 minutes after the temperature drop.
Step (3): The temperature is raised from 40 ° C. to 200 ° C. at a rate of 10 ° C./min.

  The propylene polymer of the component (A1) has a melting peak temperature of 157 ° C. or higher and 175 ° C. or lower. Component (A1) is a component that mainly imparts heat resistance to the thermoplastic elastomer composition.

  When the melting peak temperature of the component (A1) is 157 ° C. or higher, heat resistance is imparted. From this viewpoint, the melting peak temperature of the component (A1) is preferably 160 ° C. or higher. On the other hand, the upper limit is 175 ° C. or lower, preferably 170 ° C. or lower.

  In the propylene polymer of component (A1), the content of propylene units is preferably 90% by mass or more, more preferably 98 to 100% by mass, based on the total amount of monomer units constituting component (A1). It is. When the content of the propylene unit in the component (A1) is in the above range, it is preferable because the melting peak temperature is easily reached. In addition, content of each structural unit of a component (A1) can be calculated | required by infrared spectroscopy. The same applies to the components (A2) and (B) described later.

  The component (A1) may be a propylene homopolymer, a random copolymer or a block copolymer, but preferably contains a propylene homopolymer as the component (A1).

  The propylene polymer of component (A1) may have a structural unit other than propylene, and may include, for example, a copolymerized with an α-olefin other than ethylene or propylene. In this case, examples of the α-olefin unit that may be contained in the component (A1) include 1-butene unit, 1-pentene unit, 1-hexene unit, 1-heptene unit, 1-octene unit, 1-octene unit, Nonene unit, 1-decene unit, 1-undecene unit, 1-dodecene unit, 1-tridecene unit, 1-tetradecene unit, 1-pentadecene unit, 1-hexadecene unit, 1-heptadecene unit, 1-octadecene unit, 1- Nonadecene unit, 1-eicocene unit, 3-methyl-1-butene unit, 3-methyl-1-pentene unit, 4-methyl-1-pentene unit, 2-ethyl-1-hexene unit, 2,2,4- And trimethyl-1-pentene unit. The component (A1) may contain only one of these or may contain two or more. When the component (A1) includes a structural unit other than the propylene unit, preferred examples of the other structural unit include an ethylene unit and a 1-butene unit.

  The propylene random copolymer of component (A2) has a melting peak temperature of 100 ° C. or higher and lower than 157 ° C. The component (A2) is a component for improving the compatibility between the component (A) and the component (B).

  The melting peak temperature of the component (A2) is 100 ° C. or higher, and preferably 125 ° C. or higher. On the other hand, the melting peak temperature of the component (A2) is less than 157 ° C. The melting peak temperature of the component (A2) is preferably not less than the above lower limit value from the viewpoint of heat resistance, and if it is less than the above upper limit value, it is preferable from the viewpoint of compatibility between the component (A) and the component (B).

  In the propylene random copolymer of the component (A2), the content of propylene units is preferably 60 to 99% by mass, more preferably based on the total amount of monomer units constituting the component (A2). It is 80-98 mass%. It is preferable that the content of the propylene unit in the component (A2) is in the above range because the melting peak temperature is likely to be in the above range.

  The propylene random copolymer of component (A2) is a copolymer having propylene units and structural units other than propylene units. Specific examples of the structural unit other than the propylene unit include an α-olefin unit other than the ethylene unit and the propylene unit. Examples of the structural unit other than the propylene unit that may be contained in the component (A2) include, for example, an ethylene unit, 1-butene unit, 1-pentene unit, 1-hexene unit, 1-heptene unit, 1-octene unit, 1-nonene unit, 1-decene unit, 1-undecene unit, 1-dodecene unit, 1-tridecene unit, 1-tetradecene unit, 1-pentadecene unit, 1-hexadecene unit, 1-heptadecene unit, 1-octadecene unit, 1-nonadecene unit, 1-eicocene unit, 3-methyl-1-butene unit, 3-methyl-1-pentene unit, 4-methyl-1-pentene unit, 2-ethyl-1-hexene unit, 2,2, 4-trimethyl-1-pentene unit and the like can be mentioned. The component (A2) may contain only one of these or may contain two or more. Preferable examples of the structural unit other than the propylene unit contained in the component (A2) include an ethylene unit and 1-butene unit.

  As a method for producing the propylene polymer of the component (A1) and the component (A2), a known polymerization method using a known olefin polymerization catalyst is used. For example, a polymerization method using a Ziegler-Natta catalyst can be mentioned. As the polymerization method, a slurry polymerization method, a solution polymerization method, a bulk polymerization method, a gas phase polymerization method, or the like can be used, and two or more of these may be combined.

  Component (A1) and component (A2) can also be obtained as commercial products. Examples of such commercial products include Prime Polymer's Prime Polypro (registered trademark), Sumitomo Chemical's Sumitomo Noblen (registered trademark), Sun Allomer's polypropylene block copolymer, Nippon Polypro's Novatec (registered trademark) PP, LyondellBasel. Moplen (R), ExxonMobil's ExxonMobil PP, Formosa Plastics's Formolene (R), Borealis's Borealis PP, LG Chemical's SEETEC PP, A.M. Schulman's ASI POLYPROPYLENE, INEOS Olefins & Polymers, Inc. of INEOS PP, Braskem's Braskem PP, SAMSUNG TOTAL PETROCHEMICALS's Sumsung Total, Sabic's Sabic (registered trademark) PP, TOTAL PETROCHEMICALS company of TOTAL PETROCHEMICALS Polypropylene, SK Corporation of YUPLENE ( Registered trademark) and the like, which can be appropriately selected from these and used in combination.

  Only one type of component (A1) or component (A2) may be used, or two or more types having different compositions and physical properties may be used in combination.

  The content of the component (A1) is preferably 50 parts by mass or more from the viewpoint of heat resistance, rigidity, dispersibility, and the like with respect to 100 parts by mass of the total amount of the component (A1) and the component (A2). More preferably, it is more than 70 parts by mass. On the other hand, from the viewpoint of compatibility between the component (A) and the component (B), the content of the component (A1) is 95 parts by mass or less with respect to 100 parts by mass of the total amount of the component (A1) and the component (A2). It is preferable that it is 90 mass parts or less, and it is still more preferable that it is 85 mass parts or less.

  In addition, although a component (A) may contain polypropylene resin other than a component (A1) and a component (A2), when acquiring the effect of a component (A1) and a component (A2) effectively, Component (A) preferably contains 30 parts by mass or more in total of component (A1) and component (A2) in 100 parts by mass, more preferably 40 parts by mass or more, and 50 to 100 parts by mass. More preferably.

[Component (B)]
The component (B) used in the thermoplastic elastomer composition of the present invention is an ethylene / α-olefin copolymer rubber (except for those corresponding to the component (A)). Component (B) is a component that imparts flexibility to the thermoplastic elastomer of the present invention.

  The component (B) is not particularly limited as long as it is a copolymer containing at least an ethylene unit and an α-olefin unit, but is preferably an ethylene / α-olefin / nonconjugated diene copolymer further containing a nonconjugated diene unit. is there.

  The α-olefin unit contained in the component (B) includes 1-propylene unit, 1-butene unit, 2-methylpropylene unit, 1-pentene unit, 3-methyl-1-butene unit, 1-hexene unit, 4 -Methyl-1-pentene unit, 1-octene unit and the like can be exemplified. The α-olefin unit used in component (B) is preferably the number of carbons having a carbon-carbon double bond at the terminal carbon atom such as 1-propylene unit, 1-butene unit, 1-hexene unit, 1-octene unit, etc. 3 to 8 α-olefin units. Component (B) may contain only one type of these α-olefin units or may contain two or more types.

As the non-conjugated diene unit contained in the component (B), 1,4-hexadiene, 1,6-octadiene, 2-methyl-1,5-hexadiene, 6-methyl-1,5-heptadiene, 7-methyl- Units based on chain non-conjugated dienes such as 1,6-octadiene; cyclohexadiene, dicyclopentadiene, methyltetrahydroindene, 5-vinylnorbornene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, Examples thereof include units based on cyclic non-conjugated dienes such as 5-isopropylidene-2-norbornene and 6-chloromethyl-5-isopropenyl-2-norbornene. Among these, 5-ethylidene-2-norbornene units and dicyclopentadiene units are preferable.
Component (B) may contain only one kind of these non-conjugated diene units, or may contain two or more kinds.

  The content of the ethylene unit in the component (B) is preferably 30% by mass or more, more preferably 40% by mass or more, and still more preferably based on the total amount of the monomer units constituting the component (B). Is 50% by mass or more, on the other hand, preferably 90% by mass or less, more preferably 80% by mass or less. It is preferable that the content of the ethylene unit is in the above range because moderate flexibility is provided.

  In the component (B), the content of the α-olefin unit is preferably 10% by mass or more, more preferably 20% by mass or more, with respect to the total amount of the monomer units constituting the component (B). On the other hand, it is preferably 50% by mass or less, and more preferably 40% by mass or less. It is preferable that the content of the α-olefin unit is in the above range in order to provide appropriate flexibility.

  In the component (B), the content of the non-conjugated diene unit is preferably 1% by mass or more, preferably 3% by mass or more, based on the total amount of monomer units constituting the component (B). On the other hand, it is preferably 10% by mass or less, and preferably 8% by mass or less. When the content of the non-conjugated diene unit is not less than the above lower limit value, it is preferable from the viewpoint of increasing the degree of crosslinking of the thermoplastic elastomer composition, and when it is not more than the above upper limit value, it is preferable from the viewpoint of moldability.

The Mooney viscosity (ML _{1 + 4} , 125 ° C.) of the component (B) is usually 30 to 120, preferably 40 to 100. The Mooney viscosity (ML _{1 + 4} , 125 ° C.) of the component (B) is preferably in the above range from the viewpoint of moldability.

The component (B) preferably has a density of 0.850 g / cm ³ or more, more preferably 0.860 g / cm ³ or more, and preferably 0.900 g / cm ³ or less, More preferably, it is 0.890 g / cm ³ or less. The density of the component (B) is preferably not less than the above lower limit value from the viewpoint of workability, and is preferably not more than the above upper limit value from the viewpoint of flexibility. The density of the component (B) can be measured based on JIS K7112.

  Although the melt flow rate of a component (B) is not limited, Usually, it is less than 10 g / 10min. From a viewpoint of intensity | strength, Preferably it is 9.0 g / 10min or less, More preferably, it is 8.0 g / 10min or less. More preferably 7.0 g / 10 min or less. Further, the melt flow rate of the component (B) is usually 0.01 g / 10 min or more, and from the viewpoint of fluidity, it is preferably 0.05 g / 10 min or more, more preferably 0.10 g / 10 min. That's it. The melt flow rate (MFR) of the component (B) is measured under the conditions of a measurement temperature of 230 ° C. and a measurement load of 49 N according to JIS K7210.

  As a manufacturing method of a component (B), the well-known polymerization method using the well-known olefin polymerization catalyst is used. For example, a slurry polymerization method, a solution polymerization method, a bulk polymerization method, a gas phase polymerization method and the like using a complex catalyst such as a Ziegler-Natta catalyst, a metallocene complex, or a nonmetallocene complex may be used.

  A commercial item can also be used for a component (B). For example, JSR EPT manufactured by JSR, Mitsui EPT manufactured by Mitsui Chemicals, Esprene (registered trademark) manufactured by Sumitomo Chemical, Keltan (registered trademark) manufactured by LANXESS, Nordel (registered trademark) manufactured by Dow, and Vistalon (registered trademark) manufactured by ExxonMobil ) Etc., the corresponding product can be selected and used.

  As the component (B), only one type may be used, or two or more types having different compositions and physical properties may be used in combination.

[Ratio of component (A) and component (B)]
In the method for producing a thermoplastic elastomer composition of the present invention, the amount of the component (A) used is usually 100 parts by mass of the total amount of the component (A) and the component (B), and the lower limit is usually from the viewpoint of moldability. It is 40 parts by mass or more, preferably 42 parts by mass or more, and more preferably 44 parts by mass or more. On the other hand, the upper limit is usually 70 parts by mass or less, preferably 68 parts by mass or less, and more preferably 66 parts by mass or less.
From the viewpoint of moldability, the lower limit of the content of the component (B) is usually 30 parts by mass or more and 32 parts by mass or more with respect to 100 parts by mass of the total amount of the components (A) and (B). It is preferably 34 parts by mass or more. On the other hand, the upper limit is usually 60 parts by mass or less, preferably 58 parts by mass or less, and more preferably 56 parts by mass or less.

[Component (C)]
The thermoplastic elastomer composition of the present invention is obtained by crosslinking at least a part of component (B) by performing dynamic heat treatment in the presence of component (C): a crosslinking agent. By this dynamic heat treatment, the thermoplastic elastomer composition of the present invention has good rubber elasticity.

  As the crosslinking agent, organic peroxides, phenol resins, other crosslinking assistants, and the like can be used. These crosslinking agents may be used alone or in combination of two or more.

  As the organic peroxide that can be used as the cross-linking agent, any of aromatic organic peroxides and aliphatic organic peroxides can be used. Specifically, di-t-butyl peroxide, t-butylcumyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl -2,5-di (t-butylperoxy) hexyne-3, 1,3-bis (t-butylperoxyisopropyl) benzene, 1,1-di (t-butylperoxy) -3,3,5 -Dialkyl peroxides such as trimethylcyclohexane; t-butylperoxybenzoate, t-butylperoxyisopropyl carbonate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, 2,5-dimethyl-2 Peroxyesters such as, 5-di (benzoylperoxy) hexyne-3; acetyl peroxide, lauroyl peroxide, benzoy Peroxide, p- chlorobenzoyl peroxide, hydroperoxide, and the like, such as 2,4-dichlorobenzoyl peroxide and the like. Among these, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane is preferable. These organic peroxides may be used alone or in combination of two or more.

  Examples of the phenol resin that can be used as a crosslinking agent include alkylphenol formaldehyde, bromated alkylphenolanol formaldehyde, and the like. These phenol resins may be used alone or in combination of two or more.

  Examples of crosslinking aids other than organic peroxides and phenolic resins include, for example, peroxide aids such as sulfur, p-quinonedioxime, p-dinitrosobenzene, 1,3-diphenylguanidine; stannous chloride・ Cross-linking assistants for phenolic resins such as anhydride, stannous chloride / dihydrate, ferric chloride; polyfunctional vinyl compounds such as divinylbenzene, triallyl cyanurate, triallyl isocyanurate, diallyl phthalate; ethylene Examples thereof include polyfunctional (meth) acrylate compounds such as glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, and allyl (meth) acrylate. These may be used alone or in combination of two or more.

  The amount of the component (C) used is sufficiently sufficient for the crosslinking reaction to proceed with respect to a total of 100 parts by mass of the component (A), the component (B), the component (D) described later and the component (E) used as necessary. From the viewpoint of making it, it is preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, and still more preferably 0.3 parts by mass or more. On the other hand, the amount of component (C) used controls the cross-linking reaction with respect to a total of 100 parts by mass of component (A), component (B), component (D) described later and component (E) used as necessary. From this viewpoint, it is preferably 10 parts by mass or less, more preferably 8 parts by mass or less, still more preferably 6 parts by mass or less, and particularly preferably 4 parts by mass or less.

[Component (D): 4-methyl-1-pentene / ethylene and / or α-olefin copolymer]
The component (D) used in the thermoplastic elastomer composition of the present invention is 4-methyl-1-pentene / ethylene and / or α-olefin copolymer, and is a component that imparts vibration-proof properties to the thermoplastic elastomer. .

The component (D) used in the present invention preferably satisfies at least one of the requirements (x) and the following requirements (a) to (i).
In addition, the following methods are mentioned as the preparation methods of the press sheet of the component (D) for the measurement of the following various physical properties, for example.

<Method for producing press sheet for measuring various physical properties>
The component (D) is formed into a sheet at a pressure of 10 MPa using a hydraulic hot press manufactured by Shindo Metal Industry Co., Ltd. set to 190 ° C. In the case of a sheet having a thickness of 1 to 3 mm (spacer shape; 80 × 80 × 0.5 to 3 mm, 4 pieces on a 240 × 240 × 2 mm thick plate), the remaining heat is about 5 to 7 minutes, and 1 to 2 at 10 MPa. After pressurizing for a minute, using another hydraulic hot press machine manufactured by Shinfuji Metal Industry Co., Ltd. set to 20 ° C., compress at 10 MPa and cool for about 5 minutes to prepare a measurement sample. A 5 mm thick brass plate is used as the hot plate.

  Below, each suitable requirement of the component (D) used by this invention is demonstrated.

Requirement (x): When measured at a frequency of 1.6 Hz and a heating rate of 2 ° C./min, a peak of loss tangent tan δ exists at a temperature of −10 ° C. or higher. Note that the measurement modes include torsion, bending, tension, compression, and shear. In this measurement, the mode is appropriately selected.

Those having a loss tangent tan δ peak of −10 ° C. or higher are considered to be preferable from the viewpoint of imparting vibration proofing properties because they are relatively close to temperatures that are normally expected to be used in automobiles. However, if this temperature is excessively high, sufficient loss tangent tan δ cannot be obtained at the operating temperature normally assumed in automobiles, and it is considered that the vibration-proofing property is insufficient. The peak of the loss tangent tan δ is particularly preferably present at −20 to 60 ° C., more preferably −10 to 50 ° C., and still more preferably 0 to 40 ° C.
Hereinafter, the temperature at which the peak of loss tangent tan δ exists may be referred to as “peak temperature”.

  The peak value of the loss tangent tan δ at this time is preferably 0.5 to 5.0, more preferably 0.5 to 4.0, and 0.5 to 3.5. Is more preferable. It is preferable that the peak value of the loss tangent tan δ is in the above range because it is excellent in flexibility, light weight, and vibration proofing.

  The peak temperature of the component (D) and the peak value of the loss tangent tan δ can be controlled by the copolymer composition ratio of 4-methyl-1-pentene / ethylene and / or α-olefin copolymer. The requirement (x) can be satisfied by setting the content of 4-methyl-1-pentene units in the methyl-1-pentene / ethylene and / or α-olefin copolymer to 20 to 75 mol%.

Requirement (a): 4-Methyl-1-pentene unit and ethylene and / or α-olefin (excluding 4-methyl-1-pentene) unit in total 100 mol% It contains 15 to 75 mol% of 1-pentene units and 25 to 85 mol% of ethylene and / or α-olefin units.

  The proportion of the 4-methyl-1-pentene unit in component (D) is preferably 20 to 75 mol%, more preferably 20 to 65 mol%, still more preferably 20 to 33 mol%, especially Preferably it is 20-32 mol%. On the other hand, the proportion of ethylene and / or α-olefin units is preferably 25 to 80 mol%, more preferably 35 to 80 mol%, still more preferably 67 to 80 mol%, and particularly preferably 68. ˜80 mol%.

  When the ratio of the 4-methyl-1-pentene unit is within the above range, flexibility, lightness, and vibration resistance are improved.

  Examples of the α-olefin of the α-olefin unit include propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, A linear α-olefin having 3 to 20 carbon atoms, preferably 3 to 15 carbon atoms, more preferably 3 to 10 carbon atoms, such as octadecene and 1-eicosene, 3-methyl-1-butene, 3-methyl -1-pentene, 3-ethyl-1-pentene, 4,4-dimethyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4-ethyl-1-hexene, 3 Examples thereof include branched α-olefins having 5 to 20 carbon atoms, preferably 5 to 15 carbon atoms such as ethyl-1-hexene. Component (D) may contain only one type of ethylene unit and these α-olefin units, or may contain two or more types. Among these, ethylene and / or α-olefin units are preferably ethylene units, propylene units, 1-butene units, 1-pentene units, 1-hexene units and 1-octene units, and propylene units are particularly preferable.

  In addition, if a component (D) is a small quantity which does not impair the objective of this invention (for example, 10 mol% or less with respect to 100 mol% of all the monomer units which comprise a component (D)), 4- Other monomer units other than methyl-1-pentene unit, ethylene unit and α-olefin unit may be contained. Examples of other monomer units include one or more of 5-methyl-2-norbornene units, tetracyclododecene units, 5-vinyl-2-norbornene units, 5-ethylidene-2-norbornene units, and the like. Can be mentioned.

Requirement (b): The intrinsic viscosity [η] measured at 135 ° C. in decalin by the following method is in the range of 0.1 to 5.0 dL / g.

<Measurement method of intrinsic viscosity [η]>
First, 20 mg of a sample is dissolved in 15 mL of decalin, and the specific viscosity (ηsp) is measured in an atmosphere of 135 ° C. using an Ubbelohde viscometer. Next, 5 mL of decalin is further added to the decalin solution for dilution, and the same specific viscosity is measured. Based on the measurement result obtained by repeating this dilution operation and viscosity measurement twice more, the ηsp / C value when the concentration (C) is extrapolated to zero is defined as the intrinsic viscosity (η).

When the intrinsic viscosity [η] of the component (D) is in the above range, the moldability becomes good.
The intrinsic viscosity [η] of the component (D) is preferably 0.5 to 4.0 dL / g, more preferably 0.5 to 3.5 dL / g.

  The intrinsic viscosity [η] of the component (D) can be controlled from a low molecular weight to a high molecular weight by controlling the molecular weight when hydrogen is used in combination as described in JP-A-2006-56954. It can be adjusted.

Requirement (c): The ratio (molecular weight distribution; Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by gel permeation chromatography (GPC) is 1. It is in the range of 0 to 3.5.

<Measuring method of molecular weight (Mw, Mn) / molecular weight distribution (Mw / Mn)>
Liquid chromatograph: ALC / GPC 150-C plus type manufactured by Waters (integrated refractometer detector type) was used. Tosoh Corporation GMH6-HT × 2 and GMH6-HTL × 2 were connected in series as columns, Measurement is performed at 140 ° C. using o-dichlorobenzene as a mobile phase medium at a flow rate of 1.0 ml / min.
The Mw / Mn value is calculated by analyzing the obtained chromatogram by a known method using a calibration curve using a standard polystyrene sample. The measurement time per sample is 60 minutes.

When Mw / Mn of the component (D) is larger than 3.5, there is a concern about the influence of the composition distribution and the low molecular weight polymer, and the vibration damping property tends to be inferior. In addition, it is disadvantageous in expressing the mechanical properties and moldability of the copolymer, and there is a risk of stickiness at the time of molding, causing problems.
The Mw / Mn of the component (D) is preferably 1.2 to 3.0, more preferably 1.5 to 2.5.

  Component (D) satisfying the requirement (c) within the range of the intrinsic viscosity [η] indicated by the requirement (b) by using the catalyst listed in the production method described in JP-A-2006-56954 Can be obtained.

  In addition, the weight average molecular weight (Mw) of a component (D) becomes like this. Preferably it is 500-10,000,000, More preferably, it is 1,000-5,000,000, More preferably, it is 1,000-2,500, 000.

Requirement (d): The density (measured by ASTM D 1505) measured by the following method is in the range of 880 to 810 kg / m ³ .

<Density measurement method>
According to ASTM D 1505 (in-water replacement method), the weight is calculated from the mass of the sample measured in water and in air using an ALFA MIRAGE electronic hydrometer MD-300S.

The component (D) having a density in the above range is advantageous in producing a lightweight molded article.
The density of a component (D) becomes like this. Preferably it is 870-810 kg / m < ³ >, More preferably, it is 860-820 kg / m < ³ >, More preferably, it is 855-830 kg / m < ³ >.

  The density of the component (D) can be changed depending on the copolymer composition ratio of 4-methyl-1-pentene / ethylene and / or α-olefin copolymer.

Requirement (e): Maximum value of loss tangent tan δ (hereinafter referred to as “tan δ peak value” obtained by measuring dynamic viscoelasticity at a frequency of 10 rad / s in the temperature range of −40 ° C. to 150 ° C. by the following method. Is also 1.0 to 5.0.

<Measuring method of dynamic viscoelasticity>
A press sheet having a thickness of 3 mm is prepared, and a strip of 45 mm × 10 mm × 3 mm necessary for dynamic viscoelasticity measurement is cut out. The temperature dependence of dynamic viscoelasticity from −40 to 150 ° C. was measured at a frequency of 10 rad / s using MCR301 manufactured by ANTONPaar, and the loss tangent (tan δ) due to the glass transition temperature was the peak value (maximum value). ) (Hereinafter also referred to as “peak temperature”), and the value of the loss tangent (tan δ) at that time.

When the tan δ peak value of the component (D) is in the above range, it is preferable because it is excellent in flexibility, light weight, and vibration resistance. The tan δ peak value of component (D) is preferably 1.5 to 5.0, more preferably 2.0 to 4.0.
The temperature at which the value of tan δ is maximized is preferably −10 to 40 ° C., more preferably 0 to 40 ° C., and further preferably 5 to 40 ° C.

  The tan δ peak value of the component (D) can be controlled by the copolymer composition ratio of 4-methyl-1-pentene / ethylene and / or α-olefin copolymer, for example, 4-methyl-1-pentene / The requirement (e) can be satisfied by setting the content of 4-methyl-1-pentene unit in the ethylene and / or α-olefin copolymer to 20 to 75 mol%.

Requirement (f): In the method for measuring dynamic viscoelasticity, the value of the loss tangent tan δ measured at 20 ° C. is 0.5 to 5.0.
It is preferable that the loss tangent tan δ measured at 20 ° C. of the component (D) is in the above range because it is excellent in flexibility, light weight and vibration proof. The loss tangent tan δ measured at 20 ° C. of the component (D) is preferably 0.5 to 4.0, more preferably 0.5 to 3.5.

  The loss tangent tan δ measured at 20 ° C. of the component (D) can be controlled by the copolymer composition of 4-methyl-1-pentene / ethylene and / or α-olefin copolymer. The requirement (f) can be satisfied by setting the 4-methyl-1-pentene unit in the methyl-1-pentene / ethylene and / or α-olefin copolymer to 20 to 75 mol%.

Requirement (g): The extraction amount by methyl acetate, measured by the following method, is 0 to 1.5% by mass.

<Measurement method of methyl acetate extract amount>
A sample is collected in a Soxhlet extractor, heated and refluxed under methyl acetate, the mass before and after reflux is weighed, and the extraction amount (% by mass) is calculated.

The amount of methyl acetate extracted becomes an index of stickiness during molding. When this value is large, the obtained polymer has a large composition distribution and contains a low molecular weight polymer, causing problems during molding. When the methyl acetate extraction amount is within the above range, there is no problem due to stickiness during molding.
For example, by using the catalyst described in JP-A-2006-56954, a component (D) having a low stereoregularity and a small atactic component can be synthesized, and a molded product having no stickiness can be obtained.

  The amount of methyl acetate extracted from the component (D) is preferably 0 to 1.0% by mass, more preferably 0 to 0.8% by mass, and still more preferably 0 to 0.5% by mass.

Requirement (h): The rebound resilience at 40 ° C. defined by the following formula is 0 to 25%.
Rebound resilience (%) = L (mm) / 460 × 100
L in the above formula is the rebound of a 16.310 g hard sphere dropped from a height of 460 mm at 40 ° C. on a 6 mm thick press sheet made from component (D) in accordance with JIS K6400. It is height.

  It is preferable from a viewpoint of the vibration proof property at the time of making a molded article that the impact resilience rate of a component (D) is the said range. The rebound resilience of component (D) is preferably 0 to 24%, more preferably 0 to 23%.

  The rebound resilience of component (D) can be controlled by the copolymer composition of 4-methyl-1-pentene / ethylene and / or α-olefin copolymer, for example, 4-methyl-1-pentene unit By setting the content to 20 to 72 mol%, the impact resilience can be set within the above range.

Requirement (i): The Shore A hardness (measured in the state of a press sheet having a thickness of 3 mm according to JIS K6253) at 15 seconds after the start of the contact with the push needle measured by the following measurement method is 5 to 90. .

<Method for measuring Shore A hardness>
Using a press sheet having a thickness of 3 mm as a measurement sample, the scale is read immediately after the start of pressing needle contact and 15 seconds after the start of pressing needle contact. Further, the change ΔHS of the Shore A hardness value defined by the following equation is obtained as follows.
ΔHS = (Shore hardness value immediately after start of pressing needle contact−Shore hardness value 15 seconds after start of pressing needle contact).

  When the Shore A hardness of the component (D) is in the above range, it is preferable from the viewpoint of adjusting the hardness when forming a molded product. The Shore A hardness of the component (D) is more preferably 10-80. More preferably, it is 15-75, Most preferably, it is 20-70.

  The value of Shore A hardness of component (D) can be controlled by the copolymer composition of 4-methyl-1-pentene-ethylene and / or α-olefin copolymer, for example, 4-methyl-1-pentene. Shore A hardness can be made into the said range by making content of a unit into 20-75 mol%.

  The component (D) suitable for the present invention satisfying the above requirements (a) to (i) and (x) is produced, for example, by the method described in JP-A-2006-56954.

  As the component (D), only one type may be used, or two or more types having different compositions and physical properties may be used in combination.

  In this invention, the usage-amount of a component (D) shall be 0.1-100 mass parts with respect to a total of 100 mass parts of a component (A)-(C). When the component (D) is at least the lower limit of the above range, good vibration resistance can be obtained, and when it is at most the upper limit, the compression set (sagability), mechanical properties, and moldability are good. Become. Component (D) is preferably used in an amount of 10 parts by mass or more, more preferably 11 parts by mass or more, and still more preferably 12 parts by mass or more based on a total of 100 parts by mass of components (A) to (C). . Component (D) is preferably used in an amount of 95 parts by mass or less, more preferably 94 parts by mass or less, and more preferably 93 parts by mass or less, with respect to 100 parts by mass in total of components (A) to (C). Further preferred.

[Component (E)]
In the production of the thermoplastic elastomer composition of the present invention, it is preferable to use the following component (E) as a raw material from the viewpoint of improving moldability.
Component (E): Hydrocarbon softener

  Examples of the component (E) hydrocarbon rubber softener include mineral oil softeners and synthetic resin softeners, and mineral oil softeners are preferred from the viewpoint of affinity with other components. Mineral oil softeners are generally a mixture of aromatic hydrocarbons, naphthenic hydrocarbons and paraffinic hydrocarbons, with paraffinic oils in which 50% or more of all carbon atoms are paraffinic hydrocarbons, Those in which 30 to 45% of all carbon atoms are naphthenic hydrocarbons are called naphthenic oils, and those in which 35% or more of all carbon atoms are aromatic hydrocarbons are called aromatic oils. Of these, paraffinic oil is preferably used in the present invention. In addition, the hydrocarbon rubber softening agent may be used alone, or two or more may be used in any combination and ratio.

  The kinematic viscosity at 40 ° C. of the hydrocarbon rubber softener of component (E) is not particularly limited, but is preferably 20 cSt or more, more preferably 50 cSt or more, and preferably 800 cSt or less, more preferably 600 cSt or less. is there. The flash point (COC method) of the hydrocarbon rubber softener is preferably 200 ° C. or higher, more preferably 250 ° C. or higher.

  The hydrocarbon-based rubber softener of component (E) can be obtained as a commercial product. Examples of applicable commercial products include Nisshi Polybutene (registered trademark) HV series manufactured by JX Nippon Oil & Energy Corporation, and Diana (registered trademark) process oil PW series manufactured by Idemitsu Kosan Co., Ltd. Can be appropriately selected and used.

  When component (E) is used in the production of the thermoplastic elastomer composition of the present invention, the lower limit of the amount of component (E) used is preferably 80 masses from 100 mass parts of component (B) from the viewpoint of flexibility. Part or more, more preferably 81 parts by weight or more, and still more preferably 82 parts by weight or more. Further, the upper limit of the amount of component (E) used is usually 160 parts by mass or less, preferably 159 parts by mass or less, more preferably 100 parts by mass of component (B), from the viewpoint of low-temperature impact resistance. Is 158 parts by mass or less.

[Other ingredients]
In the production of the thermoplastic elastomer composition of the present invention, other components can be used as a raw material as necessary, as long as the effects of the present invention are not impaired in addition to the components (A) to (E).

  Other components include, for example, thermoplastic resins and elastomers other than component (A), component (B), and component (D), antioxidants, fillers, thermal stabilizers, light stabilizers, and ultraviolet absorption. Agent, neutralizer, lubricant, anti-fogging agent, anti-blocking agent, slip agent, dispersant, colorant, flame retardant, antistatic agent, conductivity imparting agent, metal deactivator, molecular weight modifier, antibacterial agent And various additives such as fenders and fluorescent brighteners. Any of these may be used alone or in combination.

Examples of thermoplastic resins other than component (A), component (B) and component (D) include polyphenylene ether resins; polyamide resins such as nylon 6 and nylon 66; polyester resins such as polyethylene terephthalate and polybutylene terephthalate. Resins: Polyoxymethylene resins such as polyoxymethylene homopolymers and polyoxymethylene copolymers; polymethyl methacrylate resins, polyolefin resins (but those corresponding to component (A), component (B) and component (D)) Etc.). Examples of elastomers other than component (A), component (B), and component (D) include, for example, styrene elastomers (excluding those corresponding to component (E)); polyester elastomers; polybutadiene, and the like. be able to.

  Examples of the antioxidant include phenolic antioxidants, phosphite antioxidants, thioether antioxidants, and the like. In the case of using an antioxidant, the antioxidant is usually 0.01 with respect to a total of 100 parts by mass of the component (A), the component (B), the component (D) and the component (E) used as necessary. It is used in the range of ~ 3.0 parts by mass.

  Examples of the filler include glass fiber, hollow glass sphere, carbon fiber, talc, calcium carbonate, mica, potassium titanate fiber, silica, metal soap, titanium dioxide, and carbon black. When the filler is used, the filler is usually 0.1 to 50 with respect to 100 parts by mass in total of the component (A), the component (B), the component (D) and the component (E) used as necessary. Used in parts by mass.

[Method for producing thermoplastic elastomer composition]
As described above, the thermoplastic elastomer composition of the present invention contains a predetermined amount of the component (A), the component (B), the component (D), the component (E) used as necessary, and other components. The product is obtained by dynamic heat treatment in the presence of the component (C) as a crosslinking agent. In the present invention, the method for producing such a thermoplastic elastomer composition is represented by the following steps (1) and ( 2) to manufacture.
Step (1): Step of kneading at least components (A) to (C) Step (2): Step of mixing or reacting component (D) after step (1) In step (2), component (D ) Is used in the above-mentioned preferred range with respect to 100 parts by mass of the total amount of the components (A) to (C).

  In the present invention, “dynamic heat treatment” means kneading in a molten or semi-molten state in the presence of a crosslinking agent. This dynamic heat treatment is preferably carried out by melt kneading. As a mixing and kneading apparatus therefor, for example, a non-open Banbury mixer, a mixing roll, a kneader, a twin screw extruder, or the like is used. Among these, it is preferable to use a twin screw extruder. As a preferable aspect of the manufacturing method using this twin-screw extruder, each component is supplied to the raw material supply port (hopper) of the twin-screw extruder which has a some raw material supply port, and dynamic heat processing is performed.

  The temperature at which the dynamic heat treatment is performed is usually 80 to 300 ° C, preferably 100 to 250 ° C. Moreover, the time which performs dynamic heat processing is 0.1 to 30 minutes normally.

In the case of producing the thermoplastic elastomer composition of the present invention by performing dynamic heat treatment with a twin-screw extruder, the barrel radius (R (mm)) of the twin-screw extruder and the screw rotation speed (N (rpm)) And the discharge amount (Q (kg / hour)) is preferably extruded while maintaining the relationship of the following formula (1), more preferably extruded while maintaining the relationship of the following formula (2).
2.6 <NQ / R ³ <22.6 (1)
3.0 <NQ / R ³ <20.0 (2)

  It is thermoplastic that the relationship among the barrel radius (R (mm)), screw rotation speed (N (rpm)) and discharge rate (Q (kg / hour)) of the twin screw extruder is larger than the lower limit value. It is preferable for efficiently producing an elastomer composition. On the other hand, it is preferable that the relationship is smaller than the above upper limit value because it suppresses heat generation due to shearing and makes it difficult for foreign matters that cause poor appearance to occur.

  In the present invention, in such dynamic heat treatment, at least components (A) to (C) are kneaded (step (1)), and then component (D) is added to the obtained kneaded product. Are mixed or reacted (step (2)). Thus, in order to obtain the effect of the present invention more reliably by performing the mixing in two stages, the kneading time of the components (A) to (C) until the component (D) is added, that is, the step (1) ) Is preferably 30 seconds or longer, particularly 35 seconds or longer. However, since it is not preferable in terms of production efficiency to make this time excessively long, it is preferably set to 50 seconds or less.

For example, when dynamic heat treatment is performed using a twin screw extruder, a second raw material supply port is provided in the middle of the extruder cylinder separately from the first raw material supply port upstream of the twin screw extruder (or second Using an extruder having a supply port of 2), the components (A) to (C) are charged from the first raw material supply port, and the component (D) is charged from the second raw material supply port and kneaded. can do.
In this case, the cylinder block of about 1/3 to 2/3 of the total number of cylinder blocks (for example, 13) from the upstream side to the second raw material supply port with respect to the total number of cylinder blocks (for example, 13) of the extruder. It is preferable to provide the component (D) from this position.
The kneading time after adding the component (D), that is, the time of the step (2) is preferably about 10 to 30 seconds.

  In addition to components (A) to (D), when component (E) and other additive components are used, these are kneaded with components (A) to (C) in step (1), and in step (2). Preferably, only component (D) is post-added.

[Physical properties of thermoplastic elastomer composition]
From the viewpoint of moldability, the thermoplastic elastomer composition of the present invention has a melt flow rate (MFR) of 10 g / 10 min or more measured at a measurement temperature of 230 ° C. and a measurement load of 49 N by a method based on the standard of JIS K7210. From the above, it is more preferably 15 g / 10 min or more, and further preferably 20 g / 10 min or more. From the viewpoint of moldability, the melt flow rate (MFR) is preferably 120 g / 10 min or less, more preferably 110 g / 10 min or less, and even more preferably 100 g / 10 min or less. .

  Moreover, it is preferable that the hardness duro A measured based on JISK6253 (JIS-A) about the molded object formed by shape | molding the thermoplastic elastomer composition of this invention is the range of 35-95, 40- A range of 90 is more preferable.

[Molded body / use]
The thermoplastic elastomer composition of the present invention can be formed into a molded body by various molding methods such as injection molding, extrusion molding, hollow molding, compression molding, etc., which are usually used for thermoplastic elastomer compositions. Of these, injection molding and extrusion molding are preferred. Moreover, it can also be set as the molded object which performed secondary processing, such as lamination molding and thermoforming, after performing these shaping | molding. In particular, the thermoplastic elastomer composition of the present invention is excellent in extrusion moldability, and is suitable for extrusion molding, in particular, profile extrusion molding, because it has reduced generation of eyes and foreign matters during molding.

Molded articles made of the thermoplastic elastomer composition of the present invention include automobile parts such as skins, weatherstrips, ceiling materials, interior sheets, bumper moldings, side moldings, air spoilers, air duct hoses, sealing materials; Civil engineering and building materials parts such as window frames and seal materials; Sports equipment such as grip parts of golf clubs and grip parts of tennis rackets; Industrial parts such as hose tubes and gaskets; Home appliance parts such as hoses and packings; Medical use It can be applied to a wide range of fields such as medical parts such as containers, gaskets and packings; food parts such as containers and packings; medical equipment parts; electric wires;
Among the above-mentioned moldings, the molded article made of the thermoplastic elastomer composition of the present invention is suitable as a sealing material for automobiles and a sealing material for building materials, and is suitable as a sealing material for automobiles, particularly as a glass run channel for automobiles.

  EXAMPLES Hereinafter, although the content of this invention is demonstrated more concretely using an Example, this invention is not limited by a following example, unless the summary is exceeded. The values of various production conditions and evaluation results in the following examples have meanings as preferred values of the upper limit or lower limit in the embodiment of the present invention, and preferred ranges are the upper limit or lower limit values described above, and It may be a range defined by a combination of values of the examples or values between the examples.

〔raw materials〕
The raw materials used in the following examples and comparative examples are as follows.

[Component (A): Polypropylene resin]
<A1-1>
Propylene homopolymer (melting peak temperature: 165 ° C., propylene unit content: 100 mass%) / Novatech (registered trademark) PP FY6 manufactured by Nippon Polypro Co., Ltd.

<A2-1>
Propylene / ethylene random copolymer (melting peak temperature: 138 ° C., propylene unit content: 98% by mass) / Novatech (registered trademark) PP FW4B manufactured by Nippon Polypro Co., Ltd.

[Component (B): Ethylene / α-olefin copolymer rubber]
<B-1>
Ethylene / propylene / 5-ethylidene-2-norbornene copolymer (Mooney viscosity (ML _{1 + 4} , 125 ° C.): 61, density (JIS K7112): 0.87 g / cm ³ , MFR (JIS K7210, 230 ° C., 49 N) : 6 g / 10 minutes, ethylene unit content: 65.9 mass%, ethylidene norbornene content: 4.6 mass%) / Mitsui Chemicals, Inc. Mitsui Chemicals EPT3092PM

[Component (C): Cross-linking agent]
<C-1>
A mixture of 40% by mass of 2,5-dimethyl-2,5-di (t-butylperoxy) hexane and 60% by mass of calcium carbonate / Kayahexa AD40C manufactured by Kayaku Akzo Corporation
<C-2>
Mixture of 60% by weight divinylbenzene and 40% by weight ethylvinylbenzene / Divinylbenzene manufactured by Wako Pure Chemical Industries, Ltd.

[Component (D): 4-methyl-1-pentene / ethylene and / or α-olefin copolymer]
<D-1>
4-methyl-1-pentene / propylene copolymer (peak temperature when measured at a frequency of 1.6 Hz, temperature rising rate of 2 ° C./min: 30 ° C., loss tangent tan δ peak value: 2.7 / Mitsui Chemicals, Inc. EP1001
<D-1>
Styrene-butadiene copolymer (peak temperature when measured at a frequency of 1.6 Hz, strain 0.5%: 17.1 ° C., loss tangent tan δ peak value: 1.55) / S1605 manufactured by Asahi Kasei Chemicals Corporation
<D-2>
Alicyclic saturated hydrocarbon resin / ALCON P115 manufactured by Arakawa Chemical Industries, Ltd.

[Component (E)]
<E-1>
Softening agent for paraffinic rubber (kinematic viscosity at 40 ° C .: 95.5 cSt, pour point: −15 ° C., flash point: 272 ° C.) / Diana (registered trademark) process oil PW90 manufactured by Idemitsu Kosan Co., Ltd.

[Component (F): Antioxidant]
<F-1>
Phenolic antioxidant / Irganox (registered trademark) 1010 manufactured by BASF Japan

[Evaluation method]
The evaluation method of the thermoplastic elastomer composition in the following examples and comparative examples is as follows.

  In the following measurements (1) to (3), an in-line screw type injection molding machine (“IS130” manufactured by Toshiba Machine Co., Ltd.) is used under the conditions of an injection pressure of 50 MPa, a cylinder temperature of 220 ° C., and a mold temperature of 40 ° C. Using the sheet obtained by injection molding (width 120 mm, length 80 mm, thickness 2 mm), (4) from the sheet obtained by injection molding (width 120 mm, height 80 mm, thickness 1 mm), A test piece having a length of 40 mm and a width of 5 mm was used for punching measurement.

(1) Hardness duro A
In accordance with JIS K6253 (JIS-A), the value 15 seconds after the needle was pressed against the test piece was measured.
The hardness duro A is preferably in the range of 35 to 95, particularly 40 to 98.

(2) Compression set: Measured under the conditions of 70 ° C., 22 hours, and 25% compression in accordance with JIS K6262.
Evaluation was performed according to the following criteria from the measured value CS of compression set (sagging).
◎: CS less than 60% ○: CS 60% or more and less than 72% △: CS 72% or more and less than 83% ×: CS 83% or more

(3) Melt flow rate (MFR)
Based on JIS K7210, it measured by 230 degreeC and the measurement load 49N.
From the MFR value, the moldability was evaluated according to the following criteria.
○: MFR 20 g (/ 10 minutes) or more Δ: MFR 10 g (/ 10 minutes) or more and less than 20 g (/ 10 minutes) ×: MFR less than 10 g (/ 10 minutes)

(4) Loss tangent tan δ
The frequency dependence (5, 13, 20, 32 Hz) of the loss tangent tan δ was measured with a solid viscoelasticity measuring device RSA-III (manufactured by test equipment manufacturer: TA Instruments Japan). The measurement conditions at that time were a temperature of 23 ° C., a tensile mode, a heating rate of 2 ° C./min, and an amplitude (given displacement) strain of 0.1%.
From the loss tangent tan δ at 32 Hz, which is the highest in the measurement frequency range, the anti-vibration property was evaluated according to the following criteria.
A: Loss tangent tan δ 0.35 or more O: Loss tangent tan δ 0.25 or more and less than 0.35 Δ: Loss tangent tan δ 0.17 or more and less than 0.25 ×: Loss tangent tan δ less than 0.17

[Example / Comparative Example]
<Example 1>
(A1-1) 20 parts by mass, (A2-1) 6 parts by mass, (B-1) 34 parts by mass, (E-1) 30 parts by mass, (C-1) 0.4 parts by mass (2, 5 -Dimethyl-2,5-di (t-butylperoxy) hexane 40% by mass and a mixture of calcium carbonate 60% by mass), (C-2) 0.3 part by mass (divinylbenzene 60% by mass and ethyl vinylbenzene 40 (Mass% mixture) and (F-1) 0.1 part by mass were blended with a Henschel mixer for 1 minute to obtain a mixture. A total of 15 kg / h of this mixture is supplied to the first supply section of a co-directional twin-screw extruder having two raw material supply ports (“TEX30α” manufactured by Nippon Steel Works, L / D = 46, number of cylinder blocks: 13). At a speed of 110 ° C. to 180 ° C., and melt kneading is performed (this step is referred to as step (1)), and at the same time, provided in the middle of the extruder cylinder (the eighth block position from the upstream). From the second supply port, 10 parts by mass of (D-1) was supplied at a rate of 15 kg / h and kneaded (referred to as step (2)), and pelletized to produce a thermoplastic elastomer composition. The time for step (1) was 35 seconds and the time for step (2) was 25 seconds.
The evaluation results of the obtained thermoplastic elastomer composition are shown in Table-1.

<Examples 2 to 4 and Comparative Examples 1 to 3>
Except having changed the compounding composition as shown in Table 1, it implemented like Example 1 and obtained the pellet of the thermoplastic elastomer composition. About the obtained thermoplastic elastomer composition, the result of having implemented evaluation similar to Example 1 is shown in Table-1.

<Comparative Examples 4-8>
As shown in Table 1, it was carried out in the same manner as in Example 1 except that the component (D) added in step (2) was changed to be added in step (1), and the blending composition was changed. A pellet of a thermoplastic elastomer composition was obtained. About the obtained thermoplastic elastomer composition, the result of having implemented evaluation similar to Example 1 is shown in Table-1.

<Evaluation results>
As shown in Table 1, Examples 1 to 4 are excellent in evaluation of “compression set (sagging)”, “MFR (moldability)”, and “loss tangent tan δ (vibration resistance)”.

Comparative Examples 4 to 7 are examples in which (D-1) used in Examples 1 to 4 was changed to be added in Step (1) instead of Step (2), but Comparative Examples 5 to 7 were “ It is inferior in the evaluation of “compression set (sagging property)”. In Comparative Example 3, the evaluation of “loss tangent tan δ (vibration resistance)” is inferior.
Comparative Examples 1 to 3 are examples in which (D-1) of Examples 1 and 2 were changed to (d-1) or (d-2), but “MFR (formability)”, “loss” The evaluation of “tangent tan δ (vibration resistance)” is inferior.
Comparative Example 8 is an example in which (D-1) in Example 2 was changed to (d-1) and the addition step was changed from Step (2) to Step (1). ) ”And“ loss tangent tan δ (vibration resistance) ”are inferior.

  The thermoplastic elastomer composition of the present invention comprises an automobile part such as a skin, a weather strip, a ceiling material, an interior sheet, a bumper molding, a side molding, an air spoiler, an air duct hose, a sealing material; a water-stopping material, a joint material, a window frame, Civil engineering and building materials parts such as seal materials; Sports equipment such as golf club grips and tennis racket grips; Industrial parts such as hose tubes and gaskets; Home appliance parts such as hoses and packings; Medical containers and gaskets It can be used in a wide range of fields such as medical parts such as packing; food parts such as containers and packing; medical equipment parts; electric wires; The thermoplastic elastomer composition of the present invention is suitable as a sealing material for automobiles and a sealing material for building materials among those mentioned above, and is suitable as a sealing material for automobiles, particularly as a glass run channel for automobiles.

Claims (8)

A method for producing a thermoplastic elastomer composition by kneading at least the following components (A) to (C) and a component (D) as raw materials, wherein step (1); at least components (A) to (C) The step of kneading and the step (2): the step of mixing or reacting the component (D) after the step (1), and the component (D) with respect to 100 parts by mass of the total amount of the components (A) to (C) ) Of 0.1 to 100 parts by mass of the thermoplastic elastomer composition.
Component (A): Polypropylene resin component (B): Ethylene / α-olefin copolymer rubber component (C): Crosslinker component (D): 4-methyl-1-pentene / ethylene and / or α-olefin Copolymer   The method for producing a thermoplastic elastomer composition according to claim 1, wherein the component (B) is an ethylene / α-olefin / non-conjugated diene copolymer. The method for producing a thermoplastic elastomer composition according to claim 1 or 2, wherein the component (A) is a polypropylene resin containing the following component (A1) and component (A2).
Component (A1): Propylene polymer having a melting peak temperature of 157 ° C. or higher and 175 ° C. or lower Component (A2): Propylene random copolymer having a melting peak temperature of 100 ° C. or higher and lower than 157 ° C.   The ratio of a component (A) with respect to 100 mass parts of total amounts of a component (A) and a component (B) is 40-70 mass parts, and the ratio of a component (B) is 30-60 mass parts. The manufacturing method of the thermoplastic-elastomer composition of any one of these. The thermoplastic elastomer according to any one of claims 1 to 4, wherein the following component (E) is used as a raw material, and the amount used is 80 to 160 parts by mass with respect to 100 parts by mass of the component (B). A method for producing the composition.
Component (E): Hydrocarbon softener   The manufacturing method of the molded object using the thermoplastic elastomer composition manufactured by the manufacturing method of the thermoplastic elastomer composition of any one of Claim 1 thru | or 5.   The manufacturing method of the molded object of Claim 6 which is a manufacturing method of the member for motor vehicles.   The manufacturing method of the molded object of Claim 7 which is a manufacturing method of the glass run channel for motor vehicles.