JP6972573B2 - Method for Producing Thermoplastic Elastomer Composition - Google Patents

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 isolation and compression set (sagging property) of the molded product when molded, and also have good moldability. The thermoplastic elastomer composition and the molded product produced by the present invention are useful as a sealing material for automobiles, a sealing material for building materials, and the like.

The thermoplastic elastomer composition obtained by dynamically heat-treating a mixture containing a polypropylene-based resin and an ethylene / α-olefin copolymer in the presence of a cross-linking agent is vulcanized while exhibiting properties as a rubber-like soft material. It does not require a step and has the same molding processability as a thermoplastic resin. For this reason, such thermoplastic elastomer compositions are attracting attention from the viewpoints of rationalization of manufacturing processes and recyclability, and are widely used in the fields of automobile parts, household appliances, medical equipment parts, electric wires, miscellaneous goods, and the like. ..

However, in recent years, molded products obtained by molding a thermoplastic elastomer composition obtained by performing a dynamic heat treatment, which has been widely used in the past, have been particularly sought after as a sealing material for automobiles and a sealing material for building materials. There was a problem in terms of both compression set and vibration isolation.
That is, it is difficult to achieve both of these because the compression set is a performance that becomes good when the rubber elasticity is high, and is originally a performance that is contrary to the anti-vibration property that becomes good when the rubber viscosity is high.

Conventionally, as a technique for obtaining good compression set, an olefin-based thermoplastic elastomer obtained by dynamic heat treatment has a bending elasticity (JIS K7203) of 500 MPa or less and does not have a crosslinked structure. Patent Document 1 discloses a technique for mixing a thermoplastic elastomer component. Further, regarding the anti-vibration property, it is shown in Patent Document 2 that a high anti-vibration property is exhibited when a 4-methyl-1-pentene / α-olefin copolymer is contained.

Japanese Unexamined Patent Publication No. 2006-36813 Japanese Unexamined Patent Publication No. 2016-56954

As a result of detailed studies by the present inventor, the thermoplastic elastomer composition as described in Patent Document 1 has good compression set (sagging property), but does not have sufficient anti-vibration property. Do you get it. Further, although high vibration isolation can be obtained by the technique shown in Patent Document 2, good compression permanent is obtained because the combination with the ethylene / α-olefin copolymer rubber and the cross-linking technique is not sufficiently studied. It is presumed that no strain can be obtained, and there remains a problem in terms of achieving both vibration isolation and compression set.
As described above, the present situation is that a thermoplastic elastomer composition capable of optimizing materials and processes and simultaneously improving compression set, vibration isolation, and extrusion moldability has not yet been provided.

The present invention solves the above-mentioned problems of the prior art, and is capable of molding a molded product having excellent compression set (sagging property) and vibration-proof property, and is a thermoplastic elastomer composition having good extrusion moldability. The subject is to provide a manufacturing method.

As a result of repeated studies to solve the above problems, the present inventor solves the conventional problems by using a specific propylene resin and a rubber polymer in combination as raw materials and producing by a specific method. I found that it could be done.
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 components (D) as raw materials, wherein the step (1); at least the components (A) to (D) A step of kneading C) and a step (2): a step of mixing or reacting the component (D) after the step (1) are included, and the total amount of the components (A) to (C) is 100 parts by mass. A method for producing a thermoplastic elastomer composition having a ratio of the component (D) of 0.1 to 100 parts by mass.
Component (A): Polypropylene resin component (B): Ethylene / α-olefin copolymer rubber component (C): Cross-linking agent 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-based resin containing the following component (A1) and the component (A2).
Component (A1): Propylene-based polymer having a melting peak temperature of 157 ° C. or higher and 175 ° C. or lower Component (A2): Propylene-based random copolymer having a melting peak temperature of 100 ° C. or higher and lower than 157 ° C.

[4] The ratio of the component (A) to 100 parts by mass of the total amount of the component (A) and the component (B) is 40 to 70 parts by mass, and the ratio of the component (B) is 30 to 60 parts by mass. [1] ] To [3]. The method for producing a thermoplastic elastomer composition.

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

[6] A method for producing a molded product using a 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 manufacturing a molded product according to [6], which is a method for manufacturing a member for an automobile.

[8] The method for manufacturing a molded product according to [7], which is a method for manufacturing a glass run channel for an automobile.

According to the present invention, it is possible to produce a thermoplastic elastomer composition having excellent anti-vibration property and compression set (sagging property) of the molded product when molded and having good extrusion moldability (fluidity). By using the produced thermoplastic elastomer composition, it is possible to obtain a molded product having excellent anti-vibration property and compression set (sagging property) under good productivity.
The thermoplastic elastomer composition and the molded product produced by the present invention have excellent anti-vibration properties, compression set (sagging property) and extrusion moldability (fluidity), so that they are 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 carried out without departing from the gist of the present invention. In this specification, when a numerical value or a physical property value is inserted before and after using "~", it is used as including the values before and after that.

[Manufacturing method of 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 component (D) as raw materials, and is a step ( 1); At least a step of kneading the components (A) to (C) and a step (2): a step of mixing or reacting the component (D) after the step (1) are included, and the components (A) to 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): Cross-linking agent 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 product of the present invention. The manufactured molded product may be referred to as "molded product of the present invention".

[mechanism]
According to the method for producing a thermoplastic elastomer composition of the present invention, a thermoplastic elastomer composition having excellent anti-vibration property and compression set (sagging property) and good formability (fluidity) can be obtained. The effect of being able to manufacture is achieved.
Although the details of the reason why the method for producing the thermoplastic elastomer composition of the present invention exerts such an effect are not clear, the component (D) which is a vibration-proof component: 4-methyl-1-pentene ethylene and / or By adding the α-olefin copolymer as a step (2) (post-step), the component (B), which is a component that imparts compressive permanent strain, and the component that imparts vibration isolation, which could not be achieved by conventional batch addition, It is considered that the excellent effect of the uniform dispersion of each of the components (D) is exhibited. That is, by adding the component (D) in a subsequent step, the shearing force of the step (1) is mainly used for the dispersion of the component (B): ethylene / α-olefin copolymer rubber, and is crosslinked in this state. 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 shearing force of the step (2) is mainly used for the dispersion of the component (D), and the component (D) is well on the matrix side of the matrix domain structure. Since the dynamic heat treatment is completed in the dispersed state, a composition in which each of the component (B) and the component (D) is uniformly dispersed in the component (A) is finally obtained. Since the composition of the component (D) is closer to that of the component (A), the fluidity provided by the component (A) is not impaired, and this maintains the compression set (sagging property), and then the component (D). It is presumed that this is the mechanism by which a thermoplastic elastomer composition having excellent fluidity can be obtained while effectively exhibiting the anti-vibration property.
In the conventional batch addition method in which the component (B) and the component (D) are added at the same time, not only the shearing force is distributed to the dispersion of the component (B) and the component (D), but also the crosslinking reaction proceeds at the same time. It is considered that 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 (sag).

[Ingredient (A)]
The component (A) used in the thermoplastic elastomer composition of the present invention is preferably a polypropylene-based resin containing the following components (A1) and (A2), and if these are contained, other polypropylene-based resins may be used. It may be included. In the present invention, the "polypropylene resin" means a resin having 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-based polymer having a melting peak temperature of 157 ° C. or higher and 175 ° C. or lower Component (A2): Propylene-based random copolymer having a melting peak temperature of 100 ° C. or higher and lower than 157 ° C.

The melting peak temperature of the component (A1) and the component (A2) can be measured by the following method according to JIS K7121.
That is, using a differential scanning calorimeter (DSC6220 manufactured by SSI Nanotechnology), the following steps (1) to (3) are sequentially performed to measure the melting behavior of the polypropylene-based resin.
In each step, time is plotted on the horizontal axis and the amount of heat of melting is plotted on the vertical axis to obtain a melting curve, and the peak top of the peak observed in step (3) is defined as the melting peak temperature.
Step (1): The temperature of 5 mg of the sample is raised from room temperature to 100 ° C./min from 40 ° C. to 200 ° C., and the temperature is maintained for 3 minutes after the temperature rise is completed.
Step (2): The temperature is lowered from 200 ° C. to 40 ° C. at a rate of 10 ° C./min, and after the temperature reduction is completed, the temperature is maintained for 3 minutes.
Step (3): The temperature is raised from 40 ° C. to 200 ° C. at a rate of 10 ° C./min.

The propylene-based polymer of the component (A1) has a melting peak temperature of 157 ° C. or higher and 175 ° C. or lower. The 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 point of view, 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-based polymer of the component (A1), the content of the propylene unit is preferably 90% by mass or more, more preferably 98 to 100% by mass, based on the total amount of the monomer units constituting the component (A1). Is. It is preferable that the content of the propylene unit of the component (A1) is in the above range because it tends to be in the range of the above-mentioned melting peak temperature. The content of each structural unit of the component (A1) can be determined by infrared spectroscopy. The same applies to the component (A2) and the component (B) described later.

The component (A1) may be a propylene homopolymer, a random copolymer, or a block copolymer, but it is preferable that the component (A1) contains a propylene homopolymer.

The propylene-based polymer of the component (A1) may have a structural unit other than propylene, and may include, for example, one copolymerized with an α-olefin other than ethylene or propylene. In this case, the α-olefin unit that the component (A1) may contain includes, for example, 1-butene unit, 1-pentene unit, 1-hexene unit, 1-heptene unit, 1-octene unit, 1-. Nonen 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-eicosene unit, 3-methyl-1-butene unit, 3-methyl-1-pentene unit, 4-methyl-1-pentene unit, 2-ethyl-1-hexene unit, 2,2,4- Examples include the trimethyl-1-pentene unit. The component (A1) may contain only one of these kinds, or may contain two or more kinds. When the component (A1) contains a structural unit other than the propylene unit, preferred examples of the other structural unit include ethylene unit, 1-butene unit and the like.

The propylene-based random copolymer of the 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, preferably 125 ° C. or higher. On the other hand, the melting peak temperature of the component (A2) is less than 157 ° C. When the melting peak temperature of the component (A2) is at least the above lower limit value, it is preferable from the viewpoint of heat resistance, and when 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-based random copolymer of the component (A2), the content of the propylene unit is preferably 60 to 99% by mass, more preferably, with respect to the total amount of the monomer units constituting the component (A2). It is 80 to 98% by mass. It is preferable that the content of the propylene unit of the component (A2) is in the above range because it tends to be in the range of the above-mentioned melting peak temperature.

The propylene-based random copolymer of the component (A2) is a copolymer having a propylene unit and a constituent unit other than the propylene unit. Specific examples of the constituent unit other than the propylene unit include an ethylene unit and an α-olefin unit other than the propylene unit. Examples of the constituent units other than the propylene unit that the component (A2) may contain include ethylene unit, 1-butene unit, 1-pentene unit, 1-hexene unit, 1-heptene unit, 1-octene unit, and the like. 1-Nonen unit, 1-Desen unit, 1-Undecene unit, 1-Dodecene unit, 1-Tridecene unit, 1-Tetradecene unit, 1-Pentadecene unit, 1-Hexadecene unit, 1-Heptene unit, 1-Octene unit, 1-nonadecene unit, 1-eicosene unit, 3-methyl-1-butene unit, 3-methyl-1-pentene unit, 4-methyl-1-pentene unit, 2-ethyl-1-hexene unit, 2,2 Examples thereof include 4-trimethyl-1-pentene unit. The component (A2) may contain only one of these kinds, or may contain two or more kinds. Preferred constituent units other than the propylene unit contained in the component (A2) include ethylene units and 1-butene units.

As a method for producing the propylene-based polymer of the component (A1) and the component (A2), a known polymerization method using a known catalyst for olefin polymerization 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 and the like can be used, and two or more of these may be combined.

The component (A1) and the component (A2) can also be obtained as commercial products. Commercial products that fall under these categories include Prime Polymer Co., Ltd.'s Prim Polypro (registered trademark), Sumitomo Chemical Co., Ltd.'s Sumitomo Noblen (registered trademark), Sun Aroma's polypropylene block copolymer, Japan Polypropylene Corporation's Novatec (registered trademark) PP, and Lyondell Basell. Mobil®, ExxonMobil ExxonMobil PP, Formosa Plastics Formolene®, Borealis Bolealis PP, LG Chemical 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 ( There are registered trademarks) and the like, and they can be appropriately selected from these and used in combination.

Only one kind of component (A1) and one kind of component (A2) may be used, or two or more kinds 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, preferably 60 parts by mass or more, from the viewpoint of heat resistance, rigidity, dispersibility, etc., with respect to 100 parts by mass of the total amount of the component (A1) and the component (A2). It is more preferably parts by mass or more, and even more preferably 70 parts by mass or more. 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 preferably 90 parts by mass or less, more preferably 85 parts by mass or less, and further preferably 85 parts by mass or less.

The component (A) may contain a polypropylene-based resin other than the component (A1) and the component (A2), but in order to effectively obtain the effects of the component (A1) and the component (A2), the component (A) may be contained. The component (A) preferably contains 30 parts by mass or more, more preferably 40 parts by mass or more, and 50 to 100 parts by mass of the component (A1) and the component (A2) in 100 parts by mass. Is even more preferable.

[Component (B)]
The component (B) used in the thermoplastic elastomer composition of the present invention is an ethylene / α-olefin copolymer rubber (however, excluding those corresponding to the component (A)). The 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 / non-conjugated diene copolymer further containing a non-conjugated diene unit. be.

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, and 4 Examples thereof include −methyl-1-pentene unit, 1-octene unit and the like. The α-olefin unit used in the component (B) is preferably the number of carbon atoms having an intercarbon double bond at the terminal carbon atom such as 1-propylene unit, 1-butene unit, 1-hexene unit, 1-octene unit and the like. It is an α-olefin unit of 3 to 8. The component (B) may contain only one of these α-olefin units, or may contain two or more of them.

The non-conjugated diene unit contained in the component (B) includes 1,4-hexadiene, 1,6-octadene, 2-methyl-1,5-hexadiene, 6-methyl-1,5-heptadiene, and 7-methyl-. Units based on chain non-conjugated diene such as 1,6-octadene; cyclohexadien, dicyclopentadiene, methyltetrahydroinden, 5-vinylnorbornene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, Examples include units based on cyclic non-conjugated diene such as 5-isopropyridene-2-norbornene, 6-chloromethyl-5-isopropenyl-2-norbornene and the like. Of these, 5-ethylidene-2-norbornene units and dicyclopentadiene units are preferable.
The component (B) may contain only one of these non-conjugated diene units, or may contain two or more of them.

The content of the ethylene unit of the component (B) is preferably 30% by mass or more, more preferably 40% by mass or more, still more preferably, with respect to the total amount of the monomer units constituting the component (B). Is 50% by mass or more, preferably 90% by mass or less, and more preferably 80% by mass or less. It is preferable that the content of ethylene units is in the above range because it gives appropriate flexibility.

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, based on 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. When the content of the α-olefin unit is in the above range, it is preferable to give 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 the 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 at least 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 at least 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. It is preferable that the Mooney viscosity (ML _{1 + 4} , 125 ° C.) of the component (B) is in the above range from the viewpoint of moldability.

The density of the component (B) is ^{preferably 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. It is more preferably 0.890 g / cm ^{3 or less.} When the density of the component (B) is at least the above lower limit value, it is preferable from the viewpoint of processability, while when it is at least the above upper limit value, it is preferable from the viewpoint of flexibility. The density of component (B) can be measured based on JIS K7112.

The melt flow rate of the component (B) is not limited, but is usually less than 10 g / 10 minutes, preferably 9.0 g / 10 minutes or less, and more preferably 8.0 g / 10 minutes or less from the viewpoint of strength. Yes, more preferably 7.0 g / 10 minutes or less. The melt flow rate of the component (B) is usually 0.01 g / 10 minutes or more, preferably 0.05 g / 10 minutes or more, and more preferably 0.10 g / 10 minutes from the viewpoint of fluidity. That is all. The melt flow rate (MFR) of the component (B) is measured according to JIS K7210 under the conditions of a measurement temperature of 230 ° C. and a measurement load of 49N.

As a method for producing the component (B), a known polymerization method using a known catalyst for olefin polymerization 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 Ziegler-Natta-based catalyst, a complex-based catalyst such as a metallocene-based complex or a non-metallocene-based complex can be mentioned.

A commercially available product can also be used as the component (B). For example, JSR EPT manufactured by JSR, Mitsui EPT manufactured by Mitsui Chemicals, Esplen (registered trademark) manufactured by Sumitomo Chemical, Keltan (registered trademark) manufactured by LANXESS, Nordel (registered trademark) manufactured by Dow, Vistalon (registered trademark) manufactured by ExonMobile. ) Etc. can be selected and used.

As the component (B), only one kind may be used, or two or more kinds 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 lower limit of 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) 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.
Regarding the content of the component (B), the lower limit is usually 30 parts by mass or more and 32 parts by mass or more from the viewpoint of moldability with respect to 100 parts by mass of the total amount of the component (A) and the component (B). It is preferably 34 parts by mass or more, and more 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 cross-linking at least a part of the component (B) by performing a dynamic heat treatment in the presence of the component (C): a cross-linking agent. By this dynamic heat treatment, the thermoplastic elastomer composition of the present invention has good rubber elasticity.

As the cross-linking agent, an organic peroxide, a phenol resin, other cross-linking aids and the like can be used, and these cross-linking agents may be used alone or in combination of two or more.

As the organic peroxide that can be used as a cross-linking agent, either an aromatic organic peroxide or an aliphatic organic peroxide can be used. Specifically, di-t-butyl peroxide, t-butyl cumyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl. -2,5-di (t-butylperoxy) hexin-3,1,3-bis (t-butylperoxyisopropyl) benzene, 1,1-di (t-butylperoxy) -3,3,5 -Dialkyl peroxides such as trimethylcyclohexane; t-butylperoxybenzoate, t-butylperoxyisopropylcarbonate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, 2,5-dimethyl-2 , 5-Di (benzoylperoxy) Peroxyesters such as hex-3; Hydroper such as acetyl peroxide, lauroyl peroxide, benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, etc. Examples include oxides. 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 cross-linking agent include alkylphenol formaldehyde and alkylphenol norformaldehyde bromide. These phenol resins may be used alone or in combination of two or more.

Examples of cross-linking aids other than organic peroxides and phenolic resins include peroxide aids such as sulfur, p-quinonedioxime, p-dinitrosobenzene, and 1,3-diphenylguanidine; stannous chloride. -Crossing aids for phenolic resins such as anhydrides, 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, trimethyl propantri (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 such that the cross-linking reaction proceeds sufficiently 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 needed. From the viewpoint of making the mixture, it is preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, and further preferably 0.3 parts by mass or more. On the other hand, the amount of the component (C) used controls the crosslinking reaction 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 needed. From this point of view, it is preferably 10 parts by mass or less, more preferably 8 parts by mass or less, further 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 a 4-methyl-1-pentene-ethylene and / or α-olefin copolymer, which is a component that imparts vibration isolation to the thermoplastic elastomer. ..

The component (D) used in the present invention preferably satisfies one or more of the requirements (x) and the following requirements (a) to (i).
Examples of the method for producing the press sheet of the component (D) for measuring the following physical properties include the following methods.

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

Hereinafter, each suitable requirement of the component (D) used in the present invention will be described.

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

Those having a peak of the tangent tan δ of −10 ° C. or higher are relatively close to the temperature normally expected to be used in automobiles, and are considered to be preferable from the viewpoint of imparting vibration isolation. However, if this temperature is excessively high, sufficient loss tangent tan δ cannot be obtained at the operating temperature assumed in ordinary automobiles, and it is considered that vibration isolation is insufficient. The peak of this loss tangent tan δ is particularly preferably present at −20 to 60 ° C., more preferably at −10 to 50 ° C., and even more preferably at 0 to 40 ° C.
Hereinafter, the temperature at which the peak of the 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 even more preferable. When the peak value of the loss tangent tan δ is in the above range, it becomes excellent in flexibility, lightness and vibration isolation, which is preferable.

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

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

The proportion of 4-methyl-1-pentene unit of component (D) is preferably 20 to 75 mol%, more preferably 20 to 65 mol%, still more preferably 20 to 33 mol%, and particularly. It is preferably 20 to 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 4-methyl-1-pentene unit is within the above range, flexibility, light weight, and vibration isolation are good.

Examples of the α-olefin in the α-olefin unit include propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1 -A linear α-olefin, 3-methyl-1-butene, 3-methyl having 3 to 20 carbon atoms, preferably 3 to 15 carbon atoms, more preferably 3 to 10 carbon atoms such as octadecene and 1-ehexene. -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. The component (D) may contain only one of the ethylene unit and these α-olefin units, or may contain two or more of them. Among these, as the ethylene and / or α-olefin unit, ethylene unit, propylene unit, 1-butene unit, 1-pentene unit, 1-hexene unit and 1-octene unit are preferable, and propylene unit is particularly preferable.

If the amount of the component (D) is small enough not to impair the object of the present invention (for example, 10 mol% or less with respect to 100 mol% of all the monomer units constituting the component (D)), 4-. It may contain other monomeric units other than the methyl-1-pentene unit, the ethylene unit and the α-olefin unit. Other monomer units include one or more such as 5-methyl-2-norbornene unit, tetracyclododecene unit, 5-vinyl-2-norbornene unit, 5-ethylidene-2-norbornene unit. Can be mentioned.

Requirement (b): The ultimate 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 extreme 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 a Ubbelohde viscometer. Next, 5 mL of decalin is further added to this decalin solution to dilute it, and the same specific viscosity measurement is performed. Based on the measurement result of repeating this dilution operation and viscosity measurement twice, the ηsp / C value when the concentration (C) is extrapolated to zero is defined as the ultimate viscosity (η).

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

As described in JP-A-2016-56954, the ultimate viscosity [η] of the component (D) can be freely obtained from a low molecular weight body to a high molecular weight body by using hydrogen in combination during polymerization. Can be adjusted with.

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

<Measurement method of molecular weight (Mw, Mn) / molecular weight distribution (Mw / Mn)>
Liquid chromatograph: Using ALC / GPC 150-C plus type manufactured by Waters (integrated type with a differential refractometer detector), two GMH6-HT and two GMH6-HTL manufactured by Tosoh Corporation are connected in series as columns. Using o-dichlorobenzene as a mobile phase medium, the measurement is performed at a flow rate of 1.0 ml / min and 140 ° C.
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 the 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. Further, it is disadvantageous in exhibiting the mechanical properties and moldability of the copolymer, and there is a possibility that the copolymer may become sticky and cause problems during molding.
The Mw / Mn of the component (D) is preferably 1.2 to 3.0, more preferably 1.5 to 2.5.

By using the catalyst listed in the production method described in JP-A-2016-56954, the component (D) that satisfies the requirement (c) within the range of the ultimate viscosity [η] shown in the above requirement (b). Can be obtained.

The weight average molecular weight (Mw) of the component (D) is preferably 500 to 10,000,000, more preferably 1,000 to 5,000,000, and even more preferably 1,000 to 2,500. It is 000.

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

<Density measurement method>
Calculated from the mass of a sample measured in water and air using an ALFA MIRAGE electronic hydrometer MD-300S according to ASTM D 1505 (underwater substitution method).

The component (D) having a density in the above range is advantageous for producing a lightweight molded product.
The density of the component (D) is preferably 870 to 810 kg / m ³ , more preferably 860 to 820 kg / m ³ , and even more preferably 855 to 830 kg / m ³ .

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

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

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

When the tan δ peak value of the component (D) is in the above range, it becomes excellent in flexibility, lightness and vibration isolation, which is preferable. The tan δ peak value of the 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 becomes maximum is preferably −10 to 40 ° C., more preferably 0 to 40 ° C., and even more preferably 5 to 40 ° C.

The tanδ peak value of the component (D) can be controlled by the copolymerization composition ratio of 4-methyl-1-pentene ethylene and / or the 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 above method for measuring dynamic viscoelasticity, the value of the loss tangent tan δ measured at 20 ° C. is 0.5 to 5.0.
When the loss tangent tan δ of the component (D) measured at 20 ° C. is in the above range, it is preferable because it is excellent in flexibility, light weight and vibration isolation. The loss tangent tan δ of the component (D) measured at 20 ° C. is preferably 0.5 to 4.0, more preferably 0.5 to 3.5.

The loss tangent tan δ of the component (D) measured at 20 ° C. can be controlled by the copolymerization composition of 4-methyl-1-pentene ethylene and / or the α-olefin copolymer, for example, 4-. 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 amount of extraction with methyl acetate measured by the following method is 0 to 1.5% by mass.

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

The amount of methyl acetate extracted is an index of stickiness during molding, and if this value is large, the obtained polymer has a large composition distribution and contains a low molecular weight polymer, which causes problems during molding. When the amount of methyl acetate extracted is within the above range, there is no problem due to stickiness during molding.
For example, by using the catalyst described in JP-A-2016-56954, a component (D) having a low stereoregularity and a small amount of an atactic component can be synthesized, and a non-sticky molded product 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 even more preferably 0 to 0.5% by mass.

Requirement (h): The elastic modulus at 40 ° C. defined by the following equation is 0 to 25%.
Repulsive modulus (%) = L (mm) / 460 × 100
L in the above formula is the rebound of a 16.310 g rigid sphere dropped from a height of 460 mm at 40 ° C. on a 6 mm thick press sheet prepared from the component (D) according to JIS K6400. The height.

When the elastic modulus of the component (D) is in the above range, it is preferable from the viewpoint of vibration isolation when the molded product is formed. The elastic modulus of the component (D) is preferably 0 to 24%, more preferably 0 to 23%.

The elastic modulus of the component (D) can be controlled by the copolymerization composition of 4-methyl-1-pentene-ethylene and / or the α-olefin copolymer, for example, in units of 4-methyl-1-pentene. By setting the content to 20 to 72 mol%, the repulsive modulus can be within the above range.

Requirement (i): The value of Shore A hardness (based on JIS K6253, measured in the state of a press sheet with a thickness of 3 mm) 15 seconds after the start of needle contact measured by the following measuring method is 5 to 90. ..

<Measurement method of Shore A hardness>
Using a press sheet with a thickness of 3 mm as a measurement sample, the scales are read immediately after the start of needle contact and 15 seconds after the start of needle contact. Further, the change ΔHS of the value of Shore A hardness defined by the following equation is obtained as follows.
ΔHS = (Shore hardness value immediately after the start of needle contact-Shore hardness value 15 seconds after the start of needle contact).

When the shore A hardness of the component (D) is in the above range, it is preferable from the viewpoint of hardness adjustment when forming a molded product. The shore A hardness of the component (D) is more preferably 10 to 80. It is more preferably 15 to 75, and particularly preferably 20 to 70.

The value of Shore A hardness of the component (D) can be controlled by the copolymerization composition of 4-methyl-1-pentene ethylene and / or α-olefin copolymer, for example, 4-methyl-1-pentene. By setting the content of the unit to 20 to 75 mol%, the Shore A hardness can be in the above range.

The component (D) suitable for the present invention that satisfies the above requirements (a) to (i) and (x) is produced, for example, by the method described in JP-A-2016-56954.

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

In the present invention, the amount of the component (D) used is 0.1 to 100 parts by mass with respect to a total of 100 parts by mass of the components (A) to (C). When the component (D) is at least the lower limit of the above range, good anti-vibration properties can be obtained, and when it is at least the upper limit, compressive permanent strain (sagging property), mechanical properties, and moldability are good. Become. The component (D) is preferably used in an amount of 10 parts by mass or more, more preferably 11 parts by mass or more, and further preferably 12 parts by mass or more based on 100 parts by mass of the total of the components (A) to (C). .. Further, the component (D) is preferably used in an amount of 95 parts by mass or less, more preferably 94 parts by mass or less, and 93 parts by mass or less with respect to 100 parts by mass in total of the components (A) to (C). More preferred.

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

Examples of the hydrocarbon-based rubber softener of the component (E) include mineral oil-based softeners, synthetic resin-based softeners, and the like, but mineral oil-based softeners are preferable from the viewpoint of compatibility with other components. Mineral oil-based softeners are generally a mixture of aromatic hydrocarbons, naphthenic hydrocarbons and paraffinic hydrocarbons, and 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. Among these, in the present invention, it is preferable to use paraffin oil. The hydrocarbon-based rubber softener may be used alone or in any combination and ratio of two or more.

The kinematic viscosity of the hydrocarbon softener for the component (E) at 40 ° C. 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. be. The flash point (COC method) of the hydrocarbon softener is preferably 200 ° C. or higher, more preferably 250 ° C. or higher.

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

When the component (E) is used in the production of the thermoplastic elastomer composition of the present invention, the lower limit of the amount of the component (E) used is preferably 80 parts by mass with respect to 100 parts by mass of the component (B) from the viewpoint of flexibility. It is more than a part, more preferably 81 parts by mass or more, and further preferably 82 parts by mass or more. Further, the upper limit of the amount of the component (E) used is usually 160 parts by mass or less, preferably 159 parts by mass or less, more preferably 159 parts by mass or less, with respect to 100 parts by mass of the 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 other than the components (A) to (E) can be used as raw materials as needed, as long as the effects of the present invention are not impaired.

Examples of other components include thermoplastic resins other than the components (A), (B) and (D), resins such as elastomers, antioxidants, fillers, heat stabilizers, light stabilizers, and ultraviolet absorption. Agents, neutralizers, lubricants, antifogging agents, antiblocking agents, slip agents, dispersants, colorants, flame retardants, antistatic agents, conductivity-imparting agents, metal deactivating agents, molecular weight modifiers, antibacterial agents , Various additives such as antifungal materials and fluorescent whitening agents can be mentioned. These can be used alone or in combination.

Examples of the thermoplastic resin other than the component (A), the component (B) and the component (D) include a polyphenylene ether-based resin; a polyamide-based resin such as nylon 6 and nylon 66; and a polyester-based resin such as polyethylene terephthalate and polybutylene terephthalate. Resin: Polyoxymethylene-based resin such as polyoxymethylene homopolymer and polyoxymethylene copolymer; Polymethylmethacrylate-based resin, polyolefin resin (corresponding to component (A), component (B) and component (D)) ), Etc. can be mentioned. Examples of the elastomer other than the component (A), the component (B) and the component (D) include styrene-based elastomers (excluding those corresponding to the component (E)); polyester-based elastomers; polybutadiene and the like. be able to.

Examples of the antioxidant include a phenol-based antioxidant, a sulfide-based antioxidant, a thioether-based antioxidant, and the like. When an antioxidant is used, 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 needed. It is used in the range of ~ 3.0 parts by mass.

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

[Manufacturing method of 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 dynamically heat-treating the product in the presence of the component (C) which is a cross-linking agent. In the present invention, the method for producing such a thermoplastic elastomer composition is described in the following steps (1) and ( Manufactured through 2).
Step (1); Step of kneading at least the components (A) to (C) Step (2): Step of mixing or reacting the component (D) after the step (1) In the above step (2), the component (D). ) Is used in the above-mentioned preferable 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 state or a semi-melted state in the presence of a cross-linking agent. This dynamic heat treatment is preferably performed by melt kneading, and as the mixing and kneading device for that purpose, for example, a non-open type Banbury mixer, a mixing roll, a kneader, a twin-screw extruder and the like are used. Among these, it is preferable to use a twin-screw extruder. A preferred embodiment of the manufacturing method using this twin-screw extruder is to supply each component to a raw material supply port (hopper) of a twin-screw extruder having a plurality of raw material supply ports to perform dynamic heat treatment.

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

When the thermoplastic elastomer composition of the present invention is produced by subjecting it to dynamic heat treatment with a twin-screw extruder, the barrel radius (R (mm)) and screw rotation speed (N (rpm)) of the twin-screw extruder are used. It is preferable to extrude while maintaining the relationship of the following formula (1), and it is more preferable to extrude while maintaining the relationship of the following formula (2) between the discharge amount (Q (kg / hour)).
2.6 <NQ / R ³ <22.6 (1)
3.0 <NQ / R ³ <20.0 (2)

Thermoplasticity means that the relationship between the barrel radius (R (mm)), screw rotation speed (N (rpm)) and discharge amount (Q (kg / hour)) of the twin-screw extruder is larger than the above lower limit. It is preferable for efficiently producing the elastomer composition. On the other hand, it is preferable that the relationship is smaller than the upper limit value because heat generation due to shearing is suppressed and foreign matter that causes poor appearance is less likely to be generated.

In the present invention, in such a dynamic heat treatment, at least the components (A) to (C) are kneaded (step (1)), and then the component (D) is added to the obtained kneaded product. And mix or react (step (2)). In order to more reliably obtain the effect of the present invention by performing the mixing in two steps in this way, 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 to make this time excessively long in terms of production efficiency, it is preferably 50 seconds or less.

For example, when performing dynamic heat treatment using a twin-screw extruder, a second raw material supply port is provided (or a second raw material supply port) in the middle of the extruder cylinder in addition to the first raw material supply port upstream of the twin-screw extruder. (Using an extruder having a supply port), 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 number of cylinder blocks of the second raw material supply port is about 1/3 to 2/3 of the total number of cylinder blocks (for example, 13) from the upstream side with respect to the total number of cylinder blocks of the extruder (for example, 13). It is preferable to provide the component (D) at a position and supply the component (D) from here.
The kneading time after the addition of the component (D), that is, the time of the step (2) is preferably about 10 to 30 seconds.

When the component (E) and other additive components are used in addition to the components (A) to (D), these are kneaded together with the components (A) to (C) in the step (1), and in the step (2). , It is preferable to add only the component (D) afterwards.

[Physical characteristics 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 minutes or more measured at a measurement temperature of 230 ° C. and a measurement load of 49 N by a method conforming to JIS K7210 standards. It is preferable, more preferably 15 g / 10 minutes or more, and further preferably 20 g / 10 minutes or more. Further, from the viewpoint of moldability, the melt flow rate (MFR) is preferably 120 g / 10 minutes or less, more preferably 110 g / 10 minutes or less, and further preferably 100 g / 10 minutes or less. ..

Further, for the molded product obtained by molding the thermoplastic elastomer composition of the present invention, the hardness Duro A measured in accordance with JIS K6253 (JIS-A) is preferably in the range of 35 to 95, preferably 40 to 95. It is more preferably in the range of 90.

[Molded body / use]
The thermoplastic elastomer composition of the present invention can be made into a molded product by various molding methods usually used for the thermoplastic elastomer composition, for example, injection molding, extrusion molding, hollow molding, compression molding and the like. Of these, injection molding and extrusion molding are 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. In particular, the thermoplastic elastomer composition of the present invention is excellent in extrusion moldability and reduces the generation of rheumatism and foreign matter during molding, and is therefore suitable for extrusion molding, particularly irregular shape extrusion molding.

The molded body made of the thermoplastic elastomer composition of the present invention is 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, and a sealing material; Civil engineering and building material parts such as window frames and sealing materials; Sporting goods such as golf club grips and tennis racket grips; Industrial parts such as hose tubes and gaskets; Home appliances 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; miscellaneous goods and the like.
Among those listed above, the molded product 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.

Hereinafter, the content 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 ranges are the above-mentioned upper limit or lower limit values and the following. It may be in the range specified by the value of Examples or the combination with the values of 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% by mass) / Novatec (registered trademark) PP FY6 manufactured by Japan Polypropylene Corporation

<A2-1>
Propylene / ethylene random copolymer (melting peak temperature: 138 ° C., propylene unit content: 98% by mass) / Novatec (registered trademark) PP FW4B manufactured by Japan Polypropylene Corporation

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

[Component (C): Crosslinking agent]
<C-1>
Mixture of 2,5-dimethyl-2,5-di (t-butylperoxy) hexane 40% by mass and calcium carbonate 60% by mass / Kayaku Akzo Corporation Kayahexa AD40C
<C-2>
Mixture of 60% by mass of divinylbenzene and 40% by mass of 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 measured at a frequency of 1.6 Hz, heating rate of 2 ° C / min: 30 ° C, loss tangent tan δ peak value: 2.7 / Mitsui Chemicals, Inc. Made by EP1001
<D-1>
Styrene-butadiene copolymer (peak temperature measured at frequency 1.6 Hz, strain 0.5%: 17.1 ° C, loss tangent tan δ peak value: 1.55) / Asahi Kasei Chemicals Co., Ltd. S1605
<D-2>
Alicyclic Saturated Hydrocarbon Resin / Arakawa Chemical Industry Co., Ltd. Alcon P115

[Ingredient (E)]
<E-1>
Paraffin-based rubber softener (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 / BASF Japan, Inc. Ilganox (registered trademark) 1010

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

For the following measurements (1) to (3), an in-line screw type injection molding machine (“IS130” manufactured by Toshiba Machinery 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. The sheet obtained by injection molding (width 120 mm, length 80 mm, wall thickness 2 mm) was used, and for (4), the sheet obtained by injection molding (width 120 mm, length 80 mm, wall thickness 1 mm) was used. A test piece having a length of 40 mm and a width of 5 mm was used for punching measurement.

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

(2) Compressive permanent strain: Measured under the conditions of 70 ° C., 22 hours, and 25% compression according to JIS K6262.
It was evaluated according to the following criteria from the measured value CS of the compression set.
⊚: 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)
It was measured at 230 ° C. and a measured load of 49 N according to JIS K7210.
From the value of MFR, the formability 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 10 g (/ 10 minutes) or less

(4) Loss tangent tanδ
The frequency dependence (5, 13, 20, 32 Hz) of the loss tangent tan δ was measured with a solid viscoelasticity measuring device RSA-III (testing machine manufacturer: manufactured by TA Instrument Japan). The measurement conditions at that time were a temperature of 23 ° C., a tension mode, a temperature rise rate of 2 ° C./min, and an amplitude (displacement amount) strain of 0.1%.
The anti-vibration property was evaluated according to the following criteria from the loss tangent tan δ at 32 Hz, which is the highest in the measurement frequency range.
⊚: Loss tangent tanδ 0.35 or more ○: Loss tangent tanδ 0.25 or more and less than 0.35 Δ: Loss tangent tanδ 0.17 or more and less than 0.25 ×: Loss tangent tanδ 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 calcium carbonate 60% by mass), (C-2) 0.3 parts by mass (divinylbenzene 60% by mass and ethylvinylbenzene 40) (F-1) 0.1 part by mass was blended with a Henchel mixer for 1 minute to obtain a mixture. A total of 15 kg / h of this mixture is sent to the first supply section of a isodirectional twin-screw extruder (“TEX30α” manufactured by Japan Steel Works, L / D = 46, number of cylinder blocks: 13) having two raw material supply ports. It is charged at the speed of, and the temperature is raised in the range of 110 to 180 ° C. to perform melt kneading (this is referred to as step (1)), and at the same time, it is provided in the middle of the extruder cylinder (8th block position from the upstream). 10 parts by mass of (D-1) was supplied at a rate of 15 kg / h from the second supply port and kneaded (referred to as step (2)), and pelletized to produce a thermoplastic elastomer composition. The time of the step (1) was 35 seconds, and the time of the 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>
The same procedure as in Example 1 was carried out except that the compounding composition was changed as shown in Table 1, to obtain pellets of the thermoplastic elastomer composition. Table 1 shows the results of the same evaluations as in Example 1 for the obtained thermoplastic elastomer composition.

<Comparative Examples 4 to 8>
As shown in Table 1, the same procedure as in Example 1 was carried out except that the component (D) added in the step (2) was changed to be added in the step (1) and the compounding composition was changed. Pellets of the thermoplastic elastomer composition were obtained. Table 1 shows the results of the same evaluations as in Example 1 for the obtained thermoplastic elastomer composition.

<Evaluation result>
As shown in Table 1, Examples 1 to 4 are excellent in the evaluation of "compressive permanent strain (sagging property)", "MFR (moldability)", and "loss tangent tan δ (vibration-proof property)".

Comparative Examples 4 to 7 are examples in which (D-1) used in Examples 1 to 4 is changed to be added in step (1) instead of step (2), but Comparative Examples 5 to 7 are ". It is inferior in the evaluation of "compression permanent strain (sagging property)". Further, in Comparative Example 3, the evaluation of "loss tangent tan δ (vibration-proof property)" is inferior.
Further, Comparative Examples 1 to 3 are examples in which (D-1) of Examples 1 and 2 is changed to (d-1) or (d-2), but "MFR (formability)" and "loss". The evaluation of "tangent tan δ (vibration-proof property)" is inferior.
Comparative Example 8 is an example in which (D-1) of Example 2 is changed to (d-1) and the addition step thereof is changed from the step (2) to the step (1). The evaluations of "gender)" and "loss tangent tanδ (vibration-proofing property)" are inferior.

The thermoplastic elastomer composition of the present invention is used for automobile parts such as skins, weather strips, ceiling materials, interior sheets, bumper moldings, side moldings, air spoilers, air duct hoses, sealing materials; Civil and building materials such as sealing materials; Sporting goods such as grips for golf clubs and grips for tennis rackets; Industrial parts such as hoses tubes and gaskets; Home appliances parts such as hoses and packings; Medical containers, gaskets, etc. It can be used in a wide range of fields such as medical parts such as packings; food parts such as containers and packings; medical equipment parts; electric wires; miscellaneous goods and the like. Among those listed above, 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.

Claims (8)

A method for producing a thermoplastic elastomer composition by kneading at least the following components (A) to (C) and components (D) as raw materials, wherein the step (1); at least the components (A) to (C) are used. The step of kneading and the step (2): the step of mixing or reacting the component (D) after the step (1) are included, and the component (D) with respect to 100 parts by mass of the total amount of the components (A) to (C). ) Is 0.1 to 100 parts by mass, a method for producing a thermoplastic elastomer composition.
Component (A): Polypropylene resin component (A1) containing the following component (A1) and component (A2): Propylene copolymer component (A2) having a melting peak temperature of 157 ° C. or higher and 175 ° C. or lower: melting peak temperature Propylene / ethylene random copolymer component (B): ethylene / α-olefin copolymer rubber component (C): cross-linking agent component (D): 4-methyl-1-pentene. Propylene 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. Claim 1 or 2 that the content of the component (A1) in the component (A) is 50 parts by mass or more and 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). The method for producing a thermoplastic elastomer composition according to. Claims 1 to 3 in which the ratio of the component (A) to 100 parts by mass of the total amount of the component (A) and the component (B) is 40 to 70 parts by mass, and the ratio of the component (B) is 30 to 60 parts by mass. The method for producing a thermoplastic elastomer composition according to any one of the above items. 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 thereof is 80 to 160 parts by mass with respect to 100 parts by mass of the component (B). Method for producing the composition.
Component (E): Hydrocarbon-based rubber softener A method for producing a molded product using a thermoplastic elastomer composition produced by the method for producing a thermoplastic elastomer composition according to any one of claims 1 to 5. The method for manufacturing a molded product according to claim 6, which is a method for manufacturing a member for an automobile. The method for manufacturing a molded product according to claim 7, which is a method for manufacturing a glass run channel for an automobile.