JP2022068980A - Molded body composed of polymer composition - Google Patents

Abstract

To provide a molded body excellent in wear resistance and oil permeation preventability.SOLUTION: A molded body of the present invention contains a polymer composition including an α-olefin nonconjugated polyene copolymer (A) whose ethylene-carbon number is 3-20, crystalline polyolefin (B), and silylated polyolefin (C).SELECTED DRAWING: None

Description

The present invention relates to a molded product made of a polymer composition.

Thermoplastic elastomers are used for parts or parts that require wear resistance and are used in automobile parts, industrial machine parts, electrical / electronic parts, building materials, and the like. An example of such an automobile component is a glass run channel. The glass run channel is a guide member provided between the window glass and the window frame, and is a tight (liquidtight) sealing operation between the window glass and the window frame while facilitating the operation of raising and closing the window glass. Gender is required.

In addition, thermoplastic elastomers are excellent in oil resistance and shape recovery at high temperatures, and are used in applications that require oil resistance, especially for seal members, hoses, and boots among automobile parts.

Conventional techniques for resin materials used for such parts or parts include, for example, the following.

Patent Document 1 (Japanese Unexamined Patent Publication No. 2001-232723) discloses as an object to provide a molded product having excellent appearance, wear resistance, durability, sliding characteristics, mechanical strength and rubber elasticity. .. In order to solve such a problem, in Patent Document 1, an organopolysiloxane (C) and a fluorine-based layer are used with respect to a substrate layer made of a specific olefin-based thermoplastic elastomer (A) and an olefin-based thermoplastic elastomer (B). We have adopted a laminate in which a skin layer made of an olefin-based thermoplastic elastomer composition (X) containing at least one selected from the group consisting of a polymer (D) and an antistatic agent (E) is laminated. ..

Patent Document 2 (Japanese Unexamined Patent Publication No. 54-99156) discloses as an object to provide a composition exhibiting excellent mechanical properties, oil resistance and coatability. In order to solve such a problem, Patent Document 2 uses a thermoplastic elastomer composed of a blend of a thermoplastic crystalline polyolefin resin and vulcanized EPDM rubber, and the rubber is vulcanized with a phenolic vulcanizing agent. The compact is disclosed.

Japanese Unexamined Patent Publication No. 2001-232723 Japanese Unexamined Patent Publication No. 54-99156

However, according to the studies by the present inventors, it has been found that there is room for improvement in wear resistance in the molded product described in the prior art document.

Further, the conventional thermoplastic elastomer is improved in the property of preventing the oil from permeating to the other, that is, the oil permeation prevention property, in the application where the oil comes into contact with one of them in the state of liquid, gas or mist, for example. It turns out that there is room.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a molded product having excellent wear resistance and oil permeation prevention property.

The present inventors have diligently studied in order to provide a molded product having excellent wear resistance and excellent oil permeation prevention property, and found that the conventional molded product has wear resistance of organopolysiloxane, fluorine-based polymer, etc. It was clarified that the phenomenon that the component added for improvement oozes out in liquid form (bleed) or the phenomenon of crystallization in solid form (bloom) occurs.
In addition, it was clarified that if the amount of these components was reduced in order to prevent the occurrence of bleed and bloom, the wear resistance was deteriorated this time.

Therefore, the present inventors have diligently studied in order to provide a molded body having excellent wear resistance and oil permeation prevention property. As a result, they have found that by using a specific resin and a specific silylated polyolefin, a molded product having excellent wear resistance and oil permeation prevention property can be obtained while preventing the generation of bleeding and bloom, and the present invention has been made. Was completed.

（上記式（1）において、Ａ^１、Ａ^２およびＡ^３は各々独立に、ポリオレフィン鎖または炭素数１～２０の炭化水素基である。Ｒは炭素数１～２０の炭化水素基である。各Ｒは同一でも異なっていてもよい。ｍは１～１０，０００の整数である。Ａ^３が複数存在する場合、各Ａ^３は同一でも異なっていてもよい。ただし、Ａ^１、Ａ^２、Ａ^３のうち、少なくとも１つはポリオレフィン鎖を表す。）
［３］
上記［１］、または上記［２］に記載の成形体において、
上記共重合体（Ａ）由来の成分が架橋されていることを特徴とする成形体。
［４］
上記［３］に記載の成形体において、
架橋が動的熱処理によるものであることを特徴とする成形体。
［５］
上記［１］乃至［４］のいずれか一つに記載の成形体において、
建築用シール材である成形体。
［６］
上記［１］乃至［４］のいずれか一つに記載の成形体において、
排水管用継手である成形体。
［７］
上記［１］乃至［４］のいずれか一つに記載の成形体において、
グリップ材である成形体。
［８］
上記［１］乃至［４］のいずれか一つに記載の成形体において、
ドレンホースである成形体。 The gist of the present invention is as follows.
[1]
Ethylene, α-olefin with 3 to 20 carbon atoms, non-conjugated polyene copolymer (A), and
Crystalline polyolefin (B) and
A molded product comprising a polymer composition containing a silylated polyolefin (C).
[2]
In the molded product according to the above [1],
A molded product, wherein the silylated polyolefin (C) contains a silylated polyolefin represented by the following formula (1).

(In the above formula (1), A ¹ , A ² and A ³ are independently polyolefin chains or hydrocarbon groups having 1 to 20 carbon atoms. R is a hydrocarbon group having 1 to 20 carbon atoms. Each R may be the same or different. M is an integer of 1 to 10,000. When a plurality of A ^3s exist, each A ³ may be the same or different. However, A ¹ and A ² may be different. , At ^least one of A3 represents a polyolefin chain.)
[3]
In the molded product according to the above [1] or the above [2].
A molded product characterized in that the components derived from the copolymer (A) are crosslinked.
[4]
In the molded product according to the above [3],
A molded product characterized in that the cross-linking is due to dynamic heat treatment.
[5]
In the molded product according to any one of the above [1] to [4].
A molded body that is a building sealant.
[6]
In the molded product according to any one of the above [1] to [4].
A molded body that is a joint for drainage pipes.
[7]
In the molded product according to any one of the above [1] to [4].
A molded body that is a grip material.
[8]
In the molded product according to any one of the above [1] to [4].
A molded body that is a drain hose.

According to the present invention, it is possible to provide a molded body having excellent wear resistance and oil permeation prevention property.

Hereinafter, the polymer composition according to the present invention and the molded product composed of the composition will be described in detail.
The description of the constituent elements described below may be based on the representative embodiments of the present disclosure, but the present disclosure is not limited to such embodiments.
Further, unless otherwise specified, the symbols "p to q" indicating the numerical range shall represent p or more and q or less.

<< Polymer composition >>
The polymer composition of the present invention comprises at least one kind of ethylene, an α-olefin having 3 to 20 carbon atoms, a non-conjugated polyene copolymer (A), and one or more kinds of crystalline polyolefin (B). Includes a silylated polyolefin (C).

In the present invention, the "component derived from ethylene / α-olefin / non-conjugated polyene copolymer (A) having 3 to 20 carbon atoms" refers to ethylene / α-olefin / non-conjugated polyene co-weight having 3 to 20 carbon atoms. Represents a component obtained from coalescence as a raw material.

In the present invention, a resin containing one or more types of ethylene, an α-olefin having 3 to 20 carbon atoms, a non-conjugated polyene copolymer (A), one or more types of crystalline polyolefin (B), and the above-mentioned silylated polyolefin. The present inventors presume that the polymer formed from the composition has an improved surface silicon concentration, suppressed surface free energy of the polymer, and good wear resistance.
Further, the present inventors presume that the silylated polyolefin is less likely to cause bleeding or blooming on the surface of the molded product as compared with conventional additives such as silicone-based additives and metal soaps.

<Ethylene / α-olefin / non-conjugated polyene copolymer (A) having 3 to 20 carbon atoms>
The ethylene / α-olefin / non-conjugated polyene copolymer (A) having 3 to 20 carbon atoms used in the present invention (also referred to as the copolymer (A) in the present invention) is not particularly limited, but the present invention. From the viewpoint of excellent wear resistance of the polymer and excellent oil permeation prevention property, a structural unit derived from ethylene, a structural unit derived from at least one α-olefin having 3 to 20 carbon atoms, and at least one non-polyene. It is preferably an ethylene / α-olefin / non-conjugated polyene copolymer containing a structural unit derived from a conjugated polyene.

Examples of the α-olefin having 3 to 20 carbon atoms include propylene (3 carbon atoms), 1-butene (4 carbon atoms), 1-nonen (9 carbon atoms), 1-decene (10 carbon atoms), and 1-nonadecene (10 carbon atoms). Linear α-olefins without side chains such as 19) carbons, 1-eicosene (20 carbons); 4-methyl-1-pentene, 9-methyl-1-decene, 11-methyl having side chains Examples thereof include α-olefins having side chains such as -1-dodecene and 12-ethyl-1-tetradecene. These α-olefins may be used alone or in combination of two or more. Among these, α-olefins having 3 to 10 carbon atoms are preferable, and propylene, 1-butene, 1-hexene and 1-octene are more preferable. These α-olefins may be used alone or in combination of two or more.

Non-conjugated polyenes include chains such as 1,4-hexadien, 1,6-octadien, 2-methyl-1,5-hexadien, 6-methyl-1,5-heptadiene and 7-methyl-1,6-octadien. Non-conjugated diene; cyclohexadiene, dicyclopentadiene, methyltetrahydroinden, 5-vinyl-2-norbornene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene-2-norbornene and 6 -Cyclic non-conjugated diene such as chloromethyl-5-isopropenyl-2-norbornene; 2,3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, 2-propenyl-2, 5-norbornene, 1,3,7-octatriene, 1,4,9-decatorien, 4,8-dimethyl-1,4,8-decatorien and 4-ethylidene-8-methyl-1,7-nonadien, etc. Trien and the like can be mentioned. These non-conjugated polyenes may be used alone or in combination of two or more. Among these, a mixture of cyclic non-conjugated diene such as 1,4-hexadiene, 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, 5-ethylidene-2-norbornene and 5-vinyl-2-norbornene Preferably, 5-ethylidene-2-norbornene and 5-vinyl-2-norbornene are more preferable.

Examples of the copolymer (A) include ethylene / 1-butene / 1,4-hexadiene copolymer, ethylene / 1-pentene / 1,4-hexadiene copolymer, ethylene / 1-hexene / 1,4-hexadiene. Copolymers, ethylene / 1-heptene / 1,4-hexadiene copolymers, ethylene / 1-octene / 1,4-hexadiene copolymers, ethylene / 1-nonene / 1,4-hexadiene copolymers, Ethylidene / 1-decene / 1,4-hexadiene copolymer, ethylene / 1-butene / 1-octene / 1,4-hexadiene copolymer, ethylene / 1-butene / 5-ethylidene-2-norbornene copolymer , Ethylidene 1-pentene / 5-ethylidene-2-norbornene copolymer, ethylene / 1-hexene / 5-ethylidene-2-norbornene copolymer, ethylene / 1-hepten / 5-ethylidene-2-norbornene Polymers, ethylene / 1-octene / 5-ethylidene-2-norbornene copolymer, ethylene / 1-nonen / 5-ethylidene-2-norbornene copolymer, ethylene / 1-decene / 5-ethylidene-2-norbornene Copolymers, ethylene / 1-butene / 1-octene / 5-ethylidene-2-norbornene copolymers, ethylene / 1-butene / 5-ethylidene-2-norbornene / 5-vinyl-2-norbornene copolymers, Ethylidene, 1-pentene, 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene copolymer, ethylene, 1-hexene, 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene copolymer, Ethylidene 1-hepten 5-ethylidene-2-norbornene 5-vinyl-2-norbornene copolymer, ethylene 1-octene 5-ethylidene-2-norbornene 5-vinyl-2-norbornene copolymer , Ethylidene 1-nonene 5-ethylidene-2-norbornene 5-vinyl-2-norbornene copolymer, ethylene 1-decene-5-ethylidene-2-norbornene 5-vinyl-2-norbornene copolymer And ethylene, 1-butene, 1-octene, 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene copolymer and the like can be mentioned.

The copolymer (A) may be used alone or in combination of two or more.

The ethylene / α-olefin / non-conjugated polyene copolymer (A) having 3 to 20 carbon atoms has an ethylene / α-olefin ratio, that is, a structural unit derived from ethylene [a] and a structural unit derived from α-olefin. The molar ratio [[a] / [b]] with [b] is in the range of 40/60 to 90/10. The lower limit of the molar ratio [a] / [b] is preferably 45/55, more preferably 50/50, and particularly preferably 55/45. The upper limit of the molar ratio [a] / [b] is preferably 80/20, more preferably 75/25, still more preferably 70/30, and particularly preferably 65/35.

The copolymer (A) has no particular limitation on the Mooney viscosity ML (1 + 4) (125 ° C.) at 125 ° C. obtained by measuring according to JIS K6300 (1994), but is usually 50 to 300. It is preferably 50 to 250, more preferably 50 to 230, and particularly preferably 50 to 200. When the Mooney viscosity is in the range of 50 to 300, the oil permeation prevention property is excellent.

The iodine value of the copolymer (A) is usually 2 to 50 g / 100 g, preferably 5 to 40 g / 100 g, and more preferably 7 to 30 g / 100 g. When the iodine value is at least this lower limit value, the shape recovery property at high temperature is good, and when it is at least this upper limit value, the moldability is good.

The content of the structural unit [c] derived from the non-conjugated polyene in the copolymer (A) is preferably 100 mol% based on the total of the structural units of [a], [b] and [c]. In the range of 0.1 to 6.0 mol%, more preferably 0.5 to 4.0 mol%, still more preferably 0.5 to 3.5 mol%, and particularly preferably 0.5 to 3.0 mol%. It is in. When the content of the structural unit [c] derived from the non-conjugated polyene is within the above range, an ethylene-based copolymer having sufficient crosslinkability and flexibility tends to be obtained.

The copolymer may be, for example, "Polymer Manufacturing Process (Kogyo Chosakai Co., Ltd., published p.309-330)" or JP-A-9-71617 and JP-A-9-71618 according to the application of the applicant of the present application. , JP-A-9-208615, JP-A-10-67823, JP-A-10-67824, JP-A-10-110054, WO2009 / 081792 pamphlet, WO2009 / 081794 pamphlet and the like. It can be manufactured by such a method.

Examples of the olefin polymerization catalyst preferably used in the production of the ethylene / α-olefin / non-conjugated polyene copolymer (A) used in the present invention include vanadium (V), zirconium (Zr), and titanium (Ti). ) And other known transition metal compounds and organic aluminum compounds (organic aluminum oxy compounds); transition metal metallocene compounds selected from Group 4 of the periodic table of elements, and organic aluminum oxy compounds or ionized ions. A known metallocene catalyst composed of a sex compound, for example, a metallocene catalyst described in JP-A-9-40586; a known metallocene catalyst composed of a specific transition metal compound and a co-catalyst such as a boron compound, for example, WO2009 /. The metallocene catalyst described in the 072553 pamphlet; a transition metal compound catalyst comprising a specific transition metal compound and an organic metal compound, an organic aluminum oxy compound or a compound which reacts with the transition metal compound to form an ion pair, for example. The transition metal compound catalyst described in JP-A-2011-52231; the catalyst described in JP-A-2010-2418997 can be mentioned. It can also be produced using the catalyst described in WO2016 / 152711 pamphlet. In particular, it is particularly preferable to use a metallocene catalyst because the distribution of diene becomes uniform and high cross-linking efficiency can be obtained even if the introduction of diene is small, and since the catalytic activity is high, the chlorine content derived from the catalyst can be reduced.

<Crystalular Polyolefin (B)>
The crystalline polyolefin (B) is not particularly limited as long as it is a crystalline polymer obtained from an olefin, but one or more of them are excellent from the viewpoint of excellent wear resistance and oil permeation prevention property of the molded product in the present invention. The monoolefin is preferably a polymer composed of a crystalline high molecular weight solid product obtained by polymerizing the monoolefin by either a high pressure method or a low pressure method. Examples of such a polymer include an isotactic monoolefin polymer and a syndiotactic monoolefin polymer.

The crystalline polyolefin (B) may be obtained by synthesizing it by a conventionally known method, or a commercially available product may be used.

The crystalline polyolefin (B) may be used alone or in combination of two or more.

Examples of the monoolefin used as a raw material for the crystalline polyolefin (B) include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 2-methyl-1-propene, and 3-methyl. Examples thereof include -1-pentene, 4-methyl-1-pentene and 5-methyl-1-hexene. These olefins may be used alone or in combination of two or more.

Among the crystalline polyolefins (B), a propylene homopolymer obtained from a monoolefin mainly containing propylene or a propylene-based (co) polymer which is a propylene copolymer is preferable from the viewpoint of heat resistance and oil resistance. In the case of the propylene copolymer, the content of the structural unit derived from propylene is preferably 40 mol% or more, more preferably 50 mol% or more, and as a monoolefin which is a structural unit derived from a monomer other than propylene. Is preferably the monoolefin other than propylene, more preferably ethylene or butene.

The polymerization mode may be a random type or a block type, and any polymerization mode may be adopted as long as a crystalline resinous substance can be obtained.

The crystalline polyolefin (B) has a melt flow rate (ASTM D1238-65T; 230 ° C., 2.16 kg load) of usually 0.01 to 100 (g / 10 min), preferably 0.05 to 50 (g / 10 min). g / 10 minutes), particularly preferably 0.1 to 30) (g / 10 minutes). When the melt flow rate is 0.01 (g / 10 minutes) or more, the fluidity of the polymer composition is good and the moldability is excellent, and when it is 100 (g / 10 minutes) or less, the flowability is appropriate. It has properties, is less likely to cause drawdown and burrs, and has good mechanical properties of the polymer composition.

The crystalline polyolefin (B) has a melting point (Tm) of 100 ° C. or higher, preferably 105 ° C. or higher, obtained by differential scanning calorimetry (DSC). By setting the melting point (Tm) to 100 ° C. or higher, the oil resistance and heat resistance of the polymer composition can be well maintained.

The differential scanning calorimetry is performed, for example, as follows. About 5 mg of the sample is packed in a special aluminum pan, heated from 30 ° C. to 200 ° C. at 320 ° C./min using DSCPyris1 or DSC7 manufactured by PerkinElmer Co., Ltd., held at 200 ° C. for 5 minutes, and then 200 ° C. The melting point is obtained from the endothermic curve when the temperature is lowered from 1 to 30 ° C. at 10 ° C./min, held at 30 ° C. for another 5 minutes, and then raised at 10 ° C./min. When a plurality of peaks are detected during DSC measurement, the peak temperature detected on the highest temperature side is defined as the melting point (Tm).

The crystalline polyolefin (B) plays a role in improving the fluidity and heat resistance of the polymer composition.

The blending amount of the crystalline polyolefin (B) is 20 to 150 parts by mass, preferably 20 parts by mass with respect to a total of 100 parts by mass of the components derived from the copolymer (A) from the viewpoint of flexibility and low compression permanent strain. ~ 100 parts by mass.

<Cyrilized polyolefin (C)>
The silylated polyolefin (C) according to the present embodiment may have any structure as long as it has a silicone chain and a polyolefin chain. For example, a silicone graft polyolefin having a structure in which a polyolefin is grafted to a polyolefin, a block copolymer of a polyolefin and a silicone, a structure in which a polyolefin is grafted to a silicone, a structure in which a polyolefin is grafted to a silicone portion of the block copolymer, and the like can be mentioned. Can be done. The silylated polyolefin (C) may be used alone or in combination of two or more.

Examples of the block copolymer include block copolymers bonded in the order of (polyolefin chain)-(silicone chain), block copolymers bonded in the order of (polyolefin chain)-(silicone chain)-(polyolefin chain), and the like. be able to.
As the polyolefin chain, for example, a polymer chain containing a structural unit derived from an olefin having 2 to 50 carbon atoms, preferably 2 to 20 carbon atoms can be exemplified. Among these, those having a structure represented by the following general formula (1) are preferable from the viewpoint of excellent wear resistance and oil permeation prevention property of the molded product in the present invention.

上記式（１）において、Ａ^１、Ａ^２およびＡ^３は各々独立に、ポリオレフィン鎖または炭素数１～２０の炭化水素基である。Ｒは炭素数１～２０の炭化水素基である。各Ｒは同一でも異なっていてもよい。ｍは１～１０，０００の整数である。Ａ^３が複数存在する場合、各Ａ^３は同一でも異なっていてもよい。ただし、Ａ^１、Ａ^２、Ａ^３のうち、少なくとも１つはポリオレフィン鎖を表す。

In the above formula (1), A ¹ , A ² and A ³ are independently polyolefin chains or hydrocarbon groups having 1 to 20 carbon atoms. R is a hydrocarbon group having 1 to 20 carbon atoms. Each R may be the same or different. m is an integer from 1 to 10,000. When there are a plurality of A3s ^{, each} A3 may be the same or different. However, at least one of A ¹ , A ² , and A ³ represents a polyolefin chain.

The polyolefin chain in A ¹ , A ² and A ³ is, for example, a polymer chain containing a structural unit derived from an olefin having 2 to 50 carbon atoms, preferably 2 to 20 carbon atoms.
Specific examples of the olefin having 2 to 50 carbon atoms include ethylene and α-olefin having 3 to 50 carbon atoms (propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4). -Methyl-1-pentene, 3-methyl-1-pentene, 3,4-dimethyl-1-pentene, 4-methyl-1-hexene, 3-ethyl-1-pentene, 3-ethyl-4-methyl-1 -Pentene, 3,4-dimethyl-1-hexene, 4-methyl-1-heptene, 3,4-dimethyl-1-heptene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene , 1-octadecene, 1-eikosen, vinylcyclohexane, etc.) and the like.
Of these, at least one selected from ethylene and α-olefins having 3 to 12 carbon atoms is preferable from the viewpoint of further suppressing the generation of gel-like substances and further suppressing the bleeding of lubricants, and ethylene and At least one selected from α-olefins having 3 to 8 carbon atoms is more preferable, and ethylene is even more preferable.

The polyolefin chain may be a homopolymer chain or a copolymer chain.
Among them, a polymer chain composed of only ethylene and an olefin having 2 to 50 carbon atoms selected from an α-olefin having 3 to 50 carbon atoms is preferable, and further, an ethylene homopolymer chain and a propylene homopolymer chain, Alternatively, a copolymer chain of ethylene and an α-olefin having 3 to 20 carbon atoms is preferable. In the ethylene / α-olefin copolymer chain having 3 to 20 carbon atoms, when the total structural unit is 100 mol%, the structural unit derived from the α-olefin having 3 to 20 carbon atoms exceeds, for example, 0 mol%. It can be 20 mol% or less, and can be more than 0 mol% and 10 mol% or less.

Further, the polyolefin chain may contain structural units derived from other olefins, if desired. Other olefins include olefins containing internal double bonds such as cis-2-butene; vinylidene compounds such as isobutene; arylvinyl compounds such as styrene; arylvinylidene compounds such as α-methylstyrene; functionalities such as methyl methacrylate. Group-substituted vinylidene compounds; aliphatic cyclic olefins containing internal double bonds such as 5-methyl-2-norbornene, tetracyclododecene, cyclopentadiene and dicyclopentadiene; cyclic olefins containing aromatic rings such as inden; butadiene, Examples thereof include chain or cyclic polyenes such as isoprene, etilidennorbornene and vinylnorbornene.

The content of structural units derived from other olefins was set to 100 mol% of all the structural units constituting the polyolefin chain from the viewpoint of further suppressing the generation of gel-like substances and further suppressing the bleeding of the lubricant. When, 0 to 10 mol% is preferable, and 0 to 5 mol% is more preferable.

The polyolefin chain has a number average molecular weight of 100 or more and 500,000 or less determined by the following GPC method from the viewpoint of further suppressing the generation of gel-like substances and further suppressing the bleeding of the lubricant. Preferably, it is more preferably 200 or more and 100,000 or less, further preferably 500 or more and 50,000 or less, still more preferably 700 or more and 10,000 or less.
Further, from the viewpoint of further suppressing the generation of gel-like substances and further suppressing the bleeding of the lubricant, the polyolefin chain has a molecular weight distribution (Mw / Mn) of 1.1 to that obtained by the following GPC method. It is preferably in the range of 3.0.

GPC measurement method:
The GPC measurement is carried out at a temperature of 140 ° C. using orthodichlorobenzene as a solvent, and analytical values (weight average molecular weight (Mw), number average molecular weight (Mn) and Mw / Mn) can be obtained as polyethylene equivalent values. ..
The measurement can be performed under the following conditions. Further, the molecular weight can be obtained by preparing a calibration curve using commercially available monodisperse standard polystyrene and using the following conversion method.
Equipment: Gel permeation chromatograph Alliance GPC2000 type (manufactured by Waters)
Solvent: o-dichlorobenzene Column: TSKgel column (manufactured by Tosoh Corporation) x 4
Flow rate: 1.0 ml / min Sample: 0.15 mg / mLo-dichlorobenzene solution Temperature: 140 ° C
Molecular weight conversion: PS conversion / general-purpose calibration method In addition, the coefficient of the Mark-Houwink viscosity formula shown below can be used for the calculation of general-purpose calibration.
Polystyrene (PS) coefficient: KPS = 1.38 × 10 ^-4 , aPS = 0.70
Coefficient of polyethylene (PE): KPE = 5.06 × 10 ^-4 , aPE = 0.70

In the above A ¹ , A ² , A ³ and R, examples of the hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms include an alkyl group, an arylalkyl group, an alkenyl group and an aryl group. Be done.
Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a hexyl group, a 2-ethylhexyl group, an octyl group, a decyl group and an octadecyl group. Such as linear or branched alkyl groups; cycloalkyl groups such as cyclopentyl group, cyclohexyl group and norbornyl group and the like.
Examples of the arylalkyl group include a benzyl group, a phenylethyl group, a phenylpropyl group and the like.
Examples of the alkenyl group include a vinyl group, a propenyl group, a cyclohexenyl group and the like.
Examples of the aryl group include a phenyl group, a tolyl group, a dimethylphenyl group, a trimethylphenyl group, an ethylphenyl group, a propylphenyl group, a naphthyl group and the like.

In the above equation (1), m is an integer of 1 to 10,000. From the viewpoint of further suppressing the generation of gel-like substances and further suppressing the bleeding of the lubricant, m is preferably 5 or more, and more preferably 10 or more. Further, m is preferably 1,000 or less, more preferably 300 or less, and even more preferably 50 or less.

The above A ¹ , A ² , singular or plural A ³ may be all polyolefin chains, or some groups may be polyolefin chains and others may be hydrocarbon groups having 1 to 20 carbon atoms. ..
In the above formula (1), when m is 2 or more and at least one of A ³ is different from the other A ³ , there are a plurality of types of units represented by the following general formula (2). There is no particular limitation on the order in which they are arranged, and they may be block-like or random.

As the above formula (1), the structure represented by the following (i), (ii) or (iii) is preferable, and among them, (i) is more preferable.
(I) In the above formula (1), A ¹ and A ² are polyolefin chains, and A ³ is a hydrocarbon group having 1 to 20 carbon atoms.
(Ii) In the above formula (1), one of A ¹ or A ² is a polyolefin chain, the other is a hydrocarbon group having 1 to 20 carbon atoms, and A ³ is a hydrocarbon group having 1 to 20 carbon atoms. There is a structure.
(Iii) In the above formula (1), A ¹ and A ² are hydrocarbon groups having 1 to 20 carbon atoms, and at least one of A ³ is a polyolefin chain.

In the silylated polyolefin (C) according to the present embodiment, the silicone chain / polyolefin chain (mass ratio) is not particularly limited, but is preferably, for example, 5/95 to 99/1, more preferably 10. It is / 90 to 95/5.

The method for producing the silylated polyolefin (C) according to the present embodiment is not particularly limited, and is described in, for example, paragraphs 809 to 0145 and paragraphs 0196 to 0207 of International Publication No. 2012/098865. Can be manufactured by.

<Crosslinking agent>
The polymer composition of the present invention may contain a cross-linking agent and a cross-linking aid depending on the molded product to be obtained. Examples of the cross-linking agent used in the present invention include phenol resin-based cross-linking agents and organic peroxides. From the viewpoint of excellent wear resistance and oil permeation prevention property of the molded product in the present invention, the cross-linking agent is preferably a phenol resin-based cross-linking agent or an organic peroxide.

The phenol resin-based cross-linking agent is a resol resin and is produced by condensation of alkyl-substituted phenol or unsubstituted phenol with an aldehyde in an alkaline medium, preferably with formaldehyde, or condensation of bifunctional phenol dialcohols. It is also preferable. The alkyl-substituted phenol is preferably an alkyl group substituted product having 1 to 10 carbon atoms. Further, dimethylolphenols or phenol resins substituted with an alkyl group having 1 to 10 carbon atoms at the p-position are preferable. The phenol resin-based cured resin is typically a heat-crosslinkable resin, and is also referred to as a phenol resin-based cross-linking agent or a phenol resin.

Examples of the phenol resin-based cured resin (phenol resin-based cross-linking agent) include the following general formula (3).

(In the equation, Q is a divalent group selected from the group consisting of -CH _{2- and -CH 2 -} O-CH _2- , m is 0 or a positive integer from 1 to 20, and R'. Is an organic group. R'may be the same or different from each other.)

Preferably, Q is a divalent group-CH ₂ -O-CH _2- , m is 0 or a positive integer from 1 to 10, and R'is an organic group having less than 20 carbon atoms. More preferably, m is 0 or a positive integer from 1 to 5, and R'is an organic group having 4 to 12 carbon atoms. Specific examples thereof include an alkylphenol formaldehyde resin, a methylolated alkylphenol resin, a halogenated alkylphenol resin and the like, preferably a halogenated alkylphenol resin, and more preferably a bromineed terminal hydroxyl group. An example of a phenolic resin-based cured resin having a brominated terminal is shown in the following general formula (4).

（式中、ｎは０～１０の整数、Ｒは炭素数１～１５の飽和炭化水素基である。）

(In the formula, n is an integer of 0 to 10 and R is a saturated hydrocarbon group having 1 to 15 carbon atoms.)

Examples of the product of the phenolic resin-based cured resin include Tackilol (registered trademark) 201 (alkylphenol formaldehyde resin, manufactured by Taoka Chemical Industry Co., Ltd.) and Takkiroll (registered trademark) 250-I (bromination rate of 4%). Alkylphenol formaldehyde resin, manufactured by Taoka Chemical Industry Co., Ltd.), Tackiroll (registered trademark) 250-III (brominated alkylphenol formaldehyde resin, manufactured by Taoka Chemical Industry Co., Ltd.), PR-4507 (Gunei Chemical Industry Co., Ltd.) Vulkarest 510E (Hoechst), Vulkarest 532E (Hoechst), VulkaresenE (Hoechst), Vulkaresen105E (Hoechst), Vulkaresten130E (Hoechst), Vulkeresen130E (Hoechst) (Manufactured by), Sumilite Resin (registered trademark) PR-22193 (manufactured by Sumitomo Durez Co., Ltd.), Symphon-C-100 (manufactured by Anchor Chem.), Symphonm-C-1001 (manufactured by Anchor Chem.), Tamanol (Registered Trademark) 531 (manufactured by Arakawa Chemical Co., Ltd.), Spectaday SP1059 (manufactured by Spectaday Chem.), Spectaday SP1045 (manufactured by Spectaday Chem.), CRR-0803 (manufactured by U.C.C.), Spectady SP1055F. (Chemical Chem., Brominated alkylphenol formaldehyde resin), Scientific SP1056 (Chemical Chem.), CRM-0803 (Showa Union Synthetic Co., Ltd.) and Vulkadur A (Bayer). Among them, halogenated phenol resin-based cross-linking agents are preferable, and brominated alkylphenol formaldehyde resins such as Tackylol® 250-I, Tuckyroll® 250-III and Schenectady SP1055F can be more preferably used.

Specific examples of cross-linking of thermoplastic vulcanized rubber with phenol resin include US Pat. No. 4,311,628, US Pat. No. 2,972,600 and US Pat. No. 3,287,440. Described, these techniques can also be used in the present invention.

US Pat. No. 4,311,628 discloses a phenolic curative system composed of a phenolic curing resin and a cure activator. The basic components of the system are substituted phenols in alkaline media (eg, halogen-substituted phenols, C1-C _{2 -} alkyl-substituted phenols) or unsubstituted phenols and aldehydes, preferably by condensation with formaldehyde, or bifunctional phenols. It is a phenolic resin-based cross-linking agent produced by condensation of _dialcohols (preferably dimethylolphenols in which the para position is substituted with a C5 _- C10 alkyl group). Halogenated and tarkyll-substituted phenolic resin-based crosslinkers produced by halogenation of alkyl-substituted phenolic resin-based crosslinkers are particularly suitable. Phenol resin-based cross-linking agents consisting of methylol phenol-curable resins, halogen donors and metal compounds are particularly recommended, the details of which are described in US Pat. Nos. 3,287,440 and 3,709,840. Has been done. The non-halogenated phenolic resin-based cross-linking agent is used together with the halogen donor, preferably with a hydrogen halide scavenger. Generally, a hydrogen halide phenol resin-based cross-linking agent, preferably a brominated phenol resin-based cross-linking agent containing 2 to 10% by mass of bromine, does not require a halogen donor, but for example, iron oxide, titanium oxide, or oxidation. Used simultaneously with hydrogen halide scavengers such as magnesium, magnesium silicate, silicon dioxide and zinc oxide, preferably metal oxides such as zinc oxide. These hydrogen halide scavengers such as zinc oxide are usually used in an amount of 1 to 20 parts by mass with respect to 100 parts by mass of the phenol resin-based cross-linking agent. The presence of such a scavenger promotes the cross-linking action of the phenol-resin-based cross-linking agent, but in the case of rubber that is not easily vulcanized by the phenol-resin-based cross-linking agent, it is desirable to share the halogen donor and zinc oxide. Methods for producing halogenated phenolic curable resins and their use in vulcanizing agents using zinc oxide are described in US Pat. Nos. 2,972,600 and 3,093,613. , The disclosure thereof shall be incorporated herein by reference together with the disclosure of the above-mentioned US Pat. Nos. 3,287,440 and 3,709,840. Examples of suitable halogen donors are for example stannous chloride, ferric chloride, or halogenated weights such as chlorinated paraffins, chlorinated polyethylene, chlorosulfonated polyethylene and polychlorobutadiene (neoprene rubber). Coalescence is mentioned. As used herein, the term "vulcanization accelerator" means any substance that substantially increases the cross-linking efficiency of phenolic resin-based cross-linking agents, and includes metal oxides and halogen donors, which include metal oxides and halogen donors. Used alone or in combination. For more details on phenolic vulcanizers, see "Vulcanization and Vulcanizing Agents" (W. Hoffman, Palmerton Publishing Company). Suitable phenolic resin-based crosslinkers and brominated phenolic resin-based crosslinkers are commercially available, for example such crosslinkers are described in Schenectady Chemicals, Inc. Can be purchased from the product names "SP-1045", "CRJ-352", "SP-1055F" and "SP-1056". Similar operably equivalent phenolic resin-based crosslinkers can also be obtained from other suppliers.

Specific examples of the organic peroxide include dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexane, and 2,5-dimethyl-2. 5-Di- (tert-butylperoxy) hexin-3,1,3-bis (tert-butylperoxyisopropyl) benzene, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, n -Butyl-4,4-bis (tert-butylperoxy) peroxide, benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, tert-butylperoxybenzoate, tert-butylperbenzoate, tert-butylperoxyisopropyl Examples thereof include carbonate, diacetyl peroxide, lauroyl peroxide and tert-butylcumyl peroxide.

Among these, 2,5-dimethyl-2.5-di- (tert-butylperoxy) hexane and 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexane in terms of odor and scorch stability. ) Hexin-3,1,3-bis (tert-butylperoxyisopropyl) benzene, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane and n-butyl-4,4-bis (Tert-Butylperoxy) valerate is preferred, with 1,3-bis (tert-butylperoxyisopropyl) benzene being the most preferred. The organic peroxide is preferably used in a proportion of 0.05 to 3 parts by mass, preferably 0.1 to 1 part by mass with respect to 100 parts by mass of the total amount of the crystalline polyolefin and rubber.

In the cross-linking treatment using the above organic peroxide, a uniform and mild cross-linking reaction can be expected by using a cross-linking aid such as a polyfunctional vinyl monomer. Crosslinking aids include sulfur, p-quinonedioxime, p, p'-dibenzoylquinonedioxime, N-methyl-N-4-dinitrosoaniline, nitrosobenzene, diphenylguanidine and trimethylolpropane-N, N. Peroxy cross-linking aids such as'-m-phenylenedi maleimide, or poly such as divinylbenzene, triaryl cyanurate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate and aryl methacrylate. Examples include polyfunctional vinyl monomers such as functional methacrylate monomers, vinyl butyrate and vinyl stearate.

In particular, in this embodiment, divinylbenzene is most preferable. Divinylbenzene is easy to handle, has good compatibility with crystalline polyolefin (a-1) and rubber (a-2), which are the main components of the above-mentioned crosslinked product, and has an action of solubilizing organic peroxide. Since it has and acts as a dispersant for organic peroxides, a polymer composition having a uniform cross-linking effect due to heat treatment and having a good balance between fluidity and physical properties can be obtained.

The above-mentioned cross-linking aid is preferably used in a proportion of 0.1 to 2% by mass, preferably 0.3 to 1% by mass, based on the entire cross-linked product. When the amount of the cross-linking aid or the polyfunctional vinyl monomer used is in the above range, the cross-linking reaction proceeds moderately, so that the obtained polymer composition has excellent fluidity and no unreacted compound remains. Therefore, the obtained polymer composition does not change in physical properties due to the thermal history during processing and molding.

The cross-linking agent is a suitable vulcanizing agent from the viewpoint of preventing fogging because it produces less decomposition products. The cross-linking agent is used in an amount sufficient to achieve essentially complete vulcanization of the rubber.

<Other ingredients>
The composition of the present invention includes ethylene, an α-olefin having 3 to 20 carbon atoms, a non-conjugated polyene copolymer (A), a crystalline polyolefin (B), a silylated polyolefin (C), and a molded product. Other additives may be added together with or in place of the above-mentioned cross-linking agents and cross-linking aids as long as the effects of the present invention, which are excellent in abrasion resistance and excellent in oil permeation prevention property, are not impaired. The additive is not particularly limited, but is a flame retardant such as a softener, a filler, a brominated bisphenol, a brominated epoxy resin, a brominated polystyrene, a brominated polycarbonate, a triphenyl phosphate, a phosphoric acid amide, and red phosphorus. Flame retardants such as antimony trioxide and sodium antimonate, heat stabilizers such as phosphoric acid esters and phosphite esters, antioxidants such as hindered phenols, heat resistant agents, weather resistant agents, light stabilizers. , A mold release agent, a flow modifier, a colorant, a pigment, a lubricant, an antioxidant, a crystal nucleating agent, a foaming agent and the like may be blended in an effective expression amount as necessary.

Each of these additives may be used alone or in combination of two or more.

As the softener, a softener usually used for rubber can be used. Softeners include petroleum softeners such as process oils, lubricating oils, paraffin oils, liquid paraffins, petroleum asphalt and vaseline; coal tar softeners such as koultal and koultal pitch; castor oil, flaxseed oil, rapeseed oil. Fat oil-based softeners such as soybean oil and palm oil; tall oil; sub (factis); waxes such as beeswax, carnauba wax and lanolin; ricinoleic acid, palmitic acid, stearic acid, barium stearate, calcium stearate and laurin Fatty acid or fatty acid salt such as zinc acid; naphthenic acid; pine oil, rosin or a derivative thereof; terpene resin, petroleum resin and synthetic polymer substances such as atactic polypropylene and kumaron inden resin; dioctylphthalate, dioctyl adipate, dioctyl sebake -Ester-based softeners such as oil; microcrystallin wax, liquid polybutadiene, modified liquid polybutadiene, liquid thiocol, hydrocarbon-based synthetic lubricating oil and the like.

The amount of these softeners is not particularly limited as long as the effects of the present invention are exhibited, but from the viewpoint of excellent wear resistance of the molded product and excellent oil permeation prevention property, a total of 100 components derived from the copolymer (A) are used. It is preferably 90 to 150 parts by mass, more preferably 100 to 140 parts by mass with respect to parts by mass.

Crosslinking aids include oxides or hydroxides of divalent metals such as ZnO, MgO, CaO, Mg (OH) ₂ , Ca (OH) ₂ , or hydrotalcite Mg ₆ Al ₂ (OH) ₁₆ CO ₃ -NH ₂ O is used. The ratio of these cross-linking aids is usually 20 parts by mass or less, preferably 0.1 to 10 parts by mass, and more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the copolymer (A). ..

As the filler, an inorganic filler and an organic filler can be arbitrarily used, and the inorganic filler is particularly preferably used. Examples of the inorganic filler used in this application include glass fiber, carbon fiber, silica fiber, asbestos, metal (stainless steel, aluminum, titanium, copper, etc.) fiber, carbon black, graphite, silica, silas balun, and glass beads. , Silates (calcium silicate, talc, clay, kaolin, etc.), silica soil, metal oxides (iron oxide, titanium oxide, alumina, etc.), metal carbonates (calcium carbonate, barium carbonate, basic magnesium carbonate, etc.), Metal sulfates (barium sulfate, aluminum sulfate, calcium sulfate, basic magnesium sulfate whiskers, etc.), metal sulfides (molybdenum disulfide, etc.), and various metal (magnesium, silicon, aluminum, titanium, copper, etc.) powders, Examples thereof include mica, mica powder, glass flakes, glass balls, calcium titanate whisker, aluminum borate whisker and the like. These fillers may be used alone or in combination of two or more.

Further, the blending amount of the additive other than the additive whose blending amount is described in the present specification is not particularly limited as long as the effect of the present invention is obtained, but the copolymer (A) and the crystalline polyolefin (B) are not particularly limited. The total amount is usually 5 parts by mass or less, preferably 0.01 to 5 parts by mass, and the total is usually 10 parts by mass or less, preferably 0.1 to 5 parts by mass.

<< Method of manufacturing composition >>
The method for producing the composition is not particularly limited. From the viewpoint of excellent wear resistance and oil permeation prevention property of the molded product made of the composition, for example, one or more kinds of ethylene having an ethylene / α-olefin ratio of 40/60 to 90/10 (molar ratio). An α-olefin / non-conjugated polyene copolymer (A) having 3 to 20 carbon atoms and one or more crystalline polyolefins (B) having a melting point (Tm) of 100 ° C. or higher are mixed in a melted state. It may be produced by a method including smelting (hereinafter referred to as dynamic heat treatment), and more specifically, for example, the following methods (1) and (2) may be used. good.

<Method (1)>
To a composition precursor produced by dynamically heat-treating an uncrosslinked copolymer (A), at least a part of a crystalline polyolefin (B), and if necessary, a softening agent, a cross-linking agent, and a cross-linking aid. , Cyrilized polyolefin (C), if necessary, the remaining crystalline polyolefin (B), and other components are melt-kneaded under normal conditions and then granulated or pulverized.

<Method (2)>
By dynamically heat-treating at least a part of the uncrosslinked copolymer (A), the crystalline polyolefin (B), and the silylated polyolefin (C), and if necessary, a softening agent, a cross-linking agent, and a cross-linking aid. A method for granulating or pulverizing the produced composition precursor after melt-kneading the remaining crystalline polyolefin (B) and other components under normal conditions, if necessary.

In any of the methods (1) and (2), in producing the composition of the present invention, phenol is excellent from the viewpoint of excellent wear resistance and oil permeation prevention property of the molded product made of the composition. It is desirable to use the resin-based cross-linking agent in an amount of usually 0.1 to 20 parts by mass, preferably 0.5 to 15 parts by mass with respect to 100 parts by mass of the copolymer (A).

<Physical characteristics of the composition>
The physical properties of the obtained composition are not particularly limited, but in order to maintain the shape recovery under high temperature, JIS K 6262 vulcanized rubber and thermoplastic rubber-how to obtain compression set at normal temperature, high temperature and low temperature. It is preferable that the compression set (70 ° C. × 22h, 25% compression) measured according to the above is 50% or less.

<< Molded body >>
The molded product of the present invention comprises the above-mentioned polymer composition. As a result, a molded body having excellent wear resistance and oil permeation prevention property can be obtained.
The method for producing the molded product of the present invention is not particularly limited, but is known, for example, an extrusion molding method, an injection molding method, a solution casting method, an inflation molding method, a compression molding method, a transfer molding method, a casting molding method and the like. A molding method can be mentioned. Among them, a molding method having a heating process is preferable, and a melt molding method (extrusion molding method, injection molding method, inflation molding method, compression molding method, transfer molding method, etc.) is preferable.

Further, after molding without heating, the molded product may be annealed or the like. In the case of the melt molding method, it is usually performed by heating to a temperature above the melting point of the resin and having a fluidity suitable for molding and melting the resin. In the case of heat treatment such as annealing, it is usual to heat the molded product to a temperature at which it does not melt.

<Use>
The molded body of the present invention is suitable for use as a building sealant, a drainage pipe joint, and a drain hose from the viewpoint of obtaining wear resistance and excellent oil permeation prevention property. Further, from the viewpoint of obtaining oil permeability and excellent wear resistance, it is suitable for various grip materials such as toothbrushes and golf clubs. Further, the molded product of the present embodiment can be easily manufactured and recycled, so that it is excellent in economy.

Although the embodiments of the present invention have been described above, these are examples of the present invention, and various configurations other than the above can be adopted.

Hereinafter, the present invention will be described in more detail with reference to synthetic examples and examples, but the present invention is not limited thereto.

<1. Measurement and evaluation method>
(Measurement conditions for silylated polyolefin (C)) A calibration curve was prepared using commercially available monodisperse standard polystyrene. Further, based on the following conversion method, the weight average molecular weight (Mw), the number average molecular weight (Mn) and Mw / Mn were obtained as polyethylene conversion values.
-Device: Gel permeation chromatograph Alliance GPC2000 type (manufactured by Waters)
-Solvent: o-dichlorobenzene-Column: A configuration in which four TSKgel columns manufactured by Tosoh Corporation are connected in series-Flow velocity: 1.0 ml / min-Temperature: 140 ° C.
-Sample: 0.15 mg / mLo-dichlorobenzene solution-Molecular weight conversion: PS conversion / general-purpose calibration method The coefficients of the Mark-Houwink viscosity formula shown below were used for the calculation of general-purpose calibration.
Polystyrene (PS) coefficient: KPS = 1.38 × 10 ^-4 , aPS = 0.70
Coefficient of polyethylene (PE): KPE = 5.06 × 10 ^-4 , aPE = 0.70

<2. Raw materials>
(1) Ethylene / α-olefin / non-conjugated polyene copolymer (A) having 3 to 20 carbon atoms
[Synthesis Example 1]
A polymerizer with a volume of 300 L equipped with a stirring blade was used to continuously polymerize a ternary copolymer consisting of ethylene, propylene as an α-olefin, and 5-ethylidene-2-norbornene (ENB) as a non-conjugated polyene. It was carried out at 90 ° C.
Hexane (feed amount 74 L / h) was used as the polymerization solvent, and the ethylene feed amount was 6.6 kg / h, the propylene feed amount was 3.2 kg / h, and the ENB feed amount was 0.56 kg / h. Each component was continuously supplied to the polymer so that the hydrogen feed amount was 10.9 NL / h.
While maintaining the polymerization pressure at 1.8 MPa and the polymerization temperature at 90 ° C., [N- (1,1-dimethylethyl) -1,1-dimethyl-1-[(1,2,3,3A,) was used as the main catalyst. 8A-η) -1,5,6,7-tetrahydro2-methyl-S-indasen-1-yl] silaneaminete (2-) -κN] [(1,2,3,4-η) -1 , 3-Pentadiene] -Titanium was used to continuously feed the main catalyst to a feed rate of 0.015 mmol / h. Further, the feed amount of (C ₆ H ₅ ) ₃ CB (C ₆ F ₅ ) ₄ as a co-catalyst is 0.075 mmol / h, and the feed amount of triisobutylaluminum (TIBA) as an organoaluminum compound is 10 mmol / h. Each was supplied continuously.
In this way, an ethylene / α-olefin / non-conjugated polyene copolymer composed of ethylene, propylene and ENB was obtained in a solution state of 9.1% by mass. A small amount of methanol was added to the polymerization reaction solution extracted from the lower part of the polymer to stop the polymerization reaction, and the ethylene / α-olefin / non-conjugated polyene copolymer was separated from the solvent by steam stripping treatment, and then 80. It was dried under reduced pressure at ° C for a whole day and night.
By the above operation, an ethylene / α-olefin / non-conjugated polyene copolymer (A-1) formed from ethylene, propylene and ENB was obtained at a rate of 5.3 kg / h.

(2) Crystalline polyolefin (B)
Propylene homopolymer (B-1) with a melt flow rate (ASTM D1238-65T; 230 ° C., 2.16 kg load) of 3 g / 10 min, a density of 0.91 g / cm ³ , and a melting point of 165 ° C.

(3) Synthesis of Cyrilized Polyolefin (C) [Synthesis Example 2]
(Synthesis of polyethylene having a vinyl group at one end)
A one-terminal vinyl group-containing ethylene-based polymer (P-1) was synthesized according to the method described in Synthesis Example 2 of International Publication No. 2012/098865.
¹ It was revealed by 1 H-NMR measurement that the obtained polymer was homopolyethylene and contained a double bond only at one end. The physical characteristics of this one-ended double bond-containing ethylene polymer (P-1) (elemental substance) were as follows.
Melting point (Tm) 127 ° C
Mw = 4770, Mw / Mn = 2.25 (GPC)
End unsaturated rate = 97%

[Synthesis Example 3]
(Preparation of Platinum Catalyst Composition (PT-1))
In a 50 ml sample tube containing a magnetic stirrer chip, 0.50 g of platinum (II) chloride was suspended in hydrosilane A (HS (A), manufactured by Gelest, Inc., DMS-H11) (10 ml) having the following structure. The mixture was stirred at room temperature under a nitrogen stream. After stirring for 190 hours, about 0.4 ml of the reaction solution was collected with a syringe, filtered using a 0.45 μm PTFE filter, and the filtrate was collected in a 10 ml sample tube. A platinum catalyst having a platinum concentration of 3.8% by mass was collected. The composition (PT-1) was obtained.
Hydrosilane A (HS (A)): HSi (CH ₃ ) ₂ O- (-Si (CH _{3) 2-O-) n-Si (CH 3 ) 2 H}
(N = 12-13)

[Synthesis Example 4]
(Introduction of polyethylene having a terminal vinyl group into hydrosilane)
25.1 g (11.8 mmol) of the one-terminal vinyl group-containing ethylene-based polymer (P-1) obtained in [Synthesis Example 2] was charged into a 300 ml two-necked flask, and hydrosilane A was charged under a nitrogen atmosphere. (HS (A)) 6.7 g (5.9 mmol; equivalent to 11.8 mmol as Si—H group) and the platinum catalyst composition (PT-1) prepared in [Synthesis Example 3] were added to Hydrosilane A (HS (A). )) 200-fold diluted (PT-1a) 150 μl (1.4 × ^10-6 mmol in Pt equivalent) was further charged. The above-mentioned two-necked flask was set in an oil bath whose internal temperature had been raised to 130 ° C. in advance, and the mixture was stirred. After about 3 minutes the polymer melted. Then, after 6 hours, the mixture was cooled, about 200 ml of methanol was added, the contents were taken out to a 300 ml beer, and the mixture was stirred for 2 hours. Then, the solid was collected by filtration, washed with methanol, and dried at 60 ° C. under a reduced pressure of 2 hPa or less to obtain 33.1 g of a silylated polyolefin (C-1) as a white solid. As a result of NMR analysis, the yield was 98%, the olefin conversion rate was 100%, and the isomerization rate was 2%. The MFR was equal to or higher than the upper limit of measurement (MFR> 100 g / 10 min), and the polyorganosiloxane content in (C-1) calculated from the molecular formula was 23% by mass.

[Example 1] Polymer composition and molded product Ethylene / propylene ratio obtained in [Synthesis Example 1] is 63/37 (molar ratio), iodine value is 13 g / 100 g, Mooney viscosity [ML (1 + 4) (125). ° C)] is 116 parts by mass of ethylene propylene 5-ethylidene-2-norbornen copolymer rubber (EPDM), melt flow rate (ASTM D1238-65T; 230 ° C, 2.16 kg load) is 3 g / 10 minutes. 16 parts by mass of propylene homopolymer (B-1) having a density of 0.91 g / cm ³ and a melting point of 165 ° C., 3 parts by mass of the silylated polyolefin (C-1) obtained in [Synthesis Example 4], phenol. As a resin-based cross-linking agent, 8 parts by mass of brominated alkylphenol formaldehyde resin (trade name: SP-1055F, manufactured by Spectrum) is dynamically heat-treated with a KTX-46 twin-screw extruder manufactured by Steel Manufacturing Co., Ltd. to obtain pellets of the polymer composition. Obtained. Then, using a 100t electric heating automatic press (manufactured by Shoji Co., Ltd.), the obtained pellets were press-molded at 230 ° C. for 6 minutes, and then cooled and pressed at room temperature for 5 minutes to obtain a press sheet having a thickness of 2 mm and 10 cm × 10 cm. Got

[Example 2]
Pellets of the resin composition and a press sheet were obtained in the same manner as in [Example 1] except that the amount of the silylated polyolefin (C-1) added was changed from 3 parts by mass to 5 parts by mass.

[Comparative Example 1]
Pellets of the resin composition and a press sheet were obtained in the same manner as in [Example 1] except that the silylated polyolefin (C-1) was not added.

[Comparative Example 2]
Silicone masterbatch (hereinafter referred to as silicone MB) instead of silylated polyolefin (C-1), manufactured by Toray Industries, Inc., BY27-001, a blend of ultra-high molecular weight silicone and polypropylene (silicone content: 50) Pellets of the resin composition and a press sheet were obtained in the same manner as in [Example 1] except that (% by mass)) was used.

(Abrasion resistance evaluation)
The dynamic friction coefficient of the surface of the obtained press sheet was measured under the following conditions according to the JIS K7125 plastic-film and sheet friction coefficient test method. The measured dynamic friction coefficient is shown in Table 1.
Mating material: Glass Load: 500 g (per 50 mm x 50 mm)
Tensile speed: 100 mm / min Measuring device: Universal material testing machine 2001 type (manufactured by Intesco)

(Oil permeation test)
An aluminum cup having an inner diameter of 50 mm and a depth of 50 mm was filled with 3 g of engine oil (Strong Save OW-20). The opening at the top of the aluminum cup was covered with the press sheets obtained in each example and comparative example, and the aluminum cup and the press sheet were fixed with clips and screws to prevent engine oil from leaking. The aluminum cup filled with the above engine oil was turned upside down and heated in an oven at 130 ° C. for 24 hours. Immediately after taking it out of the oven, visually observe the bleeding state (oil permeation part) of the engine oil on the surface of the press sheet (the surface that is not in contact with the engine oil), and check the area of the oil permeation part and the oil of the press sheet. The ratio of the contact area (= the area of the opening of the aluminum cup) was evaluated according to the following criteria.
Judgment criteria: ○: The area of the oil permeation part is less than 10% of the contact area with oil.
Δ: The area of the oil permeation portion is 10% or more and less than 60% of the contact area with oil.
X: The area of the oil permeation portion is 60% or more of the contact area with oil.

From Table 1, Examples 1 and 2 to which the silylated polyolefin (C-1) was added had a lower dynamic friction coefficient and excellent wear resistance as compared with Comparative Example 1 to which the silylated polyolefin was not added, and the results of the oil permeation test were also obtained. It was excellent. Further, in the system in which silicone MB was added instead of the silylated polyolefin (C-1) (Comparative Example 2), the coefficient of dynamic friction was high, the wear resistance was inferior, and the result of the oil permeation test was also inferior. Although the reason for exerting such an effect is not clear, in the present invention, the silylated polyolefin (C) is well dispersed in the ethylene / α-olefin / non-conjugated polyene copolymer (A) and the crystalline polyolefin (B). It is considered that this is linked to the property that the oil does not penetrate to the side opposite to the contact surface of the oil.

Claims (8)

Ethylene, α-olefin with 3 to 20 carbon atoms, non-conjugated polyene copolymer (A), and
Crystalline polyolefin (B) and
A molded product comprising a polymer composition containing a silylated polyolefin (C). In the molded product according to claim 1,
A molded product, wherein the silylated polyolefin (C) contains a silylated polyolefin represented by the following formula (1).

(In the above formula (1), A ¹ , A ² and A ³ are independently polyolefin chains or hydrocarbon groups having 1 to 20 carbon atoms. R is a hydrocarbon group having 1 to 20 carbon atoms. Each R may be the same or different. M is an integer of 1 to 10,000. When a plurality of A ^3s exist, each A ³ may be the same or different. However, A ¹ and A ² may be different. , And at ^least one of A3 represents a polyolefin chain.) In the molded product according to claim 1 or 2.
A molded product characterized in that the components derived from the copolymer (A) are crosslinked. In the molded product according to claim 3,
A molded product characterized in that the cross-linking is due to a dynamic heat treatment. In the molded product according to any one of claims 1 to 4.
A molded body that is a building sealant. In the molded product according to any one of claims 1 to 4.
A molded body that is a joint material for drainage pipes. In the molded product according to any one of claims 1 to 4.
A molded body that is a grip material. In the molded product according to any one of claims 1 to 4.
A molded body that is a drain hose.