JP2022119694A - Modified elastomer composition, crosslinked elastomer composition and extrudate thereof - Google Patents

Abstract

[Problem] To provide a modified elastomer composition and a crosslinked elastomer composition which are excellent in extrusion moldability, compression set, flexibility, and extrusion appearance.
A modified elastomer composition comprising the following components (A) to (D) and grafted with the following component (E). Component (G): a cross-linked elastomer composition obtained by cross-linking this modified elastomer composition with a silanol catalyst.
Component (A): Ethylene/α-olefin copolymer rubber Component (B): Propylene resin Component (C): Hydrogenated product of styrene/conjugated diene block copolymer Component (D): Unsaturated silane compound Component ( E): Peroxide [Selection drawing] None

Description

The present invention relates to modified elastomer compositions, crosslinked elastomer compositions and extrudates thereof. More specifically, the present invention relates to a modified elastomer composition and a crosslinked elastomer composition which are excellent in extrusion moldability, compression set, flexibility, extrusion appearance, and an extrudate using the same.

A thermoplastic elastomer is an elastomer that softens when heated to have fluidity and has rubber elasticity when cooled. Thermoplastic elastomers have molding processability similar to thermoplastic resins, have rubber elasticity, and are recyclable. It is widely used for the purpose of

When used in applications requiring sealability, it is important to have good rubber elasticity or compression set properties, and many studies have been made for this purpose. However, since thermoplastic elastomers contain thermoplastic resins such as polyolefins to ensure their thermoplastic properties, their compression set characteristics are insufficient compared to thermosetting rubbers, and their applications are limited. . On the other hand, thermosetting rubbers such as EPDM have excellent compression set properties, but have the drawback of requiring a long cross-linking process and being inferior in durability.

Thermoplastic elastomer compositions with improved compression set properties include, for example, ethylene/α-olefin/non-conjugated diene copolymer rubber; ethylene/α-olefin copolymer rubber containing no non-conjugated diene units; Plastic elastomer; polyethylene, polypropylene or propylene/α-olefin copolymer; modified elastomer composition obtained by graft-modifying a composition containing an unsaturated silane compound with a peroxide, or cross-linking obtained by further cross-linking this composition Elastomer compositions are known (see Patent Document 1).
In Patent Document 1, the modified elastomer composition and the crosslinked elastomer composition provide a molded article having both compression set characteristics equivalent to those of thermosetting rubber and simple moldability equivalent to those of thermoplastic elastomers. is stated.

JP 2018-154815 A

However, the modified elastomer composition and the crosslinked elastomer composition described in Patent Literature 1 have the problem of being inferior in flexibility and extruded appearance.

The present invention has been made in view of such problems, and an object of the present invention is to provide a modified elastomer composition, a crosslinked elastomer composition, and an extrudate thereof, which are excellent in extrusion moldability, compression set, flexibility, and extrusion appearance. to provide.

As a result of intensive studies to solve the above problems, the inventors of the present invention have found that ethylene/α-olefin copolymer rubber; propylene-based resin; hydrogenated styrene/conjugated diene block copolymer; and unsaturated silane compound. A molded article excellent in extrusion moldability, compression set, flexibility, and extrusion molding appearance by forming a modified elastomer composition obtained by grafting with a peroxide or a crosslinked elastomer composition obtained by further crosslinking reaction thereof. can be obtained, and has completed the present invention.
That is, the gist of the present invention resides in the following [1] to [12].

[1] A modified elastomer composition comprising the following components (A) to (D) and grafted with the following component (E).
Component (A): Ethylene/α-olefin copolymer rubber Component (B): Propylene resin Component (C): Hydrogenated product of styrene/conjugated diene block copolymer Component (D): Unsaturated silane compound Component ( E): Peroxide

[2] The modified elastomer composition according to [1], wherein the proportion of 1,2-bonds in the diene monomer units of the conjugated diene block of component (C) is 20 to 90% by mass.

[3] The modified elastomer composition according to [1] or [2], wherein the component (A) has a melting end peak temperature of 115°C or higher as measured by a differential scanning calorimeter (DSC).

[4] The modified elastomer composition according to any one of [1] to [3], wherein the component (D) is a compound represented by the following formula (1).
RSi(R') ₃ (1)
(where R is an ethylenically unsaturated hydrocarbon group, R' is independently a hydrocarbon group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, and at least one of R' is an alkoxy group having 1 to 10 carbon atoms.)

[5] Component (F): 1 to 200 parts by mass of a hydrocarbon rubber softener per 100 parts by mass in total of the component (A) and the component (B), [1] to [ 4], the modified elastomer composition according to any one of the above items.

[6] Furthermore, component (H): 1 to 200 parts by mass of a polyphenylene ether resin per 100 parts by mass of the total of the component (A) and the component (B) of [1] to [5] A modified elastomer composition according to any one of the above.

[7] Component (G): a crosslinked elastomer composition obtained by subjecting the modified elastomer composition according to any one of [1] to [6] to a crosslinking reaction using a silanol catalyst.

[8] The crosslinked elastomer composition according to [7], which has a Duro A hardness of 30 or more and 70 or less according to JIS K6253 (2012) (Duro-A).

[9] An extruded body of the modified elastomer composition according to any one of [1] to [6].

[10] An extrudate of the crosslinked elastomer composition of [7] or [8].

[11] A method for producing a modified elastomer composition, comprising a step of melt-kneading the following components (A) to (E).
Component (A): Ethylene/α-olefin copolymer rubber Component (B): Propylene resin Component (C): Hydrogenated product of styrene/conjugated diene block copolymer Component (D): Unsaturated silane compound Component ( E): Peroxide

[12] A step of melt-kneading the following components (A) to (E) to obtain a modified elastomer composition, and extruding the modified elastomer composition and component (G): a silanol catalyst to obtain an extrudate. and exposing the extruded body to a water atmosphere to obtain an extruded body made of a crosslinked elastomer composition.
Component (A): Ethylene/α-olefin copolymer rubber Component (B): Propylene resin Component (C): Hydrogenated product of styrene/conjugated diene block copolymer Component (D): Unsaturated silane compound Component ( E): Peroxide

INDUSTRIAL APPLICABILITY According to the present invention, there are provided a modified elastomer composition and a crosslinked elastomer composition capable of obtaining an extrudate having excellent extrusion moldability, compression set, flexibility and extrusion appearance, and an extrudate using the same. can do.
The modified elastomer composition and the crosslinked elastomer composition of the present invention, and the extrudates using the same, are exposed to applications requiring good rubber elasticity in which conventional thermosetting rubbers are used, and to severe usage environments. It can be expected to be developed for various uses.

Embodiments of the present invention will be described in detail below, but the present invention is not limited to the following description, and can be arbitrarily modified and implemented without departing from the scope of the present invention. In this specification, when a numerical value or a physical property value is sandwiched before and after the "~", it is used to include the values before and after it.

[Modified elastomer composition]
The modified elastomer composition of the present invention is a modified elastomer composition comprising the following components (A) to (D) and grafted with the following component (E), and more preferably the following component (F) and component ( H).
Component (A): Ethylene/α-olefin copolymer rubber Component (B): Propylene resin Component (C): Hydrogenated product of styrene/conjugated diene block copolymer Component (D): Unsaturated silane compound component ( E): Peroxide component (F): Hydrocarbon rubber softener component (H): Polyphenylene ether resin

<Mechanism>
The mechanism by which the modified elastomer composition of the present invention provides an extruded body that is excellent in extrusion moldability and compression set properties, is flexible, and has a good appearance after extrusion is presumed to be as follows.
The components (A) and (C) are grafted by the components (D) and (E), and high rubber elasticity can be obtained, resulting in excellent compression set characteristics. In addition, the use of component (C) and further component (F) can impart flexibility and good extrusion appearance. Furthermore, by adding the component (B), good extrusion moldability (molding stability) can be imparted. Furthermore, by adding the component (H), the compression set property can be improved.

<Component (A): Ethylene/α-olefin copolymer rubber>
Component (A) is an ethylene/α-olefin copolymer rubber. The ethylene/α-olefin copolymer rubber of component (A) is a copolymer containing the largest number of ethylene units among its constitutional units, and known ethylene/α-olefin copolymer rubbers are appropriately used. The ethylene unit content of the ethylene/α-olefin copolymer rubber is preferably 60 to 99% by mass, more preferably 60 to 85% by mass. When the ethylene unit content is within the above range, it tends to be easy to obtain a modified elastomer composition having excellent mechanical strength and rubber elasticity.

The density of the ethylene/α-olefin copolymer rubber (A) used in the present invention (measured according to JIS K6922-1, 2:1997) is preferably 0.855 to 0.900 g/cm ³ , It is more preferably 0.860 to 0.895 g/cm ³ , still more preferably 0.860 to 0.890 g/cm ³ , and particularly preferably 0.860 to 0.880 g/cm ³ . When the density is equal to or less than the above upper limit, there is a tendency to be flexible and to be excellent in resistance to compression set. If the density is at least the above lower limit, the tensile strength is excellent.

Specific examples of the ethylene/α-olefin copolymer rubber used in the present invention include ethylene/propylene copolymer, ethylene/1-butene copolymer, ethylene/4-methyl-1-pentene copolymer, Examples thereof include copolymer rubbers of ethylene and one or more α-olefins having 3 to 10 carbon atoms, such as ethylene/1-hexene copolymers and ethylene/1-octene copolymers.

Although the type of catalyst used in producing the ethylene/α-olefin copolymer rubber is not particularly limited, examples thereof include Ziegler-Natta catalysts and metallocene catalysts. Among these, an ethylene/α-olefin copolymer rubber produced with a metallocene catalyst is preferred.

The ethylene/α-olefin copolymer rubber used in the present invention has a melting end peak temperature (hereinafter sometimes referred to as “melting end point”) measured by a differential scanning calorimeter (DSC) of 115° C. or higher. things are preferred. When the melting end point of the ethylene/α-olefin copolymer rubber is 115° C. or higher, the shape can be maintained by crystals even at high temperatures, resulting in good compression set characteristics. From this point of view, the melting end point of the ethylene/α-olefin copolymer rubber is preferably 115° C. or higher, particularly 117° C. or higher. However, if the melting end point of the ethylene/α-olefin copolymer rubber is excessively high, there is a risk of poor appearance due to unmelted lumps during molding temperature rise and premature crystallization (melt fracture) during molding cooling. Therefore, the melting end point of the ethylene/α-olefin copolymer rubber is usually 145° C. or lower. The melting end point of the ethylene/α-olefin copolymer rubber is measured by the method described in Examples below.

The content of each structural unit of component (A) can be determined by infrared spectroscopy and NMR method. The content of each structural unit of component (B) described later can be determined by infrared spectroscopy.

The melt flow rate (MFR) of the ethylene/α-olefin copolymer rubber used in the present invention is the melt flow rate (MFR ), preferably 0.01 to 30 g/10 min. By setting the upper limit of the MFR of the ethylene/α-olefin copolymer rubber used in the present invention to 30 g/10 minutes or less, it is possible to prevent the compression set from being excessively large and to maintain good sealing properties. Further, by setting the lower limit of the MFR to 0.01 g/10 minutes or more, it is possible to suppress deterioration of productivity due to an increase in resin pressure when the modified elastomer composition of the present invention is produced by melt extrusion. From these points of view, the MFR of the ethylene/α-olefin copolymer rubber is more preferably 0.1 g/10 minutes or more, and more preferably 20 g/10 minutes or less.

The ethylene/α-olefin copolymer rubber used in the present invention is commercially available. For example, ENGAGE (registered trademark) series manufactured by Dow Chemical Company, Kernel (registered trademark) series manufactured by Japan Polyethylene Co., Ltd., Infuse (INFUSE) (registered trademark) series manufactured by Dow Chemical Company, Toughmer (registered trademark) manufactured by Mitsui Chemicals, Inc. (registered trademark) series and Mitsui Chemicals Evolue (registered trademark) series.

The ethylene/α-olefin copolymer rubber of component (A) can be used alone or in any combination and ratio of two or more.

<Component (B): Propylene resin>
The component (B) propylene-based resin used in the present invention is a propylene-based resin having a propylene unit content of 40 to 100% by mass relative to the total monomer units contained in the resin, and preferably has an ethylene unit content of It is 0 to 50% by mass.

The type of propylene-based resin of component (B) is not particularly limited, and any of propylene homopolymers, propylene random copolymers, propylene block copolymers, and the like can be used. Also, one of these may be used, or two or more may be used in combination.

When component (B) is a propylene random copolymer or a propylene block copolymer, monomers to be copolymerized with propylene include ethylene, 1-butene, 2-methylpropylene, 1-pentene, 3-methyl- One or more α-olefins such as 1-butene, 1-hexene, 4-methyl-1-pentene and 1-octene can be exemplified. Further, when the component (B) is a propylene block copolymer, it may be a propylene block copolymer obtained by polymerization in multiple stages. Examples include propylene block copolymers obtained by polymerizing propylene/ethylene copolymers in stages.

The content of propylene units in the polypropylene-based resin of component (B) is at least 40% by mass, preferably at least 50% by mass. When the propylene unit content is at least the above lower limit, moldability and molding appearance tend to be good. On the other hand, the upper limit of the propylene unit content is not particularly limited, and is usually 100% by mass.

The melt flow rate (MFR) of the propylene-based resin of component (B) is usually 0.01 g/10 minutes or more when measured according to JIS K 7210 (2014) at 230°C under a load of 21.2N. From the viewpoint, it is preferably 0.1 g/10 minutes or more, more preferably 0.2 g/10 minutes or more, and still more preferably 0.5 g/10 minutes or more. On the other hand, it is usually 100 g/10 minutes or less, preferably 30 g/10 minutes or less, more preferably 20 g/10 minutes or less, still more preferably 10 g/10 minutes or less from the viewpoint of moldability.

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

The propylene-based resin of component (B) can be obtained as a commercial product. For example, Prim Polypro (registered trademark) manufactured by Prime Polymer Co., Ltd., Sumitomo Noblen (registered trademark) manufactured by Sumitomo Chemical Co., Ltd., propylene-ethylene random copolymer manufactured by SunAllomer Co., Ltd., Novatec (registered trademark) PP manufactured by Nippon Polypro Co., Ltd., Moplen (registered trademark) manufactured by LyondellBasell Co., Ltd. Trademarks), Adflex®, Hiflex®, Hifax®, ExxonMobil PP from ExxonMobil, Formolene® from Formosa Plastics, Borealis PP from Borealis, SEETEC PP from LG Chemical, A. Ｓｃｈｕｌｍａｎ社製ＡＳＩ ＰＯＬＹＰＲＯＰＹＬＥＮＥ、ＩＮＥＯＳ Ｏｌｅｆｉｎｓ＆Ｐｏｌｙｍｅｒｓ社製ＩＮＥＯＳ ＰＰ、Ｂｒａｓｋｅｍ社製Ｂｒａｓｋｅｍ ＰＰ、ＳＡＭＳＵＮＧ ＴＯＴＡＬ ＰＥＴＲＯＣＨＥＭＩＣＡＬＳ社製Ｓｕｍｓｕｎｇ Ｔｏｔａｌ、Ｓａｂｉｃ社製Ｓａｂｉｃ（登録商標）ＰＰ、ＴＯＴＡＬ ＰＥＴＲＯＣＨＥＭＩＣＡＬＳ社製ＴＯＴＡＬ ＰＥＴＲＯＣＨＥＭＩＣＡＬＳ Ｐｏｌｙｐｒｏｐｙｌｅｎｅ、ＳＫ社製ＹＵＰＬＥＮＥ（ You can select and use the corresponding product from the registered trademark).

The propylene-based resin of component (B) can be used alone or in any combination and ratio of two or more.

<Component (C): Hydrogenated product of styrene/conjugated diene block copolymer>
The modified elastomer composition of the present invention further contains a hydrogenated styrene/conjugated diene block copolymer as component (C). When the modified elastomer composition of the present invention contains the hydrogenated product of the styrene/conjugated diene block copolymer as the component (C), it is possible to further reduce the compression set and improve the flexibility. .

The hydrogenated styrene/conjugated diene block copolymer of Component (C) used in the present invention comprises at least two polymer blocks P derived from a vinyl aromatic compound and at least one polymer block P derived from a conjugated diene. A hydrogenated block copolymer obtained by hydrogenating a block copolymer having coalescing block Q is preferred.

In the component (C), the monomeric vinyl aromatic compound constituting the block P is not particularly limited, but styrene derivatives such as styrene and α-methylstyrene are preferred. Among them, it is preferable to use styrene as a main component. Here, "mainly" in component (C) means that the content of the structural unit in the block is 50% by mass or more. In addition, the block P may contain a monomer other than the vinyl aromatic compound as a raw material.

Examples of monomers other than the above vinyl aromatic compounds include ethylene and α-olefins. Moreover, when the block P contains a monomer other than the vinyl aromatic compound as a raw material, the content thereof is 50% by mass or less, preferably 40% by mass or less. When the content of the monomer other than the vinyl aromatic compound is within this range, heat resistance and compression set tend to be good.

Although the conjugated diene of the monomer constituting the block Q is not particularly limited, it is preferably mainly composed of butadiene and/or isoprene, and more preferably mainly composed of butadiene. Note that the block Q may contain a monomer other than the conjugated diene as a raw material.

Examples of monomers other than the conjugated dienes include isobutylene and styrene. Moreover, when the block Q contains a monomer other than the conjugated diene as a raw material, the content thereof is 50% by mass or less, preferably 40% by mass or less. Bleed-out tends to be suppressed when the content of the monomer other than the conjugated diene is within this range.

Component (C) is a hydrogenated block copolymer obtained by hydrogenating a block copolymer having at least two polymer blocks P and at least one polymer block Q. More specifically, it is a hydrogenated block copolymer obtained by hydrogenating the double bond of block Q of the block copolymer. Although the hydrogenation rate of block Q is not particularly limited, it is preferably 80 to 100% by mass, more preferably 90 to 100% by mass.

Component (C) in the present invention preferably has a structure having at least two polymer blocks P and at least one polymer block Q, and may be linear, branched, or radial. is preferably a block copolymer represented by the following formula (2) or (3).

P-(Q-P) _m (2)
(PQ) _n (3)
(In the formula, P represents polymer block P, Q represents polymer block Q, m represents an integer of 1 to 5, and n represents an integer of 2 to 5.)

In formula (2) or (3), m and n are preferably large in terms of lowering the order-disorder transition temperature of the rubber-like polymer, but small in terms of ease of production and cost. good.

The mass ratio of the block P and the block Q constituting the component (C) is arbitrary, but from the point of view of the good touch feeling of the modified elastomer composition of the present invention, the more the block P, the better. From the viewpoint of suppression of bleed-out and resistance to compression set, the smaller the number of blocks P, the better.

The content of block P in component (C) is preferably 10% by mass or more, more preferably 15% by mass or more, still more preferably 20% by mass or more, and preferably 60% by mass or less, more preferably It is 50% by mass or less, more preferably 45% by mass or less.

In the hydrogenated block copolymer represented by formula (2) and/or formula (3), when block Q is composed only of butadiene, 1,2-bonds (1 , 2-addition structure) is preferably 20 to 90% by mass in order to maintain properties as an elastomer. In order to obtain flexibility and good mechanical strength, the proportion of 1,2-bonds in the microstructure of block Q is more preferably 50-90% by mass, more preferably 60-80% by mass.

The hydrogenated styrene/conjugated diene block copolymer of component (C) used in the present invention has a melt flow rate (MFR) measured under conditions of a temperature of 200° C. and a load of 49 N in accordance with JIS K7210 (2014). and preferably 10 g/10 minutes or less. By setting the upper limit of the MFR of the component (C) used in the present invention to 10 g/10 minutes or less, it is possible to suppress the compression set from becoming too large and to maintain the rubber elasticity well. Also, the MFR is more preferably 5 g/10 minutes or less, still more preferably 1 g/10 minutes or less. The MFR of the styrenic block copolymer of component (C) used in the present invention may be 0 g/10 minutes.

The density of the hydrogenated styrene/conjugated diene block copolymer of component (C) used in the present invention (measured according to JIS K6922-1, 2:1997) is usually 0.88 to 1.00 g/cm ³ . , preferably 0.89 to 0.98 g/cm ³ , more preferably 0.89 to 0.96 g/cm ³ . When the density is equal to or less than the above upper limit, the composition tends to be flexible and excellent in compression set. When the density is at least the above lower limit, the heat resistance tends to be excellent.

The method for producing component (C) in the present invention is not particularly limited as long as the above-described structure and physical properties can be obtained. For example, a block copolymer can be obtained by performing block polymerization in an inert solvent using a lithium catalyst or the like according to the method described in JP-B-40-23798. In addition, hydrogenation (hydrogenation) of block copolymers, for example, JP-B-42-8704, JP-B-43-6636, JP-A-59-133203 and JP-A-60-79005 et al., in the presence of a hydrogenation catalyst in an inert solvent.

The hydrogenated styrene/conjugated diene block copolymer of the component (C) used in the present invention includes a hydrogenated styrene/butadiene/styrene block copolymer and a styrene/isoprene/butadiene/styrene block copolymer. Among them, hydrogenated products of styrene/butadiene/styrene block copolymers are suitable.

Component (C) can be obtained as a commercial item. Commercially available products of component (C) include "Clayton (registered trademark)-G series" manufactured by Kraton Polymer Co., Ltd., "Septon (registered trademark) series" manufactured by Kuraray Co., Ltd., "Hibler (registered trademark) series" manufactured by Asahi Kasei Corporation " Tuftec (registered trademark) series” and the like.

Component (C) may be used singly or in combination of two or more having different block compositions, physical properties and the like.

<Component (D): Unsaturated silane compound>
Although the unsaturated silane compound of component (D) used in the present invention is not limited, an unsaturated silane compound represented by the following formula (1) is preferably used.
RSi(R') ₃ (1)

In the above formula (1), R is an ethylenically unsaturated hydrocarbon group, R 'is independently a hydrocarbon group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, At least one of them is an alkoxy group having 1 to 10 carbon atoms.

In formula (1), R is preferably an ethylenically unsaturated hydrocarbon group having 2 to 10 carbon atoms, more preferably an ethylenically unsaturated hydrocarbon group having 2 to 6 carbon atoms. Specific examples include alkenyl groups such as vinyl, propenyl, butenyl, and cyclohexenyl groups.

In formula (1), R' is preferably a hydrocarbon group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, more preferably a hydrocarbon group having 1 to 4 carbon atoms or 1 to 4 carbon atoms. is an alkoxy group of At least one of R' is preferably an alkoxy group having 1 to 6 carbon atoms, more preferably an alkoxy group having 1 to 4 carbon atoms. The hydrocarbon group of 1 to 10 carbon atoms for R' may be an aliphatic group, an alicyclic group, or an aromatic group, but is preferably an aliphatic group. The alkoxy group having 1 to 10 carbon atoms for R' may be linear, branched, or cyclic, but is preferably linear or branched. When R' is a hydrocarbon group, specifically, an alkyl group represented by a methyl group, an ethyl group, an isopropyl group, a t-butyl group, an n-butyl group, an i-butyl group, a cyclohexyl group, etc., or a phenyl and aryl groups typified by groups. When R' is an alkoxy group, specific examples include a methoxy group, an ethoxy group, an isopropoxy group and a β-methoxyethoxy group.

When the unsaturated silane compound is represented by the formula (1), at least one of the three R' is an alkoxy group, but two R' are preferably alkoxy groups, and all R' An alkoxy group is more preferred.

As the unsaturated silane compound, among those represented by formula (1), vinyltrialkoxysilanes represented by vinyltrimethoxysilane, vinyltriethoxysilane, propenyltrimethoxysilane and the like are desirable. This is because the vinyl group enables modification of the component (A) into the ethylene/α-olefin copolymer rubber, and the alkoxysilyl group promotes the cross-linking reaction described below. That is, the alkoxysilyl groups graft-modified and introduced into the ethylene/α-olefin copolymer rubber by the unsaturated silane compound react with water in the presence of the silanol catalyst of the component (H) and are hydrolyzed to form silanol. By generating groups and causing dehydration condensation between silanol groups, the ethylene/α-olefin copolymer rubber bonds with each other to cause a cross-linking reaction. In addition, these unsaturated silane compounds may be used individually by 1 type, and may use 2 or more types together.

<Component (E): Peroxide>
Peroxides of component (E) include hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxyesters, and organic peroxides included in the ketone peroxide group. Things are mentioned.

The hydroperoxide group includes cumene hydroperoxide, t-butyl hydroperoxide and the like, and the dialkyl peroxide group includes dicumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5 -di(t-butylperoxy)hexane, 2,5-dimethyl-2,5-di(t-butylperoxyl)-3-hexyne, di(2-t-butylperoxyisopropyl)benzene, etc. , diacyl peroxide group includes lauryl peroxide, benzoyl peroxide and the like. The peroxyester group includes t-butylperoxyacetate, t-butylperoxybenzoate, t-butylperoxyisopropyl carbonate and the like, and the ketone peroxide group includes cyclohexanone peroxide and the like.

Among these, a radical generator having a high thermal decomposition temperature is preferable from the viewpoint of graft reaction in the melt-kneading process by an extruder when manufacturing the modified elastomer composition of the present invention. From this point of view, di-t-butyl peroxide, di(2-t-butylperoxyisopropyl)benzene, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane and dicumyl peroxide are preferred. .

Peroxides of component (E) can be used singly or in any combination and ratio of two or more.

<Component (F): softener for hydrocarbon rubber>
The modified elastomer composition of the present invention can contain a hydrocarbon rubber softener as component (F) from the viewpoint of increasing flexibility and improving workability, fluidity and oil resistance.

Examples of the component (F) hydrocarbon-based rubber softener include mineral oil-based rubber softeners and synthetic resin-based rubber softeners. , mineral oil-based rubber softeners are preferred.

Mineral oil-based rubber softeners are generally mixtures of aromatic hydrocarbons, naphthenic hydrocarbons and paraffinic hydrocarbons, and the ratio of carbon of paraffinic hydrocarbons to the total carbon atoms is 50% or more. Those with a carbon ratio of 30 to 45% are called naphthenic oils, and aromatic hydrocarbons with a carbon ratio of 35% or more are called aromatic oils. ing. Among these, liquid hydrocarbon rubber softeners that are liquid at room temperature (23±2° C.) are preferred, and liquid paraffin oils that are liquid at room temperature are more preferred.
By using a liquid hydrocarbon-based rubber softener as the hydrocarbon-based rubber softener, the flexibility and elasticity of the modified elastomer composition of the present invention can be increased, and the processability and fluidity are dramatically improved. tend to improve.

The paraffin oil is not particularly limited, but preferably has a kinematic viscosity at 40° C. of usually 10 cSt (centistokes) or more, preferably 20 cSt or more, and usually 800 cSt or less, preferably 600 cSt or less. Further, the pour point is usually -40°C or higher, preferably -30°C or higher, and preferably 0°C or lower. Furthermore, the flash point (COC) is usually 200° C. or higher, preferably 250° C. or higher, and usually 400° C. or lower, preferably 350° C. or lower.

The softener for hydrocarbon rubber of component (F) can be used alone or in any combination and ratio of two or more.

<Component (G): Silanol catalyst>
By blending the component (G) silanol catalyst with the modified elastomer composition of the present invention, the modified elastomer composition can undergo an intermolecular cross-linking reaction to obtain a cross-linked elastomer composition. That is, the ethylene/α-olefin copolymer rubber of the component (A) in the modified elastomer composition, preferably the hydrogenated product of the styrene/conjugated diene block copolymer of the component (C), is graft-modified and introduced. The resulting alkoxysilyl group reacts with water in the presence of a silanol catalyst and hydrolyzes to form a silanol group, and the silanol groups undergo dehydration condensation to proceed with the cross-linking reaction, resulting in modified ethylene. - Hydrogenated products of α-olefin copolymer rubber and styrene/conjugated diene block copolymers can bond with each other to form a crosslinked elastomer composition with excellent heat resistance.

The silanol catalyst of component (G) that can be used in the present invention includes the group consisting of metal organic acid salts, titanates, borates, organic amines, ammonium salts, phosphonium salts, inorganic and organic acids, and inorganic acid esters. One or more compounds selected from and the like.

Examples of metal organic acid salts include dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin diacetate, dibutyltin dioctoate, stannous acetate, stannous octoate, cobalt naphthenate, lead octylate, lead naphthenate, and octylic acid. Zinc, zinc caprylate, iron 2-ethylhexanoate, iron octylate, iron stearate. Titanates include, for example, tetrabutyl titanate, tetranonyl titanate, bis(acetylacetonitrile) di-isopropyl titanate. Organic amines include, for example, ethylamine, dibutylamine, hexylamine, triethanolamine, tetramethylguanidine, and pyridine. Examples of ammonium salts include ammonium carbonate and tetramethylammonium hydroxide. Phosphonium salts include, for example, tetramethylphosphonium hydroxide. Examples of inorganic acids and organic acids include sulfonic acids such as sulfuric acid, hydrochloric acid, acetic acid, stearic acid, maleic acid, toluenesulfonic acid, and alkylnaphthylsulfonic acid. Examples of inorganic acid esters include phosphates such as ethylhexyl phosphate.

Among these, metal organic acid salts, sulfonic acids, and phosphoric acid esters are preferred, and metal carboxylates of tin (eg, dioctyltin dilaurate), alkylnaphthylsulfonic acids, and ethylhexyl phosphates are more preferred. .

The silanol catalysts listed above may be used alone or in combination of two or more.

The silanol catalyst is preferably used as a masterbatch in which the polyolefin and the silanol catalyst are blended. Polyolefins that can be used in this masterbatch include polyethylene, polypropylene, and ethylene/α-olefin copolymers.

Examples of polyethylene include (branched or linear) ethylene homopolymers such as low-, medium-, and high-density polyethylene; ethylene/propylene copolymers, ethylene/1-butene copolymers, ethylene/4-methyl- Ethylene/α-olefin copolymers such as 1-pentene copolymer, ethylene/1-hexene copolymer, ethylene/1-octene copolymer; ethylene/vinyl acetate copolymer, ethylene/(meth)acrylic acid Ethylene-based copolymer resins such as copolymers and ethylene/(meth)acrylic acid ester copolymers can be mentioned.

Among these, in the present invention, high-pressure low-density polyethylene, high-density polyethylene, and ethylene/α-olefin copolymer, which are excellent in balance between heat resistance and strength, are preferred. More preferably, the ethylene/α-olefin copolymer is an ethylene/1-butene copolymer, an ethylene/4-methyl-1-pentene copolymer, an ethylene/1-hexene copolymer, or an ethylene/1-octene copolymer. It is an ethylene/α-olefin copolymer such as a copolymer, and this ethylene/α-olefin copolymer contains 2 to 60% by mass of one or more α-olefins and 40 to 98% by mass of ethylene. It is more preferable to copolymerize with. The masterbatch of the silanol catalyst may use only one of these polyolefins, or a blend of two or more thereof.

When the silanol catalyst is used as a masterbatch in which a polyolefin and a silanol catalyst are blended, the content of the silanol catalyst in the masterbatch is not particularly limited, but it is usually about 0.1 to 5.0% by mass. preferable.

A commercially available product can be used as the silanol catalyst-containing masterbatch, and for example, "LZ082" and "LZ033" manufactured by Mitsubishi Chemical Corporation can be used.

<Component (H): Polyphenylene ether resin>
The component (H) polyphenylene ether resin used in the present invention is a resin having a repeating unit represented by the following formula (I).

(Here, R ¹ , R ² , R ³ and R ⁴ represent a hydrogen atom, a halogen atom, or a hydrocarbon group which may have a substituent, and may be the same or different.)

The polyphenylene ether resin used in the present invention preferably has an intrinsic viscosity of 0.1 to 0.8 dl/g at 30° C. measured in chloroform. The intrinsic viscosity of the polyphenylene ether resin is more preferably 0.2 to 0.7 dl/g, still more preferably 0.25 to 0.6 dl/g. If the intrinsic viscosity of the polyphenylene ether-based resin is 0.1 dl/g or more, the effect of improving the compression set at high temperature can be easily obtained, and if it is 0.8 dl/g or less, moldability can be sufficiently satisfied. .

As such a polyphenylene ether resin, a known resin can be used. Specific examples include poly(2,6-dimethyl-1,4-phenylene ether), poly(2-methyl-6-ethyl-1,4-phenylene ether), poly(2,6-diphenyl-1 ,4-phenylene ether), poly(2-methyl-6-phenyl-1,4-phenylene ether), poly(2,6-dichloro-1,4-phenylene ether). It is also possible to use polyphenylene ether copolymers such as copolymers of 2,6-dimethylphenol and other phenols (for example, 2,3,6-trimethylphenol and 2-methyl-6-butylphenol). can. Among these, poly(2,6-dimethyl-1,4-phenylene ether) and copolymers of 2,6-dimethylphenol and 2,3,6-trimethylphenol are preferred, and poly(2 ,6-dimethyl-1,4-phenylene ether).

These polyphenylene ether-based resins may be used singly or in combination of two or more.

As the polyphenylene ether-based resin of component (H), a commercially available product can be used, for example, "Iupital (registered trademark) PX100F" manufactured by Mitsubishi Engineering-Plastics Corporation can be used.

<Blending ratio>
The modified elastomer composition of the present invention preferably contains 1 to 100 parts by mass of component (B) per 100 parts by mass of component (A). When the content of component (B) is at least the above lower limit, there is a tendency for excellent extrusion moldability. When the content of the component (B) is equal to or less than the above upper limit, the compression set tends to be excellent. From this point of view, it is more preferable to contain 5 to 80 parts by mass of component (B) per 100 parts by mass of component (A).

The modified elastomer composition of the present invention preferably contains 1 to 100 parts by mass of component (C) per 100 parts by mass of component (A). When the content of component (C) is at least the above lower limit, mechanical properties, flexibility, and extrusion appearance tend to be excellent. When the content of the component (C) is equal to or less than the above upper limit, the compression set tends to be excellent. From this point of view, it is more preferable to contain 5 to 80 parts by mass of component (C) per 100 parts by mass of component (A).

The content of component (D) is 0.01 to 10 parts by mass with respect to a total of 100 parts by mass of component (A), component (B), component (C), and optionally used component (F). and more preferably 0.05 to 5 parts by mass, still more preferably 0.1 to 4 parts by mass, from the viewpoint of sufficiently advancing the cross-linking reaction.

The content of component (E) is 0.01 to 3 parts by mass with respect to a total of 100 parts by mass of component (A), component (B), component (C), and optionally used component (F). and more preferably 0.03 to 2 parts by mass, still more preferably 0.05 to 1 part by mass, from the viewpoint of obtaining a sufficient cross-linking reaction and maintaining a good molding appearance.

When the modified elastomer composition of the present invention contains component (F), the content of component (F) is preferably 1 to 100 parts by mass per 100 parts by mass of component (A) and component (B). When the content of the component (F) is at least the above lower limit, the component (F) can sufficiently improve the flexibility, and when it is at most the above upper limit, bleeding out from the surface can be suppressed. From this point of view, the content of component (F) is more preferably 5 to 50 parts by mass with respect to the total of 100 parts by mass of components (A) and (B).

When the silanol catalyst of component (G) is blended with the modified elastomer composition of the present invention, the blending amount is not particularly limited, but with respect to 100 parts by mass of the modified elastomer composition excluding component (G), It is preferably 0.0001 to 0.01 parts by mass, more preferably 0.0001 to 0.005 parts by mass. When the amount of the silanol catalyst is at least the above lower limit, the crosslinking reaction proceeds sufficiently, and a crosslinked elastomer composition having good heat resistance tends to be easily obtained. It is preferable because cross-linking is less likely to occur and the strand surface and product appearance tend to be less rough.

When the modified elastomer composition of the present invention contains component (H), the content of component (H) is preferably 1 to 200 parts by mass per 100 parts by mass of component (A) and component (B). When the content of component (H) is at least the above lower limit, the effect of improving compression set by component (H) can be sufficiently obtained, and when the content is at most the above upper limit, the effect of improving flexibility can be sufficiently obtained. can be done. From this point of view, the content of component (H) with respect to a total of 100 parts by mass of components (A) and (B) is more preferably 1 to 100 parts by mass, more preferably 2 to 70 parts by mass. It is preferably 5 to 50 parts by mass, and particularly preferably 5 to 50 parts by mass.

<Other ingredients>
In addition to the above components, the modified elastomer composition of the present invention contains various additives and fillers as other components, resins and elastomers other than components (A), (B), (C) and (H), and the like. can be contained within a range that does not impair the effects of the present invention.

Examples of additives include antioxidants, heat stabilizers, ultraviolet absorbers, light stabilizers, antistatic agents, crystal nucleating agents, rust inhibitors, viscosity modifiers, foaming agents, lubricants and pigments. . Among these, it is preferable to contain an antioxidant, particularly a phenolic antioxidant, a sulfur-based antioxidant or a phosphorus-based antioxidant. The antioxidant is preferably contained in an amount of 0.1 to 1 part by mass with respect to 100 parts by mass of the modified elastomer composition of the present invention.

Other resins include, for example, polyolefin resins other than components (A) and (B), polyester resins, polycarbonate resins, polymethyl methacrylate resins, rosin and its derivatives, terpene resins, petroleum resins and their derivatives, and alkyd resins. , alkylphenol resins, terpene phenol resins, coumarone-indene resins, synthetic terpene resins, alkylene resins, polyamide-based elastomers such as polyamide-polyol copolymers; polyvinyl chloride-based elastomers and polybutadiene-based elastomers; Elastomers, hydrogenated products thereof, those modified with an acid anhydride or the like to introduce a polar functional group, and those obtained by grafting, random and/or block copolymerizing other monomers may be mentioned.

<Production and molding of modified elastomer composition>
The modified elastomer composition of the present invention comprises components (A), (B) and (C), an unsaturated silane compound as component (D) and a peroxide as component (E), and optionally component (F). ), (H) and other components described above are mechanically mixed by a known method such as a Henschel mixer, a V blender, or a tumbler blender, and then mechanically melt-kneaded by a known method. can be done. For this melt-kneading, a general melt-kneader such as a Banbury mixer, various kneaders, a single-screw extruder or a twin-screw extruder can be used. Further, as shown in the examples below, when the composition of the present invention is kneaded with a single-screw or twin-screw extruder or the like, it is usually heated to 120 to 240°C, preferably 120 to 220°C. Melt-kneading can be performed at

The modified elastomer composition of the present invention is blended with the silanol catalyst described above, molded by various molding methods such as extrusion molding, injection molding, and press molding, and then exposed to a water atmosphere to cause a cross-linking reaction between silanol groups. It can be advanced to form a molded article made of the crosslinked elastomer composition. Various conditions can be adopted for the method of exposing to a water atmosphere, including a method of leaving in air containing moisture, a method of blowing air containing water vapor, a method of immersion in a water bath, and a method of sprinkling hot water in the form of a mist. and the like.

The rate of progress of the cross-linking reaction is determined by the conditions of exposure to the water atmosphere, but the temperature range is usually 0 to 130° C. and the exposure time is 5 minutes to 1 week. Particularly preferred conditions are a temperature range of 40 to 90° C. and a range of 30 minutes to 24 hours. When using moist air, the relative humidity is selected from the range of 1-100%.

The degree of cross-linking of the thus-obtained cross-linked elastomer composition of the present invention can be adjusted by changing the type and amount of the silanol catalyst and the conditions (temperature, time) for cross-linking.

<Duro A hardness>
The crosslinked elastomer composition of the present invention preferably has a Duro A hardness of 30 to 90 measured according to JIS K6253 (2012) (Duro-A). If the Duro A hardness is 30 or more, the surface hardness is excellent. On the other hand, if the Duro A hardness is 90 or less, the compression set is excellent. From the viewpoint of flexibility, the crosslinked elastomer composition of the present invention preferably has a Duro A hardness of 70 or less, more preferably 65 or less.

<Application>
Applications of the modified elastomer composition and crosslinked elastomer composition of the present invention are not particularly limited. , industrial parts, other sports, miscellaneous goods, medical parts, food parts, household appliance parts, and wire coating materials.
Since the modified elastomer composition and the crosslinked elastomer composition of the present invention are particularly excellent in extruded appearance, they are preferably applied to these uses as extruded articles, but are not limited to extruded articles.

Specific embodiments of the present invention will be described in more detail below using examples, but the present invention is not limited by the following examples as long as the gist thereof is not exceeded. Various production conditions and values of evaluation results in the following examples have the meaning of preferred values of the upper limit or the lower limit in the embodiments of the present invention, and the preferred range is the above-described upper limit or lower limit value. , the range defined by the values in the following examples or a combination of the values in the examples.

In the following examples and comparative examples, raw materials used for preparing modified elastomer compositions and methods for evaluating the obtained modified elastomer compositions are as follows.

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

<Component (A) Ethylene/α-olefin copolymer rubber>
(A): ENGAGE (registered trademark) XLT8677 (manufactured by Dow Chemical Company)
Ethylene/α-olefin copolymer rubber α-olefin: 1-octene Density: 0.870 g/cm ³
Melting end point: 123°C
MFR: 0.5g/10min (190°C, 21.2N load)

<Component (B) propylene resin>
(B): Novatec (registered trademark) PP EA9 (manufactured by Japan Polypropylene Corporation)
Propylene unit content: 100% by mass
MFR: 0.5g/10min (230°C, 21.2N load)

<Component (C) Hydrogenated product of styrene/conjugated diene block copolymer>
(C)-1: Kraton (registered trademark) G1651HU (manufactured by Kraton Polymer Co., Ltd.)
Hydrogenated styrene/butadiene/styrene block copolymer MFR: <1 g/10 min (200°C, 49N load)
Density: 0.91 g/cm ³ (catalog value)
Styrene block content: 33% by mass (catalog value)
1,2-bond ratio of butadiene part: 30% by mass
1,4-bond ratio of butadiene part: 70% by mass
(C)-2: Kraton (registered trademark) G1641HU (manufactured by Kraton Polymer Co., Ltd.)
Hydrogenated styrene/butadiene/styrene block copolymer MFR: <1 g/10 min (200°C, 49N load)
Density: 0.92 g/cm ³ (catalog value)
Styrene block content: 33% by mass (catalog value)
1,2-bond ratio of butadiene part: 70% by mass
1,4-bond ratio of butadiene part: 30% by mass
(C′)-1: Asaprene (registered trademark) T411 (manufactured by Asahi Kasei Corporation)
Styrene/butadiene/styrene block copolymer MFR: 0 g/10 min (200° C., 49 N load)
Density: 0.94g/ ^cm3
Styrene block content: 30% by mass

<Component (D) unsaturated silane compound>
(D): KBM-1003 (manufactured by Shin-Etsu Chemical Co., Ltd.)
vinyltrimethoxysilane

<Component (E) Peroxide>
(E): Trigonox 101-40C (manufactured by Kayaku Nourion Co., Ltd.)
A mixture of 40% by mass of 2,5-dimethyl-2,5-di(t-butylperoxy)hexane and 60% by mass of organic filler

<Component (F) softener for hydrocarbon rubber>
(F): Diana (registered trademark) process oil PW90 (manufactured by Idemitsu Kosan Co., Ltd.)
Paraffinic oil Kinematic viscosity at 40°C: 95.54 cSt
Pour point: -15°C
Flash point: 272°C

<Component (G) Silanol catalyst>
(G): Silanol catalyst masterbatch (MB) LZ033 (manufactured by Mitsubishi Chemical Corporation)
Linear low-density polyethylene containing 0.12 wt% tin catalyst (dioctyltin dilaurate)

<Component (H) polyphenylene ether resin>
(H): Iupital (registered trademark) PX100F (manufactured by Mitsubishi Engineering-Plastics)
Poly(2,6-dimethyl-1,4-phenylene ether)
Intrinsic viscosity at 30°C measured in chloroform: 0.38 dl/g

[Evaluation method]
<Melting end point of component (A)>
Using a differential scanning calorimeter manufactured by Hitachi High-Tech Science Co., Ltd., trade name "DSC6220", according to JIS K7121 (2012), about 5 mg of the sample is heated from 20 ° C. to 200 ° C. at a heating rate of 100 ° C./min. After heating and holding at 200 ° C. for 3 minutes, the temperature was lowered to -10 ° C. at a cooling rate of 10 ° C./min, and then the temperature was increased to 200 ° C. at a heating rate of 10 ° C./min. The peak end point (°C) was calculated and taken as the melting end point.

<Evaluation of Modified Elastomer Composition>
(1) Extrusion Moldability The sheet shape stability during extrusion molding appearance evaluation was evaluated.
〇: Shape stability passed ×: Shape stability failed

(2) Surface Hardness Duro A hardness (after 15 seconds) was measured for the sheet for surface hardness evaluation in accordance with JIS K6253 (2012) (Duro-A).

(3) Compression set The sheet for compression set evaluation conforms to the standard of JIS K6262 (2013), 70 ° C., 22 hours, 25% compression, A method (immediate release) and B method (2 at 23 ° C. time held and then released).

(4) Tensile test The sheet for tensile test evaluation was measured for tensile stress at break and elongation at break at a dumbbell shape No. 3 at a test speed of 500 mm/min according to JIS K6251 (2017).

(5) Extrusion Molding Appearance The surface condition of the sheet for extrusion molding appearance evaluation was visually confirmed, and the surface smoothness was evaluated according to the following criteria.
5: The surface is smooth and the extruded appearance is very excellent.
4: The surface is smooth and the extruded appearance is excellent.
3: The surface smoothness is slightly inferior, but the appearance of extrusion molding is within the allowable range.
2: Poor surface smoothness and inferior extrusion appearance.
1: Very poor surface smoothness and very poor extrusion appearance.

[Example 1]
As shown in Table 1, 100 parts by mass of component (A), 14 parts by mass of component (B), 14 parts by mass of component (C)-1, 2.1 parts by mass of component (D), component (E) 0.11 parts by mass (amount of 2,5-dimethyl-2,5-di(t-butylperoxy)hexane alone in component (E) (40% of the actual amount)), component (F) 14 parts by mass and 3.3 parts by mass of PC40C manufactured by Dainichiseika Co., Ltd. as a pigment were added to 100 parts by mass of the total amount of components (A) to (F) and mixed for 1 minute with a Henschel mixer. Next, the obtained mixture is introduced into the upstream supply port of a co-directional twin-screw extruder (manufactured by Japan Steel Works, Ltd., product number: TEX30, L/D = 46, number of cylinder blocks: 12) with a mass feeder. did. At a discharge rate of 25 kg/h in total, the temperature was raised from the upstream portion to the downstream portion in the range of 120 to 200° C. for melt-kneading and pelletization to produce a modified elastomer composition.
4 parts by mass of LZ033 as component (G) silanol catalyst MB (0.0048 parts by mass as tin catalyst) were added to 100 parts by mass of the modified elastomer composition obtained. Using an in-line screw type injection molding machine (manufactured by Nippon Steel Co., Ltd., product number: J110AD), the composition was injection molded under the conditions of a cylinder temperature of 220 ° C. and a mold temperature of 40 ° C. to obtain a thickness of 2 mm × A sheet having a width of 100 mm and a length of 100 mm was formed. Furthermore, it was exposed to a constant temperature and humidity machine under the conditions of 85° C. and 85% RH for 24 hours to obtain a sheet for evaluation of surface hardness, compression set and tensile test.

In addition, regarding the appearance of extrusion molding, a modified polyolefin composition containing 4 parts by mass of LZ033 as a component (G) silanol condensation catalyst MB (0.0048 parts by mass as a tin catalyst) was added to 100 parts by mass of the modified polyolefin composition. The polyolefin composition was extruded by an IKG single-screw extruder with a diameter of 40 mm (L/D = 28, compression ratio = 2.0, full-flight screw), using a sheet-shaped die with a width of 25 mm and a thickness of 1 mm, and the molding temperature was Under the hopper: Extrusion was performed under the conditions of 130° C., cylinder temperature of 160 to 200° C., die temperature of 200° C., and screw rotation speed of 30 rpm to obtain a sheet for evaluation of extrusion appearance.

Table 1 shows various physical properties of the evaluation sheet using the modified elastomer composition of Example 1 and evaluation results of extrusion molding appearance.

[Examples 2-4, Comparative Examples 1-2, Comparative Examples 5-6]
Pellets of the modified elastomer compositions of Examples 2 to 4 and Comparative Examples 1 to 2 and 5 to 6 were obtained in the same manner as in Example 1 except that the raw material composition was changed to that shown in Table 1 or Table 2. , each sheet for evaluation was molded in the same manner. Tables 1 and 2 show the evaluation results of various physical properties and extrusion appearance.

[Comparative Example 3]
As shown in Table 2, 100 parts by mass of component (A), 13 parts by mass of component (B), 1.9 parts by mass of component (D), and 0.1 part by mass of component (E) (in component (E) 2,5-dimethyl-2,5-di(t-butylperoxy)hexane alone (40% of the actual amount)), and PC40C manufactured by Dainichiseika Co., Ltd. as a pigment for components (A) to (F ) was added to the total amount of 100 parts by mass, and mixed with a Henschel mixer for 1 minute. Next, the obtained mixture is introduced into the upstream supply port of a co-directional twin-screw extruder (manufactured by Japan Steel Works, Ltd., product number: TEX30, L/D = 46, number of cylinder blocks: 12) with a mass feeder. Then, 13 parts by mass of the component (F) was supplied from the 10th position of the cylinder block from the upstream. At a discharge rate of 25 kg/h in total, the temperature was raised from the upstream portion to the downstream portion in the range of 120 to 200° C. for melt-kneading and pelletization to produce a modified elastomer composition.
Each sheet for evaluation was molded in the same manner as in Example 1 using this modified elastomer composition. Table 2 shows the evaluation results of various physical properties and extrusion molding appearance.

[Comparative Example 4]
A modified elastomer composition of Comparative Example 3 was obtained in the same manner as in Comparative Example 3 except that the raw material composition was changed to that shown in Table 2, and each sheet for evaluation was formed in the same manner. Table 2 shows the evaluation results of various physical properties and extrusion molding appearance.

[Examples 5-6]
As shown in Table 1, 20 parts by mass of component (B), 35 parts by mass of component (C), 35 parts by mass of component (F), and 10 parts by mass of component (H) are blended and mixed for 1 minute in a Henschel mixer. did. Next, the obtained mixture is introduced into the upstream supply port of a co-directional twin-screw extruder (manufactured by Japan Steel Works, Ltd., product number: TEX30, L/D = 46, number of cylinder blocks: 12) with a mass feeder. Then, at a discharge rate of 30 kg/h in total, the temperature was raised from the upstream portion to the downstream portion in the range of 210 to 240° C. for melt-kneading and pelletization to produce a composition. 100 parts by mass of the resulting composition (including 20 parts by mass of component (B), 35 parts by mass of component (C), 35 parts by mass of component (F), and 10 parts by mass of component (H)), component 100 parts by mass of (A), 3.0 parts by mass of component (D), and 0.16 parts by mass of component (E) (2,5-dimethyl-2,5-di(t- 3.3 parts by mass of PC40C manufactured by Dainichiseika Co., Ltd. as a pigment per 100 parts by mass of the total amount of components (A) to (H). The ingredients were blended and mixed in a Henschel mixer for 1 minute. Next, the obtained mixture is introduced into the upstream supply port of a co-directional twin-screw extruder (manufactured by Japan Steel Works, Ltd., product number: TEX30, L/D = 46, number of cylinder blocks: 12) with a mass feeder. Then, at a discharge rate of 25 kg/h in total, the temperature was raised from the upstream portion to the downstream portion in the range of 120 to 200° C. for melt-kneading and pelletization to produce a modified elastomer composition.
Each sheet for evaluation was molded in the same manner as in Example 1 using this modified elastomer composition. Table 1 shows the evaluation results of various physical properties and extrusion molding appearance.

In addition, in Tables 1 and 2, the description of the compounding amounts of the component (G) and other additives is omitted.

[Evaluation results]
As shown in Table 1, Examples 1-6, which correspond to the modified elastomer composition and crosslinked elastomer composition of the present invention, had good extrusion moldability, compression set properties, flexibility, and good extrusion appearance. I know there is.

On the other hand, as shown in Table 2, in Comparative Example 1, since the component (B) and the component (C) were not contained, the shape stability during extrusion was deteriorated, and the extrusion moldability was deteriorated. . Among Comparative Examples 2 to 4 which did not contain component (C), Comparative Example 2 was excellent in moldability but inferior in extrusion appearance and flexibility. In Comparative Examples 3 and 4, since the component (F) was contained, they became softer than Comparative Example 2, but the results were inferior in elongation at break and extrusion molding appearance. Among Comparative Examples 5 and 6 in which a non-hydrogenated styrene-butadiene-styrene block copolymer was used in place of the component (C), in Comparative Example 5, compared with Examples 1 and 2, flexibility and compression A result inferior to the permanent set was obtained. Comparative Example 6 was inferior to Examples 3 and 4 in terms of flexibility and compression set.

The modified elastomer composition and crosslinked elastomer composition of the present invention are excellent in extrusion moldability, resistance to compression set, tactile feel, and injection molding appearance. It can be widely and effectively used in automobile parts such as cushion pads, civil engineering and building material parts such as construction gaskets, sporting goods, industrial parts, household appliance parts, medical parts, food parts, medical equipment parts, electric wires, and miscellaneous goods. is.

Claims (12)

A modified elastomer composition comprising the following components (A) to (D) and grafted with the following component (E).
Component (A): Ethylene/α-olefin copolymer rubber Component (B): Propylene resin Component (C): Hydrogenated product of styrene/conjugated diene block copolymer Component (D): Unsaturated silane compound Component ( E): Peroxide 2. The modified elastomer composition according to claim 1, wherein the ratio of 1,2-bonds in diene monomer units of the conjugated diene block of component (C) is 20 to 90% by mass. 3. The modified elastomer composition according to claim 1, wherein the component (A) has a melting end peak temperature of 115[deg.] C. or higher as measured by a differential scanning calorimeter (DSC). The modified elastomer composition according to any one of claims 1 to 3, wherein the component (D) is a compound represented by the following formula (1).
RSi(R') ₃ (1)
(where R is an ethylenically unsaturated hydrocarbon group, R' is independently a hydrocarbon group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, and at least one of R' is an alkoxy group having 1 to 10 carbon atoms.) Any one of claims 1 to 4, further comprising 1 to 200 parts by mass of component (F): a softening agent for hydrocarbon rubber with respect to a total of 100 parts by mass of component (A) and component (B). A modified elastomer composition according to claim 1. Further component (H): Polyphenylene ether resin, 1 to 200 parts by mass with respect to a total of 100 parts by mass of the component (A) and the component (B), according to any one of claims 1 to 5 A modified elastomeric composition as described. Component (G): a crosslinked elastomer composition obtained by crosslinking the modified elastomer composition according to any one of claims 1 to 6 with a silanol catalyst. 8. The crosslinked elastomer composition according to claim 7, which has a Duro A hardness of 30 or more and 70 or less according to JIS K6253 (2012) (Duro-A). An extrudate of the modified elastomer composition according to any one of claims 1-6. An extrudate of the crosslinked elastomeric composition according to claim 7 or 8. A method for producing a modified elastomer composition comprising a step of melt-kneading the following components (A) to (E).
Component (A): Ethylene/α-olefin copolymer rubber Component (B): Propylene resin Component (C): Hydrogenated product of styrene/conjugated diene block copolymer Component (D): Unsaturated silane compound Component ( E): Peroxide A step of melt-kneading the following components (A) to (E) to obtain a modified elastomer composition, a step of extruding the modified elastomer composition and component (G): a silanol catalyst to obtain an extrudate, and A method for producing an extruded body, comprising the step of exposing the extruded body to a water atmosphere to obtain an extruded body made of the crosslinked elastomer composition.
Component (A): Ethylene/α-olefin copolymer rubber Component (B): Propylene resin Component (C): Hydrogenated product of styrene/conjugated diene block copolymer Component (D): Unsaturated silane compound Component ( E): Peroxide