JP2020147655A - Modified elastomer composition, crosslinked elastomer composition and molded body of the same - Google Patents

Abstract

To provide a modified elastomer composition which has improved balance between extrusion appearance and fusion property while having low compressive permanent strain and soft touch feeling.SOLUTION: A modified elastomer composition contains the following components (A) to (D), and is obtained by grafting with the following component (E). Component (A): ethylene-α-olefin-non-conjugated diene copolymer rubber. Component (B): ethylene-α-olefin copolymer rubber containing no non-conjugated diene unit. Component (C): propylene-based resin satisfying the following (i) to (iii): (i) a weight average molecular weight (Mw) of 10,000 to 250,000; (ii) a molecular weight distribution (Mw/Mn) of 6 or less; and (iii) there exists a peak observed on the lowest temperature of a melting endothermic curve measured by a differential scanning calorimeter at 50-100°C. Component (D): unsaturated silane compound. Component (E): peroxide.SELECTED DRAWING: None

Description

The present invention relates to a modified elastomer composition, a crosslinked elastomer composition and a molded product thereof. Specifically, the present invention comprises a novel modified elastomer composition and a crosslinked elastomer composition in which the extruded appearance and the meltability are improved in a well-balanced manner while having a low compression set and a soft feel, and molding using the same. Regarding the body.

A thermoplastic elastomer is an elastomer that softens by heating and has fluidity, and when cooled, it has rubber elasticity. Thermoplastic elastomers have the same molding processability as thermoplastic resins, have rubber elasticity, and are recyclable. Therefore, automobile parts, building parts, medical parts, electric wire coating materials, miscellaneous goods, etc. It is widely used in various applications.

When used in applications that require sealing properties, it is important to have good rubber elasticity, compressive permanent strain characteristics, and good moldability, and much research has been done for that purpose, but thermoplastic elastomers have been used. Since it contains a thermoplastic resin such as polyolefin to ensure thermoplasticity, it has insufficient compressive permanent strain characteristics as compared with thermosetting rubber, and its usable applications are limited. On the other hand, a thermosetting rubber such as EPDM has excellent compression set characteristics, but has a drawback that it requires a long cross-linking step and is inferior in durability.

Patent Documents 1 to 3 propose an elastomer composition by silane modification with improved compression set, but it is necessary to add a large amount of unsaturated silane compound to improve compression set, which is economical. There were problems with productivity and moldability. Patent Document 4 also proposes an elastomer composition by silane modification, but the compression set (70 ° C. × 22 hours) remains at a little over 50%, which is insufficient.

International Publication No. 2016/140251 International Publication No. 2016/140252 International Publication No. 2016/140253 Japanese Patent No. 5346285

The silane-modified elastomer composition described in Patent Documents 1 to 4 has a poor extruded appearance and moldability of the extruded molded product of the silane crosslinked elastomer composition obtained by subjecting the elastomer composition to a crosslinking reaction in the presence of a crosslinking catalyst. Occasionally had a problem. In addition, the meltability between the obtained molded product and other resins was also insufficient.

Focusing on the above problems, the present invention has a novel modified elastomer composition and a crosslinked elastomer composition in which the extruded appearance and the meltability are improved in a well-balanced manner while having a low compression set and a soft tactile sensation, and molding thereof. To provide the body.

As a result of diligent studies to solve the above problems, the present inventor has obtained an ethylene / α-olefin / non-conjugated diene copolymer rubber and an ethylene / α-olefin copolymer rubber containing no non-conjugated diene unit. Focusing on the weight average molecular weight and molecular weight distribution of the propylene-based resin used at the time of blending, and the crystallinity of the resin, the above-mentioned problems are solved by using a propylene-based resin in which these physical properties are controlled within a specific range. We have found what we can do and have completed the present invention.
That is, the gist of the present invention lies in the following [1] to [12].

[1] A modified elastomer composition containing the following components (A) to (D) and grafted with the following components (E).
Component (A): Ethylene / α-olefin / non-conjugated diene copolymer rubber Component (B): Ethylene / α-olefin copolymer rubber containing no non-conjugated diene unit Component (C): The following (i) to Propylene resin satisfying (iii) (i) Weight average molecular weight (Mw) is 10,000 to 250,000
(Ii) Molecular weight distribution (Mw / Mn) is 6 or less (iii) The peak observed on the lowest temperature side of the melting endothermic curve measured by a differential scanning calorimeter exists at 50 to 100 ° C.
Component (D): Unsaturated silane compound Component (E): Peroxide

[2] The modified elastomer composition according to [1], which comprises a propylene homopolymer in which the component (C) satisfies the following (iv) to (vi).
(Iv) Tensile elastic modulus at 23 ° C. is 400 MPa or less (v) Weight average molecular weight (Mw) is 10,000 to 150,000
(Vi) Molecular weight distribution (Mw / Mn) is 2.5 or less

[3] The component (A) is 5 to 30 parts by mass with respect to a total of 100 parts by mass of the component (A), the component (B) and the component (C), and the component (B) is the component. (A), the component (B) and the component (C) are 40 to 90 parts by mass with respect to a total of 100 parts by mass, and the component (C) is the component (A), the component (B) and the above. The modified elastomer composition according to [1] or [2], which is 10 to 40 parts by mass with respect to a total of 100 parts by mass of the component (C).

[4] The component (D) is 0.01 to 5 parts by mass with respect to a total of 100 parts by mass of the component (A), the component (B), and the component (C) [1] to [3]. ] The modified elastomer composition according to any one of.

[5] The amount of the component (E) used is 0.01 to 3 parts by mass with respect to a total of 100 parts by mass of the component (A), the component (B), and the component (C) [1]. The modified elastomer composition according to any one of [4].

[6] The modified elastomer composition according to any one of [1] to [5], wherein the density of the component (B) is 0.880 g / cm ³ or less.

[7] Further, the component (F): the cross-linking aid is contained in an amount of 0.001 to 2 parts by mass with respect to a total of 100 parts by mass of the component (A), the component (B) and the component (C) [1]. ] To [6]. The modified elastomer composition according to any one of.

[8] The modified elastomer composition according to any one of [1] to [7], wherein the end peak temperature of melting measured by a differential scanning calorimeter (DSC) of the component (B) is 115 ° C. or higher.

[9] The modified elastomer composition according to any one of [1] to [8], wherein the component (D) is a compound represented by the following formula (1).
RSi (R') ₃ ... (1)
(However, R is an ethylenically unsaturated hydrocarbon group, and R'is a hydrocarbon group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms independently of each other, and at least one of R'. One is an alkoxy group having 1 to 10 carbon atoms.)

[10] Further, the component (G): the softener is contained in an amount of 0.5 to 200 parts by mass with respect to a total of 100 parts by mass of the component (A), the component (B) and the component (C), [1] to The modified elastomer composition according to any one of [9].

[11] A crosslinked elastomer composition obtained by cross-linking the modified elastomer composition according to any one of [1] to [10] with a component (H): silanol condensation catalyst.

[12] A molded product obtained by molding the modified elastomer composition according to any one of [1] to [10] or the crosslinked elastomer composition according to [11].

According to the present invention, there are provided a modified elastomer composition and a crosslinked elastomer composition having a low compression set and a soft tactile sensation and improved extruded appearance and meltability in a well-balanced manner, and a molded product using the same. be able to.
The modified elastomer composition and the crosslinked elastomer composition of the present invention, and the molded article using the modified elastomer composition, and the molded article using the same, are exposed to applications in which good rubber elasticity is conventionally used, and to severe usage environments. It can be expected to be applied to various applications.

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 gist of the present invention. In addition, in this specification, when a numerical value or a physical property value is put before and after using "~", it is used as including the value before and after that.

[Modified Elastomer Composition]
The modified elastomer composition of the present invention is a modified elastomer composition containing the following components (A) to (D) and grafted with the component (E), and more preferably the following components (F) to (G). including.
Component (A): Ethylene / α-olefin / non-conjugated diene copolymer rubber Component (B): Ethylene / α-olefin copolymer rubber containing no non-conjugated diene unit Component (C): The following (i) to Propylene resin satisfying (iii) (i) Weight average molecular weight (Mw) is 10,000 to 250,000
(Ii) Molecular weight distribution (Mw / Mn) is 6 or less (iii) The peak observed on the lowest temperature side of the melting endothermic curve measured by a differential scanning calorimeter exists at 50 to 100 ° C.
Component (D): Unsaturated silane compound Component (E): Peroxide component (F): Crosslinking aid Component (G): Softener

[Crosslinked elastomer composition]
The crosslinked elastomer composition of the present invention is obtained by cross-linking the modified elastomer composition with the following component (H).
Component (H): Silanol condensation catalyst

<Mechanism>
The reason why the modified elastomer composition and the crosslinked elastomer composition of the present invention are improved in a well-balanced manner in extruded appearance and meltability while maintaining low compression set and soft touch is presumed as follows. To.
That is, when the component (A) is finely dispersed in the component (B), the cross-linking proceeds uniformly, and the effect of improving the appearance is exhibited. Further, since the component (C) has low crystallinity and a slow crystallization rate, the mold transferability at the time of molding is excellent, and the appearance is improved from this viewpoint as well. Further, in terms of fusion property, since the crystallization rate of the component (C) is slow, it is possible to increase the time for fusion with other resins and increase the fusion strength. In particular, by blending a propylene homopolymer having a specific range in tensile elastic modulus, weight average molecular weight, and molecular weight distribution as the component (C), it contributes to an increase in fusion strength with an improvement in mechanical strength.
Examples of the mating resin in which the modified elastomer composition and the crosslinked elastomer composition of the present invention exhibit good heat-sealing properties include a polyolefin-based resin composition containing partial cross-linking and complete cross-linking.

<Component (A): Ethylene / α-olefin / non-conjugated diene copolymer rubber>
The ethylene / α-olefin / non-conjugated diene copolymer rubber of the component (A) is a copolymer containing ethylene, an α-olefin, and a non-conjugated diene compound as copolymerizing components. The ethylene / α-olefin / non-conjugated diene copolymer rubber is a mixture of ethylene / α-olefin / non-conjugated diene copolymer rubber and a softener for hydrocarbon-based rubber (hereinafter, “oil-extended ethylene / α-”. There are oil-extended type ones that are "olefin / non-conjugated diene copolymer rubber") and non-oil-extended type ones that do not contain a softening agent for hydrocarbon-based rubber. In this embodiment, oil is used. Although an extension-type copolymer rubber is intended, a non-oil-extension type rubber can also be preferably used. That is, in the present invention, the ethylene / α-olefin / non-conjugated diene copolymer rubber of the component (A) can be used in either an oil spread type or a non-oil spread type, and is a non-oil spread type or an oil. Only one type of exhibition type may be used alone, or two or more types may be used in any combination and ratio, and one or more types of oil exhibition type and one or two types of non-oil exhibition type may be used. Seeds and above can also be used in any combination and ratio.
In the case of the oil spread type, the hydrocarbon-based rubber softener contained in the mixture is classified as the softener of the component (G).

Examples of the hydrocarbon-based rubber softener contained in the oil-extending type include those exemplified as the component (G) described later. Further, in the mixture of the oil-extended ethylene / α-olefin / non-conjugated diene copolymer rubber and the softening agent for hydrocarbon-based rubber, 100 mass of the oil-extended ethylene / α-olefin / non-conjugated diene copolymer rubber The ratio (oil spread amount) of the hydrocarbon-based rubber softening agent to the part is usually about 10 to 200 parts by mass.

Examples of the α-olefin in the component (A) include propylene, 1-butene, 3-methyl-1-butene, 1-pentene, 4-methyl-1-pentene, 4,4-dimethyl-1-pentene, 1-. Examples thereof include α-olefins having 3 to 20 carbon atoms, more preferably 3 to 8 carbon atoms, such as hexene, 4-methyl-1-hexene, 1-hexene, 1-octene, 1-decene, and 1-octadecene. It is not particularly limited to these. Among these, propylene, 1-butene, 3-methyl-1-butene and 1-pentene are preferable, and propylene and 1-butene are more preferable, from the viewpoint of crosslinkability and suppression of bloom-out. As the α-olefin, only one type can be used alone, or two or more types can be used in any combination and ratio.

Examples of the non-conjugated diene compound in the component (A) include dicyclopentadiene, 1,4-hexadiene, cyclohexadiene, cyclooctadiene, dicyclooctadiene, 1,6-octadien, 5-methyl-1,4-. Hexadiene, 3,7-dimethyl-1,6-octadien, 1,3-cyclopentadiene, 1,4-cyclohexadiene, 2-methyl-1,5-hexadiene, 6-methyl-1,5-heptadiene, 7- Echiliden norbornene such as methyl-1,6-octadien, tetrahydroinden, methyltetrahydroinden, 5-isopropyriden-2-norbornene, 5-vinyl-2-norbornene, vinylidene norbornene, 5-ethylidene-2-norbornene (ENB), Examples thereof include methylenenorbornene such as 5-methylene-2-norbornene (MNB), but the present invention is not particularly limited thereto. Among these, dicyclopentadiene, etylidene norbornene and vinylidene norbornene are preferable, and dicyclopentadiene, 5-ethylidene-2-norbornene and vinylidene norbornene are more preferable from the viewpoint of crosslinkability and the like. As the non-conjugated diene, only one type can be used alone, or two or more types can be used in any combination and ratio.

Specific examples of the ethylene / α-olefin / non-conjugated diene copolymer rubber include ethylene / propylene / 5-ethylidene-2-norbornene copolymer rubber, ethylene / propylene / dicyclopentadiene copolymer rubber, and ethylene / propylene.・ Ethylene propylene / non-conjugated diene copolymer rubber (EPDM) such as 1,4-hexadiene copolymer rubber, ethylene / propylene / 5-vinyl-2-norbornene copolymer rubber, and ethylene / 1-butene / Examples thereof include 5-ethylidene-2-norbornene copolymer rubber, but the present invention is not particularly limited thereto. Among these, ethylene / propylene / non-conjugated diene copolymer rubber (EPDM) is preferable from the viewpoint of crosslinkability and suppression of bloom out. As the ethylene / α-olefin / non-conjugated diene copolymer rubber, only one type can be used alone, or two or more types can be used in any combination and ratio.

The content of ethylene units in the ethylene / α-olefin / non-conjugated diene copolymer rubber is not particularly limited, but is preferably 50 to 90% by mass, more preferably 55 to 85% by mass, and further preferably 60. ~ 80% by mass. When the content of the ethylene unit is within the above preferable range, an elastomer composition having excellent mechanical strength and rubber elasticity tends to be easily obtained.

The content of the α-olefin unit in the ethylene / α-olefin / non-conjugated diene copolymer rubber is not particularly limited, but is preferably 10 to 50% by mass, more preferably 15 to 45% by mass, and further preferably. Is 20-40% by mass. When the content of the α-olefin unit is within the above preferable range, it tends to be easy to obtain an elastomer composition having excellent mechanical strength, appropriate flexibility, and rubber elasticity.

Further, the content of the non-conjugated diene unit in the ethylene / α-olefin / non-conjugated diene copolymer rubber is not particularly limited, but is preferably 0.5 to 30% by mass, more preferably 1 to 20% by mass. Yes, more preferably 2 to 10% by mass. When the content of the non-conjugated diene unit is within the above preferable range, the crosslinkability and moldability can be easily adjusted, and an elastomer composition having excellent mechanical strength and rubber elasticity tends to be easily obtained.

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

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

As the ethylene / α-olefin / non-conjugated diene copolymer rubber of the component (A), only one type can be used alone, or two or more types can be used in any combination and ratio.

<Component (B): Ethylene / α-olefin copolymer>
The ethylene / α-olefin copolymer of the component (B) is a copolymer containing an ethylene unit and an α-olefin unit and does not contain a non-conjugated diene unit, that is, an ethylene / α-olefin copolymer excluding the component (A). It is a coalescence. The type of the ethylene / α-olefin copolymer of the component (B) is not particularly limited as long as it is such a thing, and a known ethylene / α-olefin copolymer is appropriately used.

Specific examples of the ethylene / α-olefin copolymer include, for example, an ethylene / propylene copolymer, an ethylene / 1-butene copolymer, an ethylene / 4-methyl-1-pentene copolymer, and an ethylene / 1-hexene. Examples thereof include a copolymer of ethylene such as a copolymer and an ethylene / 1-octene copolymer and one or more of α-olefins having 3 to 10 carbon atoms.

The type of catalyst used in producing the ethylene / α-olefin copolymer is not particularly limited, and examples thereof include a Ziegler-Natta catalyst and a metallocene catalyst. Among these, an ethylene / α-olefin copolymer produced by a metallocene catalyst is preferable.

The ethylene / α-olefin copolymer 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. Is preferable. When the melting end point of the ethylene / α-olefin copolymer is 115 ° C. or higher, the shape can be maintained by crystals even at a high temperature. From this viewpoint, the melting end point of the ethylene / α-olefin copolymer is preferably 115 ° C. or higher. However, if the melting end point of the ethylene / α-olefin copolymer is excessively high, there is a risk that the appearance will be poor due to unmelted lumps when the temperature of the molding is raised and early crystallization (melt fracture) when the molding is cooled. Therefore, the melting end point of the ethylene / α-olefin copolymer is usually 145 ° C. or lower. The melting end point of the ethylene / α-olefin copolymer is measured by the method described in the section of Examples described later.

The density of the ethylene / α-olefin copolymer of the component (B) used in the present invention (measured by JIS K6922-1, 2: 1997) is preferably 0.850 to 0.910 g / cm ³ . more preferably 0.860~0.900g / cm ^3, more preferably from 0.860~0.880g / cm ^3. When the density is not more than the above upper limit value, it tends to be flexible and excellent in sealing performance. Further, when the density is equal to or higher than the above lower limit value, the shape can be maintained at room temperature and the hysteresis loss is small, so that the settling tends to be excellent.

The content of the ethylene unit of the ethylene / α-olefin copolymer of the component (B) is preferably 50% by mass or more, more preferably 60% by mass or more. When the content of ethylene units is at least the above lower limit, it tends to be easy to obtain an elastomer composition having excellent mechanical strength and rubber elasticity.

The melt flow rate (MFR) of the ethylene / α-olefin copolymer used in the present invention is the melt flow rate (MFR) measured under the conditions of a temperature of 190 ° C. and a load of 21.2 N in accordance with JIS K7210 (1999). The amount is preferably 0.01 to 30 g / 10 minutes. If the MFR is too large, the compression set becomes large and the sealing property may be deteriorated. Further, if the MFR is too small, the motor load at the time of modified extrusion is large, the resin pressure rises, the productivity deteriorates, and the surface after molding may be roughened. From these viewpoints, the MFR of the ethylene / α-olefin copolymer is more preferably 0.1 g / 10 minutes or more, and more preferably 10 g / 10 minutes or less.

The ethylene / α-olefin copolymer used in the present invention can be obtained as a commercially available product. For example, Dow Chemicals Engage (registered trademark) series, Japan Polyethylene Kernel (registered trademark) series, Dow Chemicals Infuse (trademark registered) series, Mitsui Chemicals Toughmer (registered trademark) series, Mitsui Applicable products can be selected and used from the Evolu (registered trademark) series manufactured by Chemicals.

As the ethylene / α-olefin copolymer of the component (B), only one type can be used alone, or two or more types can be used in any combination and ratio.

<Component (C): Propylene resin>
The propylene-based resin of the component (C) used in the present invention satisfies the following conditions (i) to (iii), and the propylene-based resin satisfying the following conditions (i) to (iii) is used. As a result, the appearance of extrusion molding and the meltability can be improved in a well-balanced manner.
(I) Weight average molecular weight (Mw) is 10,000 to 250,000
(Ii) Molecular weight distribution (Mw / Mn) is 6 or less (iii) The peak observed on the lowest temperature side of the melting endothermic curve measured by a differential scanning calorimeter exists at 50 to 100 ° C.

The method for measuring the weight average molecular weight (Mw) and the molecular weight distribution (Mw / Mn) of the propylene-based resin of the component (C) is as described in the section of Examples described later.

The weight average molecular weight (Mw) of the component (C) (i) is 10,000 to 250,000, preferably 30,000 to 240,000, and more preferably 50,000 to 230,000. The higher the weight average molecular weight (Mw), the more easily it is affected by the high molecular weight side, and the mechanical properties tend to improve. Further, as the weight average molecular weight (Mw) becomes lower, the crystallization rate decreases, so that the fusion strength tends to improve.

The (ii) molecular weight distribution (Mw / Mn) of the component (C) is 6 or less, preferably 1 to 5.5, more preferably 2.0 to 5.0, and even more preferably 3.0 to. It is 4.5.

The peak observed on the coldest side of the melting endothermic curve measured by (iii) differential scanning calorimetry (DSC) of component (C) exists at 50 to 100 ° C. This peak is obtained by measuring the melting endothermic curve obtained by holding the temperature at -10 ° C for 5 minutes under a nitrogen atmosphere and then raising the temperature at 10 ° C / min using a differential scanning calorimeter (DSC). Be done. The peak observed on the lowest temperature side is 50 to 100 ° C, preferably 60 to 95 ° C, and more preferably 70 to 90 ° C. The peak observed on the lowest temperature side is preferably the melting point of the propylene homopolymer described later, and the component (C) used in the present invention is observed on the lowest temperature side as the melting point of the propylene homopolymer described later. It is preferable that the peak is detected in the range of 100 to 170 ° C. as the melting point of the propylene resin other than the propylene homopolymer.

As long as the propylene-based resin of the component (C) satisfies the above conditions (i) to (iii), the type thereof is not particularly limited, and the propylene homopolymer, the propylene random copolymer, the propylene block copolymer and the like can be used. Both can be used. When the component (C) is a propylene random copolymer or a propylene block copolymer, the monomers copolymerizing with propylene include ethylene, 1-butene, 2-methylpropylene, 1-pentene, and 3-methyl-. One or more of α-olefins such as 1-butene, 1-hexene, 4-methyl-1-pentene and 1-octene can be exemplified. When the component (C) is a propylene block copolymer, examples thereof include a propylene block copolymer obtained by polymerizing in multiple steps. More specifically, a propylene block copolymer obtained by polymerizing polypropylene in the first step and polymerizing a propylene / ethylene copolymer in the second step can be mentioned.

The content of the propylene unit in the propylene-based resin of the component (C) is preferably 40% by mass or more, and more preferably 50% by mass or more. When the content of the propylene unit is at least the above lower limit value, the moldability and the molded appearance tend to be improved. On the other hand, the upper limit of the content of the propylene unit is not particularly limited and is usually 100% by mass.

The propylene-based resin of the component (C) has a melt flow rate (MFR) of usually 0.5 g / 10 minutes or more measured by JIS K7210 (1999) at 230 ° C. and a load of 21.2 N, and is fluid. From the viewpoint, it is preferably 1 g / 10 minutes or more, more preferably 1.5 g / 10 minutes or more, and further preferably 2 g / 10 minutes or more. On the other hand, it is usually 3000 g / 10 minutes or less, preferably 2800 g / 10 minutes or less, more preferably 2700 g / 10 minutes or less, still more preferably 2600 g / 10 minutes or less from the viewpoint of moldability.

The density of the propylene-based resin of the component (C) is usually 0.75 g / cm ³ or more as measured by JIS K 7112 (1999), and is preferably 0.85 g / cm ³ or more from the viewpoint of stickiness resistance. , More preferably 0.87 g / cm ³ or more. On the other hand, the density of the propylene-based resin of the component (C) is usually 1.0 g / cm ³ or less, preferably 0.99 g / cm ³ or less, more preferably 0.98 g / cm ³ from the viewpoint of crystallization rate. It is as follows.

The tensile elastic modulus of the component (C) at 25 ° C. is preferably 50 MPa or more, more preferably 80 MPa or more, for example, about 90 to 1500 MPa, preferably containing low-regular polypropylene from the viewpoint of meltability. is there. The tensile modulus is measured by the method described in the Examples section below.

Further, among the components (C), the melting point of the propylene-based resin other than the propylene homopolymer described later is preferably 70 to 170 ° C., more preferably 80 to 170 ° C., and particularly preferably 80 to 170 ° C. from the viewpoint of moldability. It is 80 to 165 ° C. The melting point of the propylene resin is measured by the method described in the section of Examples described later.

The physical properties of the above (i) to (iii) are values measured for the component (C) as a mixture thereof when the component (C) contains two or more kinds of propylene resins.
It is preferable that each propylene-based resin is within the above range with respect to MFR, density, tensile elastic modulus, and melting point.

As the propylene-based resin of the component (C), a commercially available applicable product can be used. As a commercially available propylene-based resin, it can be procured from the following manufacturers and the like, and can be appropriately selected. Available commercial products include Idemitsu Kosan's L-MODU (registered trademark) series, Prime Polymer's Prim Polypro (registered trademark), Sumitomo Chemical's Sumitomo Noblen (registered trademark), and Sun Aroma's polypropylene block copolymer. Novatec (registered trademark) PP of Nippon Polypro Co., Ltd., Moplen (registered trademark) of Lyondell Basell, Adflex, Hiflex, Hifax, ExxonMobile PP of ExxonMobile, Formolene (registered trademark) of Formosa Plastics, Bole SEETEC PP, A.M. Schulman's ASI POLYPROPYLENE, INEOS Olefins & Polymers, Inc. of INEOS PP, Braskem's Braskem PP, SAMSUNG TOTAL PETROCHEMICALS's Sumsung Total, Sabic's Sabic (registered trademark) PP, TOTAL PETROCHEMICALS company of TOTAL PETROCHEMICALS Polypropylene, SK Corporation of YUPLENE ( Registered trademark), Tefabloc of Mitsubishi Chemical Co., Ltd., etc.

In the present invention, the propylene-based resin of the component (C) preferably contains a propylene homopolymer satisfying the following conditions (iv) to (vi), and such a propylene homopolymer is contained in the component (C). By including it in, the fusion property can be further improved.
(Iv) Tensile elastic modulus at 23 ° C. is 400 MPa or less (v) Weight average molecular weight (Mw) is 10,000 to 150,000
(Vi) Molecular weight distribution (Mw / Mn) is 2.5 or less

Here, the tensile elastic modulus of the propylene homopolymer at (iv) 23 ° C. is 400 MPa or less, but from the viewpoint of improving the meltability, a low regular polypropylene having a low tensile elastic modulus is preferable, and is 300 MPa or less. Is preferable. The lower limit of the tensile elastic modulus is not particularly limited, and the measurement limit value is the lower limit. Specifically, the tensile elastic modulus is preferably 1 MPa or more, more preferably 5 MPa or more, still more preferably 10 MPa or more. The tensile modulus is measured by the method described in the Examples section below.
The tensile elastic modulus of the propylene homopolymer can be adjusted within a desired range by varying the polymerization conditions (reaction temperature, reaction time, catalyst, cocatalyst) of the propylene homopolymer.

The (v) weight average molecular weight (Mw) of the propylene homopolymer is 10,000 to 150,000. When the weight average molecular weight (Mw) is 10,000 to 150,000, the fluidity at the time of melting and the fusion property with other resins are excellent. From this point of view, the weight average molecular weight (Mw) of the propylene homopolymer is preferably 15,000 to 140,000, more preferably 15,000 to 130,000. The weight average molecular weight of the propylene homopolymer can be controlled by appropriately adjusting the polymerization conditions (propylene pressure, polymerization time, etc.).

The (vi) molecular weight distribution (Mw / Mn) of the propylene homopolymer is 2.5 or less. When Mw / Mn is 2.5 or less, the fluidity at the time of melting is excellent. From such a viewpoint, Mw / Mn is preferably 2.4 or less, more preferably 2.2 or less. By using a metallocene-based catalyst as a catalyst in the production of the propylene homopolymer, a propylene homopolymer having Mw / Mn 2.5 or less can be obtained.

Propylene homopolymers satisfying the above conditions (iv) to (vi) can be obtained as commercial products. For example, it can be selected and used from the above-mentioned L-MODU (registered trademark) series manufactured by Idemitsu Kosan Co., Ltd.

As the propylene-based resin of the component (C), one type may be used alone or two or more types may be used in combination as long as the above conditions (i) to (iii) are satisfied. However, it is preferable to use two or more kinds in combination from the viewpoint of improving the cohesiveness with other resins. When two or more types are used in combination, it is preferable that at least one of them contains a propylene homopolymer satisfying the above conditions (iv) to (vi).

When the propylene-based resin of the component (C) contains a propylene homopolymer satisfying the above conditions (iv) to (vi) and other propylene-based resins, the content ratio of the propylene homopolymer in the component (C). Is not particularly limited, but from the viewpoint of fusion property, the content ratio of the propylene homopolymer in the component (C) is preferably 30% by mass or more, particularly 40% by mass or more, and from the viewpoint of ear tear resistance. It is preferably 70% by mass or less, particularly preferably 60% by mass or less.

<Component (D): Unsaturated silane compound>
The unsaturated silane compound of the component (D) used in the present invention is not limited, but the 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, and R'is a hydrocarbon group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms independently of each other. At least one of them is an alkoxy group having 1 to 10 carbon atoms.

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

In the formula (1), R'is preferably a hydrocarbon group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, and more preferably a hydrocarbon group having 1 to 4 carbon atoms or 1 to 4 carbon atoms. It is an alkoxy group of. Further, at least one of R'is preferably an alkoxy group having 1 to 6 carbon atoms, and more preferably an alkoxy group having 1 to 4 carbon atoms. The hydrocarbon group having 1 to 10 carbon atoms of R'may be any of an aliphatic group, an alicyclic group, and an aromatic group, but it is preferably an aliphatic group. The alkoxy group having 1 to 10 carbon atoms of 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, or a phenyl group. Examples thereof include an aryl group typified by a group. When R'is an alkoxy group, specific examples thereof include a methoxy group, an ethoxy group, an isopropoxy group and a β-methoxyethoxy group.

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

As the unsaturated silane compound, vinyl trialkoxysilane typified by vinyltrimethoxysilane, vinyltriethoxysilane, propenyltrimethoxysilane and the like is desirable among those represented by the formula (1). This is because the vinyl group enables the modification of the component (B) to an ethylene / α-olefin copolymer, and the alkoxy group promotes the crosslinking reaction described later. That is, the alkoxy group introduced by graft-modifying the ethylene / α-olefin copolymer with an unsaturated silane compound reacts with water in the presence of a silanol condensation catalyst and hydrolyzes to generate a silanol group to generate silanol. By dehydrating and condensing the groups, the ethylene / α-olefin copolymers are bonded to each other and a cross-linking reaction occurs. As these unsaturated silane compounds, one type may be used alone, or two or more types may be used in combination.

<Component (E): Peroxide>
Examples of the peroxide of the component (E) include hydroperoxide, dialkyl peroxide, diacyl peroxide, peroxy ester, and organic peroxide contained in the ketone peroxide group. Specific examples thereof include the following. There are many things.

The hydroperoxide group includes cumene hydroperoxide, tertiary butyl hydroperoxide, etc., and the dialkyl peroxide group includes dicumyl peroxide, diterhally butyl peroxide, 2,5-dimethyl-2,5-diter. Shari butyl peroxyhexane, 2,5-dimethyl-2,5-diter Shari butyl peroxyhexin-3, di (2-tershaly butyl peroxyisopropyl) benzene, etc. are included, and the diacyl peroxide group includes lauryl. Includes peroxide, benzoyl peroxide and the like. The peroxyester group includes tertiary peroxyacetate, tertiary butylperoxybenzoate, tertiary butylperoxyisopropylcarbonate, etc., and the ketone peroxide group includes cyclohexanone peroxide, etc. These organic peroxides. May be used alone or in combination of two or more.

When used in combination with the cross-linking aid of the component (F) described later, a radical generator having a high thermal decomposition temperature is preferable. From this viewpoint, ditertiary butyl peroxide, di (2-terriary butyl peroxyisopropyl) benzene, 2,5-dimethyl-2,5-di (t-butyl peroxy) hexane, and dicumyl peroxide are preferable.

<Component (F): Crosslinking aid>
Examples of the cross-linking aid for the component (F) include silicon hydride compounds such as metrohydrogen silicon, and peroxide aids such as sulfur, p-quinonedioxime, p-dinitrosobenzene, and 1,3-diphenylguanidine. Agents: Polyfunctional vinyl compounds such as divinylbenzene, triallyl cyanurate, triallyl isocyanurate, diallyl phthalate; ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, trimethyl propane Polyfunctional (meth) acrylate compounds such as tri (meth) acrylate and allyl (meth) acrylate; having a bismaleimide structure such as N, N'-m-phenylene bismaleimide and N, N'-m-toluylene bismaleimide. Compounds: Trimethylol propane, trimethylol propane trimethacrylate, tin chloride (SnCl ₂ ) and the like. Among these, polyfunctional vinyl compounds such as divinylbenzene, triallyl cyanurate, triallyl isocyanurate, and diallyl phthalate and polyfunctional (meth) acrylate compounds are preferable.

Phenolic resins can also be used as other cross-linking aids. Examples of the phenol resin include alkylphenol formaldehyde and alkylphenol norformaldehyde bromide.

Only one of these cross-linking aids can be used alone, or two or more of them can be used in any combination and ratio.

<Component (G): Softener>
The modified elastomer composition of the present invention can contain a softening agent as a component (G) from the viewpoint of increasing flexibility and improving processability, fluidity, and oil resistance.

Examples of the component (G) include a softening agent for mineral oil-based rubber, a softening agent for synthetic resin-based rubber, and the like, and among these, softening for mineral oil-based rubber from the viewpoint of affinity with other components and the like. Agents are preferred.

The softener for mineral oil-based rubber is generally a mixture of aromatic hydrocarbons, naphthenic hydrocarbons and paraffinic hydrocarbons, and the ratio of carbon of the paraffinic hydrocarbon to the total carbon atom is 50% by mass. The above are paraffin-based oils, naphthenic hydrocarbons with a carbon content of 30 to 45% by mass are naphthenic oils, and aromatic hydrocarbons with a carbon content of 35% by mass or more are aromatic oils. It is called. Among these, as the softener, a liquid hydrocarbon-based rubber softener that is liquid at room temperature (23 ± 2 ° C.) is preferable, and a liquid paraffin oil that is liquid at room temperature is more preferable.
By using a softening agent for liquid hydrocarbon rubber as a softening agent, the flexibility and elasticity of the modified elastomer composition of the present invention can be increased, and the processability and fluidity tend to be dramatically improved. ..

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

As the softener of the component (G), only one type can be used alone, or two or more types can be used in any combination and ratio.

When an oil-extended type component (A) is used as the above-mentioned component (A), an elastomer composition is used as a mixture of an oil-extended type ethylene / α-olefin / non-conjugated diene copolymer rubber and a softening agent for hydrocarbon-based rubber. The hydrocarbon-based rubber softener introduced in the above also corresponds to the softener of the component (G). In this case, a softener may be added separately as the component (G), or an attached softener may be used. When the softening agent is attached, the hydrocarbon-based rubber softening agent contained in the oil expansion type component (A) and the attached softening agent may be the same or different. ..

<Component (H): Silanol condensation catalyst>
By blending the component (H) silanol condensation catalyst with the modified elastomer composition of the present invention, the composition can be crosslinked between molecules, and the silanol group is generated by reacting with water and hydrolyzing. Further, by dehydrating and condensing the silanol groups, the cross-linking reaction proceeds, and the modified elastomers are bonded to each other to produce a cross-linked elastomer composition having excellent heat resistance.

The silanol condensation catalyst of the component (H) that can be used in the present invention comprises a metal organic acid salt, titanate, borate, organic amine, ammonium salt, phosphonium salt, inorganic acid and organic acid, and an inorganic acid ester. Examples thereof include one or more compounds selected from the group.

Examples of metal organic acid salts include dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin diacetate, dibutyltin dioctate, stannous acetate, stannous octanoate, cobalt naphthenate, lead octylate, lead naphthenate, and octylic acid. Examples thereof include zinc, zinc caprylate, iron 2-ethylhexanoate, iron octylate, and iron stearate. Examples of the titanate include tetrabutyl ester titanate, tetranonyl titanate ester, and bis (acetylacetonitrile) di-isopropyl titanate. Examples of the organic amine include ethylamine, dibutylamine, hexylamine, triethanolamine, dimethylsoyaamine, tetramethylguanidine, pyridine and the like. Examples of the ammonium salt include ammonium carbonate, tetramethylammonium hydroxide and the like. Examples of the phosphonium salt include tetramethylphosphonium hydrooxide and the like. Examples of the inorganic acid and the organic acid include sulfonic acids such as sulfuric acid, hydrochloric acid, acetic acid, stearic acid, maleic acid, toluenesulfonic acid and alkylnaphthylsulfonic acid. Examples of the inorganic acid ester include a phosphoric acid ester and the like.

Among these, metal organic acid salts, sulfonic acids, and phosphate esters are preferable, and tin metal carboxylates, such as dioctyltin dilaurate, alkylnaphthylsulfonic acid, and ethylhexyl phosphate esters, are more preferable.

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

The silanol condensation catalyst is preferably used as a masterbatch in which a polyolefin and a silanol condensation catalyst are mixed. Examples of the polyolefin that can be used in this masterbatch include polyethylene, polypropylene, and an ethylene / α-olefin copolymer.

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

Among these, in the present invention, high-pressure low-density polyethylene, high-density polyethylene, and ethylene / α-olefin copolymer having an excellent balance between heat resistance and strength are preferable. The ethylene / α-olefin copolymer is more preferably 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 that the above is copolymerized with. Only one of these polyolefins may be used in the masterbatch of the silanol condensation catalyst, or two or more of these polyolefins may be blended and used.

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

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

<Mixing ratio>
In the modified elastomer composition of the present invention, the component (A) is 5 to 30 parts by mass, the component (B) is 40 to 90 parts by mass, and the component (C) is 10 to 40 parts by mass, for a total of 100 parts by mass. It is preferable to include it as a part.
If the content ratio of the component (A) is larger than the above upper limit and the content ratios of the component (B) and the component (C) are smaller than the above lower limit, the surface appearance tends to be inferior, and conversely, the content of the component (A). If the ratio is less than the above lower limit and the content ratio of the component (B) and the component (C) is more than the above upper limit, the stickiness tends to increase.
If the content ratio of the component (B) is larger than the above upper limit and the content ratios of the component (A) and the component (C) are smaller than the above lower limit, blocking tends to be severe and the cohesiveness tends to decrease. On the contrary, when the content ratio of the component (B) is less than the above lower limit and the content ratios of the component (A) and the component (C) are more than the above upper limit, the gloss becomes high and the compression set tends to worsen. There is.
If the content ratio of the component (C) is larger than the above upper limit and the content ratios of the component (A) and the component (B) are smaller than the above lower limit, the compression set tends to worsen, and conversely, the component (C) If the content ratio of the component (A) and the component (B) is smaller than the above lower limit and the content ratio of the component (A) and the component (B) is larger than the above upper limit, the moldability, surface appearance and fusion property tend to deteriorate.

From this point of view, the ratio of the component (A) in the total of 100 parts by mass of the component (A), the component (B) and the component (C) is more preferably 10 to 30 parts by mass, still more preferably 10 to 25 parts by mass. The proportion of the component (B) is more preferably 50 to 85 parts by mass, further preferably 55 to 80 parts by mass, and the proportion of the component (C) is more preferably 10 to 35 parts by mass, still more preferably. It is 10 to 20 parts by mass.

The content of the component (D) with respect to a total of 100 parts by mass of the component (A), the component (B) and the component (C) is preferably 0.01 to 5 parts by mass from the viewpoint of sufficiently advancing the crosslinking reaction. , More preferably 0.05 to 5 parts by mass, still more preferably 0.1 to 3 parts by mass.
The content of the component (E) is preferably 0.01 to 3 parts by mass with respect to a total of 100 parts by mass of the component (A), the component (B) and the component (C), and a sufficient cross-linking reaction can be obtained. From the viewpoint of maintaining a smooth molded appearance, it is more preferably 0.05 to 2 parts by mass, and further preferably 0.1 to 1 part by mass.

When the modified elastomer composition of the present invention contains the component (F), the content of the component (F) is preferably 0 with respect to a total of 100 parts by mass of the component (A), the component (B) and the component (C). It is .001 to 2 parts by mass, and more preferably 0.003 to 1 part by mass from the viewpoint of obtaining economic efficiency and a sufficient cross-linking reaction.

When the modified elastomer composition of the present invention contains the component (G), the component (G) (oil spread as the component (A)) with respect to a total of 100 parts by mass of the component (A), the component (B) and the component (C). When the type is used, the content of the hydrocarbon-based rubber softener in the component (A) is preferably 0.5 to 200 parts by mass. If the content of the component (G) is less than the above lower limit, the effect of improving the flexibility, fluidity, and oil resistance of the component (G) cannot be sufficiently obtained, and if the content exceeds the above upper limit, there is a risk of bleeding out from the surface. is there. From this viewpoint, the content of the component (G) with respect to a total of 100 parts by mass of the component (A), the component (B) and the component (C) is more preferably 1 to 100 parts by mass, and 5 to 80 parts by mass. Is more preferable.

When the silanol condensation catalyst of the component (H) is added to the modified elastomer composition of the present invention and subjected to a crosslinking reaction, the blending amount thereof is not particularly limited, but the modified elastomer of the present invention excluding the component (H) is not particularly limited. It is preferably 0.001 to 0.5 parts by mass, and more preferably 0.001 to 0.1 parts by mass with respect to 100 parts by mass of the composition. When the addition amount of the silanol condensation catalyst is not less than the above lower limit value, the crosslinking reaction proceeds sufficiently and the heat resistance tends to be good. Therefore, when it is not more than the above upper limit value, early crosslinking is unlikely to occur in the extruder. , Strand surface and product appearance tend to be less likely to be roughened.

<Other ingredients>
In the modified elastomer composition of the present invention, in addition to the above components, various additives and fillers, resins and elastomers other than the components (A) to (C) are used as other components without impairing the effects of the present invention. It can be contained in a range.

Examples of the additive include a heat stabilizer, an ultraviolet absorber, a light stabilizer, an antioxidant, an antistatic agent, a crystal nucleating agent, a rust preventive, a viscosity modifier, a foaming agent, a lubricant and a pigment. it can. Of 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% by mass in 100% by mass of the modified elastomer composition of the present invention.

Examples of other resins include polyolefin resins, polyester resins, polycarbonate resins, polymethylmethacrylate resins, rosins and their derivatives, terpene resins and petroleum resins and their derivatives, alkyd resins, alkylphenol resins, terpenephenol resins, and kumaron. Inden resin, synthetic terpene resin, alkylene resin, olefin-based elastomers other than the components (A) to (C), polyamide-based elastomers such as polyamide / polyol copolymers; polyvinyl chloride-based elastomers and polybutadiene-based elastomers, styrene-based elastomers, Examples thereof include those hydrogenated products, those modified with acid anhydrides and the like to introduce polar functional groups, and those obtained by grafting, random and / or block copolymerizing other monomers.

<Manufacturing and molding of modified elastomer composition>
The modified elastomer composition of the present invention comprises two copolymers of the components (A) and (B), a propylene resin of the component (C), an unsaturated silane compound of the component (D), and the component (E). Peroxides, if necessary, cross-linking aids, softeners, other components, etc. are mechanically mixed by a known method, for example, a Henschel mixer, a V-blender, a tumbler blender, etc., and then mechanically by a known method. It can be produced by melt-kneading. 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 Examples described later, when the composition of the present invention is kneaded and produced by a single-screw or twin-screw extruder or the like, it is usually heated to 120 to 240 ° C., preferably 120 to 220 ° C. Can be melt-kneaded with.

In the modified elastomer composition of the present invention, the above-mentioned silanol condensation catalyst is blended, molded by various molding methods such as extrusion molding, injection molding, and press molding, and then exposed to an aqueous atmosphere to carry out a cross-linking reaction between silanol groups. Can be advanced to obtain a crosslinked elastomer composition. Various conditions can be adopted as the method of exposing to the water atmosphere, the method of leaving in the air containing moisture, the method of blowing air containing water vapor, the method of immersing in a water bath, and the method of sprinkling hot water in a mist form. The method of doing this can be mentioned.

In this case, the hydrolyzable alkoxy group derived from the unsaturated silane compound used for the graft modification of the components (A) to (C) reacts with water and hydrolyzes in the presence of a silanol condensation catalyst to form a silanol group. Then, the silanol groups are dehydrated and condensed to proceed with the cross-linking reaction, and the modified elastomers are bonded to each other to produce a cross-linked elastomer composition.

The rate of progress of the cross-linking reaction depends on the conditions of exposure to the water atmosphere, but usually the exposure may be in the temperature range of 0 to 130 ° C. and in the range of 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 cross-linked elastomer composition thus obtained can be adjusted by changing the type and blending amount of the silanol condensation catalyst, the conditions (temperature, time) for cross-linking, and the like.

<Use>
The use of the modified elastomer composition and the crosslinked elastomer composition of the present invention is not particularly limited, but for automobile parts such as glass run channels, weather strips, hoses, wiper blades and glomets, packings, gaskets, cushions, anti-vibration rubbers, tubes and the like. It can be suitably used as a building, industrial parts, other sports, miscellaneous goods, medical parts, food parts, household appliances parts, and electric wire covering materials.

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

In the following Examples and Comparative Examples, the raw materials used for preparing the elastomer composition and the method for evaluating the obtained elastomer composition are as follows.

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

<Component (A): Oil-extended ethylene / α-olefin / non-conjugated diene copolymer rubber>
(A-1): Mitsui EPT (registered trademark) 3072EPM (manufactured by Mitsui Chemicals, Inc.)
Metallocene Catalytic Oil Exhibition EPDM
Non-conjugated diene: 5-Etylidene-2-norbornene Non-conjugated diene content: 5.4% by mass
Ethylene unit content: 64% by mass
Mooney viscosity: 51ML (value after 1 minute of preheating and 4 minutes after rotation) 125 ° C.
Oil spread: 40 parts by mass

<Component (B): Ethylene / α-olefin copolymer rubber containing no non-conjugated diene unit>
(B-1): Engage (registered trademark) XLT8677 (manufactured by Dow Chemical Co., Ltd.)
Ethylene / α-olefin copolymer α-olefin: 1-octene MFR (190 ° C., 21.2N): 0.5 g / 10 minutes Density (JIS K 6922-1,2: 1997): 0.87 g / cm ³
End point of melting: 123 ° C

<Component (C): Propylene resin>
(C-1) L-MODU (registered trademark) S400 (manufactured by Idemitsu Kosan Co., Ltd.)
Propene homopolymer MFR (230 ° C, 21.2N): 2600g / 10 minutes (* converted value from viscosity data)
Density (JIS K7112: 1999): 0.870 g / cm ³
Melting point: 80 ° C
(Iv) Tensile modulus: 100 MPa
(V) Mw: 45,000
(Vi) Mw / Mn: 2.0

(C-2) Novatec (registered trademark) FY6 (manufactured by Japan Polypropylene Corporation)
Propylene homopolymer MFR (230 ° C., 21.2N): 2.5 g / 10 minutes Density (JIS K7112: 1999): 0.90 g / cm ³
Melting point: 160 ° C
(Iv) Tensile modulus: 1400 MPa
(V) Mw: 373,800
(Vi) Mw / Mn: 5.2

(C-3) Novatec (registered trademark) MG03TH (manufactured by Japan Polypropylene Corporation)
Propylene / ethylene copolymer (propylene unit content 40% by mass or more)
MFR (230 ° C., 21.2N): 30 g / 10 minutes Density (JIS K7112: 1999): 0.90 g / cm ³
Melting point: 148 ° C
(Iv) Tensile modulus: 850 MPa
(V) Mw: 180, 162
(Vi) Mw / Mn: 5.1

<Component (D): Unsaturated silane compound>
(D-1) Vinyltrimethoxysilane: KBM-1003 (manufactured by Shin-Etsu Chemical Co., Ltd.)

<Component (E): Organic peroxide>
(E-1) 2,5-dimethyl-2,5-di (t-butylperoxy) hexane: Kayahexa AD40C (manufactured by Kayaku Akzo Corporation, 2,5-dimethyl-2,5-di (t-butyl) Peroxy) A mixture of 40% by mass of hexane and 60% by mass of organic filler)

<Component (F): Crosslinking aid>
(F-1) Divinylbenzene (mixture of 55% by mass of divinylbenzene manufactured by Wako Pure Chemical Industries, Ltd. and 45% by mass of ethylvinylbenzene)

<Component (G): Softener>
(G-1) Softening agent for paraffinic rubber: Diana (registered trademark) Process oil PW90 (paraffin oil manufactured by Idemitsu Kosan Co., Ltd.)
40 ° C kinematic viscosity: 95.54 cSt (Centistokes)
Pour point: -15 ° C
Flash point: 272 ° C

<Component (H): Catalyst masterbatch (MB)>
(H-1) Silanol Condensation Catalyst MB: LZ033 (manufactured by Mitsubishi Chemical Corporation, 1.2% tin catalyst (dioctyl tin dilaurate) -containing linear low-density polyethylene, MFR of low-density polyethylene: 2 g / 10 minutes (190 ° C., 21.2N load), density of low density polyethylene: 0.92g / cm ³ )

<Other ingredients>
(X-1) Partially Crosslinked Olefin-based Thermoplastic Elastomer: 3655B (manufactured by Mitsubishi Chemical Corporation)

[Measurement of melting end point of component (B)]
Using a differential scanning calorimeter manufactured by Hitachi High-Tech Science Co., Ltd., trade name "DSC6220", the temperature of about 5 mg of the sample was raised from 20 ° C to 200 ° C at a heating rate of 100 ° C / min according to JIS K7121. After 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 raised to 200 ° C. at a heating rate of 10 ° C./min. (° C.) was calculated and used as the melting end point.

[Component (C): Measurement of propylene-based resin conditions (i) to (iii) and propylene homopolymer conditions (iv) to (vi)]
<Measurement of weight average molecular weight (Mw) ((i), (v)) and molecular weight distribution (Mw / Mn) ((ii), (vi)) of component (C)>
The weight average molecular weight (Mw) and the molecular weight distribution (Mw / Mn) were determined by gel permeation chromatography (GPC) method. For the measurement, the following devices and conditions were used to obtain polystyrene-equivalent weight average molecular weight (Mw) and number average molecular weight (Mn).
<GPC measuring device>
Equipment: Tosoh HLC-8321GPC / HT
Detector: RI (built-in device)
Mobile phase: Reagent special grade ODCB
Flow velocity: 1.0 mL / min Injection: 0.1% by mass x 500 μl
Column: TSKgel GMH6-HT (7.8 mm ID x 30 cm L x 4)
Column temperature: 135 ° C
Calibration sample: Monodisperse polystyrene (PST)
Calibration method: Polypropylene (PP) conversion (general-purpose calibration curve method)
Calibration curve approximation formula: cubic formula Analysis program: Tosoh 8321GPC Staticis Version 1.01
For the sample, the calibration curve prepared using the monodisperse PST was converted into PP conversion using the concept of the general-purpose calibration curve. The coefficients used are Kpst = 1.38 × 10 ^-4 , αpst = 0.70, Kpp = 1.03 × 10 ^-4 , αpp = 0.78.

<Measurement of tensile elastic modulus (iv) of component (C)>
The sample was press-molded to prepare a test piece, and the tensile elastic modulus (MPa) of the sample was measured under the following conditions in accordance with JIS K 7113.
Test piece (No. 2 dumbbell) Thickness: 1 mm
Crosshead speed: 100mm / min
Load cell: 100N
Measurement temperature: 23 ° C

<Measurement of peak (iii) and melting point of melting endothermic curve of component (C)>
The peak of the melting endothermic curve of component (C) is obtained by holding it at −10 ° C. for 5 minutes under a differential scanning calorimeter (DSC) and then raising the temperature at 10 ° C./min. The endothermic curve was measured and the temperature at the time of the peak was measured.
Further, for the melting points of the respective components (C-1) to (C-3), the peak of the melting endothermic curve was measured in the same manner as described above, and the peak was taken as the melting point.

[Evaluation method]
Various evaluation methods of the elastomer composition in Examples and Comparative Examples are shown below.

(1) Surface hardness The obtained molded sheet was measured for Dulo A hardness (after 15 seconds) in accordance with JIS K6253 (Duro-A).

(2) Permanent compression strain The obtained molded sheet was measured at 70 ° C. for 22 hours under 25% compression conditions in accordance with JIS K6262 standards (unit:%).

(3) Extrusion Moldability The obtained crosslinked elastomer composition is 0.5 mm thick x width at a cylinder set temperature of 160 ° C. to 200 ° C. and a rotation speed of 20 rpm using a single-screw extruder with a diameter of 20 mm and a full flight screw. A 35 mm sheet was formed, and visually observed the presence or absence of bumps on the sheet surface and the presence or absence of cuts in the ears were observed, and the judgment was made according to the following criteria.
<Buts>
〇: Good (smooth without convex appearance defects on the surface of the extruded sheet)
Δ: Slightly bad (there are less than 10 convex appearance defects on the surface of the extruded sheet)
X: Poor (10 or more convex appearance defects exist on the surface of the extruded sheet)
<Ear resistance>
〇: Good (smooth without cuts at both ends of the extruded sheet)
Δ: Slightly bad (there are notches of about 1 mm at both ends of the extruded sheet)
X: Bad (there are notches of 2 mm or more at both ends of the extruded sheet)

(4) Fusion property An injection-molded sheet of the obtained cross-linked elastomer composition and an injection-molded sheet of (X-1) partially cross-linked olefin-based thermoplastic elastomer: 3655B (manufactured by Mitsubishi Chemical Corporation) (thickness 2 mm x width). The end faces (120 mm x 80 mm in length) were combined and pressed under two conditions of 155 ° C and 145 ° C, respectively, cut into No. 3 dumbbells so as to include the joint, and then the tensile strength when tested at a tensile speed of 100 mm / min. (Unit: MPa) was confirmed.

[Example 1]
With the raw material blending shown in Table-1, each raw material other than (G-1) was blended and mixed with a Henschel mixer for 1 minute. Next, the obtained mixture is charged into the upstream supply port of the same-direction twin-screw extruder (manufactured by Japan Steel Works, Ltd., product number: TEX30, L / D = 46, number of cylinder blocks: 12) by a mass feeder. did. Then, the component (G-1) is supplied from the supply port in the middle of the extruder by the liquid addition pump, and the temperature rises from the upstream portion to the downstream portion in the range of 120 to 200 ° C. with a total discharge amount of 25 kg / h. The mixture was melt-kneaded and the strands were cut to pelletize the modified elastomer composition. A crosslinked elastomer composition containing the catalyst MB by adding 4 parts by mass (0.048 parts by mass as a tin catalyst) of LZ033 as the component (H-1) silanol condensation catalyst MB to 100 parts by mass of the obtained modified elastomer composition. I got something. The composition was injection-molded using an in-line screw type injection molding machine (manufactured by Toshiba Machine Co., Ltd., product number: IS130) under the conditions of an injection pressure of 50 MPa, a cylinder temperature of 220 ° C., and a mold temperature of 40 ° C. A sheet having a thickness of 2 mm, a width of 120 mm, and a length of 80 mm was molded. Further, it was exposed to a constant temperature and humidity chamber at 85 ° C. and 85% RH for 24 hours to prepare a sheet for evaluating surface hardness, compression set, and fusion property.
Table 1 shows the evaluation results of the obtained elastomer composition of Example 1.

[Example 2 and Comparative Examples 1 and 2]
Treatment was carried out in the same manner as in Example 1 except for changing to the raw material composition shown in Table 1, to obtain pellets of the modified elastomer compositions of Example 2 and Comparative Examples 1 and 2, respectively, and each evaluation sheet was similarly obtained. It was molded and evaluated in the same manner. The results are shown in Table-1.

In Table-1, the component (A-1) is shown not by the actual blending amount but by the blending amount of only EPDM of the component excluding the oil spreading oil.
Similarly, for the component (E-1), not the actual amount, but only 2,5-dimethyl-2,5-di (t-butylperoxy) hexane of the component (E-1). It is shown by the amount (40% of the actual compounding amount), and the component (F-1) is not the actual compounding amount, but the compounding amount of only divinylbenzene among the components (F-1) (55% of the actual compounding amount). Indicated by.

[Evaluation results]
As shown in Table 1, it can be seen that all of Examples 1 and 2 corresponding to the elastomer composition of the present invention are excellent in compression set, extrusion moldability (bumps, ear tear resistance), and fusion property. ..
On the other hand, it can be seen that the elastomer compositions of Comparative Examples 1 and 2 are inadequate in any of compression set, extrusion moldability (bump, ear tear resistance), and fusion property.
From these results, it was found that the elastomer composition of the present invention has good sealing properties, molded appearance, and fusion property.

The elastomer composition of the present invention is excellent in compressive permanent strain, moldability and extruded appearance, and is also excellent in fusion with other resins. Therefore, various applications in which these are required, for example, glass run channel Widely and effectively used in automobile parts such as weather strips, civil engineering / building material parts such as building gaskets, sporting goods, industrial parts, home appliances parts, medical parts, food parts, medical equipment parts, electric wires, miscellaneous goods, etc. It is available.

Claims (12)

A modified elastomer composition containing the following components (A) to (D) and grafted with the following components (E).
Component (A): Ethylene / α-olefin / non-conjugated diene copolymer rubber Component (B): Ethylene / α-olefin copolymer rubber containing no non-conjugated diene unit Component (C): The following (i) to Propylene resin satisfying (iii) (i) Weight average molecular weight (Mw) is 10,000 to 250,000
(Ii) Molecular weight distribution (Mw / Mn) is 6 or less (iii) The peak observed on the lowest temperature side of the melting endothermic curve measured by a differential scanning calorimeter exists at 50 to 100 ° C.
Component (D): Unsaturated silane compound Component (E): Peroxide The modified elastomer composition according to claim 1, wherein the component (C) contains a propylene homopolymer satisfying the following (iv) to (vi).
(Iv) Tensile elastic modulus at 23 ° C. is 400 MPa or less (v) Weight average molecular weight (Mw) is 10,000 to 150,000
(Vi) Molecular weight distribution (Mw / Mn) is 2.5 or less The component (A) is 5 to 30 parts by mass with respect to a total of 100 parts by mass of the component (A), the component (B) and the component (C), and the component (B) is the component (A). 40 to 90 parts by mass with respect to a total of 100 parts by mass of the component (B) and the component (C), and the component (C) is the component (A), the component (B) and the component (C). The modified elastomer composition according to claim 1 or 2, wherein the amount is 10 to 40 parts by mass with respect to 100 parts by mass in total. 1. The modified elastomer composition described. Claims 1 to 4, wherein the amount of the component (E) used is 0.01 to 3 parts by mass with respect to a total of 100 parts by mass of the component (A), the component (B), and the component (C). The modified elastomer composition according to any one. The modified elastomer composition according to any one of claims 1 to 5, wherein the density of the component (B) is 0.880 g / cm ³ or less. Further, the component (F): the cross-linking aid is contained in 0.001 to 2 parts by mass with respect to a total of 100 parts by mass of the component (A), the component (B) and the component (C), claims 1 to 6. The modified elastomer composition according to any one of. The modified elastomer composition according to any one of claims 1 to 7, wherein the end peak temperature of melting measured by a differential scanning calorimeter (DSC) of the component (B) is 115 ° C. or higher. The modified elastomer composition according to any one of claims 1 to 8, wherein the component (D) is a compound represented by the following formula (1).
RSi (R') ₃ ... (1)
(However, R is an ethylenically unsaturated hydrocarbon group, and R'is a hydrocarbon group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms independently of each other, and at least one of R'. One is an alkoxy group having 1 to 10 carbon atoms.) Further, the component (G): any of claims 1 to 9, wherein the softener is contained in an amount of 0.5 to 200 parts by mass with respect to a total of 100 parts by mass of the component (A), the component (B) and the component (C). The modified elastomer composition described in Crab. A crosslinked elastomer composition obtained by subjecting the modified elastomer composition according to any one of claims 1 to 10 to a crosslinking reaction with a component (H): silanol condensation catalyst. A molded product obtained by molding the modified elastomer composition according to any one of claims 1 to 10 or the crosslinked elastomer composition according to claim 11.