阅读说明：本技术 改性弹性体组合物、交联弹性体组合物和它们的成形体 (Modified elastomer composition, crosslinked elastomer composition, and molded article thereof ) 是由 加藤麻奈美 松本诚司 广田保史 于 2019-01-21 设计创作，主要内容包括：包含下述成分(A)～(D),由成分(E)接枝而成的改性弹性体组合物。优选在成分(A)与成分(B)的合计100质量份中成分(A)为5～70质量份,成分(B)为95～30质量份,相对于成分(A)与成分(B)的合计100质量份,成分(C)为1～200质量份,成分(D)为0.01～3质量份。成分(A)：乙烯-α-烯烃-非共轭二烯共聚物橡胶成分(B)：乙烯单元含量60～99质量％,非共轭二烯单元非含有的乙烯-α-烯烃共聚物橡胶成分(C)：聚乙烯,和/或,丙烯单元含量40～100质量％的丙烯类树脂成分(D)：不饱和硅烷化合物成分(E)：过氧化物。(A modified elastomer composition comprising the following components (A) to (D) and a component (E) grafted thereto. Preferably, the amount of the component (A) is 5 to 70 parts by mass and the amount of the component (B) is 95 to 30 parts by mass based on 100 parts by mass of the total of the component (A) and the component (B), and the amount of the component (C) is1 to 200 parts by mass and the amount of the component (D) is 0.01 to 3 parts by mass based on 100 parts by mass of the total of the component (A) and the component (B). Component (A): ethylene- α -olefin-non-conjugated diene copolymer rubber component (B): an ethylene-alpha-olefin copolymer rubber component (C) containing 60 to 99 mass% of ethylene units and not containing a non-conjugated diene unit: polyethylene, and/or a propylene resin component (D) having a propylene unit content of 40 to 100 mass%: unsaturated silane compound component (E): a peroxide.)

1. A modified elastomer composition comprising the following components (A) to (D) and grafted with the following component (E),

component (A): ethylene-alpha-olefin-non-conjugated diene copolymer rubber

Component (B): ethylene-alpha-olefin copolymer rubber having an ethylene unit content of 60 to 99% by mass and containing no non-conjugated diene unit

Component (C): propylene resin and/or polyethylene having a propylene unit content of 40 to 100 mass%

Component (D): unsaturated silane compound

Component (E): a peroxide.

2. The modified elastomer composition according to claim 1, wherein,

the content of the component (A) is 5-70 parts by mass in 100 parts by mass of the total of the component (A) and the component (B), the content of the component (B) is 95-30 parts by mass in 100 parts by mass of the total of the component (A) and the component (B), the content of the component (C) is 1-200 parts by mass relative to 100 parts by mass of the total of the component (A) and the component (B), and the content of the component (D) is 0.01-3 parts by mass relative to 100 parts by mass of the total of the component (A) and the component (B).

3. The modified elastomer composition according to claim 1 or 2, wherein,

the components (A) to (B)B) Has a density of 0.880g/cm³The following.

4. The modified elastomer composition according to any one of claims 1 to 3, wherein,

the amount of the component (E) is 0.01 to 3 parts by mass based on 100 parts by mass of the total of the component (A) and the component (B).

5. The modified elastomer composition according to any one of claims 1 to 4, further comprising a component (F): and a crosslinking assistant, wherein the amount of the component (F) is 0.001 to 2 parts by mass per 100 parts by mass of the total of the component (A) and the component (B).

6. The modified elastomer composition according to any one of claims 1 to 5, wherein,

the component (D) is a compound represented by the following formula (1):

RSi(R’)₃…(1)

wherein R is an ethylenically unsaturated hydrocarbon group, R 'are each independently a hydrocarbon group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, and at least 1 of R' is an alkoxy group having 1 to 10 carbon atoms.

7. The modified elastomer composition according to any one of claims 1 to 6, further comprising an ingredient (G): a softening agent, wherein the component (G) is 0.5 to 200 parts by mass relative to 100 parts by mass of the total of the component (A) and the component (B).

8. The modified elastomer composition according to any one of claims 1 to 7, wherein,

the component (C) is a propylene resin and/or polyethylene having an ethylene unit content of 0 to 50 mass%.

9. A crosslinked elastomer composition obtained by polymerizing a component (H): a silanol condensation catalyst obtained by crosslinking the modified elastomer composition according to any one of claims 1 to 8.

10. A molded article obtained by molding the modified elastomer composition according to any one of claims 1 to 8 or the crosslinked elastomer composition according to claim 9.

11. A modified elastomer composition comprising the following components (A), (B') and (D) and grafted with the following component (E),

component (A): ethylene-alpha-olefin-non-conjugated diene copolymer rubber

Component (B'): an ethylene-alpha-olefin copolymer rubber having a melting end peak temperature of 90 ℃ or higher as measured by a Differential Scanning Calorimeter (DSC) and containing no nonconjugated diene unit

Component (D): unsaturated silane compound

Component (E): a peroxide.

12. The modified elastomer composition according to claim 11, wherein,

the content of the component (A) is 5 to 80 parts by mass based on 100 parts by mass of the total of the component (A) and the component (B '), the content of the component (B') is 95 to 20 parts by mass based on 100 parts by mass of the total of the component (A) and the component (B '), and the content of the component (D) is 0.01 to 5 parts by mass based on 100 parts by mass of the total of the component (A) and the component (B').

13. The modified elastomer composition according to claim 11 or 12, wherein,

the amount of the component (E) is 0.01 to 3 parts by mass based on 100 parts by mass of the total of the component (A) and the component (B').

14. The modified elastomer composition according to any one of claims 11 to 13, wherein,

the component (B') had a density of 0.880g/cm³The following.

15. The modified elastomer composition of any one of claims 11 to 14, further comprising ingredient (F): and a crosslinking assistant, wherein the component (F) is 0.001 to 2 parts by mass relative to 100 parts by mass of the total of the component (A) and the component (B').

16. The modified elastomer composition according to any one of claims 11 to 15, wherein,

the component (D) is a compound represented by the following formula (1):

RSi(R’)₃…(1)

wherein R is an ethylenically unsaturated hydrocarbon group, R 'are each independently a hydrocarbon group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, and at least 1 of R' is an alkoxy group having 1 to 10 carbon atoms.

17. The modified elastomer composition of any one of claims 11 to 16, further comprising ingredient (G): a softening agent, wherein the component (G) is 0.5 to 200 parts by mass relative to 100 parts by mass of the total of the component (A) and the component (B').

18. A crosslinked elastomer composition obtained by polymerizing a component (H): a silanol condensation catalyst obtained by crosslinking the modified elastomer composition according to any one of claims 11 to 17.

19. A molded article obtained by molding the modified elastomer composition according to any one of claims 11 to 17 or the crosslinked elastomer composition according to claim 18.

Technical Field

The present invention relates to a modified elastomer composition, a crosslinked elastomer composition, and a molded article thereof.

The invention of claim 1 relates to a modified elastomer composition and a crosslinked elastomer composition excellent in compression set, durability and appearance in extrusion molding, and a molded article using the same.

The invention 2 relates to a novel low-gloss modified elastomer composition and a crosslinked elastomer composition having excellent compression set, durability, blocking resistance and moldability, and a molded article using the same.

Background

The thermoplastic elastomer is an elastomer which softens and has fluidity when heated and has rubber elasticity when cooled. The thermoplastic elastomer has the same moldability as the thermoplastic resin and also has rubber elasticity. Thermoplastic elastomers are widely used for applications such as vehicle parts, building parts, medical parts, electric wire coating materials, and miscellaneous goods, because they can be recycled.

When used in applications requiring sealing properties, it is important to have good rubber elasticity or compression set characteristics, good moldability, and extrusion molded appearance.

Since a thermoplastic elastomer is blended with a thermoplastic resin such as polyolefin in order to secure thermoplasticity, the compression set property is insufficient compared with a thermosetting rubber, and the use is limited. Although the thermosetting rubber such as EP DM has excellent compression set characteristics, it requires a long crosslinking step and is inferior in durability.

Patent documents 1 to 3 propose silane-modified elastomer compositions having improved compression set. In patent documents 1 to 3, it is necessary to add a large amount of an unsaturated silane compound in order to improve compression set, and there is a problem in terms of economy and productivity. Also, there are the following problems: it is not suitable as a sealing material having a high gloss and is liable to block during or after granulation.

Patent document 4 also proposes an elastomer composition based on silane modification. In patent document 4, the compression set (70 ℃ C.. times.22 hours) is not more than 50%.

Patent document 5 proposes a dynamic crosslinking thermoplastic elastomer composition using a crosslinking agent such as a phenol resin. In patent document 5, since the non-crosslinked thermoplastic resin is contained in the above-mentioned components, the compression set is insufficient.

Disclosure of Invention

The object of the invention 1 is to provide: the modified elastomer composition, the crosslinked elastomer composition and the molded products thereof exhibit the same compression set characteristics as those of conventional thermosetting rubbers, have the same durability and moldability as those of thermoplastic elastomer compositions, and have good extrusion molded appearance.

The inventors of the present invention have completed the invention of the present invention 1 by finding that: a rubber composition comprising an ethylene- α -olefin-non-conjugated diene copolymer rubber; an ethylene- α -olefin copolymer rubber containing no non-conjugated diene unit; polyethylene, polypropylene or propylene-alpha-olefin copolymers; a modified elastomer composition obtained by graft-modifying a composition of an unsaturated silane compound, or a crosslinked elastomer composition obtained by further subjecting the modified elastomer composition to a crosslinking reaction, can simultaneously have compression set characteristics equivalent to those of a thermosetting rubber which are not considered to be possible in the first place and simple extrusion moldability equivalent to that of a thermoplastic elastomer, and can give a molded article having excellent compression set and good extrusion appearance.

The gist of the invention 1 lies in the following [1] to [10 ].

[1] A modified elastomer composition comprising the following components (A) to (D) and grafted with the following component (E),

component (A): ethylene-alpha-olefin-non-conjugated diene copolymer rubber

Component (B): ethylene-alpha-olefin copolymer rubber having an ethylene unit content of 60 to 99% by mass and containing no non-conjugated diene unit

Component (C): a propylene resin and/or polyethylene component (D) having a propylene unit content of 40 to 100 mass%: unsaturated silane compound

Component (E): a peroxide.

[2] The modified elastomer composition according to [1], wherein,

the content of the component (A) is 5-70 parts by mass in 100 parts by mass of the total of the component (A) and the component (B), the content of the component (B) is 95-30 parts by mass in 100 parts by mass of the total of the component (A) and the component (B), the content of the component (C) is 1-200 parts by mass relative to 100 parts by mass of the total of the component (A) and the component (B), and the content of the component (D) is 0.01-3 parts by mass relative to 100 parts by mass of the total of the component (A) and the component (B).

[3] The modified elastomer composition according to [1] or [2], wherein,

the density of the component (B) is 0.880g/cm³The following.

[4] The modified elastomer composition according to any one of [1] to [3], wherein,

the amount of the component (E) is 0.01 to 3 parts by mass based on 100 parts by mass of the total of the component (A) and the component (B).

[5] The modified elastomer composition according to any one of [1] to [4], further comprising a component (F): and a crosslinking assistant, wherein the amount of the component (F) is 0.001 to 2 parts by mass per 100 parts by mass of the total of the component (A) and the component (B).

[6] The modified elastomer composition according to any one of [1] to [5], wherein,

the component (D) is a compound represented by the following formula (1):

RSi(R’)₃…(1)

wherein R is an ethylenically unsaturated hydrocarbon group, R 'are each independently a hydrocarbon group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, and at least 1 of R' is an alkoxy group having 1 to 10 carbon atoms.

[7] The modified elastomer composition according to any one of [1] to [6], further comprising a component (G): a softening agent, wherein the component (G) is 0.5 to 200 parts by mass relative to 100 parts by mass of the total of the component (A) and the component (B).

[8] The modified elastomer composition according to any one of [1] to [7], wherein,

the component (C) is a propylene resin and/or polyethylene having an ethylene unit content of 0 to 50 mass%.

[9] A crosslinked elastomer composition obtained by polymerizing a component (H): a silanol condensation catalyst, wherein the modified elastomer composition according to any one of [1] to [8] is crosslinked.

[10] A molded article obtained by molding the modified elastomer composition according to any one of [1] to [8] or the crosslinked elastomer composition according to [9 ].

The object of the invention 2 is to provide: a modified elastomer composition, a crosslinked elastomer composition, and molded articles thereof, which exhibit the same compression set characteristics as conventional thermosetting rubbers and have the same durability, blocking resistance, and moldability as thermoplastic elastomer compositions and low gloss.

The inventors 2 have completed the invention 2 by finding that: the modified elastomer composition obtained by graft-modifying a composition comprising an ethylene- α -olefin-non-conjugated diene copolymer rubber, an ethylene- α -olefin copolymer rubber not containing a non-conjugated diene unit, and an unsaturated silane compound, or a crosslinked elastomer composition obtained by further subjecting the modified elastomer composition to a crosslinking reaction can have compression set characteristics equivalent to those of thermosetting rubbers, and blocking resistance and moldability equivalent to those of thermoplastic elastomers, which are considered to be impossible.

The gist of the invention 2 resides in the following [11] to [19 ].

[11] A modified elastomer composition comprising the following components (A), (B') and (D) and grafted with the following component (E),

component (A): ethylene-alpha-olefin-non-conjugated diene copolymer rubber

Component (B'): an ethylene-alpha-olefin copolymer rubber having a melting end peak temperature of 90 ℃ or higher as measured by a Differential Scanning Calorimeter (DSC) and containing no nonconjugated diene unit

Component (D): unsaturated silane compound

Component (E): a peroxide.

[12] The modified elastomer composition according to [11], wherein,

the content of the component (A) is 5 to 80 parts by mass based on 100 parts by mass of the total of the component (A) and the component (B '), the content of the component (B') is 95 to 20 parts by mass based on 100 parts by mass of the total of the component (A) and the component (B '), and the content of the component (D) is 0.01 to 5 parts by mass based on 100 parts by mass of the total of the component (A) and the component (B').

[13] The modified elastomer composition according to [11] or [12], wherein,

the amount of the component (E) is 0.01 to 3 parts by mass based on 100 parts by mass of the total of the component (A) and the component (B').

[14] The modified elastomer composition according to any one of [11] to [13],

the component (B') had a density of 0.880g/cm³The following.

[15] The modified elastomer composition according to any one of [11] to [14], further comprising a component (F): and a crosslinking assistant, wherein the component (F) is 0.001 to 2 parts by mass relative to 100 parts by mass of the total of the component (A) and the component (B').

[16] The modified elastomer composition according to any one of [11] to [15], wherein,

the component (D) is a compound represented by the following formula (1).

RSi(R’)₃…(1)

Wherein R is an ethylenically unsaturated hydrocarbon group, R 'are each independently a hydrocarbon group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, and at least 1 of R' is an alkoxy group having 1 to 10 carbon atoms.

[17] The modified elastomer composition according to any one of [11] to [16], further comprising a component (G): a softening agent, wherein the component (G) is 0.5 to 200 parts by mass relative to 100 parts by mass of the total of the component (A) and the component (B').

[18] A crosslinked elastomer composition obtained by polymerizing a component (H): the modified elastomer composition according to any one of [11] to [17] which is obtained by crosslinking reaction of a silanol condensation catalyst.

[19] A molded article obtained by molding the modified elastomer composition according to any one of [11] to [17] or the crosslinked elastomer composition according to [18 ].

Effects of the invention

According to the invention of claim 1, there can be provided a modified elastomer composition and a crosslinked elastomer composition which are excellent in compression set characteristics and excellent in durability, extrusion moldability and extrusion molded appearance, and a molded article using the same.

According to the invention 2, a low-gloss modified elastomer composition and a crosslinked elastomer composition which are excellent in compression set characteristics and excellent in durability, blocking resistance and moldability, and a molded article using the same can be provided.

The modified elastomer composition and the crosslinked elastomer composition of the present invention and the molded article using them are expected to be applied to applications requiring good rubber elasticity, such as vehicle parts such as glass run channels and weather strips, in which thermosetting rubbers have been conventionally used, and to obtain products having better quality than ever.

Detailed Description

The 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 within a range not departing from the gist of the present invention.

In the present specification, when a numerical value or a physical property value is represented by using "to" in the specification, the numerical value or the physical property value is used to include the values before and after the numerical value or the physical property value.

In the present specification, the term "present invention" means an invention including the 1 st invention and the 2 nd invention, and is a part common to the 1 st invention and the 2 nd invention.

[ modified elastomer composition and crosslinked elastomer composition of the invention 1]

The modified elastomer composition and the crosslinked elastomer composition of the invention 1 will be described below.

[ modified elastomer composition of the invention 1]

The modified elastomer composition of the invention 1 is a modified elastomer composition comprising the following components (a) to (D) and grafted with the following component (E), and preferably further comprises the following components (F) to (G).

Component (A): ethylene-alpha-olefin-non-conjugated diene copolymer rubber

Component (B): ethylene-alpha-olefin copolymer rubber having an ethylene unit content of 60 to 99% by mass and containing no non-conjugated diene unit

Component (C): a propylene resin and/or polyethylene component (D) having a propylene unit content of 40 to 100 mass%: unsaturated silane compound

Component (E): peroxides and their use in the preparation of pharmaceutical preparations

Component (F): crosslinking aid

Component (G): softening agent

The content of the component (A) is preferably 5 to 70 parts by mass based on 100 parts by mass of the total of the component (A) and the component (B).

The content of the component (B) is preferably 95 to 30 parts by mass based on 100 parts by mass of the total of the component (A) and the component (B).

The content of the component (C) is preferably 1 to 200 parts by mass relative to 100 parts by mass of the total of the component (a) and the component (B).

The content of the component (D) is preferably 0.01 to 3 parts by mass based on 100 parts by mass of the total of the components (a) and (B).

The component (E) is preferably used in an amount of 0.01 to 3 parts by mass based on 100 parts by mass of the total of the components (A) and (B).

The content of the component (F) is preferably 0.001 to 2 parts by mass relative to 100 parts by mass of the total of the component (a) and the component (B).

The content of the component (G) is preferably 0.5 to 200 parts by mass based on 100 parts by mass of the total of the component (A) and the component (B).

[ crosslinked elastomer composition of the invention 1]

The crosslinked elastomer composition of the invention 1 is obtained by crosslinking the modified elastomer composition of the invention 1 with the following component (H).

Component (H): silanol condensation catalyst

< mechanism >

The mechanism by which the modified elastomer composition and the crosslinked elastomer composition of the invention 1 exhibit the effects of excellent compression set characteristics and good durability is presumed to be as follows.

The crosslinking degree of the components (A) and (B') can be significantly improved by the effects of the components (D), (E) and (H) and the components (E) and (F), and high rubber elasticity can be obtained. Further, good durability can be obtained from the viewpoint that no residual double bonds are present.

< ingredient (a): ethylene-alpha-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 copolymerization components. In the ethylene- α -olefin-non-conjugated diene copolymer rubber, there are an oil-extended type which is a mixture of the ethylene- α -olefin-non-conjugated diene copolymer rubber and a softening agent for hydrocarbon rubber (hereinafter, sometimes referred to as "oil-extended ethylene- α -olefin-non-conjugated diene copolymer rubber") and an oil-extended type which does not contain the softening agent for hydrocarbon rubber.

In the present embodiment, the term "oil-extended copolymer rubber" is intended, but non-oil-extended copolymer rubbers may be used.

In the present invention, the ethylene- α -olefin-non-conjugated diene copolymer rubber of the component (a) may be either an oil-extended type or a non-oil-extended type. Only 1 non-oil-extended type or oil-extended type may be used alone, or 2 or more types may be used in any combination and ratio. 1 or 2 or more oil-extended types and 1 or 2 or more non-oil-extended types may be used in any combination and ratio.

In the case of the oil-extended type, the softener for hydrocarbon rubber contained in the mixture is classified as the softener of the component (G).

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

The α -olefin in the component (a) is preferably an α -olefin having 3 to 20 carbon atoms such as propylene, 1-butene, 3-methyl-1-butene, 1-pentene, 4-methyl-1-pentene, 4-dimethyl-1-pentene, 1-hexene, 4-methyl-1-hexene, 1-heptene, 1-octene, 1-decene, 1-octadecene, etc., and more preferably an α -olefin having 3 to 8 carbon atoms, but is not particularly limited thereto. Among them, propylene, 1-butene, 3-methyl-1-butene, and 1-pentene are preferable, and propylene and 1-butene are more preferable, from the viewpoints of crosslinkability, suppression of blooming, and the like. The α -olefin may be used alone in 1 kind or in any combination and ratio of 2 or more kinds.

Examples of the non-conjugated diene compound in the component (a) include: ethylidene norbornene such as dicyclopentadiene, 1, 4-hexadiene, cyclohexadiene, cyclooctadiene, bicyclooctadiene, 1, 6-octadiene, 5-methyl-1, 4-hexadiene, 3, 7-dimethyl-1, 6-octadiene, 1, 3-cyclopentadiene, 1, 4-cyclohexadiene, 2-methyl-1, 5-hexadiene, 6-methyl-1, 5-heptadiene, 7-methyl-1, 6-octadiene, tetrahydroindene, methyltetrahydroindene, 5-isopropylidene-2-norbornene, 5-vinyl-2-norbornene, vinylidene norbornene, 5-ethylidene-2-norbornene (ENB), methylene norbornene such as 5-methylene-2-norbornene (MNB), etc., but is not particularly limited thereto. Among them, dicyclopentadiene, ethylidene 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. The non-conjugated diene may be used alone in 1 kind or in any combination and ratio of 2 or more kinds.

Specific examples of the ethylene- α -olefin-non-conjugated diene copolymer rubber include: ethylene-propylene-nonconjugated diene copolymer rubber (EPDM) such as ethylene-propylene-5-ethylidene-2-norbornene copolymer rubber, ethylene-propylene-dicyclopentadiene copolymer rubber, ethylene-propylene-1, 4-hexadiene copolymer rubber and ethylene-propylene-5-vinyl-2-norbornene copolymer rubber, and ethylene-1-butene-5-ethylidene-2-norbornene copolymer rubber, but are not particularly limited thereto. Among them, ethylene-propylene-non-conjugated diene copolymer rubber (EPDM) is preferable from the viewpoints of crosslinkability, suppression of blooming, and the like. The ethylene- α -olefin-non-conjugated diene copolymer rubber may be used alone in 1 kind or in any combination and ratio in 2 or more kinds.

The content of the ethylene unit 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 still more preferably 60 to 80% by mass. When the content of the ethylene unit is within the above-described preferable range, an elastomer composition excellent in 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 still more preferably 20 to 40% by mass. When the content of the α -olefin unit is within the above-described preferable range, an elastomer composition having excellent mechanical strength, appropriate flexibility, and rubber elasticity tends to be easily obtained.

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, and still more preferably 2 to 10% by mass. When the content of the non-conjugated diene unit is within the above-mentioned preferable range, the adjustment of the crosslinking property and the moldability becomes easy, and an elastomer composition excellent in mechanical strength and rubber elasticity tends to be easily obtained.

The content of each constituent unit of component (a), component (B'), and component (C), such as component (a) and component (B) described later, can be determined by infrared spectroscopy.

Particularly preferred as the component (A) is an ethylene-propylene-non-conjugated diene copolymer rubber copolymer having an ethylene unit content of 55 to 75% by mass, a propylene unit content of 15 to 40% by mass, and a content of at least 1 non-conjugated diene unit selected from the group consisting of dicyclopentadiene, 5-ethylidene-2-norbornene and vinylidene norbornene of 1 to 10% by mass.

The ethylene- α -olefin-non-conjugated diene copolymer rubber of the component (a) may be used alone in 1 kind or in any combination and ratio in 2 or more kinds.

< ingredient (B): ethylene-alpha-olefin copolymer >

The ethylene- α -olefin copolymer of the component (B) is a copolymer having an ethylene unit content of 60 to 99% by mass and containing no non-conjugated diene unit, that is, an ethylene- α -olefin copolymer other than the component (A). The ethylene- α -olefin copolymer as the component (B) is not particularly limited in kind as long as it is such a copolymer, and a known ethylene- α -olefin copolymer can be suitably used.

Specific examples of the ethylene- α -olefin copolymer include copolymers of ethylene and 1 or 2 or more α -olefins having 3 to 10 carbon atoms, such as an ethylene-propylene copolymer, an ethylene-1-butene copolymer, an ethylene-4-methyl-1-pentene copolymer, an ethylene-1-hexene copolymer, and an ethylene-1-octene copolymer.

The kind of the catalyst used in the production of the ethylene- α -olefin copolymer is not particularly limited, and examples thereof include: ziegler natta catalysts, metallocene catalysts. Among them, ethylene- α -olefin copolymers produced by a metallocene catalyst are preferred.

The ethylene- α -olefin copolymer of the component (B) is preferably one having a melting end peak temperature (hereinafter, sometimes referred to as "melting end point") of 115 ℃ or higher as measured by a Differential Scanning Calorimeter (DSC). When the melting end point of the ethylene- α -olefin copolymer is 115 ℃ or more, the shape can be maintained by crystallization even at high temperature. From this viewpoint, the ethylene- α -olefin copolymer preferably has a melt end point of 115 ℃ or higher. When the melting end point of the ethylene- α -olefin copolymer is too high, there is a risk that the appearance will be deteriorated due to unmelted material at the time of molding temperature rise or early crystallization (melt fracture) at the time of molding cooling, and therefore, the melting end point of the ethylene- α -olefin copolymer is usually 145 ℃ or lower. The melting end point of the ethylene- α -olefin copolymer was measured by the method described in the section of examples described later.

Preferably, the ethylene- α -olefin copolymer of the component (B) has a density (measured by JIS K6922-1,2: 1997) of 0.850 to 0.910g/cm³More preferably 0.860 to 0.900g/cm³More preferably 0.860 to 0.880g/cm³. When the density is not more than the above upper limit, the flexibility and the sealing property tend to be excellent. When the density is not less than the lower limit, the shape can be maintained at room temperature, the hysteresis loss is also small, and the plastic deformation (compression set) tends to be excellent.

The ethylene- α -olefin copolymer of the component (B) has an ethylene unit content of 60 to 99% by mass, preferably 60 to 85% by mass. When the content of the ethylene unit is within the above range, an elastomer composition excellent in mechanical strength and rubber elasticity tends to be easily obtained.

The ethylene-alpha-olefin copolymer of the component (B) preferably has a Melt Flow Rate (MFR) of 0.01 to 30g/10min as measured at 190 ℃ under a load of 21.2N in accordance with JIS K7210 (1999). When the MFR is too large, there is a risk that compression set becomes large and sealability is lowered. When the MFR is too small, there is a risk of surface roughening after molding, in addition to a large motor load at the time of the reforming extrusion, an increase in resin pressure, and deterioration in productivity. From these viewpoints, the MFR of the ethylene- α -olefin copolymer is more preferably from 0.1g/10min to 10g/10 min.

The ethylene- α -olefin copolymer used in the present invention is commercially available. For example, the product can be selected from the group consisting of ENGAGE (registered trademark) series manufactured by Dow chemical, KERNEL (registered trademark) series manufactured by JAPAN POLYETHYLENE, INFUSE (registered trademark) series manufactured by Dow chemical, TAFMER (registered trademark) series manufactured by Mitsui chemical, EVOLUE (registered trademark) series manufactured by Mitsui chemical, and the like.

The ethylene- α -olefin copolymer of the component (B) may be used alone in 1 kind or in any combination and ratio in 2 or more kinds.

< ingredient (C): propylene resin and/or polyethylene >

The component (C) is a propylene resin and/or polyethylene having a propylene unit content of 40 to 100 mass%. The component (C) contributes to moldability.

As the component (C), only 1 kind of polyethylene may be used, and 2 or more kinds of polyethylenes having different physical properties may be used. Only 1 type of propylene resin may be used, and 2 or more types of propylene resins having different compositions and physical properties may be used. 1 or 2 or more kinds of polyethylene and 1 or 2 or more kinds of propylene-based resin may be used in combination.

In the component (C), as the polyethylene (ethylene homopolymer), 1 or 2 or more selected from high density polyethylene (low pressure polyethylene), low density polyethylene (high pressure polyethylene), linear low density polyethylene, and the like are preferably used. High density polyethylene is particularly preferred.

Density of polyethylene (JIS)K6922-1,2) is preferably 0.91-0.97 g/cm³More preferably 0.94 to 0.97g/cm³. At a density of less than 0.91g/cm³In the case of (b), there is a possibility that the melting point of the composition is lowered and the heat distortion temperature is lowered. The density is more than 0.97g/cm³The manufacture of polyethylene of (a) is often difficult.

The melt index (MFR) of the polyethylene as the component (C), measured at 190 ℃ under a load of 21.2N in accordance with JIS K7210(1999), is usually 0.01g/10min or more, preferably 0.05g/10min or more, more preferably 0.1g/10min or more from the viewpoint of fluidity. On the other hand, it is usually 50g/10min or less, preferably 40g/10min or less, more preferably 20g/10min or less, from the viewpoint of moldability.

In the component (C), the propylene resin is a propylene resin having a propylene unit content of 40 to 100% by mass, preferably an ethylene unit content of 0 to 50% by mass, based on all monomer units contained in the propylene resin.

The propylene resin as the component (C) is not particularly limited in kind, and any of a propylene homopolymer, a propylene random copolymer, a propylene block copolymer and the like can be used. These may be used alone in 1 kind or in combination of 2 or more kinds.

When the component (C) is a propylene random copolymer or a propylene block copolymer, examples of the monomer copolymerizable with propylene include: 1 or 2 or more kinds of alpha-olefins such as ethylene, 1-butene, 2-methylpropene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene and 1-octene. When the component (C) is a propylene block copolymer, a propylene block copolymer obtained by multistage polymerization can be mentioned. More specifically, there may be mentioned a propylene block copolymer obtained by polymerizing polypropylene in the first stage and a propylene-ethylene copolymer in the second stage.

The content of the propylene unit in the polypropylene resin of the component (C) is 40 mass% or more, preferably 50 mass% or more. When the content of the propylene unit is not less than the lower limit, moldability and molded appearance tend to be good. The upper limit of the content of the propylene unit is not particularly limited, and is usually 100% by mass.

The Melt Flow Rate (MFR) of the propylene-based resin of the component (C), measured at 230 ℃ under a 21.2N load according to JIS K7210(1999), is usually 0.01g/10min or more, preferably 0.05g/10min or more, more preferably 0.1g/10min or more, and still more preferably 0.5g/10min or more, from the viewpoint of fluidity. On the other hand, it is usually 200g/10min or less, and from the viewpoint of moldability, it is preferably 100g/10min or less, more preferably 70g/10min or less, and still more preferably 50g/10min or less.

As the polyethylene as the component (C), commercially available polyethylene can be used. Examples of commercially available polyethylene include: NoVATEC (registered trademark) HD available from JAPANPOLYETHYLENE, HI-ZEX (registered trademark) available from PRIME PO LYMER, SUMIKATHENE (registered trademark) available from Sumitomo chemical company, and the like can be appropriately selected.

As the propylene-based resin as the component (C), commercially available ones can be used. The commercially available propylene-based resin can be purchased from manufacturers and the like as exemplified below, and can be selected as appropriate. Commercially available products that can be purchased include: prim Polypro (registered trademark) by PRIME POLYMER, sumitomoblock (registered trademark) by sumitomo Chemical, POLYPROPYLENE block copolymer by sunailomer, NOVATEC (registered trademark) PP by JAPAN POLYMER, Moplen (registered trademark) PP by Lyo delllbasell, Adflex, Hiflex, Hifax, ExxonMobil PP by ExxonMobil, Formolene (registered trademark) by fortmos Plastics, Borealis PP by Borealis, setec PP by LG Chemical, ASI polyperpolypylene by a schulman, init Olefins & POLYMERs, init eos PP by B raskem, cottpspp by roctals, and petalit Total of sampalon, and petalit (registered trademark) PP by sabotal company, and petalit copolymer.

< ingredient (D): unsaturated silane Compound >

The unsaturated silane compound of the component (D) used in the present invention is not limited, and an unsaturated silane compound represented by the following formula (1) is preferably used.

RSi(R’)₃···(1)

In 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, and at least 1 of R' 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. Specifically, there may be mentioned: alkenyl groups such as vinyl, propenyl, butenyl, cyclohexenyl and the like.

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 an alkoxy group having 1 to 4 carbon atoms. At least 1 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 having 1 to 10 carbon atoms of R' may be any of an aliphatic group, an alicyclic group, and an aromatic group, and is preferably an aliphatic group. The alkoxy group having 1 to 10 carbon atoms represented by R' may be linear, branched or cyclic, and is preferably linear or branched. When R' is a hydrocarbon group, specific examples thereof include an alkyl group represented by a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, a n-butyl group, an isobutyl group, a cyclohexyl group and the like, an aryl group represented by a phenyl group and the like. When R' is an alkoxy group, specific examples thereof include: methoxy, ethoxy, isopropoxy, beta-methoxyethoxy.

In the case where the unsaturated silane compound is represented by formula (1), at least 1 of 3R's is an alkoxy group, preferably 2R's are alkoxy groups, and more preferably all R's are alkoxy groups.

Among the unsaturated silane compounds represented by formula (1), preferred are vinyltrialkoxysilanes typified by vinyltrimethoxysilane, vinyltriethoxysilane, propenyltrimethoxysilane, and the like. This is because the component (B) (component (B') in the invention 2 described later) can be modified into the ethylene- α -olefin copolymer by the vinyl group, and the crosslinking reaction described later can be performed by the alkoxy group. The alkoxy group introduced by graft modification of the ethylene- α -olefin copolymer with the unsaturated silane compound is hydrolyzed by reaction with water in the presence of a silanol condensation catalyst to generate silanol groups, and the silanol groups are dehydrated and condensed with each other to bond the ethylene- α -olefin copolymers to each other to cause a crosslinking reaction. These unsaturated silane compounds may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

< ingredient (E): peroxide >

Examples of the peroxide as the component (E) include organic peroxides contained in the group consisting of hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxyesters, and ketone peroxides. Specific examples thereof include those described below.

The hydroperoxide group includes cumene hydroperoxide, tert-butyl hydroperoxide and the like.

The dialkyl peroxides include diisopropylphenyl peroxide, di-t-butyl peroxide, 2, 5-dimethyl-2, 5-di-t-butylperoxyhexane, 2, 5-dimethyl-2, 5-di-t-butylperoxyhexyne-3, di (2-t-butylperoxyisopropyl) benzene, and the like.

The diacyl peroxide group includes lauryl peroxide, benzoyl peroxide and the like.

The peroxyester group includes t-peroxyacetate, t-butylperoxybenzoate, t-butylperoxyisopropyl carbonate, and the like.

The ketone peroxide group contains cyclohexanone peroxide and the like.

These organic peroxides may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

When used in combination with a crosslinking assistant of the component (F) described later, a radical generator having a high thermal decomposition temperature is preferred. From this viewpoint, di-t-butyl peroxide, bis (2-t-butylperoxyisopropyl) benzene, 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexane, and diisopropylphenyl peroxide are preferable.

< ingredient (F): crosslinking Co-agent >

As the crosslinking assistant of component (F), for exampleExamples thereof include: hydrogen silicon compounds such as Metro hydrogen silicon, sulfur, p-benzoquinone dioxime, p-dinitrosobenzene, 1, 3-diphenylguanidine, and other peroxide auxiliaries; polyfunctional vinyl compounds such as divinylbenzene, triallyl cyanurate, triallyl isocyanurate, diallyl phthalate, and the like; polyfunctional (meth) acrylate compounds such as ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, allyl (meth) acrylate, and the like; compounds having a bismaleimide structure such as N, N '-m-phenylene bismaleimide and N, N' -m-toluene bismaleimide; trimethylolpropane, trimethylolpropane trimethacrylate, stannic chloride (SnCl)₂) And the like. Among them, polyfunctional vinyl compounds such as divinylbenzene, triallylcyanurate, triallylisocyanurate and diallyl phthalate, and polyfunctional (meth) acrylate compounds are preferable.

As other crosslinking aids, phenolic resins may be used. Examples of the phenolic resin include: alkylphenol formaldehydes, brominated alkylphenol formaldehydes, and the like.

These crosslinking assistants may be used alone in 1 kind or in any combination and ratio of 2 or more.

< ingredient (G): softening agent >

The modified elastomer composition of the present invention may contain a softening agent as the component (G) from the viewpoint of improving processability, fluidity and oil resistance while increasing flexibility.

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

Generally, the softener for mineral oil-based rubber is a mixture of aromatic hydrocarbons, naphthenic hydrocarbons, and paraffinic hydrocarbons. Paraffinic oil in which the carbon content of paraffinic hydrocarbons is 50 mass% or more, naphthenic oil in which the carbon content of naphthenic hydrocarbons is 30 to 45 mass%, and aromatic oil in which the carbon content of aromatic hydrocarbons is 35 mass% or more are all referred to as paraffinic oil. Among them, as the softener, a softener for liquid hydrocarbon rubber which is liquid at normal temperature (23 ± 2 ℃) is preferable, and a liquid paraffin oil which is liquid at normal temperature is more preferable.

By using a liquid hydrocarbon rubber softener as the softener, the modified elastomer composition of the present invention tends to have increased flexibility and elasticity and dramatically improved processability and fluidity.

The paraffin oil is not particularly limited, and has a kinematic viscosity at 40 ℃ of usually not less than 10cSt (centistoks), preferably not less than 20cSt, usually not more than 800cSt, preferably not more than 600 cSt. As the paraffin oil, those having a pour point of usually-40 ℃ or higher, preferably-30 ℃ or higher and 0 ℃ or lower are suitably used. As the paraffinic oil, a paraffin oil having a flash point (COC) of usually 200 ℃ or higher, preferably 250 ℃ or higher, usually 400 ℃ or lower, preferably 350 ℃ or lower is suitably used.

The softener of the component (G) may be used alone in 1 kind or in any combination and ratio in 2 or more kinds.

In the case of using an oil-extended type as the component (a), the hydrocarbon rubber softener to be introduced into the elastomer composition as a mixture of the oil-extended type ethylene- α -olefin-non-conjugated diene copolymer rubber and the hydrocarbon rubber softener corresponds to the softener of the component (G). In this case, a softener may be additionally added as the component (G), and an additionally added softener may be used. In the case where a softening agent is separately added, the softening agent for hydrocarbon rubber contained in the oil-extended component (a) may be the same as or different from the softening agent separately added.

< ingredient (H): silanol condensation catalyst >

The modified elastomer composition of the present invention can be subjected to intermolecular crosslinking reaction by mixing the component (H), a silanol condensation catalyst, with the composition. In this case, as described above, the alkoxy groups introduced by graft-modifying the components (a) and (B) with the unsaturated silane compound of the component (D) react with water in the presence of the silanol condensation catalyst of the component (H) to hydrolyze, thereby forming silanol groups, and the silanol groups are further dehydrated and condensed with each other to undergo a crosslinking reaction, thereby bonding the modified elastomers to each other to form a crosslinked elastomer composition having excellent heat resistance.

Examples of the silanol condensation catalyst of the component (H) include 1 or more compounds selected from organic acid salts, titanate esters, borate salts, organic amines, ammonium salts, phosphonium salts, inorganic acids, organic acids, and inorganic acid esters.

Examples of the organic acid metal salts include: dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin diacetate, dibutyltin dioctoate, stannous acetate, stannous octoate, cobalt naphthenate, lead octoate, lead naphthenate, zinc octoate (caprilic acid), iron 2-ethylhexanoate, iron octoate, iron stearate, and the like.

Examples of the titanate include: tetrabutyl titanate, tetranonyl titanate, bis (acetoacetonitrilyl) di-isopropyl titanate, and the like.

Examples of the organic amine include: ethylamine, dibutylamine, hexylamine, triethanolamine, dimethylsoyamine, tetramethylguanidine, pyridine, and the like.

Examples of ammonium salts include: ammonium carbonate, tetramethylammonium hydroxide, and the like. Examples of the phosphonium salt include tetramethylphosphonium hydroxide 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, alkylnaphthalenesulfonic acid, and the like.

Examples of the inorganic acid ester include phosphoric acid esters.

Of these, organic acid salts, sulfonic acids, and phosphoric acid esters of metals are preferable, and metal carboxylates of tin are more preferable, and for example, dioctyltin dilaurate, alkylnaphthalenesulfonic acid, and ethylhexylphosphoric acid ester are included.

The silanol condensing catalyst may be used alone in 1 kind or in combination of 2 or more kinds.

The silanol condensing catalyst is preferably used as a master batch in which polyolefin and the silanol condensing catalyst are mixed. Examples of polyolefins that can be used in the masterbatch include: polyethylene, polypropylene, ethylene-alpha-olefin copolymers, and the like.

Examples of polyethylene include: a (branched or straight chain) ethylene homopolymer such as low, medium or high density polyethylene; ethylene- α -olefin copolymers such as ethylene-propylene copolymers, ethylene-1-butene copolymers, ethylene-4-methyl-1-pentene copolymers, ethylene-1-hexene copolymers, and ethylene-1-octene copolymers; ethylene copolymer resins such as ethylene-vinyl acetate copolymers, ethylene- (meth) acrylic acid copolymers, and ethylene- (meth) acrylate copolymers. Among them, ethylene- α -olefin copolymers such as ethylene-propylene copolymers, ethylene-1-butene copolymers, ethylene-4-methyl-1-pentene copolymers, ethylene-1-hexene copolymers, and ethylene-1-octene copolymers are preferable.

Among them, in the present invention, high-pressure low-density polyethylene, high-density polyethylene, and ethylene- α -olefin copolymer, which are excellent in the balance between heat resistance and strength, are preferable. The ethylene- α -olefin copolymer is more preferably an ethylene- α -olefin copolymer such as an ethylene-1-butene copolymer, an ethylene-4-methyl-1-pentene copolymer, an ethylene-1-hexene copolymer, or an ethylene-1-octene copolymer. More preferably, the ethylene-alpha-olefin copolymer is obtained by copolymerizing 2 to 60 mass% of 1 or 2 or more kinds of alpha-olefins with 40 to 98 mass% of ethylene.

Only 1 kind of the above polyolefin may be used in the master batch of the silanol condensation catalyst, or 2 or more kinds may be used in combination.

When the silanol condensation catalyst is used as a masterbatch obtained by mixing a polyolefin and a silanol condensation catalyst, the content of the silanol condensation catalyst in the masterbatch is not particularly limited, and is preferably about 0.1 to 5.0 mass%.

As the master batch containing the silanol condensing catalyst, commercially available products can be used. For example, "LZ 082" and "LZ 033" manufactured by MITSUBISHICHIMICAL (KOKAI) may be used.

< mixing ratio >

The modified elastomer composition of claim 1 preferably contains the component (a) and the component (B) in such a proportion that the component (a) is 5 to 70 parts by mass and the component (B) is 95 to 30 parts by mass, and the total is 100 parts by mass. When the content of the component (a) is higher than the upper limit and the content of the component (B) is lower than the lower limit, good appearance tends not to be obtained. When the content ratio of the component (a) is less than the lower limit and the content ratio of the component (B) is greater than the upper limit, the gloss tends to be high or blocking tends to occur. From such a viewpoint, the proportion of the component (a) in 100 parts by mass of the total of the component (a) and the component (B) is more preferably 5 to 70 parts by mass, still more preferably 5 to 50 parts by mass, and the proportion of the component (B) is more preferably 95 to 30 parts by mass, still more preferably 95 to 50 parts by mass.

The content of the component (C) is preferably 1 to 200 parts by mass, more preferably 5 to 80 parts by mass, and still more preferably 10 to 50 parts by mass, based on 100 parts by mass of the total of the components (a) and (B), from the viewpoint of maintaining a smooth molding appearance and flexibility.

From the viewpoint of sufficiently advancing the crosslinking reaction, the content of the component (D) is preferably 0.01 to 5 parts by mass, more preferably 0.05 to 5 parts by mass, and still more preferably 0.1 to 3 parts by mass, relative to 100 parts by mass of the total of the component (a) and the component (B).

The content of the component (E) is preferably 0.01 to 3 parts by mass based on 100 parts by mass of the total of the component (a) and the component (B), and more preferably 0.05 to 2 parts by mass, and even more preferably 0.1 to 1 part by mass, from the viewpoint of obtaining a sufficient crosslinking reaction and maintaining a smooth molded appearance.

When the modified elastomer composition of claim 1 contains the component (F), the content of the component (F) is 0.001 to 2 parts by mass relative to 100 parts by mass of the total of the component (a) and the component (B), and is preferably 0.003 to 1 part by mass from the viewpoint of economy and obtaining a sufficient crosslinking reaction.

When the modified elastomer composition of claim 1 contains the component (G), the content of the component (G) (including the hydrocarbon rubber softener in the component (a) is 0.5 to 200 parts by mass based on 100 parts by mass of the total of the component (a) and the component (B) in the case where an oil-extended type is used as the component (a)). When the content of the component (G) is less than the lower limit, the effect of improving flexibility, fluidity, and oil resistance by the component (G) cannot be sufficiently obtained. When the content of the component (G) is more than the upper limit, there is a risk of bleeding out from the surface. From this viewpoint, the content of the component (G) is preferably 1 to 100 parts by mass, and more preferably 5 to 80 parts by mass, based on 100 parts by mass of the total of the component (a) and the component (B).

When the silanol condensation catalyst of the component (H) is added to the modified elastomer composition of the invention 1 to cause the crosslinking reaction, the amount of the silanol condensation catalyst added is not particularly limited, but is preferably 0.001 to 0.5 part by mass, and more preferably 0.001 to 0.1 part by mass, based on 100 parts by mass of the modified elastomer composition of the invention 1 excluding the component (H). When the amount of the silanol condensation catalyst added is not less than the lower limit, the crosslinking reaction tends to sufficiently proceed, and the heat resistance tends to be good, which is preferable. When the amount of the silanol condensation catalyst added is not more than the above upper limit, the early crosslinking in the extruder tends to be less likely to occur, and cracks tend to be less likely to occur on the surface of the strand or the appearance of the product, which is preferable.

< other ingredients >

In the modified elastomer composition of the present invention, various additives, fillers, resins other than the components (a) to (C), elastomers, and the like may be contained as other components in addition to the above components within a range not impairing the effects of the present invention.

Examples of the additives include: heat stabilizers, ultraviolet absorbers, light stabilizers, antioxidants, antistatic agents, crystallization nucleating agents, rust inhibitors, viscosity modifiers, foaming agents, lubricants, pigments, and the like. Among them, it is preferable to contain an antioxidant, particularly a phenolic antioxidant, a sulfur antioxidant or a phosphorus antioxidant.

The antioxidant is preferably contained in an amount of 0.1 to 1% by mass based on 100% by mass of the modified elastomer composition of the present invention.

Examples of the other resins include: polyamide-based elastomers such as polyolefin resins other than the component (C), polyester resins, polycarbonate resins, polymethyl methacrylate resins, rosins and derivatives thereof, terpene resins, petroleum resins and derivatives thereof, alkyd resins, alkylphenol resins, terpene phenol resins, coumarone-indene resins, synthetic terpene resins, alkylene resins, olefin-based elastomers other than the components (a) to (B), and polyamide-polyol copolymers; polyvinyl chloride elastomers, polybutadiene elastomers, styrene elastomers, hydrogenated products thereof, products obtained by modifying with an acid anhydride or the like and introducing a polar functional group, products obtained by further grafting another monomer and subjecting the resulting product to random and/or block copolymerization, and the like.

< production and Molding of modified elastomer composition >

The modified elastomer composition of the invention 1 can be produced by mechanically mixing the components (A) to (C), the unsaturated silane compound of the component (D), the peroxide of the component (E), and, if necessary, the crosslinking assistant, the softener, and other components by a known method, for example, Henschel mixer, V mixer, drum mixer, etc., and then mechanically melt-kneading them by a known method. In the melt kneading, a general melt kneader such as a Banbury MIXER (BANBURY MIXER), various kneaders, a single-screw or twin-screw extruder, or the like can be used. As shown in examples described later, when the composition of the present invention is produced by kneading with a single-screw or twin-screw extruder, the melt kneading may be carried out in a state of heating to 120 to 240 ℃ in general, and preferably 120 to 220 ℃.

The modified elastomer composition of the present invention may be obtained by mixing the above-mentioned silanol condensation catalyst, molding the mixture by various molding methods such as extrusion molding, injection molding and press molding, and then exposing the mixture to an aqueous atmosphere to cause a crosslinking reaction between silanol groups. Various conditions can be employed for the method of exposure to the aqueous atmosphere, and examples thereof include: a method of placing in air containing moisture, a method of blowing air containing water vapor, a method of immersing in a water bath, a method of spraying warm water in the form of mist, and the like.

In this case, the hydrolyzable alkoxy group derived from the unsaturated silane compound used for graft modification of the components (a) and (B) is hydrolyzed by reaction with water in the presence of a silanol condensation catalyst to form silanol groups, and the silanol groups are further dehydrated and condensed with each other to cause a crosslinking reaction to bond the modified elastomers to each other to form a crosslinked elastomer composition.

The rate of progress of the crosslinking reaction depends on the conditions of exposure to the water atmosphere, and is usually within a temperature range of 0 to 130 ℃ and within a range of 5 minutes to 1 week. Particularly preferred conditions are a temperature in the range of 40 to 90 ℃ and a temperature in the range of 30 minutes to 24 hours. In the case of using air containing moisture, the relative humidity is selected from the range of 1 to 100%.

The degree of crosslinking of the crosslinked elastomer composition obtained in this way can be adjusted by changing the kind and mixing amount of the silanol condensation catalyst, the conditions (temperature, time) for crosslinking, and the like.

[ modified elastomer composition and crosslinked elastomer composition of the invention 2]

The modified elastomer composition and the crosslinked elastomer composition of the invention 2 will be described below.

[ modified elastomer composition of the invention 2]

The modified elastomer composition of the invention 2 is a modified elastomer composition comprising the following components (a), (B') and (D) and grafted with the component (E), and preferably further comprises the following components (F) to (G).

Component (A): ethylene-alpha-olefin-non-conjugated diene copolymer rubber

Component (B'): an ethylene-alpha-olefin copolymer rubber having a melting end peak temperature of 90 ℃ or higher as measured by a Differential Scanning Calorimeter (DSC) and containing no nonconjugated diene unit

Component (D): unsaturated silane compound

Component (E): peroxides and their use in the preparation of pharmaceutical preparations

Component (F): crosslinking aid

Component (G): softening agent

The content of the component (A) is preferably 5 to 80 parts by mass based on 100 parts by mass of the total of the component (A) and the component (B').

The content of the component (B ') is preferably 95 to 20 parts by mass based on 100 parts by mass of the total of the component (A) and the component (B').

The content of the component (D) is preferably 0.01 to 5 parts by mass based on 100 parts by mass of the total of the component (a) and the component (B').

The component (E) is preferably used in an amount of 0.01 to 3 parts by mass based on 100 parts by mass of the total of the components (A) and (B').

The content of the component (F) is preferably 0.001 to 2 parts by mass relative to 100 parts by mass of the total of the component (a) and the component (B').

The content of the component (G) is preferably 0.5 to 200 parts by mass based on 100 parts by mass of the total of the component (A) and the component (B').

[ crosslinked elastomer composition of the invention 2]

The crosslinked elastomer composition of the invention 2 is obtained by crosslinking the modified elastomer composition of the invention 2 with the following component (H).

Component (H): silanol condensation catalyst

< mechanism >

The mechanism by which the modified elastomer composition and the crosslinked elastomer composition of the invention 2 exhibit the effects of excellent compression set characteristics, good durability, blocking resistance, and low gloss is presumed to be as follows.

By the effects of the components (D), (E), (H) and (F), the crosslinking degree of the components (a) and (B ') can be significantly improved to obtain high rubber elasticity, and the component (a) is finely dispersed in the component (B'), thereby obtaining low gloss by diffuse reflection and exhibiting the effect of suppressing blocking. Further, good durability can be obtained from the viewpoint that no residual double bonds are present.

< ingredient (a): ethylene-alpha-olefin-non-conjugated diene copolymer rubber >

The ethylene- α -olefin-non-conjugated diene copolymer rubber as the component (a) used in the invention 2 can be the same as the ethylene- α -olefin-non-conjugated diene copolymer rubber as the component (a) in the invention 1, and the same effects and preferable modes thereof can be also applied. Therefore, the description of the component (A) of the invention 2 applies as it is to the component (A) of the invention 1.

< ingredient (B'): ethylene-alpha-olefin copolymer >

The ethylene- α -olefin copolymer of the component (B') used in the invention (2) is a copolymer having a melting end peak temperature (melting end point) of 90 ℃ or higher as measured by a Differential Scanning Calorimeter (DSC), containing an ethylene unit and an α -olefin unit, and containing no nonconjugated diene unit, that is, an ethylene- α -olefin copolymer other than the component (A). The ethylene- α -olefin copolymer as the component (B') is not particularly limited in kind, and a known ethylene- α -olefin copolymer can be suitably used.

Specific examples of the ethylene- α -olefin copolymer as the component (B') include copolymers of ethylene and 1 or 2 or more α -olefins having 3 to 10 carbon atoms, such as an ethylene-propylene copolymer, an ethylene-1-butene copolymer, an ethylene-4-methyl-1-pentene copolymer, an ethylene-1-hexene copolymer, and an ethylene-1-octene copolymer.

The kind of the catalyst used in the production of the ethylene- α -olefin copolymer of the component (B') is not particularly limited, and examples thereof include: ziegler natta catalysts, metallocene catalysts. Among them, ethylene- α -olefin copolymers produced by a metallocene catalyst are preferred.

The ethylene- α -olefin copolymer of the component (B') has a melting end point of 90 ℃ or higher, preferably 115 ℃ or higher. In the case where the melting end point of the ethylene- α -olefin copolymer becomes high, the shape can be maintained by crystallization even at high temperature. However, when the melting end point of the ethylene- α -olefin copolymer is too high, there is a risk of appearance deterioration due to unmelted material at the time of molding temperature rise and early crystallization (melt fracture) at the time of molding cooling, and therefore, the melting end point of the ethylene- α -olefin copolymer is usually 145 ℃ or lower. The melting end point of the ethylene- α -olefin copolymer of the component (B') 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') (according to JIS K6922-1) is preferred2:1997 determination) is 0.850-0.910 g/cm³More preferably 0.860 to 0.900g/cm³More preferably 0.860 to 0.880g/cm³. When the density is not more than the above upper limit, the flexibility and the sealing property tend to be excellent. When the density is not less than the lower limit, the shape can be maintained at room temperature, and the hysteresis loss is also small, and therefore, the plastic deformation tends to be excellent.

The ethylene- α -olefin copolymer of the component (B') preferably has an ethylene unit content of 50 to 99% by mass, more preferably 60 to 95% by mass. When the content of the ethylene unit is within the above range, an elastomer composition excellent in mechanical strength and rubber elasticity tends to be easily obtained.

The ethylene- α -olefin copolymer of the component (B') preferably has a Melt Flow Rate (MFR) of 0.01 to 30g/10min as measured at 190 ℃ under a load of 21.2N in accordance with JIS K7210 (1999). When the MFR is too large, there is a risk that compression set becomes large and sealability is lowered. When the MFR is too small, there is a risk that the motor load at the time of the reforming extrusion is large, the resin pressure is increased, the productivity is deteriorated, and the surface after molding is also rough. From these viewpoints, the MFR of the ethylene- α -olefin copolymer of the component (B') is more preferably from 0.1g/10min to 10g/10 min.

The ethylene- α -olefin copolymer of the component (B') is commercially available as an ethylene- α -olefin copolymer. For example, the product can be selected from the group consisting of ENGAGE (registered trademark) series manufactured by Toho chemical, KERNEL (registered trademark) series manufactured by JAPAN POLYET HYLENE, INFUSE (registered trademark) series manufactured by Toho chemical, TAFMER (registered trademark) series manufactured by Mitsui chemical, EVOL UE (registered trademark) series manufactured by Mitsui chemical, and the like.

The ethylene- α -olefin copolymer of the component (B') may be used alone in 1 kind or in any combination and ratio in 2 or more kinds.

< ingredient (D): unsaturated silane Compound >

As the unsaturated silane compound of the component (D) used in the invention 2, the same ones as those of the component (D) of the invention 1 can be used, and the same effects and preferable modes thereof are also applicable. Therefore, the description of the component (D) of the invention 2 applies as it is to the component (D) of the invention 1.

< ingredient (E): peroxide >

The peroxide as the component (E) used in the invention 2 can be the same as the peroxide as the component (E) of the invention 1, and the same effects and preferable modes are also applicable. Therefore, the description of the component (E) of the invention 2 applies as it is to the component (E) of the invention 1.

< ingredient (F): crosslinking Co-agent >

The crosslinking assistant of the component (F) used in the invention 2 can be the same as the crosslinking assistant of the component (F) of the invention 1, and the same effects and preferred modes thereof can be obtained. Therefore, the description of the component (F) of the invention 2 applies as it is to the component (F) of the invention 1.

< ingredient (G): softening agent >

As the softener of the component (G) used in the invention 2, the same softeners as those of the component (G) of the invention 1 can be used, and the same effects and preferable modes thereof can be obtained. Therefore, the description of the component (G) of the invention 2 applies as it is to the component (G) of the invention 1.

< ingredient (H): silanol condensation catalyst >

The silanol condensation catalyst as the component (H) used in the invention 2 can be the same as the silanol condensation catalyst as the component (H) of the invention 1, and the same effects and preferred embodiments can be obtained. Therefore, the description of the component (H) of the invention 2 applies as it is to the component (H) of the invention 1.

< mixing ratio >

The modified elastomer composition of claim 2 preferably contains the component (a) and the component (B ') in such a proportion that the component (a) is 5 to 80 parts by mass and the component (B') is 95 to 20 parts by mass and the total is 100 parts by mass. When the content ratio of the component (a) is higher than the upper limit and the content ratio of the component (B') is lower than the lower limit, there is a risk that a good appearance cannot be obtained. When the content ratio of the component (a) is lower than the lower limit and the content ratio of the component (B') is higher than the upper limit, there is a risk that the gloss becomes high and blocking is liable to occur. From such a viewpoint, the proportion of the component (a) in 100 parts by mass of the total of the component (a) and the component (B ') is more preferably 5 to 70 parts by mass, still more preferably 5 to 50 parts by mass, and the proportion of the component (B') is more preferably 95 to 30 parts by mass, still more preferably 95 to 50 parts by mass.

From the viewpoint of sufficiently advancing the crosslinking reaction, the content of the component (D) is preferably 0.01 to 5 parts by mass, more preferably 0.05 to 5 parts by mass, and still more preferably 0.1 to 3 parts by mass, relative to 100 parts by mass of the total of the component (a) and the component (B').

The content of the component (E) is preferably 0.01 to 3 parts by mass based on 100 parts by mass of the total of the component (a) and the component (B'), more preferably 0.05 to 2 parts by mass, and still more preferably 0.1 to 1 part by mass from the viewpoint of obtaining a sufficient crosslinking reaction and maintaining a smooth molded appearance.

When the modified elastomer composition of claim 2 contains the component (F), the content of the component (F) is 0.001 to 2 parts by mass relative to 100 parts by mass of the total of the component (a) and the component (B'), and preferably 0.003 to 1 part by mass from the viewpoint of economy and obtaining a sufficient crosslinking reaction.

When the modified elastomer composition of claim 2 contains the component (G), the content of the component (G) (including the hydrocarbon rubber softener in the component (a)) is 0.5 to 200 parts by mass based on 100 parts by mass of the total of the component (a) and the component (B'). When the content of the component (G) is less than the lower limit, the effect of improving flexibility, fluidity, and oil resistance by the component (G) cannot be sufficiently obtained. When the content of the component (G) is more than the upper limit, there is a risk of bleeding out from the surface. From this viewpoint, the content of the component (G) is preferably 1 to 100 parts by mass, and more preferably 5 to 80 parts by mass, based on 100 parts by mass of the total of the component (a) and the component (B').

When the silanol condensation catalyst of the component (H) is added to the modified elastomer composition of the invention 2 to cause the crosslinking reaction, the amount of the silanol condensation catalyst added is not particularly limited, but is preferably 0.001 to 0.5 part by mass, and more preferably 0.001 to 0.1 part by mass, based on 100 parts by mass of the modified elastomer composition of the invention 2 excluding the component (H). When the amount of the silanol condensation catalyst added is not less than the lower limit, the crosslinking reaction tends to sufficiently proceed, and the heat resistance tends to be good, which is preferable. When the amount of the silanol condensation catalyst added is not more than the above upper limit, the early crosslinking in the extruder tends to be less likely to occur, and cracks tend to be less likely to occur on the surface of the strand or the appearance of the product, which is preferable.

< other ingredients >

The modified elastomer composition of claim 2 may contain, in addition to the above components, various additives, fillers, resins, elastomers, and the like other than the components (a) to (B') as other components within a range not impairing the effects of the present invention.

The additives include those which can be contained in the modified elastomer composition of claim 1.

In the invention 2, as in the invention 1, it is preferable to contain an antioxidant, particularly a phenolic antioxidant, a sulfur antioxidant or a phosphorus antioxidant.

The antioxidant is preferably contained in an amount of 0.1 to 1% by mass based on 100% by mass of the modified elastomer composition according to claim 2.

As the other resin, there may be mentioned other resins which the modified elastomer composition of the invention 1 may contain.

< production and Molding of modified elastomer composition >

The modified elastomer composition of the invention 2 can be produced by melt-kneading the 2 copolymers of the components (A) and (B') with the unsaturated silane compound of the component (D) and the peroxide of the component (E), and if necessary, the crosslinking assistant, the softening agent, other components, and the like by a known method. The melt kneading, the molding method using a silanol condensation catalyst, and the like can be applied as described in the section of < production and molding of a modified elastomer composition > in the invention 1.

[ use ]

The use of the modified elastomer composition and the crosslinked elastomer composition of the present invention is not particularly limited. For example, the resin composition can be suitably used as a vehicle member such as a glass run, a weather strip, a hose, a wiper, or a grommet, a building such as a packing, a gasket, a seat cushion, a vibration-proof rubber, or a pipe, an industrial member, other sports goods, miscellaneous goods, medical members, food members, home electric appliances, or an electric wire covering material.