JP4343870B2 - Ethylene / α-olefin / non-conjugated polyene copolymer, copolymer composition and use thereof - Google Patents

Description

  The present invention relates to an ethylene / α-olefin / non-conjugated polyene copolymer, a copolymer composition comprising the same, and uses thereof. More specifically, the present invention relates to an ethylene / α-olefin / non-conjugated polyene copolymer, a copolymer composition capable of obtaining a crosslinked product composed of the copolymer and an SiH group-containing compound and excellent in tensile properties, and uses thereof.

  Conventionally, in various industries such as electric / electronic parts / transport equipment, civil engineering / civil engineering, medical care, leisure, curable materials are used for sealing, coating, potting, or bonding objects. As such a curable material, a curable material (composition) comprising an organic polymer having a hydroxyl group or a hydrolyzable group bonded to a silicon atom and having a silicon-containing group that can be crosslinked by forming a siloxane bond. It has been known. However, this curable material requires moisture at the time of curing, and has a problem that it takes a long time to cure.

  In order to solve this problem, a polyorganosilane having an average of two or more vinyl groups in the molecule is crosslinked with an organohydrogensiloxane having two or more hydrogen atoms bonded to silicon atoms in one molecule. A composition was developed. This composition can be used as a curable material by utilizing its excellent weather resistance, water resistance, and heat resistance. However, such a composition has a problem that its use is limited because it is expensive, has poor adhesion, easily generates mold, and has poor gas permeation resistance.

  The inventors of the present invention have a fast crosslinking rate at room temperature, and are excellent in productivity, weather resistance, ozone resistance, heat aging resistance, pressure compression permanentness, and moldability and adhesion of the crosslinked copolymer molded body. A copolymer composition comprising an ethylene / α-olefin / non-conjugated polyene random copolymer and a SiH group-containing compound was proposed (Patent Document 1). However, although this copolymer is excellent in adhesiveness, the mechanical properties, particularly tensile properties, are not satisfactory for the cured material.

Conventionally, attempts have been made to improve the dispersibility and processability of fillers and crosslinking compounds in the rubber composition by adding a plasticizer to the rubber composition. However, although such plasticizers are excellent in processability, there are cases where the mechanical strength and rubber elasticity (compression set) of the crosslinked product are inferior, and the plasticizer oozes out from the crosslinked product. It has been found that there are some points to be improved, such as volatiles by heating or contamination of the surroundings, extraction and migration by solvents.
International Publication No. 01/98407 Pamphlet

The present invention is intended to solve the above-mentioned points to be improved.
The present invention provides an ethylene / α-olefin / non-conjugated polyene copolymer capable of obtaining a crosslinked product excellent in tensile properties.
When used as a plasticizer for polymers such as rubber, the present invention provides an ethylene / α-olefin / non-conjugated polymer that gives a polymer excellent in processability, cross-linked mechanical strength, rubber elasticity (compression set), etc. A polyene copolymer is provided.
Furthermore, this invention provides the crosslinkable copolymer composition which can obtain the crosslinked body excellent in mechanical strength, such as a tensile characteristic.
The present invention also provides use of the ethylene / α-olefin / non-conjugated polyene copolymer and the crosslinkable copolymer composition.

The present invention relates to a structural unit derived from at least one of a structural unit derived from ethylene, a structural unit derived from an α-olefin having 3 to 20 carbon atoms, and a non-conjugated polyene represented by the following general formula [I] or [II]. A copolymer comprising
The weight ratio (ethylene / α-olefin) of the structural unit derived from ethylene and the structural unit derived from α-olefin having 3 to 20 carbon atoms is in the range of 40/60 to 95/5,
The total weight of the structural units derived from the non-conjugated polyene represented by the general formulas [I] and [II], the structural unit derived from ethylene, the structural unit derived from an α-olefin having 3 to 20 carbon atoms, and the preceding general formula When the ratio to the total weight of the structural units derived from non-conjugated polyenes represented by [I] and [II] is V wt%, V is in the range of 0.01 to 20 in a 135 ° C. decalin solution. The measured intrinsic viscosity [η] is in the range of 0.01 to 2.0 dl / g,
At least one of the ethylene, the α-olefin having 3 to 20 carbon atoms, and the non-conjugated polyene represented by the following general formula [I] or [II] is a vanadium compound represented by the following general formula (Y): Provided is an ethylene / α-olefin / non-conjugated polyene copolymer (A) produced by polymerization in the presence of an organoaluminum compound represented by the following general formula (Z) ;

［式中、ｎは０〜１０の整数であり、Ｒ^１は水素原子又は炭素原子数１〜１０のアルキル基であり、Ｒ^２は水素原子又は炭素原子数１〜５のアルキル基である。］

[Wherein, n is an integer of 0 to 10, R ¹ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R ² is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms]. ]

［式中、Ｒ^３は水素原子又は炭素原子数１〜１０のアルキル基である。］。
（Ｙ） ＶＯ（ＯＲ） _ｎ Ｘ _３−ｎ
（式中、Ｒは炭化水素基であり、Ｘはハロゲン原子であり、ｎは１〜３の整数である）
（Ｚ） Ｒ’ _ｍ ＡｌＸ’ _３−ｍ
（式中、Ｒ’は炭化水素基であり、Ｘ’はハロゲン原子であり、ｍは１．２０〜１．８０である）。

[Wherein, R ³ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. ].
(Y) VO (OR) _n X _3-n
(In the formula, R is a hydrocarbon group, X is a halogen atom, and n is an integer of 1 to 3)
(Z) R ′ _m AlX ′ _3-m
(In the formula, R ′ is a hydrocarbon group, X ′ is a halogen atom, and m is 1.20 to 1.80).

  The ethylene / α-olefin / non-conjugated polyene copolymer (A) having an intrinsic viscosity [η] measured in the 135 ° C. decalin solution of 0.01 dl / g or more and less than 0.5 dl / g is the present invention. This is a preferred embodiment.

The present invention provides a vanadium compound represented by the following general formula (Y), wherein at least one of ethylene, an α-olefin having 3 to 20 carbon atoms, and a non-conjugated polyene represented by the general formula [I] or [II] is used. And a method for producing the above-mentioned ethylene / α-olefin / non-conjugated polyene copolymer (A) polymerized in the presence of an organoaluminum compound represented by the following general formula (Z).
(Y) VO (OR) _n X _3-n
(In the formula, R is a hydrocarbon group, X is a halogen atom, and n is an integer of 1 to 3)
(Z) R ′ _m AlX ′ _3-m
(In the formula, R ′ is a hydrocarbon group, X ′ is a halogen atom, and m is 1.20 to 1.80).

  The above-mentioned ethylene / α-olefin / non-conjugation is carried out under the conditions that the polymerization pressure is 1.2 MPa or more, the polymer concentration of the copolymer is 5 g / L to 100 g / L, and the polymerization temperature is 30 to 60 ° C. The production method of the polyene copolymer (A) is a preferred embodiment of the present invention.

  The present invention provides a crosslinkable copolymer composition comprising the above-described ethylene / α-olefin / nonconjugated polyene copolymer (A) and a crosslinking agent (B).

  A crosslinkable copolymer composition in which the crosslinking agent (B) is a SiH group-containing compound (B1) having two or more hydrogen bonded to silicon in one molecule is a preferred embodiment of the present invention.

  The crosslinkable copolymer composition further containing a catalyst (C) is a preferred embodiment of the crosslinkable copolymer composition of the present invention.

  What the said crosslinkable copolymer composition contains further at least 1 sort (s) chosen from reaction inhibitor (D) and a silane coupling agent (E) is preferable of the crosslinkable copolymer composition of this invention. It is an aspect.

  The present invention provides the above-mentioned ethylene / α-olefin / non-conjugated polyene copolymer (A) for sealing material, potting material, coating material or adhesive.

  The present invention provides a sealing material, potting material, coating material or adhesive comprising the copolymer composition described above.

  The present invention provides a plasticizer comprising the above-described ethylene / α-olefin / non-conjugated polyene copolymer.

The present invention provides an ethylene / α-olefin / non-conjugated polyene copolymer capable of obtaining a crosslinked product having excellent mechanical strength such as tensile properties.
According to the present invention, when used as a plasticizer for a polymer such as rubber, ethylene / α-olefin / non-conjugated which gives a polymer excellent in processability, cross-linked mechanical strength, rubber elasticity (compression set), etc. A polyene copolymer is provided.
ADVANTAGE OF THE INVENTION According to this invention, the crosslinkable copolymer composition which can obtain the crosslinked body which was further excellent in mechanical strength, such as a tensile characteristic, is provided.
The present invention also provides a sealing material, a potting material, a coating material, an adhesive, or the like as a use of the crosslinkable copolymer composition obtained from the ethylene / α-olefin / non-conjugated polyene copolymer.

The ethylene / α-olefin / non-conjugated polyene copolymer (A) according to the present invention includes a structural unit derived from ethylene, a structural unit derived from an α-olefin having 3 to 20 carbon atoms, and the following general formula [I] or [II]: A copolymer comprising structural units derived from at least one of the non-conjugated polyenes represented by
The weight ratio (ethylene / α-olefin) of the structural unit derived from ethylene and the structural unit derived from α-olefin having 3 to 20 carbon atoms is in the range of 40/60 to 95/5,
The total weight of the structural units derived from the non-conjugated polyene represented by the general formulas [I] and [II], the structural unit derived from ethylene, the structural unit derived from an α-olefin having 3 to 20 carbon atoms, and the preceding general formula When the ratio to the total weight of the structural units derived from non-conjugated polyenes represented by [I] and [II] is V wt%, V is in the range of 0.01 to 20 in a 135 ° C. decalin solution. The measured intrinsic viscosity [η] is in the range of 0.01 to 2.0 dl / g ,
At least one of the ethylene, the α-olefin having 3 to 20 carbon atoms, and the non-conjugated polyene represented by the following general formula [I] or [II] is a vanadium compound represented by the following general formula (Y): It is an ethylene / α-olefin / non-conjugated polyene copolymer (A) polymerized in the presence of an organoaluminum compound represented by the following general formula (Z) .

  The ethylene / α-olefin / non-conjugated polyene copolymer, copolymer composition and use thereof according to the present invention will be specifically described below.

Ethylene / α-olefin / non-conjugated polyene copolymer (A)
The ethylene / α-olefin / non-conjugated polyene copolymer (A) of the present invention is a random copolymer of ethylene, an α-olefin having 3 to 20 carbon atoms, and a non-conjugated polyene.

Specific examples of such α-olefins having 3 to 20 carbon atoms include propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-nonadecene, 1-eicosene, 9-methyl-1-decene, 11- Examples thereof include methyl-1-dodecene and 12-ethyl-1-tetradecene. Among these, α-olefins having 3 to 10 carbon atoms are preferable, and propylene, 1-butene, 1-hexene, 1-octene and the like are particularly preferably used.
These α-olefins are used alone or in combination of two or more.

The ethylene / α-olefin / non-conjugated polyene copolymer (A) of the present invention is a weight ratio (ethylene / α-olefin) of a structural unit derived from ethylene and a structural unit derived from an α-olefin having 3 to 20 carbon atoms. Is in the range of 40/60 to 95/5, preferably in the range of 45/55 to 90/10, more preferably 50/50 to 85/15, and particularly preferably 50/50 to 80 /. A range of 20.
When this weight ratio is within the above range, a copolymer composition is obtained that is excellent in processability, excellent in heat aging resistance, strength characteristics and rubber elasticity, and can provide a crosslinked product excellent in cold resistance.

  The non-conjugated polyene used in the present invention is at least one selected from non-conjugated polyenes represented by the following formulas [I] and [II].

In general formula (I), n is an integer of 0 to 10,
R ¹ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
Specific examples of the alkyl group having 1 to 10 carbon atoms represented by R ¹ include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a t-butyl group. N-pentyl group, isopentyl group, t-pentyl group, neopentyl group, hexyl group, isohexyl group, heptyl group, octyl group, nonyl group, decyl group and the like.
R ² is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
Specific examples of the alkyl group having 1 to 5 carbon atoms represented by R ² include alkyl groups having 1 to 5 carbon atoms among the specific examples of R ¹ described above.

In the general formula (II), R ³ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
Specific examples of the alkyl group having 1 to 10 carbon atoms represented by R ³ include the same alkyl groups as the specific examples of the alkyl group having 1 to 10 carbon atoms represented by R ¹ .

The non-conjugated polyene represented by the general formula (I) or (II) is a terminal vinyl group-containing norbornene compound. Specific examples of such norbornene compounds include 5-methylene-2-norbornene, 5-vinyl-2-norbornene, 5- (2-propenyl) -2-norbornene, and 5- (3-butenyl) -2. -Norbornene, 5- (1-methyl-2-propenyl) -2-norbornene, 5- (4-pentenyl) -2-norbornene, 5- (1-methyl-3-butenyl) -2-norbornene, 5- ( 5-hexenyl) -2-norbornene, 5- (1-methyl-4-pentenyl) -2-norbornene, 5- (2,3-dimethyl-3-butenyl) -2-norbornene, 5- (2-ethyl- 3-butenyl) -2-norbornene, 5- (6-heptenyl) -2-norbornene, 5- (3-methyl-5-hexenyl) -2-norbornene, 5- (3,4-dimethyl) 4-pentenyl) -2-norbornene, 5- (3-ethyl-4-pentenyl) -2-norbornene, 5- (7-octenyl) -2-norbornene, 5- (2-methyl-6-heptenyl) -2 -Norbornene, 5- (1,2-dimethyl-5-hexyl) -2-norbornene, 5- (5-ethyl-5-hexenyl) -2-norbornene, 5- (1,2,3-trimethyl-4- Pentenyl) -2-norbornene and the like. Among these, 5-vinyl-2-norbornene, 5-methylene-2-norbornene, 5- (2-propenyl) -2-norbornene, 5- (3-butenyl) -2-norbornene, 5- (4-pentenyl) ) -2-norbornene, 5- (5-hexenyl) -2-norbornene, 5- (6-heptenyl) -2-norbornene and 5- (7-octenyl) -2-norbornene are preferred.
These norbornene compounds can be used alone or in combination of two or more.

  The non-conjugated polyene content of the ethylene / α-olefin / non-conjugated polyene copolymer of the present invention is the total of the weights of the structural units derived from the non-conjugated polyene represented by the general formula [I] or [II]. The ratio of the structural unit derived from ethylene, the structural unit derived from an α-olefin having 3 to 20 carbon atoms, and the weight of the structural unit derived from the non-conjugated polyene represented by the general formula [I] or [II] to the total weight is V V is in the range of 0.01 to 20, preferably 0.1 to 18, more preferably 0.5 to 15, particularly preferably 1.5 to 12 when the weight percentage is used. It is.

  When this non-conjugated polyene content is within the above range, a copolymer composition having a fast crosslinking rate at room temperature can be obtained, which is excellent in compression set resistance and environmental degradation resistance (= heat aging resistance). A copolymer composition capable of providing a crosslinked product can be obtained. The non-conjugated polyene content may exceed 20% by weight, which can be costly disadvantageous.

  In the present invention, in addition to the non-conjugated polyene represented by the above [I] or [II], other non-conjugated polyenes shown below may be used in combination as long as the physical properties intended by the present invention are not impaired. it can. In this case, the other non-conjugated polyene is derived from the ethylene-derived structural unit, the structural unit derived from an α-olefin having 3 to 20 carbon atoms, and the non-conjugated polyene represented by the general formula [I] or [II]. Although about 0.01 to 15% by weight may be used with respect to 100% by weight of the total weight of the structural units, it is also a preferable aspect that no other polyene is contained.

Specific examples of such other non-conjugated polyenes include 1,4-hexadiene, 3-methyl-1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4- Chain non-conjugated dienes such as hexadiene, 4,5-dimethyl-1,4-hexadiene, 7-methyl-1,6-octadiene;
Methyltetrahydroindene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene-2-norbornene, 5-vinylidene-2-norbornene, 6-chloromethyl-5-isopropenyl-2-norbornene , Cyclic non-conjugated dienes such as dicyclopentadiene;
Trienes such as 2,3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, 2-propenyl-2,2-norbornadiene and the like can be mentioned.

  The intrinsic viscosity [η] measured in a 135 ° C. decalin solution of the ethylene / α-olefin / non-conjugated polyene copolymer (A) of the present invention is in the range of 0.01 to 2.0 dl / g, preferably 0. 0.02-1.8 dl / g, more preferably 0.05-1.5 dl / g, particularly preferably 0.1-1.4 dl / g, most preferably 0.01-less than 0.5 dl / g. Particularly preferably, it is desirable to be 0.01 to 0.45 dl / g. When this intrinsic viscosity [η] is within the above range, a copolymer composition excellent in fluidity and moldability that can provide a crosslinked product excellent in strength properties and compression set resistance can be obtained.

The molecular weight distribution Mw / Mn of the ethylene / α-olefin / non-conjugated polyene copolymer (A) of the present invention is within the range represented by the following formula (P): 2 + 0.05 × V × [η] ≦ Mw / Mn ≦ 2 + 4.8 × V × [η] (P)
(Where V is the polyene content described above.)
Preferably, it is within the range represented by the following formula (P1),
2 + 0.2 × V × [η] ≦ Mw / Mn ≦ 2 + 4.0 × V × [η] (P1)
More preferably, it is within the range represented by the following formula (P2),
2 + 0.5 × V × [η] ≦ Mw / Mn ≦ 2 + 3.0 × V × [η] (P2)
Especially preferably, it exists in the range represented by a following formula (P3).
2 + 0.5 × V × [η] ≦ Mw / Mn ≦ 2 + 1.24 × V × [η] (P3)
When the molecular weight distribution Mw / Mn is in the above range, a copolymer composition is obtained that is excellent in processability and can provide a crosslinked product excellent in strength properties, particularly tensile properties.

Production Method of Ethylene / α-Olefin / Nonconjugated Polyene Copolymer (A) A preferred method for producing the ethylene / α-olefin / nonconjugated polyene copolymer (A) of the present invention will be described below. .

The ethylene / α-olefin / nonconjugated polyene copolymer (A) of the present invention comprises at least ethylene, an α-olefin having 3 to 20 carbon atoms, and a nonconjugated polyene represented by the general formula [I] or [II]. One type can be produced by polymerizing in the presence of a vanadium compound represented by the following general formula (Y) and an organoaluminum compound represented by the following general formula (Z) .

Vanadium compounds, Ru vanadium Monodea represented by the following general formula (Y).
(Y) VO (OR) _n X _3-n
In the formula, R is a hydrocarbon group, and X is a halogen atom.
n is an integer of 1 to 3, but is preferably 1 or 2.

Preferable specific examples of the vanadium compound represented by the general formula (Y) include VO (OC ₂ H ₅ ) Cl ₂ , VO (OC ₂ H ₅ ) ₂ Cl, and VO (O-iso-C ₃ H ₇ ) Cl _2. , and the like can be exemplified _{VO (O-n-C 4} H 9) Cl 2, VO (OC 2 H 5) 3, VO (O-n-C 4 H 9) 3.

Organic aluminum compounds, Ru organoaluminum compound Monodea represented by the following general formula (Z).
(Z) R ′ _m AlX ′ _3-m
In the formula, R ′ is a hydrocarbon group, and X ′ is a halogen atom.
m is 1.20 to 1.80, preferably 1.20 to 1.75, more preferably 1.25 to 1.75.

  Specific examples of the organoaluminum compound include compounds in which m is adjusted within the above range by individually or mixing the following components. In the present invention, it is sufficient that the value of m is set at the time of polymerization. For example, those having m of 1 and those having m of 2 may be separately subjected to the polymerization reaction. Two of them may be mixed and used for polymerization.

Specifically, as a specific example of the organoaluminum compound suitably used for preparing the organoaluminum compound used in the present invention,
Trialkylaluminums such as triethylaluminum, tributylaluminum, triisopropylaluminum;
Dialkylaluminum halides such as diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide;
Partially halogenated alkylaluminums such as alkylaluminum sesquihalides such as ethylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquibromide, alkylaluminum dihalides such as ethylaluminum dichloride, propylaluminum dichloride, butylaluminum dibromide And so on.

In the present invention, among the vanadium compounds represented by the general formula (Y), a soluble vanadium compound of VO (OC ₂ H ₅ ) Cl ₂ , and among the organoaluminum compounds represented by the general formula (Z), Al ( Use of a blend of C ₂ H ₅ ) _1.5 Cl _1.5 as a catalyst component is preferable because an ethylene / α-olefin / non-conjugated polyene copolymer (A) having a narrow molecular weight distribution can be obtained.

In the ethylene / α-olefin / non-conjugated polyene copolymer (A) of the present invention, the halogen / Al of the organoaluminum compound represented by the general formula (Z) for obtaining the copolymer is usually 1. It is 20 to 1.80, preferably 1.25 to 1.80, more preferably 1.25 to 1.75.
When the halogen / Al of the organoaluminum compound of the compound (Z) is in the above range, an ethylene / α-olefin / nonconjugated polyene copolymer (A) having a narrow molecular weight distribution can be obtained.

  The copolymerization of the ethylene / α-olefin / non-conjugated polyene copolymer (A) of the present invention has a polymerization temperature of 30 to 60 ° C., preferably 30 to 59 ° C., and a polymerization pressure of 1.2 MPa or more, preferably 1. 2-5 MPa, the copolymer concentration in the polymerization vessel is 5 g / L to 100 g / L, preferably 30 g / L to 70 g / L, ethylene, an α-olefin having 3 to 20 carbon atoms, and the above general formula It can be obtained by random copolymerization with a non-conjugated polyene represented by [I] or [II]. The copolymerization is preferably carried out in a hydrocarbon medium. Here, in the present invention, the polymerization pressure refers to a gauge pressure.

In the present invention, Mw / Mn can be brought close to the upper limit in the formula (P) by a method of increasing the concentration of the copolymer in the copolymerization or a method of reducing the concentration of the copolymer. In the above formula (P), Mw / Mn can be brought close to the lower limit by a method of decreasing the concentration of the copolymer in the polymerization or a method of increasing the polymerization pressure. Further, it used as a catalyst at the time of copolymerization (Y) a vanadium compound _{VO (OR) n X 3-} n
On the other hand, by using a small amount of the vanadium compound represented by VOCl ₃ , Mw / Mn can be brought close to the upper limit in the formula (P).

  Further, the ethylene / α-olefin / non-conjugated polyene random copolymer used in the present invention is grafted with a polar monomer such as an unsaturated carboxylic acid or a derivative thereof (such as an acid anhydride or ester) as a graft modifier (graft monomer). It may be denatured.

  Specific examples of such unsaturated carboxylic acids include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, tetrahydrophthalic acid, and bicyclo [2.2.1] hept-2-ene. -5,6-dicarboxylic acid and the like.

  Specific examples of the unsaturated carboxylic acid anhydride include maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, bicyclo [2.2.1] hept-2-ene-5,6- And dicarboxylic acid anhydride. Among these, maleic anhydride is preferable.

  Specific examples of the unsaturated carboxylic acid ester include methyl acrylate, methyl methacrylate, dimethyl maleate, monomethyl maleate, dimethyl fumarate, dimethyl itaconate, diethyl citraconic acid, dimethyl tetrahydrophthalate, and bicyclo [2. 2.1] Dimethyl hept-2-ene-5,6-dicarboxylate and the like. Among these, methyl acrylate and ethyl acrylate are preferable.

  The above-mentioned graft modifiers (graft monomers) such as unsaturated carboxylic acids are used singly or in combination of two or more. In any case, the above-mentioned ethylene / α-olefin / nonconjugated polyene before graft modification is used. The graft amount is preferably 0.1 mol or less per 100 g of the copolymer.

  When an ethylene / α-olefin / non-conjugated polyene random copolymer having a graft amount in the above range is used, a cross-linked product excellent in cold resistance can be provided, and fluidity (molding processability) is excellent. A copolymer composition is obtained.

  The graft-modified ethylene / α-olefin / nonconjugated polyene random copolymer comprises the above-mentioned unmodified ethylene / α-olefin / nonconjugated polyene copolymer and an unsaturated carboxylic acid or a derivative thereof as a radical initiator. It can be obtained by reacting in the presence.

  This grafting reaction can be performed as a solution or in a molten state. When the graft reaction is performed in a molten state, it is most efficient and preferable to perform it continuously in an extruder.

Specific examples of the radical initiator used in the graft reaction include dicumyl peroxide, di-t-butyl peroxide, di-t-butylperoxy-3,3,5-trimethylcyclohexane, and t-butyl. Cumyl peroxide, di-t-amyl peroxide, t-butyl hydroperoxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, 2,5-dimethyl-2,5 -Dialkyl such as di (benzoylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, α, α'-bis (t-butylperoxy-m-isopropyl) benzene Peroxides;
t-butyl peroxyacetate, t-butyl peroxyisobutyrate, t-butyl peroxypivalate, t-butyl peroxymaleic acid, t-butyl peroxyneodecanoate, t-butyl peroxybenzoate, di Peroxyesters such as -t-butylperoxyphthalate; ketone peroxides such as dicyclohexanone peroxide; and mixtures thereof.

  Among them, organic peroxides having a half-life of 1 minute in the range of 130 to 200 ° C. are preferable, and in particular, dicumyl peroxide, di-t-butyl peroxide, di-t-butylperoxy-3,3. , 5-trimethylcyclohexane, t-butylcumyl peroxide, di-t-amyl peroxide, and t-butyl hydroperoxide are preferred.

  In addition, as polar monomers other than unsaturated carboxylic acids or derivatives thereof (for example, acid anhydrides and esters), a hydroxyl group-containing ethylenically unsaturated compound, an amino group-containing ethylenically unsaturated compound, an epoxy group-containing ethylenically unsaturated compound, Aromatic vinyl compounds, vinyl ester compounds, vinyl chloride and the like can be mentioned.

Crosslinkable copolymer composition Since the present invention provides a crosslinkable copolymer composition comprising the above-mentioned ethylene / α-olefin / nonconjugated polyene copolymer (A) and a crosslinking agent (B). Hereinafter, the crosslinkable copolymer composition of the present invention will be described.

Cross-linking agent (B)
There is no restriction | limiting in particular as a crosslinking agent (B) used by this invention, Although sulfur, an organic peroxide, the SiH group containing compound (B1) shown below etc. are mentioned, Especially a SiH group containing compound is preferable.

  When using sulfur, it is preferable to use 0.1-10 weight part with respect to 100 weight part of copolymers (A). Moreover, when using an organic peroxide, it is preferable to use 0.05-15 weight part with respect to 100 weight part of copolymers (A). Moreover, when using a SiH group containing compound (B1), it is preferable to use it in the quantity as described below.

SiH group-containing compound (B1)
The SiH group-containing compound (B1) used in the present invention reacts with the copolymer (A) and acts as a crosslinking agent. The molecular structure of the SiH group-containing compound (B1) is not particularly limited. For example, a resinous material having a linear, cyclic, branched structure, or three-dimensional network structure can be used. It is necessary that one molecule contains a hydrogen atom directly bonded to at least two silicon atoms, that is, a SiH group. As such SiH group-containing compound (B1), a compound represented by the following general composition formula can be usually used.
R ⁴ _b H _c SiO _{(4-b-c) / 2}

In the above general composition formula, R ⁴ is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, particularly 1 to 8 carbon atoms (excluding those having an aliphatic unsaturated bond). is there. Examples of such a monovalent hydrocarbon group include a phenyl group and a halogen-substituted alkyl group such as a trifluoropropyl group in addition to the alkyl group exemplified for R ¹ . Among these, a methyl group, an ethyl group, a propyl group, a phenyl group, and a trifluoropropyl group are preferable, a methyl group and a phenyl group are particularly preferable, and a phenyl group is most preferable.

  Further, b is 0 ≦ b <3, preferably 0.6 <b <2.2, particularly preferably 1.5 ≦ b ≦ 2, and c is 0 <c ≦ 3, preferably 0.002. ≦ c <2, particularly preferably 0.01 ≦ c ≦ 1, and b + c is 0 <b + c ≦ 3, preferably 1.5 <b + c ≦ 2.7.

  The SiH group-containing compound (B1) preferably has 2 to 100, more preferably 2 to 4, particularly preferably 2 to 3, most preferably 2 silicon atoms in one molecule. Genpolysiloxane is preferred.

Specific examples thereof include 1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethyltetracyclosiloxane, 1,3,5,7,8-pentamethylpentacyclosiloxane, and the like. Siloxane oligomers: molecular chain both ends trimethylsiloxy group-blocked methylhydrogenpolysiloxane, molecular chain both ends trimethylsiloxy group-blocked dimethylsiloxane / methylhydrogensiloxane copolymer, molecular chain both ends silanol group-blocked methylhydrogenpolysiloxane, Silanol group-blocked dimethylsiloxane / methylhydrogensiloxane copolymer, molecular chain both ends dimethylhydrogensiloxy group-blocked dimethylpolysiloxane, molecular chain both ends dimethylhydrogensiloxy group-blocked methylhydrogenpolysilo Sun, both molecular terminals with dimethylhydrogensiloxy groups dimethylsiloxane-methylhydrogensiloxane ^copolymer, composed of a _R 4 2 _{(H) SiO 1/2} units and _{SiO 4/2} units, optionally ^R ₄ 3 SiO Mention may be made of _½ units, R ⁴ ₂ SiO _2/2 units, R ⁴ (H) SiO _2/2 units, (H) SiO _3/2 or silicone resins that may contain R ⁴ SiO _3/2 units. it can.

Examples of the methylhydrogenpolysiloxane blocked with a trimethylsiloxy group at both ends of the molecular chain include, for example, a compound represented by the following formula, and further, in the following formula, a part or all of the methyl group is an ethyl group, a propyl group, a phenyl group, a trifluoropropyl group. And the like.
_{(CH 3) 3 SiO - (} - SiH (CH 3) -O-) d -Si (CH 3) 3
D in the formula is an integer of 2 or more, preferably 2 to 4, more preferably 2 to 3, and most preferably 2.

As the dimethylsiloxane / methylhydrogensiloxane copolymer blocked with trimethylsiloxy group at both ends of the molecular chain, a compound represented by the following formula, and further, in the following formula, part or all of the methyl group is ethyl group, propyl group, phenyl group, Examples include compounds substituted with a trifluoropropyl group and the like.
_{(CH 3) 3 SiO - (} - Si (CH 3) 2 -O-) e - (- SiH (CH 3) -O-) f -Si (CH 3) 3
E in the formula is an integer of 1 or more. f is an integer of 2 or more, preferably 2 to 4, more preferably 2 to 3, and most preferably 2.

Examples of the methyl hydrogen polysiloxane blocked with silanol groups at both ends of the molecular chain include, for example, a compound represented by the following formula, and a part or all of the methyl group in the following formula: ethyl group, propyl group, phenyl group, trifluoropropyl group, etc. And the like.
_{HOSi (CH 3) 2 O -} (- SiH (CH 3) -O-) 2 -Si (CH 3) 2 OH

Examples of the dimethylsiloxane / methylhydrogensiloxane copolymer blocked with silanol groups at both ends of the molecular chain include, for example, a compound represented by the following formula, and further a part or all of the methyl group in the following formula: an ethyl group, a propyl group, a phenyl group, Examples include compounds substituted with a trifluoropropyl group and the like.
_{HOSi (CH 3) 2 O -} (- Si (CH 3) 2 -O-) e - (- SiH (CH 3) -O-) f -Si (CH 3) 2 OH
E in the formula is an integer of 1 or more. f is an integer of 2 or more, preferably 2 to 4, more preferably 2 to 3, and most preferably 2.

Examples of the dimethylpolysiloxane blocked with a dimethylhydrogensiloxy group at both ends of the molecular chain include, for example, a compound represented by the following formula, and further, in the following formula, a part or all of the methyl group is an ethyl group, a propyl group, a phenyl group, a trifluoropropyl group. And the like.
_{HSi (CH 3) 2 O -} (- Si (CH 3) 2 -O-) e -Si (CH 3) 2 H
(E in the formula is an integer of 1 or more.)

Examples of the methyl hydrogen polysiloxane blocked with dimethylhydrogensiloxy group blocked at both ends of the molecular chain include, for example, a compound represented by the following formula, and further a part or all of the methyl group in the following formula: ethyl group, propyl group, phenyl group, trifluoro And compounds substituted with a propyl group.
_{HSi (CH 3) 2 O -} (- SiH (CH 3) -O-) e -Si (CH 3) 2 H
E in the formula is an integer of 0 or more, preferably 0 to 2, more preferably 0 to 1, and most preferably 2.

Examples of the dimethylhydrogensiloxy group-blocked dimethyl siloxane / methyl hydrogen siloxane copolymer having both ends of the molecular chain include, for example, a compound represented by the following formula, and further a part or all of the methyl group in the following formula: ethyl group, propyl group, And compounds substituted with a phenyl group, a trifluoropropyl group, and the like.
_{HSi (CH 3) 2 O -} (- Si (CH 3) 2 -O-) e - (- SiH (CH 3) -O-) h -Si (CH 3) 2 H
E in the formula is an integer of 1 or more. f is an integer of 0 or more, preferably 0 to 2, more preferably 0 to 1, and most preferably 0.

  Such a compound can be produced by a known method, for example, octamethylcyclotetrasiloxane and / or tetramethylcyclotetrasiloxane and hexamethyldisiloxane or 1,3-dihydro-1,1 which can be a terminal group. , 3,3-tetramethyldisiloxane and other compounds containing a triorganosilyl group or a diorganohydrogensiloxy group in the presence of a catalyst such as sulfuric acid, trifluoromethanesulfonic acid, methanesulfonic acid, etc. It can be easily obtained by equilibrating at a temperature of about ~ 40 ° C.

  The SiH group-containing compound (B1) is 0.1 to 100 parts by weight, preferably 0.1 to 75 parts by weight, more preferably 0.1 to 50 parts by weight with respect to 100 parts by weight of the copolymer (A). More preferably 0.2 to 30 parts by weight, particularly preferably 0.2 to 20 parts by weight, even more preferably 0.5 to 10 parts by weight, most preferably 0.5 to 5 parts by weight. . When the SiH group-containing compound (B1) is used in a proportion within the above range, a copolymer composition having excellent compression set resistance, moderate crosslinking density, and excellent strength and elongation properties can be obtained.

Catalyst (C)
The catalyst (C) used as an optional component in the crosslinkable copolymer composition of the present invention is an addition reaction catalyst, and the alkenyl group of the copolymer (A) and the SiH group-containing compound (B1) SiH. It promotes an addition reaction with a group (alkene hydrosilylation reaction). Specifically, for example, an addition reaction catalyst composed of a platinum group element such as a platinum-based catalyst, a palladium-based catalyst, or a rhodium-based catalyst (a group 8 metal catalyst such as a group 8 metal, a group 8 metal complex, or a group 8 metal compound in the periodic table) Among them, platinum-based catalysts are preferable.

  The platinum-based catalyst may be a known one that is usually used for addition-curing type curing, such as a finely powdered platinum metal catalyst described in US Pat. No. 2,970,150, US Pat. No. 2,823, No. 218, chloroplatinic acid catalyst, U.S. Pat. No. 3,159,601 and U.S. Pat. No. 159,662, complex compounds of platinum and hydrocarbons, U.S. Pat. Complex of chloroplatinic acid and olefin described in US Pat. No. 5,516,946, platinum and vinylsiloxane described in US Pat. No. 3,775,452 and US Pat. No. 3,814,780 And complex compounds. More specifically, platinum alone (platinum black), chloroplatinic acid, a platinum-olefin complex, a platinum-alcohol complex, or a carrier in which platinum is supported on alumina, silica, or the like can be used.

The palladium-based catalyst is composed of palladium, a palladium compound, palladium chloride acid, and the like, and the rhodium-based catalyst is composed of rhodium, rhodium compound, rhodium chloride acid, and the like.
Examples of the catalyst (C) other than the above include Lewis acid and cobalt carbonyl.

  A catalyst (C) is 0.1-100,000 weight ppm with respect to a copolymer (A) as a metal atom, Usually 0.1-10000 weight ppm, Preferably it is 1-5000 weight ppm, More preferably, it is 5- Used at a rate of 1000 ppm by weight.

  When the catalyst (C) is used in a proportion within the above range, a crosslinkable copolymer composition capable of forming a crosslinked product having a moderate crosslinking density, excellent strength properties and elongation properties, and having a small amount of volatile components can be obtained.

  In the present invention, the uncrosslinked molded product of the crosslinkable copolymer composition (copolymer composition) not containing the catalyst (C) is irradiated with light, γ rays, electron beams or the like to crosslink. A molded body can also be obtained.

Reaction inhibitor (D)
Examples of the reaction inhibitor (D) used as an optional component together with the catalyst (C) in the crosslinkable copolymer composition of the present invention include benzotriazole, ethynyl group-containing alcohol (for example, ethynylcyclohexanol), acrylonitrile, amide compound (For example, N, N-diallylacetamide, N, N-diallylbenzamide, N, N, N ′, N′-tetraallyl-o-phthalic acid diamide, N, N, N ′, N′-tetraallyl-m-phthalic acid Diamide, N, N, N ′, N′-tetraallyl-p-phthalic acid diamide, etc.), sulfur, phosphorus, nitrogen, amine compound, sulfur compound, phosphorus compound, tin, tin compound, tetramethyltetravinylcyclotetrasiloxane, Examples thereof include organic peroxides such as hydroperoxide.

The reaction inhibitor (D) is 0 to 50 parts by weight, usually 0.0001 to 50 parts by weight, preferably 0.001 to 30 parts by weight, more preferably 0 to 100 parts by weight of the copolymer (A). 0.005 to 20 parts by weight, more preferably 0.01 to 10 parts by weight, and particularly preferably 0.05 to 5 parts by weight.
When the reaction inhibitor (E) is used at a ratio of 50 parts by weight or less, a copolymer composition having a high crosslinking speed and excellent productivity of a crosslinked molded product can be obtained. If the reaction inhibitor (D) is used in a proportion exceeding 50 parts by weight, it is not preferable because it is disadvantageous in terms of cost.

Silane coupling agent (E)
The silane coupling agent (E) used as an optional component together with the catalyst (C) in the present invention is used for the purpose of further improving self-adhesion. Examples of such silane coupling agents (E) include acrylic (methacrylic) functional silane coupling agents, epoxy functional silane coupling agents, amino (imino) functional silane coupling agents, and the like.

  Specific examples of the acrylic (methacrylic) functional silane coupling agent include 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, and 3-acryloxypropyltriethoxy. Examples include silane, methacryloxymethyltrimethoxysilane, methacryloxymethyltriethoxysilane, acryloxymethyltrimethoxysilane, and acryloxymethyltriethoxysilane.

  Specific examples of the epoxy functional silane coupling agent include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane and the like.

Specific examples of amino (imino) functional silane coupling agents include:
H ₂ NCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ,
H ₂ NCH ₂ CH ₂ NHCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ,
H ₂ NCH ₂ CH ₂ NHCH ₂ CH ₂ CH ₂ Si (CH ₃ ) (OCH ₃ ) ₂ ,
_{(C 2 H 5 O) 3} Si (CH 2) 3 NH (CH 2) 2 NH (CH 2) 3 Si (OC 2 H 5) 3
An amino group and / or an imino group-containing alkoxysilane, such as
The amino group and / or imino group-containing alkoxysilane;

Reaction products with epoxy silane compounds such as
The amino group and / or imino group-containing alkoxysilane;
_{CH 2 = C (CH 3)} COOCH 2 CH 2 CH 2 Si (OCH 3) 3,
_{CH 2 = C (CH 3)} COOCH 2 CH 2 CH 2 Si (OCH 2 CH 2 OCH 3) 3
Reaction products with methacryloxysilane compounds such as

  The silane coupling agent (E) is preferably 0.01 to 100 parts by weight of the total amount of the ethylene / α-olefin / non-conjugated polyene random copolymer (A) and the SiH group-containing compound (B1). It is used in a proportion of 10 parts by weight, more preferably 0.1 to 5 parts by weight.

Plasticizer (F)
As the plasticizer (F) used in the present invention, a softener usually used in rubber can be used. Specifically, paraffinic process oil, naphthenic process oil, aromatic process oil, ethylene, Petroleum softeners such as co-oligomers with α-olefins, paraffin wax, liquid paraffin, white oil, petrolatum, lubricating oil, petroleum asphalt, petrolatum;
Coal tar softeners such as coal tar and coal tar pitch; fatty oil softeners such as castor oil, linseed oil, rapeseed oil and coconut oil; tall oil;
Synthetic polymer materials such as petroleum resins, atactic polypropylene, coumarone indene resins;
Phthalic acid derivatives, isophthalic acid derivatives, tetrahydrophthalic acid derivatives, adipic acid derivatives, azelaic acid derivatives, sebacic acid derivatives, dodecane-2-acid derivatives, maleic acid derivatives, fumaric acid derivatives, trimellitic acid derivatives, pyromellitic acid derivatives, Citric acid derivatives, itaconic acid derivatives, oleic acid derivatives, ricinoleic acid derivatives, stearic acid derivatives, phosphoric acid derivatives, sulfonic acid derivatives, glycerin derivatives, glutaric acid derivatives, epoxy derivatives, glycol derivatives, paraffin derivatives, silicone oil, etc. Can do.

  Of these, ethylene and α-olefin co-oligomers that do not inhibit the silylation reaction, process oil, and paraffin derivatives are preferably used, and paraffin-based process oils and ethylene and α-olefin co-oligomers are particularly preferably used. It is done.

The plasticizer (F) is 0 to 1,000 parts by weight, usually 1 to 1,000 parts by weight, preferably 5 to 100 parts by weight of the ethylene / α-olefin / non-conjugated polyene random copolymer (A). -800 parts by weight, more preferably 10-700 parts by weight, still more preferably 20-500 parts by weight, particularly preferably 30-300 parts by weight.
When the plasticizer (F) is used in the above ratio, the fluidity is improved and the moldability is improved.

  In the copolymer composition of the present invention, it is desirable to exclude the plasticizer composed of the copolymer (A) described later as the plasticizer used for the copolymer (A).

In addition to the other components and the copolymer composition according to the present invention, conventionally known rubber reinforcing agents, inorganic fillers, softeners, anti-aging agents, processing aids, processing aids, additives, etc., depending on the intended use of the crosslinked product. Additives such as a sulfur accelerator, an organic peroxide, a crosslinking aid, a foaming agent, a foaming aid, a colorant, a dispersant, and a flame retardant can be blended within a range that does not impair the object of the present invention. Among these, for example, when (B) the crosslinking agent is a SiH group-containing compound (B1), those that do not inhibit the hydrosilylation reaction of the alkene are preferable.

  The rubber reinforcing agent has an effect of improving mechanical properties such as tensile strength, tear strength, and wear resistance of the crosslinked rubber. Specific examples of such rubber reinforcing agents include carbons such as SRF, GPF, FEF, HAF, ISAF, SAF, FT, and MT, and those carbons that have been surface-treated with a silane coupling agent. Examples thereof include black, finely divided silicic acid, and silica.

Specific examples of silica include fumed silica and precipitated silica. These silicas may be surface-treated with a reactive silane such as hexamethyldisilazane, chlorosilane, or alkoxysilane, or a low molecular weight siloxane. The specific surface area of silica (BED method) is preferably ^{50 m} 2 / g or more, more preferably 100 to 400 m ² / g.

  The type and blending amount of these rubber reinforcing agents can be appropriately selected depending on the application, but the blending amount of the rubber reinforcing agent is usually at most 300 parts by weight, preferably at most, with respect to 100 parts by weight of copolymer (A). 200 parts by weight.

  Specific examples of the inorganic filler include light calcium carbonate, heavy calcium carbonate, talc, and clay.

  The kind and blending amount of these inorganic fillers can be appropriately selected depending on the application, but the blending amount of the inorganic filler is usually 300 parts by weight at the maximum with respect to 100 parts by weight of the copolymer (A), preferably the largest. 200 parts by weight.

  Examples of the anti-aging agent include amine-based, hindered phenol-based, and sulfur-based anti-aging agents. These anti-aging agents are used within the range not impairing the object of the present invention as described above. It is done.

  Although there is no restriction | limiting in the kind of amine-type antiaging agent used by this invention, Diphenylamines, phenylenediamine, etc. are mentioned as a preferable example. Specific examples thereof include 4,4 '-(α, α-dimethylbenzyl) diphenylamine, N, N'-di-2-naphthyl-p-phenylenediamine, and the like.

  These compounds can be used alone or in combination of two or more.

The hindered phenol-based anti-aging agent used in the present invention is not particularly limited in type. For example, (1) tetrakis- [methylene-3- (3 ′, 5′-di-t-butyl-4′-] Hydroxyphenyl) propionate methane,
(2) 3,9-bis [2- {3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4-8,10- Tetraoxaspiro [5,5] undecane,
(3) 2,2′-methylene-bis- (4-methyl-6-tert-butylphenol)
Etc. can be mentioned preferably.

As the sulfur-based anti-aging agent used in the present invention, a sulfur-based anti-aging agent usually used for rubber is used.
Although there is no restriction | limiting in particular in the sulfur type anti-aging agent to be used, In particular, 2-mercaptobenzimidazole, the zinc salt of 2-mercaptobenzimidazole, 2-mercaptomethylbenzimidazole, the zinc salt of 2-mercaptomethylbenzimidazole, pentaerythritol- Tetrakis- (β-lauryl-thiopropionate) is preferred.

As said processing aid, the compound used for processing of a normal rubber can be used. Specifically, higher fatty acids such as ricinoleic acid, stearic acid, palmitic acid and lauric acid; salts of higher fatty acids such as barium stearate, zinc stearate and calcium stearate; ricinoleic acid, stearic acid, palmitic acid and lauric acid And higher fatty acid esters.
Such a processing aid is usually used in a proportion of 10 parts by weight or less, preferably 5 parts by weight or less, based on 100 parts by weight of the copolymer (A). It is desirable to determine the optimal amount.

  In the present invention, in addition to the catalyst (C) described above, an organic peroxide may be used to perform both addition crosslinking and radical crosslinking. The organic peroxide is used at a ratio of about 0.1 to 10 parts by weight with respect to 100 parts by weight of the ethylene / α-olefin / non-conjugated polyene copolymer (A). As the organic peroxide, a conventionally known organic peroxide that is usually used in crosslinking of rubber can be used.

  Moreover, when using an organic peroxide, it is preferable to use a crosslinking aid in combination. Specific examples of the crosslinking aid include sulfur; quinone dioxime compounds such as p-quinone dioxime; methacrylate compounds such as polyethylene glycol dimethacrylate; allyl compounds such as diallyl phthalate and triallyl cyanurate; maleimide Compounds such as divinylbenzene. Such a crosslinking aid is desirably used in an amount of 0.5 to 2 moles, preferably about equimolar to 1 mole of the organic peroxide used.

  Further, the crosslinkable copolymer composition according to the present invention can be blended with other known rubbers within a range not impairing the object of the present invention. Examples of such other rubber include natural rubber (NR) and isoprene rubber (IR), isoprene-based rubber, butadiene rubber (BR), styrene-butadiene rubber (SBR), acrylonitrile-butadiene rubber (NBR), and chloroprene rubber. Mention may be made of conjugated diene rubbers such as (CR).

  Furthermore, conventionally known ethylene / α-olefin copolymer rubber can be used, for example, other than ethylene / propylene random copolymer (EPR) and the ethylene / α-olefin / non-conjugated polyene random copolymer (A). An ethylene / α-olefin / polyene copolymer (for example, EPDM) can be used.

Copolymer composition and use thereof The crosslinkable copolymer composition according to the present invention can be suitably used for, for example, a sealing material, a coating material, a potting material, and an adhesive. Here, the sealing material refers to a material to be sealed (sealed or sealed). Therefore, materials used for the purpose of watertightness and airtightness of joints and contacts in various industries such as machinery, electricity, and chemistry are also broadly defined sealing materials. The sealing material may be pasty or fixed. If it is necessary about the sealing material, "Building sealing material-basics and correct usage-" (first edition, Japan Sealing Materials Association, Kobunsha Co., Ltd.) p141 can be referred to. Here, a sealant of a type that is cured after filling in a gap or the like, or a sealant of a type that is cured after being applied between objects can be particularly preferably exemplified.

  Specific applications will be described below.

  The crosslinkable copolymer composition according to the present invention is used for electric / electronic parts, transportation equipment, civil engineering / architecture, medical or leisure use.

  Specific applications of electrical / electronic components include heavy electrical components, weak electrical components, electrical / electronic equipment circuit and board sealing materials, potting materials, coating materials or adhesives; wire coating repair materials; electrical wire joints Insulating seal material for parts; roll for OA equipment; vibration absorber; or encapsulant for gel or capacitor.

  The sealing material is suitably used as a sealing material for, for example, a refrigerator, a freezer, a washing machine, a gas meter, a microwave oven, a steam iron, and an electric leakage breaker.

  The potting material is suitably used for potting, for example, a transformer high-voltage circuit, a printed circuit board, a high-voltage transformer with a variable resistance section, an electrical insulation component, a semiconductive component, a conductive component, a solar cell, or a television flyback transformer. .

  The coating material is, for example, various circuit elements such as high voltage thick film resistors or hybrid ICs; HICs, electrical insulation components; semiconductive components; conductive components; modules; printed circuits; ceramic substrates; It is preferably used for coating a buffer material; a semiconductive element; or an optical fiber for optical communication.

  The adhesive is suitably used for bonding, for example, a cathode ray tube wedge, a neck, an electrically insulating part, a semiconductive part or a conductive part.

  Applications of the transport aircraft include automobiles, ships, airplanes, and railway vehicles.

  Automotive applications include, for example, automotive engine gaskets, electrical components or oil filter sealing materials; igniter HIC or automotive hybrid IC botting materials; automotive bodies, automotive window glass, engine control board coating materials; or oils Examples include gaskets such as pans or timing belt covers, moldings, headlamp lenses, sunroof seals, and mirror adhesives.

  Examples of the use of the ship include a wiring connection branch box, an electrical system component or a sealing material for electric wires; and an adhesive for electric wires or glass.

  The above civil engineering construction uses, for example, joint joints for glass screens in commercial buildings, joints around glass with sashes, interior joints in toilets, washrooms or showcases, joints around bathtubs, for prefabricated houses Sealant for building materials used for joints for exterior walls of sizing boards and joints for sizing boards; Sealant for double-glazed glass; Sealant for civil engineering used for road repairs; Paint / bonding for metal, glass, stone, slate, concrete or tile Agent; or an adhesive sheet, a waterproof sheet or a vibration-proof sheet.

  Examples of the medical use include medical rubber plugs, syringe gaskets, and decompression blood vessel rubber plugs.

  Examples of the above-mentioned leisure use include swimming members such as swimming caps, diving masks, and earplugs; gel cushioning members such as sports shoes and baseball gloves.

  The crosslinkable copolymer composition according to the present invention is suitably used as a sealing material (sealing material), a potting material, a coating material, and an adhesive in applications such as electric / electronic parts, transportation equipment, civil engineering, and leisure. be able to.

  The ethylene / α-olefin non-conjugated polyene copolymer (A) of the present invention is suitably used as a sealing material (seal material), potting material, coating material, and adhesive.

Preparation of copolymer composition and cross-linked product thereof To produce a cross-linked product from the cross-linkable copolymer composition according to the present invention, ethylene / α- is generally used in the same manner as general room temperature cross-linked rubber (RTV rubber). Olefin non-conjugated polyene copolymer (A), SiH group-containing compound (B1), and optionally catalyst (C), reaction inhibitor (D), silane coupling agent (E), plasticizer (F), Depending on the intended use of the crosslinked product, conventionally known rubber reinforcing agents, inorganic fillers, anti-aging agents, processing aids, vulcanization accelerators, organic peroxides, crosslinking aids, foaming agents, foaming aids , Colorants, dispersants, flame retardants, and other additives are mixed, then the composition is formed into the desired shape (filled in gaps, applied between objects, or coated on objects) Or potting objects) and then leaving at room temperature Crosslinking may be carried out (vulcanization). Moreover, you may heat in order to accelerate | stimulate a crosslinking reaction.

  That is, the crosslinkable copolymer composition according to the present invention is prepared by using a kneading apparatus such as a planetary mixer or a kneader to produce an ethylene / α-olefin non-conjugated polyene copolymer (A), a SiH group-containing compound (B), And, if necessary, a conventionally known rubber reinforcing agent, depending on the use of the catalyst (C), reaction inhibitor (D), silane coupling agent (E), plasticizer (F), intended vulcanizate, etc. By mixing additives such as inorganic fillers, anti-aging agents, processing aids, vulcanization accelerators, organic peroxides, crosslinking aids, foaming agents, foaming aids, colorants, dispersants, flame retardants, etc. Can be prepared.

  In the present invention, the ethylene / α-olefin / non-conjugated polyene copolymer (A) can be kneaded with a rubber reinforcing agent, an inorganic filler, etc. at a high temperature, but an SiH group-containing compound (B) and a catalyst can be used. (C) may be cross-linked (scorched) if kneaded at a high temperature at the same time, so when adding SiH group-containing compound (B) and catalyst (C) at the same time, kneading at 80 ° C. or lower It is preferable to do. When one component is added among the SiH group-containing compound (B) and the catalyst (C), they can be kneaded even at a high temperature exceeding 80 ° C. In some cases, it is preferable to use cooling water against heat generated by kneading.

  The crosslinkable copolymer composition according to the present invention prepared as described above is used to fill a gap, to be applied between objects, to coat an object, and to pot an object. In addition, by various molding methods using an extrusion molding machine, calendar roll, press, injection molding machine, transfer molding machine, etc., it is molded into the intended shape, and then the crosslinking reaction proceeds by leaving it at room temperature. A crosslinked body (crosslinked molded body) can be obtained. Moreover, you may heat in order to accelerate | stimulate a crosslinking reaction.

Plasticizer comprising copolymer (A) The ethylene / α-olefin / non-conjugated polyene copolymer (A) of the present invention can be suitably used as a plasticizer, and more preferably as an embodiment of a reactive plasticizer. Used. Here, the reactive plasticizer in the present invention refers to a substance which is added to a polymer, functions as a plasticizer during processing, and becomes a polymer or an addition reaction to a rubber molecule after vulcanization. (Refer to “Glossary of Rubber Terms” and “Reactive Plasticizers” published by Rubber Association)
The plasticizer of the present invention is particularly preferably a rubber plasticizer. The rubber is preferably used for a rubber made of a hydrocarbon polymer, more preferably used for an olefin polymer, and most preferably ethylene, an α-olefin having 3 to 20 carbon atoms and, if necessary, a non-conjugated polyene. (However, it is preferable that the copolymer does not satisfy the requirements of the copolymer (A)).

The plasticizer of the present invention can be used in the same manner as when used for ordinary rubber or resin.
The plasticizer of the present invention can impart processability to rubber and resin, and can impart flexibility and processability. Further, when rubber or resin is crosslinked, excellent mechanical properties can be obtained. In addition, the plasticizer hardly oozes from the crosslinked body. The reason for this is presumed that after crosslinking, as described above, the polymerization or the addition reaction is caused to the rubber molecule.

  The plasticizer comprising the copolymer (A) of the present invention is usually 0.5 to 1,000 parts by weight, preferably 1 to 1,000 parts by weight, more preferably 100 parts by weight of the resin or rubber. 5 to 800 parts by weight, more preferably 10 to 700 parts by weight, particularly preferably 20 to 500 parts by weight, and most preferably 30 to 300 parts by weight.

  EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these Examples at all.

The composition, intrinsic viscosity [η], and molecular weight distribution (Mw / Mn) of the copolymers used in Examples and Comparative Examples were measured or determined by the following methods.
(1) Composition of copolymer The composition of the copolymer was measured by ¹³ C-NMR method.
(2) Intrinsic viscosity [η]
The intrinsic viscosity [η] of the copolymer was measured in decalin at 135 ° C.
(3) Molecular weight distribution (Mw / Mn)
The molecular weight distribution of the copolymer was represented by the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) determined by GPC. For GPC, Tosoh Co., Ltd. GMH-HT and GMH-HTL were used for the column, and orthodichlorobenzene was used for the solvent.
(Production Example 1)
[Production of ethylene / propylene / 5-vinyl-2-norbornene copolymer (A-1)]
A ternary copolymerization of ethylene, propylene and 5-vinyl-2-norbornene was continuously carried out using a stainless steel polymerization vessel (stirring rotation speed = 250 rpm) having a substantial internal volume of 100 L equipped with stirring blades. From the side of the polymerization vessel to the liquid phase, 45.5L of hexane, 1.4kg of ethylene, 6.8kg of propylene, 170g of 5-vinyl-norbornene, 300NL of hydrogen, catalyst VO (OEt) Cl ₂ 16 mmol and Al (Et) _1.5 Cl _1.5 were continuously fed at a rate of 112 mmol.

  When the copolymerization reaction was carried out under the conditions as described above, a random copolymer ethylene / propylene / 5-vinyl-norbornene copolymer (A-1) was obtained in a uniform solution state.

  Thereafter, a small amount of methanol is added to the polymerization solution continuously withdrawn from the lower part of the polymerization vessel to stop the polymerization reaction, and the copolymer is separated from the solvent by steam stripping treatment, and then vacuumed at 55 ° C. for 48 hours. Drying was performed.

Table 1 shows the physical properties of the ethylene / propylene / 5-vinyl-norbornene copolymer (A-1) obtained as described above.
(Production Examples 2 to 5)
In Production Example 1, by changing the polymerization conditions to those in Table 1, random copolymers having different properties, ethylene / propylene / 5-vinyl-norbornene copolymers (A-2), (A-3), (A-4) and (A-5) were obtained. Table 1 shows the physical properties of the obtained copolymers (A-2), (A-3), (A-4) and (A-5).

Example 1
First, 100 parts by weight of the ethylene / propylene / 5-vinyl-norbornene copolymer (A-1) obtained in Production Example 1, C ₆ H ₅ Si (—OSiMe ₂ H) ₃ (B) [Shin-Etsu Chemical ( Co., Ltd.] 4.3 parts by weight and 0.3% by weight of 2% chloroplatinic acid isopropyl alcohol solution (C) were kneaded at room temperature using a lab plast mill to obtain a copolymer composition.
The obtained copolymer composition was poured into a metal frame having a depth of 2 mm and then allowed to stand at room temperature for 3 days to obtain a crosslinked sheet having a thickness of 2 mm.

About the obtained crosslinked sheet, the tension test was done in accordance with the following method.
Tensile test :
According JIS K-6251, measurement temperature 23 ° C., subjected to tensile test at a tensile rate of 500 mm / min condition was measured elongation _{E B} Tensile and tensile strength _{T B} leaves boy crosslinked sheet.
The results are shown in Table 2.

(Example 2)
In Example 1, instead of the ethylene / propylene / 5-vinyl-norbornene copolymer (A-1) used in Example 1, the ethylene / propylene / 5-vinyl-norbornene copolymer obtained in Production Example 2 was used. The same procedure as in Example 1 was performed except that the coalescence (A-2) was used. The results are shown in Table 2.

(Example 3)
In Example 1, instead of the ethylene / propylene / 5-vinyl-norbornene copolymer (A-1) used in Example 1, the ethylene / propylene / 5-vinyl-norbornene copolymer obtained in Production Example 3 was used. The same procedure as in Example 1 was performed except that the coalescence (A-3) was used. The results are shown in Table 2.

(Comparative Example 1)
In Example 1, instead of the ethylene / propylene / 5-vinyl-norbornene copolymer (A-1) used in Example 1, the ethylene / propylene / 5-vinyl-norbornene copolymer obtained in Production Example 4 was used. The same procedure as in Example 1 was performed except that the coalescence (A-4) was used. The results are shown in Table 2.

(Comparative Example 2)
In Example 1, instead of the ethylene / propylene / 5-vinyl-norbornene copolymer (A-1) used in Example 1, the ethylene / propylene / 5-vinyl-norbornene copolymer obtained in Production Example 5 was used. The same procedure as in Example 1 was carried out except that the coalescence (A-5) was used. The results are shown in Table 2.

(Example 4)
Using ethylene / propylene / diene copolymer rubber (manufactured by Mitsui Chemicals, trade name Mitsui EPT3085) and the ethylene / propylene / 5-vinyl-norbornene copolymer (A-2) obtained in Production Example 2, According to the formulation of various compounding agents shown in 3, a compound 1 was obtained by kneading for 4 minutes at a temperature of 150 ° C. using a 2.95 L capacity Banbury mixer.
The composition 1 obtained above was wound around an 8-inch open roll, and mercaptobenzothiazole (MBT) was added as a vulcanizing agent to the open roll on the basis of 100 parts by weight of the copolymer rubber (Mitsui EPT3085). 5 parts by weight, 1 part by weight of tetramethylthiuram disulfide (TMTD) with respect to 100 parts by weight of copolymer rubber (Mitsui EPT3085), and 1.100 parts by weight of sulfur with respect to 100 parts by weight of copolymer rubber (Mitsui EPT3085). After adding 5 parts by weight and kneading, an unvulcanized rubber sheet 1 was obtained. The roll temperature at this time is 50 ° C. for both the front roll and the rear roll.
The sheet obtained as described above was pressed at 160 ° C. for 15 minutes to prepare a vulcanized rubber sheet having a thickness of 2 mm. Moreover, the sample for compression set measurement based on JISK6262 was produced by pressing at 160 degreeC for 20 minute (s).
About the obtained sample, the measurement of each item shown in Table 4 was performed. The measurement conditions of each item were performed by the method shown below. Table 4 shows the measurement results.

Measuring method:
(I) Encroaching time 900 g of formulation 1 was passed through an 8-inch roll under the conditions of a pre-roll temperature of 50 ° C., a post-roll temperature of 50 ° C., and a roll gap of 0.2 mm, and the time until the entire amount passed was measured. .
(Ii) ML (1 + 4) 125 ° C
Based on JIS K6300, Mooney viscosity of Formulation 1 was measured at 125 ° C.
(iii) tc (90)
Based on JIS K6300, a 90% vulcanization time (tc (90)) at 160 ° C. of a sample obtained from the unvulcanized rubber sheet 1 was measured using a rheometer.
(Iv) Modulus, TB, EB
According to JIS K 6251, a tensile test was performed under the conditions of a measurement temperature of 25 ° C. and a tensile speed of 500 mm / min, and the modulus when the gap between the marked lines was 200% and 300%, respectively, was determined as M200 and M300. In the same tensile test, strength TB and elongation EB at break were measured.

(V) Hardness HA
It measured according to JIS K 6253.
(Vi) Compression set CS
It measured according to JIS K 6262. The temperature during compression was 100 ° C., and the compression time was 24 h.
(Vii) Solvent extraction rate A vulcanized rubber sheet having a shape of 20 mm × 20 mm was immersed in toluene under conditions of 37 ° C. × 72 h. The sample taken out was vacuum-dried at 80 ° C. for 2 hours. The weight before the test was W1, the weight after vacuum drying was W2, and the weight change rate (W1-W2) / W1 × 100 was the solvent extraction rate.

(Comparative Examples 3 and 4)
In Example 4, instead of the ethylene / propylene / 5-vinyl-norbornene copolymer (A-2), the ethylene / propylene / 5-vinyl-norbornene copolymer (A-5) obtained in Production Example 5 was used. Formulations 2 and 3 were obtained in the same manner except that it was used (Comparative Example 3) or the use of the same copolymer (A-2) was omitted (Comparative Example 4). The formulations of Formulations 2 and 3 are as shown in Table 3. Unvulcanized rubber sheets 2 and 3 were obtained in the same manner as in Example 4 for the resulting blend. These were vulcanized in the same manner as in Example 4 and measured for each item. Table 4 shows the measurement results.

  As shown in Table 4, Formulation 1 obtained in Example 4 has processability equivalent to that of oil, is superior to conventional liquid EPT, and further has improved mechanical strength and solvent extraction rate. The copolymer (A-2) of Examples was found to have a function higher than that of a conventional plasticizer.

The ethylene / α-olefin / non-conjugated polyene copolymer of the present invention can provide a crosslinked product having excellent mechanical strength such as tensile properties.
The ethylene / α-olefin / non-conjugated polyene copolymer provided by the present invention and the composition containing the copolymer are a sealing material, a hotting material, a coating material, and an adhesive having improved tensile properties after crosslinking. Can be provided.
When added to rubber, the ethylene / α-olefin / non-conjugated polyene copolymer provided by the present invention not only provides processability equivalent to conventional plasticizers and oils, but also has co-crosslinking properties. Therefore, the strength is improved at the time of crosslinking, and the solvent extraction resistance is excellent, so that it can be suitably used as a plasticizer.

Claims (14)

A copolymer comprising a structural unit derived from ethylene, a structural unit derived from an α-olefin having 3 to 20 carbon atoms, and a structural unit derived from at least one of non-conjugated polyenes represented by the following general formula [I] or [II] Because
The weight ratio (ethylene / α-olefin) of the structural unit derived from ethylene and the structural unit derived from α-olefin having 3 to 20 carbon atoms is in the range of 40/60 to 95/5,
The structural unit derived from ethylene, the structural unit derived from an α-olefin having 3 to 20 carbon atoms, and the general formula of the total weight of the structural units derived from the non-conjugated polyene represented by the general formulas [I] and [II] When the ratio to the total weight of the structural units derived from non-conjugated polyenes represented by [I] and [II] is V wt%, V is in the range of 0.01 to 20 in a 135 ° C. decalin solution. The measured intrinsic viscosity [η] is in the range of 0.01 to 2.0 dl / g,
At least one of the ethylene, the α-olefin having 3 to 20 carbon atoms, and the non-conjugated polyene represented by the following general formula [I] or [II] is a vanadium compound represented by the following general formula (Y): An ethylene / α-olefin / non-conjugated polyene copolymer (A) produced by polymerization in the presence of an organoaluminum compound represented by the following general formula (Z );

[Wherein, n is an integer of 0 to 10, R ¹ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R ² is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms]. ]

[Wherein, R ³ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. ].

(Y) VO (OR) _n X _3-n
(In the formula, R is a hydrocarbon group, X is a halogen atom, and n is an integer of 1 to 3)
(Z) R ′ _m AlX ′ _3-m
(In the formula, R ′ is a hydrocarbon group, X ′ is a halogen atom, and m is 1.20 to 1.80).   The intrinsic viscosity [η] measured in a decalin solution at 135 ° C is 0.01 dl / g or more and less than 0.5 dl / g. Polymer (A). At least one of ethylene, an α-olefin having 3 to 20 carbon atoms and a non-conjugated polyene represented by the general formula [I] or [II], a vanadium compound represented by the following general formula (Y) and the following general formula The method for producing an ethylene / α-olefin / non-conjugated polyene copolymer (A) according to claim 1, wherein polymerization is performed in the presence of an organoaluminum compound represented by (Z);
(Y) VO (OR) _n X _3-n
(In the formula, R is a hydrocarbon group, X is a halogen atom, and n is an integer of 1 to 3)
(Z) R ′ _m AlX ′ _3-m
(In the formula, R ′ is a hydrocarbon group, X ′ is a halogen atom, and m is 1.20 to 1.80).   The ethylene according to claim 3, wherein the polymerization pressure is 1.2 MPa or higher, the polymer concentration of the copolymer is 5 g / L to 100 g / L, and the polymerization temperature is 30 to 60 ° C. -Manufacturing method of alpha olefin * nonconjugated polyene copolymer (A).   A crosslinkable copolymer composition comprising the copolymer (A) according to claim 1 or 2 and a crosslinking agent (B).   The crosslinkable copolymer composition according to claim 5, wherein the crosslinking agent (B) is a SiH group-containing compound (B1) having two or more hydrogen bonded to silicon in one molecule. object.   The crosslinkable copolymer composition according to claim 6, further comprising a catalyst (C).   The crosslinkable copolymer composition according to claim 7, further comprising at least one selected from a reaction inhibitor (D) and a silane coupling agent (E).   The ethylene / α-olefin / non-conjugated polyene copolymer (A) according to claim 1 or 2, which is used for a sealing material, a potting material, a coating material or an adhesive. The sealing material which consists of a copolymer composition in any one of Claims 5-8. A potting material comprising the copolymer composition according to claim 5. The coating material which consists of a copolymer composition in any one of Claims 5-8. An adhesive comprising the copolymer composition according to claim 5. A plasticizer comprising the ethylene / α-olefin / non-conjugated polyene copolymer according to claim 1.