JP2002105261A - VNB ETHYLENE-alpha-OLEFIN-NON-CONJUGATED DIENE COPOLYMER RUBBER-CROSSLINKED THERMOPLASTIC ELASTOMER COMPOSITION - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic elastomer composition using VNB(vinylnorbornene)ethylene-α-olefin-non-conjugated diene copolymer, in which formation of crosslinked particles is surpressed, appearance of a molded article and mechanical intensity are improved, and which has excellent rubber elasticity, oil resistance, chemical resistance, weather resistance, thermostability and economical effect of reducing an amount of a crosslinking agent. SOLUTION: The composition consists of (A) a VNB ethylene-α-olefin non- conjugated diene copolymer rubber, (B) a thermoplastic resin, (C) a inhibitor of forming prescribed crosslinking particles, and is manufactured by crosslinking (A).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a thermoplastic resin comprising an ethylene-α-olefin-nonconjugated diene copolymer rubber composed of vinyl norbornene, which is partially or completely crosslinked to be dispersed in a thermoplastic resin matrix. It relates to an elastomer (TPV) composition. More specifically, in the presence of a cross-linking agent, an ethylene-α-olefin-non-conjugated diene copolymer rubber composed of vinyl norbornene and a thermoplastic resin are kneaded, and a cross-linked thermoplastic produced by a dynamic cross-linking process. The present invention relates to an elastomer composition.

[0002]

2. Description of the Related Art As a typical thermoplastic elastomer,
Using polypropylene as a matrix, ethylene-α
There is a composition in which fine crosslinked particles of an olefin-ethylidene norbornene copolymer rubber are dispersed. Studies are underway to elucidate the rubber elasticity mechanism of this thermoplastic elastomer and to improve properties such as elasticity, heat resistance, weather resistance, oil resistance, chemical resistance, and strength. The point of improvement in these properties is the degree of crosslinking of the ethylene-α-olefin-ethylidene norbornene copolymer rubber, and research on a crosslinking agent for increasing the degree of crosslinking has been conducted. On the other hand, in recent years, ethylene-α-olefin-
Non-conjugated diene copolymer rubbers have been developed. An ethylene-α-olefin-non-conjugated diene copolymer comprising vinyl norbornene is a conventional ethylene-α-olefin comprising ethylidene norbornene when a hydrosilylation agent and a hydrosilylation catalyst or an organic peroxide are used as a crosslinking agent. -Extremely high crosslinking efficiency compared to non-conjugated diene copolymers. Therefore, even if the amount of the hydrosilylation agent and the hydrosilylation catalyst or the organic peroxide is significantly reduced, the effective network chain is equal to or more than that of the conventional ethylene-α-olefin-nonconjugated diene copolymer composed of ethylidene norbornene. Ethylene with excellent rubber elasticity (small permanent set and compression set), oil resistance and chemical resistance
A crosslinked product of an α-olefin-non-conjugated diene copolymer is obtained. Also, ethylene-α composed of vinyl norbornene
-The olefin-non-conjugated diene copolymer has an advantage of being excellent in weather resistance and heat resistance since the amount of residual non-conjugated diene not involved in crosslinking is small. And, a thermoplastic elastomer composition using the copolymer and a method for producing the same,
WO98 / 38226 and WO97 / 00288.

[0003]

SUMMARY OF THE INVENTION However, WO9
8/38226, WO97 / 00288, the thermoplastic elastomer composition described in 0.05 to 3 mm
Ethylene-α-olefin-non-conjugated diene copolymer crosslinked particles or ethylene-α incorporating thermoplastic resin
A large number of crosslinked particles of an olefin / non-conjugated diene copolymer (hereinafter simply referred to as crosslinked particles) are generated, and a crosslinked product of ethylene / α-olefin / nonconjugated diene copolymer composed of vinyl norbornene is used as a thermoplastic resin. .1 μm to 50
It cannot be finely dispersed on the order of μm. Also,
On the surface of the obtained molded article, unevenness of the crosslinked particles (bubbles) occurs, lacks thermoplasticity (fluidity), mechanical strength decreases,
There is a problem that only molded articles having poor appearance and durability can be obtained. Therefore, a thermoplastic elastomer composition using an ethylene-α-olefin-nonconjugated diene copolymer composed of vinyl norbornene has heat resistance, weather resistance, oil resistance,
Although it has properties such as chemical resistance, economy, and rubber elasticity retention in a wide temperature range (about -60 to 155 ° C.), it has not been put to practical use.

[0004] In view of the above circumstances, the present invention suppresses the formation of crosslinked particles, improves the appearance and mechanical strength of molded articles, and provides excellent rubber elasticity, oil resistance, chemical resistance, weather resistance, heat resistance, An object of the present invention is to provide a thermoplastic elastomer composition using an ethylene-α-olefin-non-conjugated diene copolymer comprising vinyl norbornene, which has an economic effect of cold resistance and reduction of a crosslinking agent.

[0005]

Means for Solving the Problems The present inventors have conducted intensive studies in order to achieve the above object, and found that the formation of crosslinked particles has a high crosslinking efficiency of vinyl norbornene, that is, a crosslink that is intended to be continuously penetrated. Make sure the reaction is the cause,
The present invention was completed by presuming that the coalescence due to secondary cross-linking between cross-linking points was the mechanism of generation of cross-linked particles, and finding a suitable cross-linked particle generation inhibitor. That is, the present invention is a thermoplastic elastomer composition according to claims 1 and 2.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The crosslinked particle formation inhibitor (C) component used in the present invention effectively acts regardless of hydrosilylation crosslinking and radical crosslinking by an organic peroxide and the like, and is composed of ethylene-α-olefin-non-conjugated diene composed of vinylnorbornene. Advantages of the copolymer rubber, that is, improvement of the appearance of the molded product,
It exerts the economic effects of mechanical strength, rubber elasticity, oil resistance, chemical resistance, weather resistance, heat resistance, and reduction of cross-linking agent, furthermore, shortens the time for dynamic cross-linking and kneading, and reduces the L / D can be shortened. In the present invention, the above-mentioned component (C) is used as a crosslinked particle formation inhibitor. FIGS. 1 and 2 show the torque behavior of dynamic crosslinking and kneading with a Labo Plastomill when these are used. FIG. 1 shows the torque behavior when the component (C) is used in the hydrosilylation crosslinking, and FIG.
FIG. 3 is a view showing a torque behavior when the component (C) is used in the organic peroxide crosslinking. In addition, in FIGS.
As → becomes ×, it indicates that there are many occurrences of bumps. Normal,
Regardless of hydrosilylation cross-linking or organic peroxide cross-linking, in the pattern in which cross-linked particles are generated, the torque is considered to be due to the binding action of the entire system (sticking accompanied by a cross-linking reaction between cross-linking points) for a long time. A rise is observed. Conversely, in the pattern in which no crosslinked particles are generated, a fine sea-island structure is formed.
(Shortening of the cross-linked body by the thermoplastic resin) A short-time decrease in torque, which is considered to be caused by the thermoplastic resin, is observed. As can be seen from FIGS. 1 and 2, when the component (C) is used, a decrease in torque in a short time is observed. That is, the crosslinked particle formation inhibitor (C) component used in the present invention has an effect of preventing binding between crosslinked portions of an ethylene-α-olefin-non-conjugated diene copolymer composed of vinyl norbornene. This effect has the following that the crosslinked particle formation inhibitor has,
It is considered that any of the above-mentioned effects or the combined effect of the above-mentioned effects is brought about, and these effects tend to be added.

That is, the cross-linking reaction of an ethylene-α-olefin-non-conjugated diene copolymer comprising vinyl norbornene is accelerated to form a cross-linked product in a short period of time, so that a cross-linking reaction between cross-linked portions does not occur. Co-crosslinking of an ethylene-α-olefin-non-conjugated diene copolymer composed of vinyl norbornene and a crosslinked particle formation inhibitor, or of an ethylene-α-olefin-non-conjugated diene copolymer composed of vinyl norbornene and a crosslinked particle formation inhibitor By dispersion or compatibility, to obtain a fine particle size of the cross-linked body which is distinguished from the single cross-linking, giving a high torque in the initial stage of the cross-linking reaction, effectively using mechanical energy for kneading,
It promotes the formation of a sea-island structure.

[0008] As the crosslinking particle formation inhibitor of the component (C) used in the present invention, at least one selected from the components (C-1), (C-2) and (C-3) is used. The crosslinked particle formation inhibitor of the component (C-1) is a compound having at least five acryloyl groups in one molecule and having no structural unit of the formula (1). It will be described later that the number of acryloyl groups is less than 5.
Except for the components (C-2) and (C-3), there is no effect of preventing the formation of crosslinked particles. The number of acryloyl groups is preferably from 10 to 50, and more preferably from 10 to 30. If it exceeds 50, cured product particles of the component (C-1) itself may be formed. Further, the flexibility of the thermoplastic elastomer composition may be reduced. The molecular weight of the component (C-1) is 30.
The range is from 0 to 10000, preferably from 400 to 5000. Within this range, the thermoplastic elastomer composition is easy to handle in production. The amount of component (C-1) added is (A)
The amount is preferably 0.05 to 50 parts by weight, more preferably 0.3 to 15 parts by weight, based on 100 parts by weight of the component. Within this range, the formation of cross-linked particles is excellently prevented, which is economical.

The component (C-1) includes acrylic acid, alcohol, polyol polyacrylate, polyester acrylate, urethane acrylate, acrylic polymer having at least 5 acryloyl groups in one molecule. And specific examples include Chemical Formulas 4 to 9.

[0010]

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[0011]

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[0012]

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[0013]

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[0014]

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[0015]

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Compounds having the structural units of formulas (2) and (3) are also included in the component (C-1) under the condition of 5 or more acryloyl groups, and are a preferred group of crosslinked particle formation inhibitors.
Chemical formulas 10 to 12 are exemplified. Although those having the structural unit of Chemical Formula 1 are also effective in preventing the formation of crosslinked particles under the condition of 5 or more acryloyl groups, the preferable number of acryloyl groups, the molecular weight range, and the addition amount range are remarkably wide.
Further, since it has additional properties such as excellent slidability, scratch resistance and cold resistance, it is not included in the component (C-1).

[0017]

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[0018]

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[0019]

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The crosslinked particle formation inhibitor of the component (C-2) is
It has 2 to 5 acryloyl groups in the molecule and has a structural unit of the formula (2) or (3). Even if the number of acryloyl groups is as small as 2 to 5 in a molecule, the effect of preventing the formation of crosslinked particles can be improved. There is a feature. As the component (C-2),
1,9-nonandiodiol diacrylate, 1,8-nonandiodiol diacrylate, tricyclodecanedimethanol diacrylate, 2-ethyl-2-propyl-propanediol diacrylate, And the like.

[0021]

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[0022]

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[0023]

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[0024]

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[0025]

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[0026]

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[0027]

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[0028]

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[0029]

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The molecular weight of the component (C-2) is from 200 to 100.
00, preferably 235-5000. 1
If it exceeds 0000, the effect of preventing the formation of crosslinked particles becomes poor, and if it is less than 200, the compound cannot be constituted by an acryloyl group, chemical formulas 2 and 3, The amount of the component (C-2) is (A)
The amount is preferably 0.05 to 50 parts by weight, more preferably 0.3 to 20 parts by weight, based on 100 parts by weight of the component.
If less than 0.05 parts by weight, there is no gel formation preventing effect,
Amounts exceeding 50 parts by weight are economically disadvantageous. (C-
2) The component is ethylene-α composed of vinyl norbornene.
-Good compatibility with olefin-non-conjugated diene copolymer rubber.

The components (C-1) and (C-2) are highly efficient cross-linking (action) of the component (A) in a short period of time by utilizing high-speed reactivity with an acryloyl group hydrosilylating agent or an organic peroxide.
It is presumed that the formation of crosslinked particles is suppressed. Above all, it is presumed that the structure of the portion other than the acryloyl group in the component (C-2), ie, chemical formulas 2 and 3, brings some advantages, and expresses high-speed reactivity even if the number of acryloyl groups is small. You. The superiority of Chemical formulas 2 and 3 is good compatibility with ethylene-α-olefin-non-conjugated diene copolymer rubber composed of vinyl norbornene.

The crosslinked particle formation inhibitor of the component (C-3) is
It has a structural unit represented by Chemical Formula 1, and has two or more unsaturated groups such as an acryloyl group, a methacryloyl group, a vinyl group, a propenyl group, a 2-butenyl group, and an allyl group in one molecule. The unsaturated group is an acryloyl group,
Vinyl and allyl groups are preferred. Two or more unsaturated groups are required in one molecule, preferably 2 to 5000, more preferably 2 to 2000. If the number of unsaturated groups is less than 2, there is no effect of preventing the formation of crosslinked particles, and the mechanical strength may be reduced and the thermoplastic elastomer may have a sticky feeling. On the other hand, excessive insertion of the unsaturated group promotes an increase in the amount of the crosslinking agent. In Chemical Formula 1, R ² represents the same or different C1 to C3 alkyl group, phenyl group, and xylyl group, and a is a number satisfying 1 ≦ a ≦ 2.4. The organopolysiloxane may be linear or branched containing R ² SiO _3/2 or R ² SiO _4/2 units. R ²
As such, a highly versatile methyl group or phenyl group is desirable. The molecular weight of the component (C-3) is 500 to 1,000,000
And preferably from 1,000 to 700,000.
If it exceeds 1,000,000, uniform dispersion with the components (A) and (B) may be difficult. Component (C-3) is added in an amount of 0.05 to 60 with respect to 100 parts by weight of component (A).
0 parts by weight, preferably 0.5 to 400 parts by weight, more preferably 1 to 400 parts by weight. If the amount is less than 0.05 part by weight, the effect of preventing the formation of crosslinked particles is poor, and if it exceeds 600 parts by weight, the mechanical strength is reduced, and the component (C-3) having a high content of phenyl groups and unsaturated groups has flexibility. descend. The component (C-3) is not only an acryloyl group that exhibits high-speed reactivity with a hydrosilylating agent or an organic peroxide, but also has many unsaturated groups. It is presumed that they also have a splitting and dispersing action (action) of the crosslinked component. Specific examples of the component (C-3) include Chemical formulas 22 to 33.

[0033]

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[0035]

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[0038]

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[0039]

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[0040]

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[0041]

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[0042]

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[0043]

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[0044]

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Each of the components (C-1), (C-2) and (C-3) can be used in combination in the same component, or can be used in combination among these components. When used together in the same component, it is preferable that the total amount is a preferable addition amount of each component. In the case of combined use between components, (C-1), (C-
When 2) is used in combination, the total thereof is (A) Component 1
It is preferable to adjust the amount to be 0.05 to 50 parts by weight based on 00 parts by weight. In the case of the combination containing (C-3), the total of (C-1) and (C-2) does not exceed 50 parts by weight, and (C-1), (C-2), (C-3) Is 0.
The amount is adjusted to be 0.5 to 600 parts by weight, preferably 0.5 to 450 parts by weight, and more preferably 1 to 400 parts by weight.

The mixture of (A), (B) and (C) is used to add (D-1), (D-2) and (D-2) to the thermoplastic elastomer composition of the present invention obtained by crosslinking (A). D-3),
It is preferable to add at least one component (D) which is an olefin-based or styrene-based copolymer selected from the components (D-4). By adding the component (D), the prevention of the formation of crosslinked particles is not hindered, and a product having improved mechanical strength, rubber elasticity, and cold resistance can be obtained. In addition, effects such as gloss imparting and moldability improvement (deformable extrusion, high-speed extrusion, high fluidity, etc.) are exhibited.

The component (D-1) has a density of 0.85 to 0.5.
An ethylene-α-olefin copolymer of 91 g / cm ² , comprising ethylene and at least one C3-C15 α-olefin. As α-olefin, C
3-C8 is preferred. As the component (D1), 1) a uniform linear ethylene copolymer having a molecular weight distribution Mw / Mn of about 2: "TAFMERP" (trade name) manufactured by Mitsui Chemicals, Inc., Ex
"Ex" manufactured by son Chemical Company
act) (trade name), 2) Heterogeneous linear ethylene copolymer: "Excellen VL" (trade name) manufactured by Sumitomo Chemical Co., Ltd., "LUMITAC" (trade name) manufactured by Toso Corporation, Do
w “Atta” manufactured by Chemical Company
ne "(trade name), 3) Substantially linear ethylene copolymer having long-chain branching: Dow Chemical
Ethylene 1-octene copolymer manufactured by Company
POE "Engage.EG" (trade name), Dow C
POP "AFF" manufactured by Chemical Company
INIY ”(brand name), 4) Random (amorphous rubber-like)
Strong ethylene copolymer: ethylene-propylene copolymer and ethylene-butene-1 copolymer are exemplified. Further, a composition obtained by dispersing the ethylene copolymer having strong randomness in 4) in propylene at a content of 50% by weight or more may be used. Specifically, Montell-J
Company "Catalloy" (trade name), "Monte
Reactor-made TPO such as [Adsyl] (trade name) manufactured by II-JP and “PER” (trade name) manufactured by Tokuyama Corporation are suitable. Other 5) CEBC “DYNARON6” manufactured by JSR manufactured from living anion polymerization
200P "(product name).

Amorphous propylene-α of component (D-2)
-The olefin copolymer is 30 to 45% by weight of an FPO having an atactic ratio of more than 5% by weight in propylene.
Is preferred. For example, Huntsman Corporation in which 2 to 15% by weight of ethylene is copolymerized.
There is “REXflex” (trade name) manufactured by n company.

The hydrogenated styrene random copolymer (D-3) is obtained by hydrogenating a random styrene-conjugated diene copolymer. Styrene-butadiene copolymer hydrogenated product HSBR “DYNAR” manufactured by JSR Corporation
ON1320P "(product name)," DYNARON132 "
1P "(trade name) and hydrogenated styrene-isoprene copolymer.

The hydrogenated styrene block copolymer (D-4) is obtained by hydrogenating a copolymer composed of a styrene polymer block and a conjugated diene polymer block. As the conjugated diene, butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-3,4
-Butadiene and the like. As hydrogenated styrene-based block copolymers, Asahi Kasei Corporation's SEBS “Toughtec” (trade name), Asahi Kasei Corporation's SBBS “Toughtec P”
Series ”(trade name), Shell-JP SEBS
"Clayton" (trade name), Kuraray SEPS "Septon" (trade name), JSR SEBC "DYNA"
RON4600P "(product name).

The above (D-1), (D-2), (D-3),
Each component of (D-4) is used alone or in combination. The amount of the component (D) is preferably 1 to 510 parts by weight based on 100 parts by weight of the component (A).

The ethylene-α-olefin-non-conjugated diene copolymer rubber comprising vinyl norbornene (A) used in the present invention uses vinyl norbornene (5-vinyl-2-norbornene, VNB) as the non-conjugated diene. , Α
-It is an amorphous random elastic copolymer using olefins of C-3 to C15. As the α-olefin, propylene and butene are suitable from the viewpoint of easy availability, and propylene is most commonly used. Therefore,
As the component (A), an ethylene-propylene-vinylnorbornene copolymer rubber is most preferred.

In the present invention, not only vinyl norbornene alone but also those used in combination with other non-conjugated dienes (eg, ethylidene norbornene, methylene norbornene, dicyclopentadiene, 1,4-hexadiene) are preferably used. For example, ethylene-propylene-vinyl norbornene / ethylidene norbornene copolymer (quaternary) rubber can be used. In addition, ethylene-propylene-
For both vinyl norbornene copolymer rubber and ethylene-propylene-vinyl norbornene / ethylidene norbornene copolymer rubber, Mitsui Chemicals in Japan
The V-Series (trade name) has begun to be sold.

The ethylene / α-olefin ratio of the component (A) is from 20/80 to 90/10 by weight, preferably 40/80.
/ 60 to 80/20. The content of vinyl norbornene is 0.3% by weight or more, preferably 0.5 to 10% by weight, more preferably 0.8 to 6% by weight.
If the content of vinyl norbornene is less than 0.3% by weight, the economic effect of reducing the amount of the crosslinking agent, rubber elasticity, oil resistance and chemical resistance cannot be exhibited, and the content of vinyl norbornene is 10%.
If the content exceeds 10% by weight, not only no improvement in rubber elasticity, oil resistance, and chemical resistance is observed, but also mechanical strength may be reduced. The (A) component has a 100 ° C mono-viscosity (ML + 4 ° C) of 30 to 350, preferably 50 to 3.
00, more preferably 70 to 200. If the 100 ° C. Mooney viscosity is less than 30, the mechanical strength is reduced, and
If it exceeds 0, workability will deteriorate. When the crosslinked particle formation inhibitor of the present invention is not used, the ethylene-α-olefin-non-conjugated diene copolymer rubber composed of vinyl norbornene having a high mu-viscosity that is difficult to disperse in a thermoplastic resin has many bumps. And a Mooney viscosity of 7
If it exceeds 0, it becomes extremely large.

The thermoplastic resin (B) used in the present invention is not particularly limited as long as it is compatible with or homogeneously dispersed with the component (A). For example, polyolefin-based, polystyrene-based, polycarbonate-based, polyphenylene-based
Thermoplastic resins such as tellurium, polyvinyl chloride, polyamide, polyester, polyphenylene sulfide, and polymethacrylate can be used. In particular, a propylene resin or a density of 0.91 to 0.97 g / c
Polyolefin-based resins such as m ³ ethylene-based resins (HDPE, LLDPE) are preferred.

The propylene resin most preferably used in the present invention is a homopolymer having an isotactic or syndiotactic crystal structure, or an α · such as ethylene, 1-butene, 1-pentene or 1-hexene. Copolymers with olefins may be mentioned. Copolymers with other α-olefins and those with an atactic crystal structure lower the softening temperature of the propylene-based resin that becomes the sea (matrix) of the thermoplastic elastomer composition, and the high temperature range of the thermoplastic elastomer composition May decrease the rubber elasticity of the rubber composition, which may not be preferable depending on the purpose of use. Particularly preferred propylene resins include homopolypropylene, block polypropylene, random polypropylene, polypropylene having an isotactic + atactic structure, and a copolymer of polypropylene having an isotactic + atactic structure and ethylene. The isotactic + atactic polypropylene and the copolymer of isotactic + atactic polypropylene and ethylene are sold by Idemitsu Petrochemical as IDEMITU TOPE series (trade name). The propylene resin preferably has a melt index (MI) of 0.1 to 100 g / 10 min (230 ° C., 2.16 kg),
More preferably, the range is 0.5 to 60 g / 10 minutes.
The content of α-olefin in the propylene-α-olefin copolymer is preferably 50% by weight or less, and the atactic ratio in the propylene-based resin is preferably 0 to 50% by weight.

In the present invention, at least one kind of the thermoplastic resin (B) is added to 100 parts by weight of an ethylene-α-olefin-non-conjugated diene copolymer rubber composed of vinyl norbornene (A). And 5-300
Parts by weight, more preferably 10 to 100 parts by weight, even more preferably 20 to 100 parts by weight. Within this range, the thermoplastic elastomer composition is excellent in fluidity, processability, and flexibility.

The thermoplastic elastomer composition of the present invention comprises:
The component (A) is cross-linked, and as a means for cross-linking, a method of hydrosilylation cross-linking or radical cross-linking is employed. The hydrosilylation crosslinking is carried out with an organohydrogenpolysiloxane (hydrosilylation agent, (E1)) containing at least two hydrogen atoms bonded to silicon atoms in one molecule and a hydrosilylation catalyst (E2). The hydrosilylation agent is added to the vinyl group of the component (A), and crosslinking proceeds. It is the hydrosilylation catalyst that activates this crosslinking. The component (E1) is not limited as long as it is an organohydrogen containing two or more hydrogen atoms bonded to a silicon atom in one molecule. For example, the average composition formula H _b R ⁵ _c
SiO _{(4-bc) / 2} (wherein R ⁵ is an unsubstituted or substituted monovalent hydrocarbon group excluding the same or different aliphatic unsaturated groups,
Particularly those having 1 to 10 carbon atoms, for example, alkyl groups such as methyl group, ethyl group, propyl group and butyl group, aryl groups such as phenyl group and tolyl group, benzyl group, β-phenylethyl group and the like. Aralkyl groups, cycloalkyl groups such as cyclohexyl groups, and the like, b is a number of 0.002 to 1.0, c is a number of 0.80 to 2.10, b + c is 0.9 to
3.0. ) Or having 1 to 4 unsubstituted or substituted divalent or trivalent aromatic rings having at least two or more SiH groups in one molecule,
Alternatively, those represented by an organohydrogenpolysiloxane having an alkylene group having 2 to 30 carbon atoms are exemplified.

Component (E1) is added in an amount of 0.1 to 10 mol, preferably 0.1 to 10 mol, of hydrogen atoms bonded to silicon atoms of the organohydrogenpolysiloxane, based on 1 mol of the total number of unsaturated groups in the thermoplastic elastomer composition. 0.5
５5 mol. Here, the number of unsaturated groups in the thermoplastic elastomer composition is defined as the number of vinyl norbornenes in the component (A) and the non-conjugated diene if the component (A) forms a multi-element with another non-conjugated diene. number,
And the number obtained by adding the number of unsaturated groups of the component (C), and (D)
The number of unsaturated groups in the component is not counted. The unsaturated group of the component (D) refers to, for example, those remaining after the hydrogenation operation of (D-4) and (D-5).

Examples of the hydrosilylation catalyst of the component (E2) include transition metals of Group VIII such as palladium, rhodium and platinum, and complexes thereof. From the viewpoint of versatility, platinum-based catalysts are preferred. Platinum-based catalysts include platinum, platinum black, chloroplatinic acid, alcohol-modified chloroplatinic acid,
There are complexes of chloroplatinic acid with olefins, aldehydes, vinyl siloxanes or acetylene alcohols. It is desirable to use a complex (complex salt) having higher activity than platinum or platinum black. Typical examples, H ₂ PtC1 ₆ (6H
₂ O), ((CH ₂ = CH) (CH ₃ ) ₂ Si) ₂ O) ₂ Pt or ((CH ₂ = CH) (CH ₃ ) ₂ S
i ₂ O] ₂ O (CH ₂ CHCH) (CH ₃ ) ₂ SiOSi (CH ₃ ) ₂ (OH) Pt-based complexes substantially free of inorganic halogens, such as isopropanol, 2- It is commercially available after being diluted with ethylene-hexanol and toluene / xylene. The addition amount of the platinum-based catalyst is 0.05% in terms of platinum with respect to the component (A).
-30 ppm is preferred. If it is less than 0.05 ppm, no crosslinking reaction occurs, and if it exceeds 30 ppm, it is economically disadvantageous. Usually, 0.4 to 10 ppm is sufficient. This is because the non-conjugated diene is vinyl norbornene, so that a very small amount of platinum can be realized.When cross-linking with another non-conjugated diene using a simple system comprising a hydrosilylating agent and a platinum-based catalyst, 5-5- 100 times more platinum is required.

Next, the radical initiator (E3) for crosslinking the vinyl group of the component (A) using a radical will be described. An organic peroxide or an organic azo compound is used as the radical initiator. In particular, an organic peroxide having a one-minute half-life temperature exceeding 140 ° C. is preferable. More preferably, there is an organic peroxide having a one-minute half-life temperature of 150 to 260 ° C. This includes 1,1-bis (t-butyl par-
Oxy) -3,3,5-trimethylcyclohexane, 1,1
-Di-t-butylperoxycyclohexene, 2,2-
(t-butylperoxy) butane, 4,4-di-tert-butylperoxyvaleric acid-n-butyl ester, 1,1-bis- (tert-butylperoxy) cyclododecane, di-tert-butylpar -Oxide, dicumylperoxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3, t -Butylcumyl peroxide, α, α'-bis (t-butylperoxyoxy) benzene, tris- (t-butylperoxy) triazine, 1,6-bis (t-butylperoxycarboxy) hexane, diethylene glycol -Bis (t-butylperoxycarbonate), t-butylperoxyisopropylcarbonate, t-butylperoxy-2-ethylhexylcarbonate, - Buchirupa - oxy-3,3,5-trimethylhexamethylene root - DOO, t
-Butyl peroxylaurate, 2,5-dimethyl-
2,5-bis (benzoylperoxy) hexane, t-butylperoxyacetate, t-butylperoxybenzoate, t-hexylperoxyoxybenzoate, p-
Menthane hydroperoxide, di-isopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, t-hexyl hydroperoxide, and diisopropylbenzene bis-hydroperoxide. These radical initiators are used in an amount of 0.005 to 100 parts by weight of the component (A).
To 5 parts by weight, more preferably 0.02 to 2 parts by weight.

In the present invention, a softener (F) can be blended for improving workability, adjusting hardness and flexibility, and reducing costs. (F) Component softeners include process oils such as paraffinic and naphthenic and ethylene-α.
・ Synthetic oils such as olefin cooligomers are preferred,
0 to 300 parts by weight is used per 100 parts by weight of the component (A). In particular, the range of 5 to 100 parts by weight is preferable because improvement in processability and imparting of flexibility can be achieved without impairing the characteristics of the thermoplastic elastomer of the present invention. Examples of process oils such as paraffinic and naphthenic oils include DIANA PROCESS OIL “PW, P” manufactured by Idemitsu Kosan Co., Ltd.
"S series", "NR, NS, NM series" (trade name), and "LUCANT" (trade name) manufactured by Mitsui Chemicals, Inc. as an ethylene-α-olefin col-oligomeric synthetic oil. Can be In the case of hydrosilylation crosslinking, it is known that nitrogen compounds and sulfur compounds act as reaction retardants or catalyst poisons. The total content of nitrogen and sulfur in the softener is preferably less than 3000 ppm,
There are no severe conditions of less than 000 ppm and less than 500 ppm. For example, DIANA PROC manufactured by Idemitsu Kosan Co., Ltd.
ESSOIL "PS-430" (trade name) is 1600
Although containing a sulfur content of ppm, the ethylene-α-olefin-nonconjugated diene copolymer rubber composed of (A) vinylnorbornene can be crosslinked within the range of the hydrosilylation agent and the hydrosilylation catalyst described above.

In the present invention, synthetic silica such as fumed silica and precipitated silica, magnesium hydroxide, aluminum hydroxide, FEF and HAF are used to increase mechanical strength and rubber elasticity and to improve processability. It is preferable to add fine powders such as carbon black, clay and talc. Among them, synthetic silica is preferred from the viewpoint of physical properties and coloring properties. Specific surface area of synthetic silica is 50
m ² / g or more, it is preferred to employ those 75~500m ² / g. What blocked the hydroxyl group of the silica surface with dimethyldichlorosilane and hexamethyldisilazane can also be used suitably. This fine powder is composed of (A) component 1
It is used in a range of 150 parts by weight or less based on 00 parts by weight.
Preferably 1 to 100 parts by weight, more preferably 5 to 8 parts
The range is 0 parts by weight.

Further, in the present invention, a maleic anhydride-modified, acrylic-modified, or epoxy-modified (D) component may be used as long as its characteristics are not impaired. Further, modified thermoplastic resins such as maleic anhydride-modified, water-crosslinking silane-modified olefin-based resins, maleic anhydride-modified, acrylic-modified, and epoxy-modified styrene-based resins, and ethylene-propylene-non-conjugated diene rubbers containing no vinyl norbornene ( Dicyclopentadiene (DCPD), 5- (2-methyl-2-butenyl) -2-norbornene (MBN), 5
-Ethylidene-2-norbornene, methyltetrahydroindene (MTHI), 1,4-hexadiene (HD)
Ethylene-propylene-non-conjugated diene rubber composed of non-conjugated diene such as SIS, SBS, IIR, BR, NB
Elastomers having unsaturated double bonds such as R, various thermoplastic elastomers, polymer-crosslinked particles, polymer-uncrosslinked particles, calcium carbonate, glass fiber, mica, titanium oxide, etc., inorganic fillers, lubricants for adjusting moldability , Polymer-based molding aids, ultraviolet absorbers, light stabilizers, antioxidants, pigments, plasticizers such as phthalate esters and adipic esters, phosphorus-based, zinc-based, tin-based flame retardants, and foaming agents , Copper, lead, tin, silver, gold, graphite, long structure car
Conductive agent such as filler or fiber such as bon, antistatic agent, copper damage inhibitor, nucleating agent, other TPV, antibacterial agent, silicone oil, silicone copolymer, fluorine resin, etc. It is optional to contain an agent or a sliding agent, a silane coupling agent, a titanate coupling agent, a filler for generating far-infrared rays, an induction heating agent such as ferrite, iron powder and the like.

The process for producing the thermoplastic elastomer composition of the present invention is carried out by using a conventional resin composition, a Banbury mixer, a kneader, a single screw extruder, a twin screw extruder, etc. used for the production of an elastomer composition. Although a general method can be adopted, a twin-screw extruder is preferably used when productivity is emphasized. The twin-screw extruder uniformly and finely disperses (A) an ethylene-α-olefin-non-conjugated diene copolymer rubber composed of vinyl norbornene and (B) a thermoplastic resin, and further forms (C) crosslinked particles. It is also more suitable for uniformly and finely dispersing an inhibitor, a cross-linking agent, and other components to cause a cross-linking reaction to continuously produce the thermoplastic elastomer composition of the present invention.

The process for producing the thermoplastic elastomer composition of the present invention comprises the steps (A) and (B)
The process is divided into a component kneading step (step 1) and a cross-linking kneading step (step 2). The cross-linking reaction start operation indicates a cross-linking agent addition operation that triggers the start of the cross-linking reaction. As shown in FIG. 3, which is an example of the case where the component (C) was used, each component constituting the thermoplastic elastomer composition of the present invention was prepared in Step 1,
It is charged into the crosslinking reaction starting operation, step 2, and kneaded. Table 1 shows examples of combinations of components used in eq \ o \ ac (, a) and eq \ o \ ac (, a) in FIG. FIG.
In the formula, (G) represents a modifier added in a range that does not impair the fine powder or characteristics. Step 1 involves kneading at a temperature of 80 to 260 ° C. and a condition of 0.05 to 1.5 kwh / kg. When a twin-screw extruder is used, the L / D does not matter, but the L / D is 5 to 40, and the above conditions can be achieved. Step 2 is performed at a temperature of 130 to 260 ° C. and 0.1 to 2.5.
kwh / kg, residence time 0.2-5 minutes, preferably 0.
Kneading under conditions of 5 to 2 minutes, L / D is 25 to 10
Zero twin screw extruders are preferred. The cross-linking reaction start operation is (E
This is an operation in which the component (1), (E2) or (E3) is inserted into the twin-screw extruder in step 2 using a known pump or feeder. At this time, it is preferable to insert the component (C) at the same time, or to insert a component prepared by mixing and kneading the components (C), (E1) and (E2) in advance.

[0067]

[Table 1]

The thermoplastic elastomer composition of the present invention thus obtained may be in the form of pellets, powder, pail, seal, or the like.
It is shaped into a shape and bulk, and is used as a raw material for various molded products or as a modifier for thermoplastic resins, thermoplastic elastomers, thermosetting resins, and thermosetting rubbers. Alternatively, instead of using pellet, powder, pail, sheet, or bulk raw materials, a die for a molded product is attached to the tip of the twin-screw extruder in step 2, and extrusion is continuously performed from step 2. Alternatively, it is used to perform secondary processing such as injection molding, compression molding, blow molding, calendar molding, rotational molding, vacuum molding, drawing, painting, printing, bonding, etc., and directly process it into a molded product.

The above-mentioned molded product includes a door glass outer material.
Weather strip (belt mold), door glass inner
Strip (Inner Mall), Sanle Weather Strip, Weather Strip Around Door, Mold Under Door, Various Molds Around Window, Outside Mirror Packing, Glass Run Channel, Drip Mold, Bumper Mall,
Exterior parts for automobiles such as stainless steel skin mold, flush mount mold, wiper, instrument panel, door trim,
Headrest, seat belt cover, air bag cover, armrest, shift lever knob, hand brake grip, horn pad, assist grip, grommet, seat cover, bead, crash hat, glove box, handle Automotive interior parts such as covers and console boxes, brake hoses, radiator hoses,
Hoses for automobiles such as heater hoses and air cleaner hoses, hoses for water supply, hoses for gas, and hoses for industrial machines such as ink jet waste tube. , Blood transfusion, blood collection tube, infusion tube, respiratory gas delivery tube
, Artificial dialysis packing, syringe packing, enema container,
Medical components such as balloon catheters, engine mounts, liquid seal engine mounts, damper pulleys, chains
Damper, carburetor mount, torsional damper, strut mount, rubber bush, bumper rubber, helper rubber, spring sheet, shock absorber, air spring, body mount, bumper Guard, muffler support, rubber coupling, center
Bearing support, rubber for clutch, differential mount,
Suspension bush, sliding bush, cushion strud bar, stopper, hand re-damper, radiator supporter, muffler hanger etc. Materials, anti-vibration members for industrial machines such as expand band joints, flexible joints, bushes, mounts, O-rings, waterproof packing, V-belts, flat belts, toothed belts, cylindrical belts, rough top belts, belts with flanges Conveyor belts such as belts with U-shaped guides, electric wire joints, anode caps, plug caps, plug butts, grommets, conductor coating, sheaths, earphone jacks, etc., electric wire members, papermaking rolls ,
Industrial rolls such as printing rolls, charging rolls, cleaning rolls, transfer rolls, developing rolls, toner conveying rolls
Roller for copy machine such as paper roll, paper roll, camera,
Eye patch for headphones, video cameras, etc.
Earpatch, wallpaper, leather, floor tile, glass run, glass window, sliding member of sliding door, baseboard, corner
Architectural components such as guards, mobile phones, remote controls, keyboard switch components, electronic components such as connectors for liquid crystal displays, food packaging wraps, packaging materials for electronic components, multilayer films, food packaging cups Food storage containers, furniture seismic stoppers, notebook covers, shoes, sandals, toys, toothbrushes and the like.

As the modifier, the low hardness and high strength properties of the thermoplastic elastomer composition of the present invention are used.
Used as a strength improver or rubber elasticity improver for other thermoplastic elastomers and thermoset rubbers. Further, it is used as an impact strength improver or a cold resistance improver for thermoplastic resins and thermosetting resins. The thermoplastic elastomer composition of the present invention comprising the component (C-3) is added to and mixed with another thermoplastic elastomer, a thermosetting rubber, a thermoplastic resin, and a thermosetting resin. Used as an anti-measuring agent during molding and as a variable extrusion molding aid.

[0071]

EXAMPLES Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples.

Example 1, Comparative Example 1 A co-rotating twin-screw extruder (30 mmφ) comprising the raw materials shown in Table 2 and a forward, neutral, and reverse kneading disc and a forward / reverse screw element was used. , L / D = 35), the cylinder temperature was adjusted to 160 to 200 ° C., and the mixture was kneaded at a screw rotation speed of 200 rpm to produce an uncrosslinked kneaded material pellet. Next, Examples 1-1 to 1-16 and Comparative Example 1-
In 1 to 1-6, 45 g of pellets were put into a Labo Plastomill (trade name) manufactured by Toyo Seiki Seisakusho, whose temperature was controlled at 180 ° C., melted at 70 rpm for 3 minutes, and the mixture shown in Table 3 was added. Minutes of dynamic crosslinking. In Examples 1-17 to 1-21, a total of 4 shown in Table 4 was used.
5 g of the raw materials were put into a Labo Plastomill whose temperature was controlled at 180 ° C., and were melted and kneaded at 110 rpm for 3 minutes.
The mixture was melt-kneaded at 2 rpm for 2 minutes, the platinum-based catalyst shown in Table 4 was added, and dynamic crosslinking was performed at 110 rpm for 4 minutes. After the above crosslinking, the thermoplastic elastomer composition was taken out of the Labo Plastomill, and a sheet having a thickness of about 1.5 mm was produced with a two-roll thermostat at 180 ° C. In an arbitrary 50 mm square of the sheet, the number of bumps (projections) of 0.3 mm or more is counted.
○, 30 to 49 △, and 50 or more were evaluated as × to evaluate the effect of preventing the formation of crosslinked particles. The sheet prepared by the roll was pressed at 190 ° C. to prepare a sample for hardness and tensile test. Hardness is JISK 7215 (after 10 seconds),
The tensile test was measured based on JIS K 6723.
The results are shown in Tables 3 and 4. As can be seen from Tables 3 and 4, in Examples, the formation of crosslinked particles was suppressed and the tensile strength was excellent. In Table 4, KE-151
U is a compound containing fumed silica manufactured by Shin-Etsu Chemical Co., Ltd.
Similar vinyl methyl-polysiloxane, molecular weight 60
Cat-PL-50T is a platinum-based hydrosilylation catalyst manufactured by Shin-Etsu Chemical Co., Ltd., and a vinyl-methylsiloxane mixed complex. , The platinum concentration was 0.5% by weight, which had already been diluted in toluene. In Examples and Comparative Examples,
This Cat-PL-50T is further diluted with toluene.

[0073]

[Table 2]

[0074]

[Table 3]

[0075]

[Table 4]

Example 2, Comparative Example 2 Uncrosslinked kneaded material pellets were prepared under the same conditions as in Example 1, except that the hydrosilylating agent was omitted from the raw materials shown in Table 2. Next, 45 g of the pellets were put into a Labo Plastomill whose temperature was controlled at 180 ° C., melted at 70 rpm for 2 minutes, and the component (C) or the compound shown in Table 5 was added.
After kneading for 30 minutes, the mixture was kneaded at 30 rpm for 3 minutes with or without changing the set temperature. Subsequently, the organic peroxides shown in Table 5 were added, and dynamic crosslinking was performed at 110 rpm for 4 minutes. Thereafter, the thermoplastic elastomer composition was taken out of Labo Plastmill and evaluated in the same manner as in Example 1. Table 5 shows the results. As can be seen from Table 5, in Examples, the formation of crosslinked particles was suppressed, and the tensile strength,
The tensile elongation was excellent. In Table 5, Perhexa 25B-40 was manufactured by NOF CORPORATION, and 2,5-dimethyl-2,5-bis (t
-Butylperoxy) hexane with calcium carbonate 40
It was diluted to% by weight.

[0077]

[Table 5]

Example 3, Comparative Example 3 The pellets of Example 1 or the pellets of Example 2, and the 1,9-
Nonanediol diacrylate, E2900 and the component (D) were charged into a Labo Plastomill controlled at 180 ° C. at the compounding amounts shown in Table 6, melt-kneaded at 110 rpm for 3 minutes, and melt-kneaded at 70 rpm for 2 minutes. (C) shown in Table 6
Mixing the components 1,9-nonanediol diacrylate,
Add a platinum-based catalyst or organic peroxide and add 110 rpm
For 4 minutes for dynamic crosslinking. The temperature set during the dynamic crosslinking was changed from 110 rpm for 3 minutes to 70 rpm for 3 minutes. The thermoplastic elastomer composition was taken out of the Labo Plastomill and subjected to the same evaluation as in Example 1 and the relative evaluation of gloss using the roll sheet of Example 3-1 as a standard. The glossiness was displayed every time the number increased from 1 to 5. Table 6 shows the results. As can be seen from Table 6, in Examples, the formation of crosslinked particles was suppressed, and the tensile strength and tensile elongation were excellent. In addition, gloss and tensile strength tended to increase as the proportion of the component (D) increased. In Table 6, EBM 3021P is a highly random copolymer of ethylene-butene-1 manufactured by JSR Corporation and has a density of 0.8.
6, MI 2.1g / 10min (230 ℃, 2.16kg), Engage.EG-8100
Is a substantially linear ethylene 1-octene copolymer 14% crystal, density 0.87, MI
1.0 g / 10 min (including long chain branches close to the main chain in a uniform polymer), TAFMER P-0680 is manufactured by Mitsui Chemicals, Inc., ethylene-α-olefin copolymer, density 0.87, MI 0.7g
/ 10 min, DYNARON1320P is manufactured by JSR Corporation, HSBR, styrene content 10% by weight, density 0.89, MI 3.5 g / 10 min, DYNARON46
00P is manufactured by JSR, SEBC, styrene content 20% by weight, density 0.
91, MI 2.5g / 10min, DYNARON6200P, manufactured by JSR, CEB
C, styrene content 0% by weight, density 0.88, MI 2.5g / 10 mi
n, REXflex WL216, manufactured by Huntsman Corporation, FPO-
Ethylene copolymer, density 0.88, MI 15g / 10min, PER
R210E is manufactured by Tokuyama Corporation, polymerization type TPO, density 0.88, MI
1.5g / 10min, Tuftec L513 is manufactured by Asahi Kasei Corporation, SEBS,
The styrene content is 18% by weight, the density is 0.89, and the MI is 4.5 g / 10 min.

[0079]

[Table 6]

Example 4 and Comparative Example 4 A co-rotating twin-screw extruder (58 m) composed of forward, neutral and reverse screwing discs and a forward and reverse screw element.
mφ, L / D = 62), cylinder-temperature 140-170
Temperature, die temperature 200 ℃, screw rotation speed 150r
At pm, the raw material mixture shown in Table 6 was fed through a hopper-mouth. Plunger pumps were connected at 0.15 L and 0.25 L from the hopper port, respectively, and a mixture of the hydrosilylation agent and the hydrosilylation catalyst shown in Table 7 was press-fitted.
About the obtained pellet, the same evaluation as Example 1 was performed. Table 7 shows the results. As can be seen from Table 7, in Examples, the formation of crosslinked particles was suppressed, and the tensile strength and tensile elongation were excellent, and the same results as in Examples 1-1 and 3-2 were obtained.

[0081]

[Table 7]

Example 5, Comparative Example 5 The raw materials shown in Table 8 were used by setting the humidity of the Labo Plastomill from 160 ° C. to 190 ° C.
The mixture was kneaded at 110 rpm for 5 minutes while the temperature was raised to ℃, the set temperature was lowered to 180 ° C, and the mixture was further kneaded at 70 rpm for 3 minutes. A mixture of the platinum-based catalysts shown in Table 8 was added, and 110
Dynamic crosslinking was performed for 5 minutes at rpm. Thereafter, the thermoplastic elastomer composition was taken out of Labo Plastmill and evaluated in the same manner as in Example 1. Further, the dynamic viscoelasticity was measured to determine a loss tangent tan δ. The lower the tan δ, the better the rubber elasticity. Table 8 shows the results. As can be seen from Table 8, ethylene-
The thermoplastic elastomer of the example using the propylene-vinyl norbornene copolymer rubber was superior to the comparative example of the ethylene-propylene-ethylidene norbornene copolymer rubber in tensile strength and rubber elasticity in a high temperature range.
The measurement of dynamic viscoelasticity was made by Rheometric Scientific SOLID
It was measured by S ANALYZER (trade name) based on JIS K 7198. In Table 8, R-4835 is manufactured by Mitsui Chemicals, Inc.
20 phr ethylene-propylene-VNB copolymer oil, before oil
100 ° C mu-vis viscosity ML _{1 + 4} 110, 100 ° C mu-viscosity ML _{1 +} 491 after oil addition, VNB content 2.4% by weight, ethylene content 66
R-4834, manufactured by Mitsui Chemicals, Inc., ethylene-propylene-VNB copolymer 20 phr oil-added, 100 ° C mu-viscosity ML _{1 + 4} 110 before oil addition, 100 ° C mu-ni after oil addition Viscosity ML _{1 + 4} 88, VN
B content 2.2% by weight, ethylene content 59% by weight, PX-046
Is Mitsui Chemicals, ethylene-propylene-VNB copolymer, 100 ° C. Mooney viscosity ML _{1 +} 458, VNB content 4.5% by weight, ethylene content 57% by weight, EP503EF is manufactured by JSR Ethylene-propylene-ENB polymer 20 phr oil, 120 after oil
° C. beam - D - viscosity ML _{1 + 8} 74,100 ℃ arm - two - in terms of viscosity ML 1 _{+ 4} of about 100, ENB content 4.5 wt%, an ethylene content of 66 wt%, WINGSTAY L-HLS (trade name ) Is Goodye
It is an antioxidant manufactured by arTIRE & RUBBER COMPANY.

[0083]

[Table 8]

Example 6 In the same manner as in Example 5, the thermoplastic elastomer compositions shown in Table 9 were prepared and evaluated. As a result, both were unpleasant. In Example 6-2, the change in the dynamic storage modulus E ′ at a temperature lower than 0 ° C. was smaller, and the cold resistance was superior.

[0085]

[Table 9]

[0086]

According to the present invention, the appearance, mechanical strength, rubber elasticity, oil resistance, chemical resistance, weather resistance, heat resistance,
It is made of vinyl norpoleneene, which has the economic effect of reducing the amount of the cross-linking agent, the productivity of shortening the dynamic cross-linking and kneading time, the L / D of the dynamic cross-linking and kneading extruder, and the economical effect on equipment investment. A thermoplastic elastomer composition comprising a crosslinked product of an ethylene-α-olefin-non-conjugated diene copolymer rubber can be provided.

[Brief description of the drawings]

FIG. 1 is a view showing a torque behavior when a component (C) is used in hydrosilylation crosslinking.

FIG. 2 is a diagram showing a torque behavior when a component (D) is used in organic peroxide crosslinking.

FIG. 3 is an explanatory view showing the production process of the present invention when the component (C) is used.

────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] December 14, 2001 (2001.12.
14)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Claims

[Correction method] Change

[Correction contents]

[Claims]

Embedded image

Embedded image

Embedded image

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0066

[Correction method] Change

[Correction contents]

The process for producing the thermoplastic elastomer composition of the present invention comprises the steps (A) and (B)
The process is divided into a component kneading step (step 1) and a cross-linking kneading step (step 2). The cross-linking reaction start operation indicates a cross-linking agent addition operation that triggers the start of the cross-linking reaction. As shown in FIG. 3, which is an example of the case where the component (C) was used, each component constituting the thermoplastic elastomer composition of the present invention was prepared in Step 1,
It is charged into the crosslinking reaction starting operation, step 2, and kneaded. Table 1 shows examples of combinations of the components used in ( a) and (b) in FIG. In FIG. 3, (G) represents the fine powder and the modifier added within a range that does not impair the characteristics. Step 1 is performed at a temperature of 80 to 260 ° C. and a temperature of 0.05 to 1.5.
Kneading is performed under the condition of kwh / kg. When using a twin-screw extruder, L / D does not matter, but L / D is 5 to 40.
Thus, the above conditions can be achieved. Step 2 includes 130 to 260
Kneading at a temperature of 0.1 to 2.5 kWh / kg and a residence time of 0.2 to 5 minutes, preferably 0.5 to 2 minutes at a temperature of 25 ° C. A screw extruder is preferred. The crosslinking reaction starting operation is an operation of inserting the component (E1), (E2) or (E3) into the twin-screw extruder in step 2 using a known pump or feeder. At this time, the component (C) is inserted at the same time, or the components (C) and (E) are
1), a mixture prepared by mixing and kneading the components (E2),
Preferably, it is inserted.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 101/00 C08L 101/00 (72) Inventor Shuyasu Noda 1-406-1, Yoshino-cho, Omiya-shi, Omiya-shi, Saitama Etsu Polymer Co., Ltd. Tokyo Factory (72) Nakajiro Yoshida 1-406-1, Yoshinocho, Omiya City, Saitama Prefecture Shin-Etsu Polymer Co., Ltd. Tokyo Factory F-term (reference) 4J002 BB002 BB051 BB054 BB144 BB151 BB203 BC002 BC054 BD022 BG002 BP013 BP014 CF002 CG002 CH072 CL002 CN012 CP033 CP093 CP163 EH076 EP016 EP036 EU196 FD203 FD206

Claims (2)

[Claims] 1. A thermoplastic elastomer composition comprising the following components (A), (B) and (C), wherein (A) is crosslinked. (A) Ethylene-α-olefin-non-conjugated diene copolymer rubber composed of vinyl norbornene (B) thermoplastic resin (C) From the following components (C-1), (C-2) and (C-3) (C-1) a compound having at least 5 acryloyl groups in the molecule and having no structural unit of the formula (C-2) 2 to 5 acryloyl in the molecule With a base,
Compound having the structural unit of formula 2 or 3 (C-3) having at least two unsaturated groups selected from an acryloyl group, a methacryloyl group, a vinyl group, a propenyl group, a 2-butenyl group, and an allyl group in the molecule. , Chemical 1
Compound having a structural unit of the formula Embedded image Embedded image 2. (A), (B), and (C) according to claim 1.
A thermoplastic elastomer composition comprising the following component (D) in addition to the above component (A), wherein (A) is crosslinked. (D) The following (D-1), (D-2), (D-3), (D-
(D-1) Ethylene-α-olefin copolymer having a density of 0.86 to 0.91 g / cm ³ (D-2) Non-crystalline propylene α-Olefin copolymer (D-3) Hydrogenated styrene-based random copolymer (D-4) Hydrogenated styrene-based block copolymer