JPH10231391A - Olefinic thermoplastic elastomer composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition that can given molded products excellent in low-temperature behaviors and molding stability by subjecting a crystalline polyolefin resin and a specific rubber to dynamic heat treatment in the presence of a quinone dioxime. SOLUTION: (A) 10-60 pts.wt. of crystalline polyolefin resin and (B) 40-90 pts.wt. of an ethylene-α-olefin-non-conjugated polyene terpolymer resin are blended and 100 pts.wt. of the polymer blend are subjected to dynamic heat treatment in the presence of a quinone dioxide to prepare a partially or perfectly crosslinked thermoplastic resin. The component B comprises (i) ethylene, (ii) a 3-20C olefin at a molar ratio i/ii of 40/60-95/5 and (iii) a branched-chain polyene of the formula (n is 1-5; R<1> is a 1-5C alkyl; R<2> and R<3> are each H, R1 ) in a molar % of 0.1-10 and shows an intrinsic viscosity [η] of 0.1-10dl (at 135 deg.C in decalin). This composition may contain a softening agent, inorganic filler and the like in addition to the components A, B and C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an olefin-based thermoplastic elastomer composition, and more particularly, to low-temperature properties, tensile strength, elongation at break, molding stability (mold contamination during injection molding, and extrusion molding). The present invention relates to an olefin-based thermoplastic elastomer composition capable of providing a molded article excellent in die stainability), solvent resistance, metal stainability and rubber-like properties (for example, permanent elongation and compression set).

[0002]

BACKGROUND OF THE INVENTION Olefin-based thermoplastic elastomers are widely used as energy-saving and resource-saving elastomers, especially as substitutes for vulcanized (cross-linked) rubbers for automobile parts, industrial machine parts, electronic / electric equipment parts, building materials, etc. It is used.

[0003] Olefin-based thermoplastic elastomers can be classified into crosslinked and non-crosslinked types. Since the non-crosslinked thermoplastic elastomer does not involve a crosslinking reaction, there is little variation in quality and the production cost is low. However, when comparing crosslinked thermoplastic elastomers and non-crosslinked thermoplastic elastomers in terms of performance, the crosslinked thermoplastic elastomers have a higher tensile strength, elongation at break, or rubber-like properties than non-crosslinked thermoplastic elastomers. (Eg, permanent elongation, compression set) and heat resistance.
As a crosslinked type thermoplastic elastomer, the appearance of an olefin-based thermoplastic elastomer having better low-temperature properties, tensile strength, elongation at break, and rubber properties than conventionally known vulcanized rubbers is desired.

[0004] Crosslinking in a crosslinked olefin-based thermoplastic elastomer is roughly classified into sulfur crosslinking, organic peroxide crosslinking, resin crosslinking, quinone dioxime crosslinking, and the like, depending on the type of crosslinking agent used.

[0005] Sulfur-crosslinked olefinic thermoplastic elastomers have a drawback of poor heat resistance because they are crosslinked by sulfur atoms. Organic peroxide-crosslinked olefinic thermoplastic elastomers have excellent heat resistance and flexibility, but the molecular chain is cut off by the organic peroxide, and low molecular weight components are generated. It may cause contamination and may cause eyeburn during extrusion molding. It also has an adverse effect on recyclability and solvent resistance.

[0006] Resin crosslinked olefinic thermoplastic elastomers are excellent in oil resistance, but because halogen compounds are used as oxidizing agents, residual halogen compounds may adversely affect products. It has been known.

Further, the conventional quinone dioxime cross-linking has a low cross-linking efficiency, so that it is necessary to incorporate a large amount of an oxidizing agent (activator) such as lead tin (lead oxide). Was difficult.

Therefore, compared with the conventional cross-linked olefin-based thermoplastic elastomer, low-temperature characteristics, tensile strength, elongation at break, molding stability (die contamination during injection molding and die contamination during extrusion molding), and resistance to resistance are improved. Solvent, metal stain and rubbery properties (e.g. permanent elongation,
There is a demand for an olefin-based thermoplastic elastomer composition capable of forming a molded article having excellent compression set.

[0009]

SUMMARY OF THE INVENTION The object of the present invention is to solve the problems associated with the prior art as described above, and has a lower temperature characteristic, tensile strength, elongation at break, and lower temperature than conventional crosslinked olefin-based thermoplastic elastomers. Molding with excellent molding stability (contamination of mold during injection molding and contamination of dies during extrusion), solvent resistance, contamination to metals and rubber-like properties (for example, permanent elongation and compression set) It is an object of the present invention to provide an olefin-based thermoplastic elastomer composition that can be used.

[0010]

SUMMARY OF THE INVENTION An olefinic thermoplastic elastomer composition according to the present invention comprises a crystalline polyolefin resin (A) 1.
0 parts by weight or more and less than 60 parts by weight, and ethylene / α-olefin / non-conjugated polyene copolymer rubber (B) 90 parts by weight or more and more than 40 parts by weight [components (A) and (B)
Is 100 parts by weight]. The thermoplastic elastomer composition which has been partially or completely crosslinked by dynamic heat treatment in the presence of a quinonedioxime compound (C) Wherein the ethylene / α-olefin / non-conjugated polyene copolymer rubber (B) comprises ethylene, an α-olefin having 3 to 20 carbon atoms, and at least one kind of a branch represented by the following general formula [I]. (I) ethylene and 3 carbon atoms
A molar ratio (ethylene / α-olefin) to α-olefin of from 20 to 20 in the range of 40/60 to 95/5;
i) The content of the branched polyene compound is 0.1 to 10 mol%
And (iii) the intrinsic viscosity [η] measured in decalin at 135 ° C. is in the range of 0.1 to 10 dl / g.

[0011]

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[In the formula [I], n is an integer of 1 to 5,
R ¹ is an alkyl group having 1 to 5 carbon atoms, and R ² and R ³ are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. The olefin-based thermoplastic elastomer composition according to the present invention is based on 100 parts by weight of the total amount of the crystalline polyolefin resin (A) and the ethylene / α-olefin / non-conjugated polyene copolymer rubber (B). , 2 to 120 parts by weight of a softener (D) and / or 2 to 100 parts by weight of an inorganic filler (E).

[0013]

DETAILED DESCRIPTION OF THE INVENTION The olefin-based thermoplastic elastomer composition according to the present invention will be specifically described below.

The olefin-based thermoplastic elastomer composition according to the present invention comprises a blend comprising a crystalline polyolefin resin (A) and an ethylene / α-olefin / non-conjugated polyene copolymer rubber (B), This is a thermoplastic elastomer composition partially or completely crosslinked by dynamic heat treatment in the presence of the oxime compound (C).

Crystalline polyolefin resin (A) Crystalline polyolefin resin (A) used in the present invention
Consists of a crystalline high molecular weight solid product obtained by polymerizing one or more monoolefins by either the high-pressure method or the low-pressure method. Such resins include, for example, isotactic and syndiotactic monoolefin polymer resins. These representative resins are commercially available.

Suitable starting olefins for the crystalline polyolefin resin (A) include, specifically, ethylene,
Propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 2-methyl-1-propene, 3-methyl-1
-Pentene, 4-methyl-1-pentene, 5-methyl-1-hexene and the like. These olefins are used alone or in combination of two or more.

Regarding the polymerization mode, any type of polymerization mode may be employed as long as a resinous material can be obtained, whether it is a random type or a block type. The crystalline polyolefin resin (A) used in the present invention is an MFR (ASTMD 1238-6).
5T, 230 ° C.) is usually 0.01 to 100 g / 10 minutes,
In particular, it is preferably in the range of 0.05 to 50 g / 10 minutes.

These crystalline polyolefin resins may be used alone or in combination of two or more. The crystalline polyolefin resin (A) has a role of improving the fluidity and heat resistance of the composition.

In the present invention, the crystalline polyolefin resin (A) is used based on 100 parts by weight of the total amount of the crystalline polyolefin resin (A) and the ethylene / α-olefin / non-conjugated polyene copolymer rubber (B). It is used in an amount of 10 parts by weight or more and less than 60 parts by weight, preferably 20 to 55 parts by weight.

When the crystalline polyolefin resin (A) is used in the above amount, an olefin-based thermoplastic elastomer composition having excellent rubber elasticity and excellent moldability can be obtained.

Ethylene / α-olefin / non-conjugated polyether
Copolymer rubber (B) The ethylene / α-olefin / non-conjugated polyene copolymer rubber (B) used in the present invention is a random copolymer rubber, which is composed of ethylene and C 3-20 carbon atoms. It comprises an α-olefin and a branched polyene compound.

Examples of such an α-olefin having 3 to 20 carbon atoms include propylene, 1-butene,
1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-
Pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene,
Examples thereof include 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene. Among them, propylene, 1-butene, 1-hexene and 1-octene are preferably used.

These α-olefins can be used alone or in combination of two or more. The branched polyene compound is represented by the following general formula [I].

[0024]

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In the formula [I], n is an integer of 1 to 5;
¹ is an alkyl group having 1 to 5 carbon atoms, and R ² and R ³ are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

As the alkyl group having 1 to 5 carbon atoms,
Specifically, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-pentyl group, i-pentyl group, etc. Is mentioned.

Examples of such a branched polyene compound (hereinafter, also referred to as a branched polyene compound [I]) include the following compounds (1) to (24). Among them, (5), (6), (9),
The branched polyene compounds (11), (14), (19) and (20) are preferably used. (1) 4-ethylidene-1,6-octadiene (2) 7-methyl-4-ethylidene-1,6-octadiene (3) 7-methyl-4-ethylidene-1,6-nonadiene (4) 7-ethyl -4-ethylidene-1,6-nonadiene (5) 6,7-dimethyl-4-ethylidene-1,6-octadiene (6) 6,7-dimethyl-4-ethylidene-1,6-nonadiene (7) 4 -Ethylidene-1,6-decadiene (8) 7-methyl-4-ethylidene-1,6-decadiene (9) 7-methyl-6-propyl-4-ethylidene-1,6-octadiene (10) 4-ethylidene -1,7-nonadiene (11) 8-methyl-4-ethylidene-1,7-nonadiene (EM
N) (12) 4-ethylidene-1,7-undecadiene (13) 8-methyl-4-ethylidene-1,7-undecadiene (14) 7,8-dimethyl-4-ethylidene-1,7-nonadiene (15 ) 7,8-Dimethyl-4-ethylidene-1,7-decadiene (16) 7,8-Dimethyl-4-ethylidene-1,7-undecadiene (17) 8-Methyl-7-ethyl-4-ethylidene-1 , 7-Undecadiene (18) 7,8-Diethyl-4-ethylidene-1,7-decadiene (19) 9-Methyl-4-ethylidene-1,8-decadiene (20) 8,9-Dimethyl-4-ethylidene -1,8-decadiene (21) 10-methyl-4-ethylidene-1,9-undecadiene (22) 9,10-dimethyl-4-ethylidene-1,9-undecadiene (23) 11-methyl-4-ethylidene -1,10-dodecadiene (24) 10,11-dimethyl-4-ethylidene-1,10-dodecadiene These can be used alone or in combination of two or more.

The above-mentioned branched polyene compound [I] is
It may be a mixture of the trans form and the cis form, or may be the trans form alone or the cis form alone. Such a branched polyene compound is disclosed in JP-A-8-325334.
Can be prepared by the method described in Japanese Patent Application Laid-Open No. H10-260, 1988.

That is, it can be produced by reacting a compound having a conjugated diene represented by the following [Ia] with ethylene in the presence of a catalyst comprising a transition metal compound and an organoaluminum compound.

[0030]

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(In the formula [Ia], n, R ¹ , R ² and R
³ represents n in the general formula [I] described above,
Same as R ¹ , R ² and R ³ . The ethylene / α-olefin / non-conjugated polyene copolymer rubber (B) used in the present invention is a structural unit derived from the monomer of each of the ethylene, α-olefin and branched polyene compound as described above. Have a branched structure caused by the branched polyene compound and are randomly arranged, and the main chain has a substantially linear structure.

The fact that the copolymer rubber has a substantially linear structure and substantially does not contain a gel-like crosslinked polymer means that the copolymer rubber is dissolved in an organic solvent and the insoluble matter is substantially reduced. It can be confirmed by not including it. For example, when the intrinsic viscosity [η] is measured, it can be confirmed that the copolymer rubber is completely dissolved in decalin at 135 ° C.

In such an ethylene / α-olefin / non-conjugated polyene copolymer rubber (B), the structural unit derived from the branched polyene compound is substantially represented by the following formula [II]: It has a structure.

[0034]

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[In the formula [II], n, R ¹ , R ² and R ³
Are n, R ¹ , and R in the general formula [I], respectively.
Same as R ² and R ³ . It should be noted that the fact that the structural unit derived from the branched polyene compound has the above structure means that the ¹³ C-
It can be confirmed by measuring the NMR spectrum.

The ethylene / α-olefin / non-conjugated polyene copolymer rubber (B) used in the present invention has the following composition and properties. (I) This ethylene / α-olefin / non-conjugated polyene copolymer rubber (B) is composed of ethylene and C 3-20
Has a molar ratio (ethylene / α-olefin) of 40/60 to 95/5, preferably 50/50 to
90/10, more preferably 55/45 to 85/15
In the range.

The ethylene / α-olefin / non-conjugated polyene copolymer rubber having such an ethylene component / α-olefin component ratio has excellent low-temperature flexibility, impact resistance at low temperatures, and heat resistance. I have. In addition, ethylene
When the olefin / non-conjugated polyene copolymer rubber has an ethylene / α-olefin component ratio of more than 95/5, the olefin / non-conjugated polyene copolymer rubber exhibits resin properties and lowers low-temperature flexibility.
If it is less than 40/60, the heat resistance tends to decrease.

(Ii) The ethylene / α-olefin / non-conjugated polyene copolymer rubber (B) has a branched polyene compound content of 0.1 to 10 mol%, preferably 0.2 to 10 mol%.
7 mol%, more preferably in the range of 0.4 to 4 mol%.

When the ethylene / α-olefin / non-conjugated polyene copolymer rubber (B) having the content of the branched polyene compound in the above range is used, an olefin-based thermoplastic elastomer composition having a high crosslinking rate can be obtained. Can be

(Iii) The ethylene / α-olefin /
The non-conjugated polyene copolymer rubber (B) has an intrinsic viscosity [η] measured in decalin at 135 ° C. of 0.1 to 10 dl /.
g, preferably 0.5 to 5 dl / g, more preferably 1 to 5 dl / g.

When the ethylene / α-olefin / non-conjugated polyene copolymer rubber (B) having the intrinsic viscosity [η] in the above range is used, an olefin-based thermoplastic elastomer composition having excellent moldability can be obtained. can get.

The ethylene / α-olefin /
The non-conjugated polyene copolymer rubber (B) is obtained by copolymerizing ethylene, an α-olefin having 3 to 20 carbon atoms, and a branched polyene compound represented by the above general formula [I] in the presence of a catalyst. It can be obtained by polymerization.

As such a catalyst, a Ziegler catalyst comprising a transition metal compound such as vanadium (V), zirconium (Zr) or titanium (Ti) and an organic aluminum compound (organic aluminum oxy compound) can be used.

In the present invention, [a] a catalyst comprising a soluble vanadium compound and an organoaluminum compound, or [b] a metallocene compound of a transition metal selected from Group IVB of the periodic table, and an organoaluminum oxy compound or ionized ionic compound A catalyst comprising a compound is particularly preferably used.

In the present invention, the catalyst [a] (a catalyst comprising a soluble vanadium compound and an organoaluminum compound) or the catalyst [b] (a metallocene compound of a transition metal selected from Group IV of the periodic table) and an organic Ethylene in the presence of an aluminum oxy compound or a catalyst comprising an ionized ionic compound) and ethylene having an α of 3 to 20 carbon atoms.
-The olefin and the branched polyene compound are usually copolymerized in the liquid phase.

In this case, a hydrocarbon solvent is generally used, but an α-olefin such as propylene may be used as the solvent. Specific examples of such hydrocarbon solvents include pentane, hexane, heptane, octane, decane, dodecane, aliphatic hydrocarbons such as kerosene and halogen derivatives thereof, cyclohexane, methylcyclopentane,
Alicyclic hydrocarbons such as methylcyclohexane and halogen derivatives thereof, aromatic hydrocarbons such as benzene, toluene and xylene, and halogen derivatives such as chlorobenzene are used.

These solvents may be used in combination.
The copolymerization of ethylene, an α-olefin having 3 to 20 carbon atoms and a branched polyene compound may be performed by a batch method or a continuous method. When the copolymerization is carried out by a continuous method, the above-mentioned catalyst is used in the following concentration.

In the present invention, when the above-mentioned catalyst [a], that is, a catalyst comprising a soluble vanadium compound and an organoaluminum compound, is used, the concentration of the soluble vanadium compound in the polymerization system is usually 0.01 to 5%. Mmol / liter (polymerization volume), preferably 0.05 to 3 mmol / liter. This soluble vanadium compound is desirably supplied at a concentration of 10 times or less, preferably 1 to 7 times, more preferably 1 to 5 times the concentration of the soluble vanadium compound present in the polymerization system.

The organoaluminum compound has a ratio of aluminum atoms to vanadium atoms in the polymerization system (A
1 / V), and is supplied in an amount of 2 or more, preferably 2 to 50, more preferably 3 to 20.

The catalyst [a] comprising a soluble vanadium compound and an organoaluminum compound is usually diluted with the above-mentioned hydrocarbon solvent and / or a liquid α-olefin having 3 to 20 carbon atoms and a branched polyene compound. Supplied. At this time, the soluble vanadium compound is desirably diluted to the concentration described above, and the organoaluminum compound is diluted to, for example, 50% of the concentration in the polymerization system.
It is desirable to adjust the concentration to an arbitrary concentration of 2 times or less and supply it to the polymerization system.

In the present invention, when a catalyst [b] comprising a metallocene compound and an organic aluminum oxy compound or an ionized ionic compound (also referred to as an ionic ionized compound or an ionic compound) is used, a polymerization system is used. The concentration of the metallocene compound in is usually 0.1.
0.0005-0.1 mmol / liter (polymerization volume),
Preferably it is 0.0001-0.05 mmol / l.

The organic aluminum oxy compound is
It is supplied in an amount of 1 to 10,000, preferably 10 to 5,000 in terms of the ratio of aluminum atoms to the metallocene compound in the polymerization system (Al / transition metal).

In the case of the ionized ionic compound, the molar ratio of the ionized ionic compound to the metallocene compound in the polymerization system (ionized ionic compound / metallocene compound) is 0.5 to 20, preferably 1 to 10. Supplied.

When an organoaluminum compound is used, it is generally used in an amount of about 0 to 5 mmol / L (polymerization degree), preferably about 0 to 2 mmol / L.

In the present invention, when ethylene, an α-olefin having 3 to 20 carbon atoms and a branched polyene compound are copolymerized in the presence of a catalyst [a] comprising a soluble vanadium compound and an organoaluminum compound. In
The copolymerization reaction is usually carried out at a temperature of -50 ° C to 100 ° C, preferably -30 ° C to 80 ° C, more preferably -20 ° C to
At 60 ° C., the pressure is 50 kg / cm ² or less, preferably ² kg / cm 2.
It is performed under the condition of 0 kg / cm ² or less. However, the pressure is not zero.

In the present invention, ethylene, an α-olefin having 3 to 20 carbon atoms and a branched polyene compound are added in the presence of a catalyst [b] comprising a metallocene compound and an organic aluminum oxy compound or an ionized ionic compound. When the copolymerization is carried out, the temperature of the copolymerization reaction is usually −20 ° C. to 150 ° C., preferably 0 ° C. to 12 ° C.
0 ° C., more preferably 0 ° C. to 100 ° C., and a pressure of 80 ° C.
It is carried out under the condition of not more than kg / cm ² , preferably not more than 50 kg / cm ² . However, the pressure is not zero.

The reaction time (average residence time when the copolymerization is carried out by a continuous method) varies depending on conditions such as the catalyst concentration and the polymerization temperature, but is usually 5 minutes to 5 hours, preferably 10 minutes to 5 minutes. 3 hours.

In the present invention, ethylene, C 3 -C 2
The α-olefin of 0 and the branched polyene compound are
The ethylene / α-olefin / non-conjugated polyene copolymer rubber having the specific composition described above is supplied to the polymerization system in such an amount as to obtain the rubber. Further, upon copolymerization, a molecular weight regulator such as hydrogen may be used.

As described above, ethylene and carbon atoms 3
When an α-olefin and a branched polyene compound of from 20 to 20 are copolymerized, an ethylene / α-olefin / non-conjugated polyene copolymer rubber (B) is usually obtained as a polymerization liquid containing the same. This polymerization solution is treated by a conventional method to obtain an ethylene / α-olefin / non-conjugated polyene copolymer rubber (B).

Ethylene / α-olefin / non-conjugated polyene copolymer rubber (B) [unsaturated ethylene copolymer]
The above-mentioned preparation method is described in detail in JP-A-8-325334.

In the present invention, the ethylene / α-olefin / non-conjugated polyene copolymer rubber (B) comprises a crystalline polyolefin resin (A) and an ethylene / α-olefin / non-conjugated polyene copolymer rubber (B) Total amount of 100
It is used in an amount of 90 to 40 parts by weight, preferably 80 to 45 parts by weight, based on parts by weight.

Quinone Dioxime Compound (C) Examples of the quinone dioxime compound (C) used as a crosslinking agent in the present invention include p-quinone dioxime and p, p'-dibenzoylquinone dioxime. Oxime, tetrachlorobenzoquinone dioxime, poly (p-dinitrosobenzoquinone dioxime) and the like.

Of these, p-quinone dioxime and p, p'-dibenzoylquinone dioxime are preferred in view of scorchability and productivity (crosslinking rate). Particularly, p-quinone dioxime is preferred.

Such a quinone dioxime compound (C) is used in an amount of 100 parts in total, that is, the total amount of the crystalline polyolefin resin (A) and the ethylene / α-olefin / non-conjugated polyene copolymer rubber (B). 0.01 to 10 parts by weight, preferably 0.05 to 7 parts by weight, based on parts by weight
Parts by weight, more preferably 0.1 to 5 parts by weight. When the quinone dioxime compound (C) is used at a compounding ratio within the above range, a molded article having a high degree of crosslinking having excellent heat resistance, tensile properties, elastic recovery and rebound resilience can be obtained. Since it does not become too much, it does not cause a reduction in elongation at break.

In the present invention, an oxidizing oxide such as leadtan (Pb ₃ O ₄ ), 2-benzothiazole disulfide, or the like may be used in the partial or complete crosslinking with the quinone dioxime compound (C). Oxidizing thiazole compounds such as mercaptobenzothiazole, N-cyclohexyl-2-benzothiazolesulfenamide, dicumyl peroxide, di-tert-butyl peroxide, 2,
5-dimethyl-2,5-di- (tert-butylperoxy) hexane, 2,5-dimethyl-2,5-di- (tert-butylperoxy)
Hexin-3, 1,3-bis (tert-butylperoxyisopropyl) benzene, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, n-butyl-4,4
-Bis (tert-butylperoxy) valerate, benzoyl peroxide, p-chlorobenzoyl peroxide,
Organic peroxides such as 2,4-dichlorobenzoyl peroxide, tert-butylperoxybenzoate, tert-butylperbenzoate, tert-butylperoxyisopropyl carbonate, diacetyl peroxide, lauroyl peroxide, tert-butylcumyl peroxide, tetrachlorobenzoquinone, etc. An activator such as a quinone-based compound having an oxidizing ability can be blended.

By using an activator as described above,
A uniform and rapid crosslinking reaction can be expected. The above-mentioned activator is used in a proportion of usually 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the whole object to be treated.

When the above thiazole oxidizing agent is used, sulfur may be used in combination to further enhance the activation of the crosslinking agent by the thiazole oxidizing agent. Other Components The olefin-based thermoplastic elastomer composition according to the present invention includes a crystalline polyolefin resin (A), ethylene-α
-In addition to the olefin / non-conjugated polyene copolymer rubber (B) and the quinone dioxime compound (C), a softener (D) and / or an inorganic filler (E) can be included.

As the softener (D) used in the present invention, a softener usually used for rubber can be used. Specifically, petroleum-based substances such as process oil, lubricating oil, paraffin, liquid paraffin, petroleum asphalt, petrolatum; coal tars such as coal tar and coal tar pitch; castor oil, linseed oil, rapeseed oil, soybean oil, Fatty oils such as coconut oil; waxes such as tall oil, beeswax, carnauba wax and lanolin; fatty acids such as ricinoleic acid, palmitic acid, stearic acid, barium stearate and calcium stearate or metal salts thereof;
Synthetic polymer substances such as coumarone indene resin and atactic polypropylene; ester plasticizers such as dioctyl phthalate, dioctyl adipate and dioctyl sebacate; other microcrystalline waxes, sub (factice), liquid polybutadiene, modified liquid polybutadiene, liquid thiocol And the like.

In the present invention, the softener (D) is used in combination with the crystalline polyolefin resin (A) and the ethylene / α-olefin / non-conjugated polyene copolymer rubber (B).
2 to 120 parts by weight, preferably 2 to 120 parts by weight, per 100 parts by weight
100 parts by weight, more preferably 5 to 80 parts by weight. When the softening agent (D) is used in the above ratio, the obtained thermoplastic elastomer composition has excellent fluidity at the time of molding and does not lower the mechanical properties of the molded product. In the present invention, the amount of the softener (D) used is 1
If it exceeds 20 parts by weight, the heat resistance and heat aging resistance of the obtained thermoplastic elastomer composition tend to decrease.

As the inorganic filler (E) used in the present invention, specifically, calcium carbonate, calcium silicate, clay, kaolin, talc, silica, diatomaceous earth,
Mica powder, asbestos, alumina, barium sulfate, aluminum sulfate, calcium sulfate, basic magnesium carbonate, molybdenum disulfide, graphite, glass fiber, glass sphere, shirasu balloon, basic magnesium sulfate whisker, calcium titanate whisker, aluminum borate whisker And the like.

In the present invention, the inorganic filler (E) is
Crystalline polyolefin resin (A) and ethylene α-
It is used in an amount of 2 to 100 parts by weight, preferably 2 to 50 parts by weight, based on 100 parts by weight of the total amount of the olefin / non-conjugated polyene copolymer rubber (B). In the present invention, when the amount of the inorganic filler (E) used exceeds 100 parts by weight, the rubber elasticity of the obtained thermoplastic elastomer composition,
Moldability tends to decrease.

The olefin thermoplastic elastomer composition according to the present invention includes a crystalline polyolefin resin (A), an ethylene / α-olefin / non-conjugated polyene copolymer rubber (B), a quinone dioxime compound ( C),
In addition to the softener (D) and the inorganic filler (E), an ethylene / propylene copolymer rubber (EPR) and an ethylene / propylene / non-conjugated diene copolymer rubber (EPDM) can be included.

Specific examples of the ethylene / propylene / non-conjugated diene copolymer rubber include ethylene / propylene / 5-
Ethylidene-2-norbornene copolymer rubber, ethylene
Propylene / dicyclopentadiene copolymer rubber and the like.

In the present invention, the above-mentioned ethylene / propylene copolymer rubber (EPR) and ethylene / propylene
Propylene / non-conjugated diene copolymer rubber (EPDM)
Is a crystalline polyolefin resin (A) and ethylene
It is preferably 10 to 200 parts by weight based on 100 parts by weight of the total amount of the α-olefin / non-conjugated polyene copolymer rubber (B).
It is desirable to use it in a ratio of 10 parts by weight, more preferably 10 to 150 parts by weight.

Further, in the present invention, a conventionally known heat-resistant stabilizer, an anti-aging agent, a weather-resistant stabilizer, an antistatic agent, a metal soap, a lubricant such as wax, etc. are added to the olefin-based thermoplastic elastomer. It can be added in a range that does not impair the purpose.

The partially or completely crosslinked olefinic thermoplastic elastomer composition according to the present invention comprises the above-mentioned crystalline polyolefin resin (A) and ethylene
α-olefin / non-conjugated polyene copolymer rubber (B)
And a mixture of a softener (D) and / or an inorganic filler (E) and the like, which are blended as required, are dynamically heat-treated in the presence of the quinonedioxime compound (C) as described above. And partially or completely crosslinked.

Here, “dynamically heat-treating” means kneading in a molten state. The dynamic heat treatment in the present invention is preferably performed in a non-open type apparatus, and is preferably performed in an atmosphere of an inert gas such as nitrogen or carbon dioxide. The temperature of the heat treatment ranges from the melting point of the crystalline polyolefin resin (A) to 300 ° C.
The temperature is 250C, preferably 170C to 225C. The kneading time is usually 1 to 20 minutes, preferably 1 to 10 minutes. The applied shearing force is 10 to 1 at the shear rate.
00,000 sec ^-1 , preferably 100 to 50,000
The range is ⁰ sec ^-1 .

As a kneading apparatus, a mixing roll, an intensive mixer (for example, Banbury mixer, kneader), a single-screw or twin-screw extruder can be used, but a non-open type apparatus is preferable.

According to the present invention, the crystalline polyolefin resin (A) and ethylene
A partially or completely crosslinked olefinic thermoplastic elastomer composition comprising the α-olefin / non-conjugated polyene copolymer rubber (B) is obtained.

In the present invention, "the thermoplastic elastomer composition is partially crosslinked" means that the gel content measured by the following method is preferably 20% by weight or more and 99.5% or more.
%, Particularly preferably in the range of 45 to 98% by weight. Further, "the thermoplastic elastomer composition is completely crosslinked" means that the gel content is 99.5% by weight or more. [Measurement Method of Gel Content] A 100 mg sample of the thermoplastic elastomer composition was sampled and 0.5 mm × 0.5 mm
A sample cut into × 0.5 mm strips is immersed in 30 ml of cyclohexane at 23 ° C. for 48 hours in a closed container, then the sample is taken out on a filter paper and dried at room temperature for at least 72 hours until a constant weight is obtained. I do.

From the weight of the dried residue, the weight of all cyclohexane-insoluble components (fibrous filler, filler, pigment, etc.) other than the polymer component, and the weight of the crystalline polyolefin resin (A) in the sample before immersion in cyclohexane were determined. The reduced value is referred to as “corrected final weight (Y)”.

On the other hand, the weight of the ethylene / α-olefin / non-conjugated polyene copolymer rubber (B) in the sample is referred to as “corrected initial weight (X)”. Where the gel content is
It is obtained by the following equation.

Gel content [% by weight] = [corrected final weight (Y) / corrected initial weight (X)] × 100

[0084]

The olefin-based thermoplastic elastomer composition according to the present invention has a lower temperature characteristic, tensile strength, elongation at break, and a lower temperature than conventional cross-linked olefin-based thermoplastic elastomers.
Molding with excellent molding stability (contamination of mold during injection molding and contamination of dies during extrusion), solvent resistance, contamination to metals and rubber-like properties (for example, permanent elongation and compression set) can do.

[0085]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

The methods for measuring physical properties of the olefin-based thermoplastic elastomer compositions of Examples and Comparative Examples are as follows. [Measurement method of physical properties] (1) Tensile strength: 200 in accordance with JIS K6301
The tensile strength at break was measured at a tensile speed of mm / min. (2) Elongation at break: 200 in accordance with JIS K 6301
The breaking elongation at break was measured at a tensile speed of mm / min. (3) Permanent elongation: Measured according to JIS K6301. However, the retained length was a length corresponding to 100% elongation.

[0087]

[Reference Example 1] [Preparation of catalyst] Under an argon atmosphere, anhydrous cobalt (II) chloride 4 was placed in a 50 ml flask containing a stirrer stirrer.
3 mg (0.33 mmol), 263 mg (0.66 mmol) of 1,2-bis (diphenylphosphino) ethane and 23 ml of anhydrous decane were added, and the mixture was stirred at 25 ° C. for 2 hours.

Then, a catalyst was prepared by adding 17 ml of a 1 mol / l triethylaluminum / toluene solution (17 mmol of triethylaluminum) at 25 ° C. and stirring for 2 hours.

[Synthesis of 4-ethylidene-8-methyl-1,7-nonadiene (EMN)]

[0090]

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In a 300 ml stainless steel (SUS316) autoclave, 7-methyl-3-
100 g of methylene-1,6-octadiene (β-myrcene)
(734 mmol) and the catalyst prepared as described above were added in total and sealed.

Next, an ethylene cylinder was directly connected to the autoclave, and ethylene was introduced thereinto.
The pressure was increased to 5 kg / cm ² . Then heat to 95 ° C,
The consumed ethylene is added intermittently 5 times, for a total of 1
The reaction was performed for 5 hours.

After the reaction was completed, the autoclave was cooled and opened, and the obtained reaction mixture was poured into 100 ml of water to separate an organic layer and an aqueous layer. The separated organic layer
After removing low-boiling substances with an evaporator, 20-stage precision vacuum distillation was performed. 83 g of the desired EMN was obtained (yield 69%, β-myrcene conversion 90%). As a reaction by-product, 16 g of 5,9-dimethyl-1,4,8-decatriene was produced (yield: 13%).

The 4-ethylidene-8-methyl- obtained above
The analysis results of 1,7-nonadiene (EMN) are shown below. (1) Boiling point: 103 to 105 ° C./30 mmHg (2) GC-MS (gas chromatography-mass spectrometry): m / z 164 (M ⁺ molecular ion peak), 149, 1
23, 93, 79, 41, 27 (Gas chromatography measurement conditions: Column: J & W Scientific Capillary column DB-1701 0.25 mm × 30
m Vaporization temperature: 250 ° C Column temperature: Hold at 60 ° C for 5 minutes, then 10 to 200 ° C
(The temperature is raised at a rate of ° C / min.) (3) Infrared absorption spectrum (neat) Absorption peak: 3080 cm ^-1 , 2975 cm ^-1 , 292
^{5cm -1, 2825cm -1, 1670cm -1} , 1640
^{cm -1, 1440cm -1, 1380cm -1} , 1235c
^{m -1, 1110cm -1, 910cm -1} , 830cm -1 (4) 1 H-NMR spectrum (solvent: CDCl ₃₎ shows an absorption peak in Table 1.

[0095]

[Table 1]

[Preparation of ethylene / α-olefin / non-conjugated polyene copolymer rubber] Using a 15-liter capacity polymerization vessel equipped with stirring blades, ethylene and propylene
A copolymerization reaction with 4-ethylidene-8-methyl-1,7-nonadiene (EMN) was continuously performed.

That is, first, 3 liters of dehydrated and purified hexane and bis (1,
0.1 L / h of a hexane solution of 3-dimethylcyclopentadienyl) zirconium dichloride (concentration: 0.05 mmol / L) and 0.2 L / h of a hexane solution of triisobutylaluminium (Concentration: 20 mmol / L) 0.5 liter / hour of a hexane slurry solution of methylalumoxane (3 mg atom / liter in terms of aluminum atom) and 1.2 liter / hour of a hexane solution of EMN (concentration: 0.20 liter / liter). Supplied.

Further, ethylene was continuously supplied from the upper part of the polymerization vessel to 260 liters / hour, propylene was supplied to 540 liters / hour, and hydrogen was continuously supplied so that the concentration of the gas phase became 0.004 mol%. This copolymerization reaction is 5
Performed at 0 ° C.

Next, a small amount of methanol was added to the polymerization solution withdrawn from the lower part of the polymerization vessel to stop the polymerization reaction.
After separating the copolymer from the solvent by a steam strip treatment, at 100 ° C. under reduced pressure (100 mmHg),
Dry for 24 hours.

By the above operation, ethylene / propylene / E
MN copolymer rubber was obtained at a rate of 240 g per hour. The obtained ethylene-propylene-EMN copolymer rubber (B
-1) has a molar ratio of ethylene to propylene (ethylene / propylene) of 80/20 and an EMN content of 0.1.
The intrinsic viscosity [η] measured in decalin at 135 ° C. was 2.8 dl / g.

[0101]

Reference Examples 2 and 3 The same operation as in Reference Example 1 was carried out to obtain ethylene / α-olefin / EMN copolymer rubbers (B-2, B-3) shown in Table 2.

[0102]

[Table 2]

[0103]

Example 1 50 parts by weight of the ethylene / propylene / EMN copolymer rubber (B-1) obtained in Reference Example 1 above and MFR (ASTM D1238-65T, 230 ° C) of 11 g / 10 min. Is obtained by adding 1.5 parts by weight of p-benzoquinone dioxime as a quinone dioxime-based compound (C) to 50 parts by weight of a propylene homopolymer of 0.91 g / cm ³ and thoroughly mixing in a Henschel mixer. The resulting composition was kneaded at 180 ° C. for 10 minutes using a Banbury mixer, and then passed through an open roll and cut with a sheet cutter to obtain square pellets.

Next, a predetermined test piece was prepared by injection molding using the square pellet, and its physical properties were measured according to the above-mentioned measuring methods. Table 3 shows the results.

[0105]

Example 2 In Example 1, the ethylene / 1-butene / EMN copolymer rubber (B) obtained in Reference Example 2 was used instead of the ethylene / propylene / EMN copolymer rubber (B-1).
Except for using -2), an olefin-based thermoplastic elastomer composition was prepared and the physical properties were measured in the same manner as in Example 1.

Table 3 shows the results.

[0107]

Example 3 In Example 1, the ethylene / 1-octene / EMN copolymer rubber (B-3) obtained in Reference Example 3 was used instead of the ethylene / propylene / EMN copolymer rubber (B-1). An olefin-based thermoplastic elastomer composition was prepared and the physical properties were measured in the same manner as in Example 1 except for using.

Table 3 shows the results.

[0109]

Comparative Example 1 In Example 1, the molar ratio of ethylene to propylene (ethylene / propylene) was 80 instead of the ethylene / propylene / EMN copolymer rubber (B-1).
/ Propylene propylene / 5-ethylidene-2-norbornene copolymer rubber (EPDM (ENB)) having a / 20, 5-ethylidene-2-norbornene content of 1.5 mol% and an intrinsic viscosity [η] of 2.8 dl / g ) Except that) was used, an olefin-based thermoplastic elastomer composition was prepared in the same manner as in Example 1, and the physical properties were measured.

The results are shown in Table 3.

[0111]

[Table 3]

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI C08L 23/18 C08L 23/18 47/00 47/00 (72) Inventor Kyoko Kobayashi 3 Chigusa Coast, Ichihara-shi, Chiba Mitsui Petrochemical Industry Co., Ltd.

Claims (2)

[Claims] 1. An amount of from 10 to less than 60 parts by weight of the crystalline polyolefin resin (A) and an amount of from more than 40 to 90 parts by weight of ethylene / α-olefin / non-conjugated polyene copolymer rubber (B). [The total amount of the components (A) and (B) is 100 parts by weight.] In the presence of the quinonedioxime compound (C) by a dynamic heat treatment to partially or completely A crosslinked thermoplastic elastomer composition, wherein the ethylene / α-olefin / non-conjugated polyene copolymer rubber (B) comprises ethylene, an α-olefin having 3 to 20 carbon atoms,
It comprises at least one kind of branched polyene compound represented by the following general formula [I], and (i) a molar ratio of ethylene to an α-olefin having 3 to 20 carbon atoms (ethylene /
α-olefin) in the range of 40/60 to 95/5, and (ii) the content of the branched polyene compound is 0.1 to 10
(Iii) an olefin-based thermoplastic elastomer composition characterized in that the intrinsic viscosity [η] measured in decalin at 135 ° C. is in the range of 0.1 to 10 dl / g; ] [In Formula [I], n is an integer of 1 to 5, R ¹ is an alkyl group having 1 to 5 carbon atoms, and R ² and R ³ are each independently a hydrogen atom or a carbon atom number. 1 to 5 alkyl groups]. 2 to 120 parts by weight based on 100 parts by weight of the total amount of the crystalline polyolefin resin (A) and the ethylene / α-olefin / non-conjugated polyene copolymer rubber (B).
The olefin-based thermoplastic elastomer composition according to claim 1, wherein the composition contains 1 part by weight of a softening agent (D) and / or 2 to 100 parts by weight of an inorganic filler (E).