WO2001064783A1

WO2001064783A1 - Olefin rubber composition

Info

Publication number: WO2001064783A1
Application number: PCT/JP2000/001140
Authority: WO
Inventors: Hajime Nishihara
Original assignee: Asahi Kasei Kabushiki Kaisha
Priority date: 2000-02-28
Filing date: 2000-02-28
Publication date: 2001-09-07
Also published as: JP4758588B2; DE10084514B4; DE10084514T1

Abstract

A partly or wholly crosslinked olefin rubber composition comprising (A) 1 to 99 parts by weight of an ethylene/α-olefin copolymer comprising ethylene units and C3-20 α-olefin units and (B) 1 to 99 parts by weight of an olefin resin (the sum of components (A) and (B) is 100 parts by weight), wherein the component (A) has a degree of crosslinking of 50 % or higher and a degree of swelling of 5 to 40.

Description

Description Olefin rubber, composition Technical field

The present invention relates to an olefin rubber composition. More specifically, the present invention relates to an olefin rubber composition having excellent mechanical strength, heat resistance, and oil resistance.

Background art

Radical crosslinkable olefin-based rubber and olefinic resin without radical crosslinkability such as polypropylene (PP) are crosslinked by melt-kneading in an extruder in the presence of a radical initiator in the presence of a radical initiator. The composition is a known technique, and is widely used for applications such as automobile parts.

Examples of such an olefin rubber include an ethylene-propylene-gen rubber (EPDM) composition or an olefin-based elastomer composition produced by a metallocene catalyst (Japanese Patent Application Laid-Open Nos. 8-120127 and 9-191). No. 1,370,001, Japanese Patent Application Laid-Open No. Hei 9-110787, Japanese Patent Application Laid-Open No. Hei 10-87912) are known. However, the above composition does not always have sufficient mechanical strength, and there is a need for an olefin rubber composition that can withstand practical use.

Disclosure of the invention

An object of the present invention is to provide an olefin rubber composition which does not have the above-mentioned problems in view of the current situation, that is, has excellent mechanical properties. The present inventors have conducted intensive studies to obtain an olefin rubber composition having excellent mechanical strength, and as a result, it has been found that an olefin rubber composition containing ethylene and hyolefin and having a specific crosslinked structure is surprising. Finally, they found that the mechanical strength was dramatically improved, and completed the present invention.

That is, the present invention relates to (A) 1 to 99 parts by weight of an ethylene / α-olefin copolymer containing ethylene and a carbon-containing unit having 3 to 20 carbon atoms, and 1 to 99 parts by weight of a (Β) olefin resin ( A partially or completely crosslinked composition containing (Α) and (Β) in a total amount of 100 parts by weight, wherein the degree of crosslinking of (Α) is 50% or more; And said BEST MODE FOR degree of swelling out the _c invention is to provide a Orefin rubber composition which is 5-4 0 (A)

Hereinafter, the present invention will be described in detail.

The composition of the present invention comprises (A) an ethylene / α-olefin copolymer having a specific crosslinked structure, and (Β) an olefin resin.

Here, (Α) is important that the degree of cross-linking is 50% or more, preferably 60% or more, more preferably 70% or more, most preferably 80% or more, and extremely preferably. Is 90% or more. If the degree of crosslinking is less than 50%, the mechanical strength such as tensile strength and permanent compression set (C-set), oil resistance, and heat resistance are reduced.

Further, it is essential that (A) has a swelling degree of 5 to 40, preferably 10 to 35, more preferably 10 to 30 and most preferably 10 to 25, It is preferably from 10 to 20. The degree of swelling is a measure of the crosslink density, whereas conventional olefin rubbers had a degree of swelling of less than 5, but the present inventor has obtained excellent mechanical properties, only when the degree of swelling is between 5 and 40. The inventors have found that heat resistance and oil resistance develop, and have completed the present invention.

Hereinafter, each component of the present invention will be described in detail.

In the present invention, (A) the ethylene-ct-olefin copolymer is, for example, an ethylene-α-olefin copolymer containing an ethylene unit and an α-olefin unit having 3 to 20 carbon atoms.

Examples of the α-olefins having 3 to 20 carbon atoms include propylene, butene-11, pentene-11, hexene-1, 4-methylpentene-11, heptene-1, otaten-1, nonene-1 and decene-1. 1, Dedecene-1 and Dodesen-1 etc. Among them, hexene-1, 4-methylpentene-11 and octene-11 are preferred, and octene-11 is particularly preferred. Otathene-11 is excellent in the effect of softening the copolymer even in a small amount, and the obtained copolymer is excellent in mechanical strength.

The ethylene'hydroolefin copolymer used in the present invention is preferably produced by using a known metacene catalyst or a Ziegler catalyst.

In general, meta-acene catalysts are composed of a cyclopentenyl derivative of a Group IV metal such as titanium or zirconium and a co-catalyst. Compared with the Ziegler-based catalyst, the molecular weight distribution of the obtained polymer is narrow, and the distribution of the comonomer α-olefin having 3 to 20 carbon atoms in the copolymer is uniform.

The ethylene'-olefin copolymer used in the present invention has an α-olefin copolymerization ratio of 1 to 50% by weight. /. It is preferably, more preferably 1 0 to 40 wt ^_0/0, most preferably from 20 to 30 wt%. When the co-polymerization ratio of hyolefine exceeds 50% by weight, the hardness and tensile strength of the composition are greatly reduced, while when it is less than 1% by weight, the hardness of the composition is high and the mechanical strength tends to be reduced. It is in.

The density of (Α) is preferably in the range of 0.8 to 0.9 gZcm °. The use of the ethylene / thioolefin copolymer having a density in this range makes it possible to obtain a thermoplastic rubber composition having excellent flexibility and low hardness.

The (A) ethylene'α-olefin copolymer used in the present invention preferably has a long-chain branch. The presence of long-chain branching enables the density to be lower than the ratio (% by weight) of copolymerized hyolephine without lowering the mechanical strength. Low hardness and high strength rubber can be obtained. Olefin rubbers having long chain branches are described in US Pat. No. 5,278,272 and the like.

Further, it is preferable that (A) the ethylene-thioolefin copolymer has a DSC melting point peak at a temperature of room temperature or higher. When the copolymer has a melting point peak, in a temperature range below the melting point, the copolymer has a stable morphology, is excellent in handleability, and has little stickiness.

Further, the melt index of (A) used in the present invention is preferably in the range of 0.01 to 100 gZlO content (190 ° C, 2.16 kg load), and more preferably 0.1 to 100 kg. 2-: 10 gZl 0 min.

In the present invention, (A) contains an ethylene unit and an α-olefin unit as essential components, and may contain other vinyl monomer units as necessary. In addition, it is only necessary that (Α) has an ethylene unit and a hyolef 単位 in unit. Examples thereof include polystyrene, polyolefin, polyester, polyurethane, 1,2 polybutadiene, and polychlorinated vinyl. Hydrogenated thermoplastic elastomers, and finally copolymers containing ethylene units and _α- olefin units in the structure are also included in (Α). It is.

As (A) used in the present invention, a plurality of types may be mixed and used. In such a case, the workability can be further improved. In the present invention, (B) the olefin resin may be an isotactic copolymer resin of polyethylene, homo isotactic polypropylene, propylene and other olefins such as ethylene, butene-11, pentene-11, and hexene-1 ( And random copolymers).

At least one resin selected from these resins is used in a composition ratio of 1 to 99 parts by weight based on a total of 100 parts by weight of (A) and (B). Preferably it is 5 to 90 parts by weight, more preferably 20 to 80 parts by weight. If the amount is less than 1 part by weight, the fluidity and processability of the composition decrease, and if it exceeds 99 parts by weight, the flexibility of the composition is insufficient, which is not desirable.

The melt index of the olefin resin used in the present invention is 0.:! It is preferably in the range of ~ 10 g / 10 min (230 ° C, 2.16 kg load). If it exceeds 100 gZl 0 minutes, the heat resistance and mechanical strength of the thermoplastic elastomer composition will be insufficient, and if it is less than 0.1 gZi 0 minutes, the fluidity will be poor and the moldability will be reduced. Is not preferred.

In the composition of the present invention, (C) a softening agent can be blended as needed to improve processability.

As (C) above, process oils such as paraffinic and naphthenic are preferred. These are used in an amount of 5 to 50 parts by weight, preferably 10 to 150 parts by weight, for adjusting the hardness and flexibility of the composition. If the amount is less than 5 parts by weight, flexibility and workability are insufficient, and if it exceeds 500 parts by weight, oil bleeding becomes remarkable, which is not preferable.

The composition of the present invention can be obtained by combining (A) a specific ethylene.co-olefin copolymer, (B) an olefin resin, and (C) a softening agent in a specific composition ratio, thereby obtaining a mechanical The balance between strength, flexibility and workability is improved, and it can be used preferably.

The composition provided in the present invention needs to be partially cross-linked by (D) a cross-linking initiator or (D) and (E) a cross-linking aid. In this bridge This makes it possible to further improve wear resistance, mechanical strength, heat resistance, and the like. (D) above crosslinking initiator, also Fuyunoru crosslinking agent for performing a dynamic cross-linking of (A) is a radical generator or the like, for example, an organic peroxide or an organic § zo compounds is preferably les, _c which This makes it possible to improve wear resistance, mechanical strength, heat resistance, and the like.

Here, the organic peroxide preferably used has a one-minute half-life temperature T, of preferably 100 to 250 ° C, and more preferably 150 to 200 ° C. More preferred. Further, the crosslinking efficiency ε calculated from the hydrogen abstraction ability in the pentadecane molecule is preferably from 20 to 60, and more preferably from 30 to 50.

Specific examples of such radical initiators include 1,1-bis (t-butyloxy) 13,3,5-trimethylcyclohexane, 1,1-bis (t-hexyloxy) 13, 3,5-Trimethylcyclohexane, 1,1-bis (t-hexyloxy) cyclohexane, 1,1-bis (t-butylperoxy) cyclododecane, 1,1-bis (t-butylperoxy) cyclo Veroxy such as xane, 2,2-bis (t-butylperoxy) octane, n-butynolee 4,4-bis (t-butylperoxy) butane, n-butyl-4,4-bis (t-butylperoxy) valerate Ketals; di-t-butylperoxide, dicumylperoxide, t-butylcumylperoxide, α, a'-bis (t-butylperoxide-1m-a Propyl) benzene, a, a'-Bis (t-butylperoxy) diisopropylbenzene, 2,5-dimethinoley 2,5-bis (t-butylperoxy) hexane and 2,5-dimethyl-2,5-bis (t-butyl) Butyl peroxy) hexine-dialkylperoxides such as 3;

Acetylperoxide, isobutyrylperoxide, octanoylperoxide, decanolylperoxide, lauroylbeloxide, 3,5,5-trimethylhexanoylperoxide, benzoy Diperoxides such as ruperoxide, 2,4-dichlorobenzene benzoyl peroxide and m-trioylperoxide; t-butylperoxyacetate, t-butylperoxysitol Butyrate, t-butylperoxy-l-2-ethynolehexanoate, t-butyl-peroxyloxylate, t-butylperoxybenzoate, g-t-butylperoxysofta 2,5-dimethyl-2,5-di (benzoylberoxy) hexane, t-butylperoxymaleic acid, t-butylperoxyisopropyl carbonate, and tamylperoxy Peroxyesters such as citrate; and t-butylhydroxyperenoxide, cumenehydroperoxide, diisopropylpropylbenzenehydroperoxide, 2,5-dimethylhexane-1,2,5-dihydroperoxide and 1,1,3,3,1 Hydroperoxides such as 3-tetramethylbutylhydroxide belloxide can be mentioned.

Among these compounds, 1,1-bis (t-butylperoxy) -1,3,3,5-trimethinolecyclohexane, di-t-butylperoxide, dicumylperoxide, 2,5-dimethyl-2, 5-bis (t-butylperoxy) hexane and 2,5-dimethyl-2,5-bis (t-butylperoxy) hexine-13 are preferred.

These (D) crosslinking initiators are used in an amount of 0.02 to 3 parts by weight, preferably 0.05 to 1 part by weight, per 100 parts by weight of the composition comprising (A) and (B). Used. If the amount is less than 0.02 parts by weight, the crosslinking is insufficient, and if it exceeds 3 parts by weight, the physical properties of the composition are not improved, which is not preferable.

Further, (E) a crosslinking assistant includes a monofunctional monomer or a polyfunctional monomer. The monofunctional monomer is preferably a radical polymerizable vinyl monomer, and is an aromatic vinyl monomer, an unsaturated nitrile monomer such as acrylonitrile and methacrylonitrile, and an acrylate monomer. And methacrylic acid ester monomers, acrylic acid monomers, methacrylic acid monomers, maleic anhydride monomers, and N-substituted maleimide monomers. The polyfunctional monomers include divinylbenzene, triallyl isocyanurate, triaryl cyanurate, diacetone diacrylamide, polyethylene glycol diatalylate, polyethylene glycol dimethacrylate, and trimethylolpropane trimethacrylate. , Trimethylolpropane triatalylate, ethylene glycolone resin methacrylate, triethylene glycolone resin methacrylate, diethylene glycol dimethacrylate, diisopropenyl benzene, p-quinone dioxime, ρ, ρ'-dibenzoylquinone dioxime, phenyl maleimimi De, ant ^^ methacrylate, N, N'-m-phenylenebismaleimide, jia Rylphthalate, tetraaryloxetane, 1,2-polybutadiene and the like are preferably used. These crosslinking aids may be used in combination of two or more. These crosslinking aids are used in an amount of 0.1 to 5 parts by weight, preferably 0.5 to 2 parts by weight, per 100 parts by weight of the composition comprising (A) and (B). When the amount is less than 0.1 part by weight, the crosslinking is insufficient. When the amount exceeds 5 parts by weight, the physical properties of the composition are not improved and an excessive amount of the crosslinking aid remains, which is not preferable.

In addition, other resins and elastomers may be added to the composition of the present invention to such an extent that its characteristics are not impaired.

Further, the composition of the present invention can contain an inorganic filler and a plasticizer to such an extent that the characteristics thereof are not impaired. The inorganic filler used here includes, for example, calcium carbonate, magnesium carbonate, silica, carbon black, glass fiber, titanium oxide, clay, Myriki, Tanorek, magnesium hydroxide, aluminum hydroxide and the like. Examples of the plasticizer include phthalic acid esters such as polyethylene glycol and octyl phthalate (D〇P). Also, other additives such as organic and inorganic pigments, heat stabilizers, antioxidants, ultraviolet absorbers, light stabilizers, flame retardants, silicone oils, antiblocking agents, foaming agents, antistatic agents, antibacterial agents, etc. Are also preferably used.

For the production of the composition of the present invention, a general method using a Banbury mixer, a kneader, a single-screw extruder, a twin-screw extruder, etc., which are used for the production of ordinary resin compositions and rubber compositions, is employed. It is possible to In order to achieve dynamic crosslinking particularly efficiently, a twin-screw extruder is preferably used. The twin-screw extruder uniformly and finely disperses the olefin-based elastomer and the propylene-based resin, and further adds other components to cause a crosslinking reaction, thereby continuously producing the composition of the present invention. More suitable for

In the present invention, (A) and (B) are preferably in a finely divided form such as pellets, powders and crumbs.

As a specific example, the composition of the present invention can be produced via the following processing steps. That is, (A) and (B) are mixed well and put into a hopper of an extruder. The crosslinking initiator and the crosslinking assistant may be added together with (A) and (B) from the beginning. Alternatively, it may be added in the middle of the extruder. Also, (C) may be added from the middle of the extruder, or may be added separately at the beginning and during the middle. (A) and (B) may be partially added in the middle of the extruder. When heat-melting and kneading in an extruder, (A) and the above-mentioned crosslinking initiator and crosslinking assistant undergo a crosslinking reaction, and (C) is further added and melt-kneaded, whereby the crosslinking reaction and kneading dispersion are sufficiently performed. After doing so, remove the composition from the extruder. Can be pelletized to obtain a pellet of the composition of the invention _c

In the present invention, the degree of crosslinking and the degree of swelling of (A) are defined as follows. The weight of the composition, W _0, is refluxed in 200 ml of orthodichlorobenzene for 20 hours, the solution is filtered through a filter, and the weight of the swelling composition (W ^ is measured. After vacuum drying the composition at 1 oo ° C., the weight (w ₂ ) is measured again, and the degree of crosslinking and the degree of swelling are calculated as follows.

Degree of crosslinking = (W ₂ W ₀ ) X 1 0 0 (%)

Swelling degree = _{W l} Zw ₂

The degree of crosslinking and the degree of swelling are controlled by adjusting the types and amounts of the crosslinking initiator and the crosslinking aid, the reaction temperature, the reaction method, the method of adding the softener, and the like.

For example, an increase in the degree of crosslinking can be achieved by increasing the amount of a crosslinking initiator or a crosslinking aid and performing a reaction at a temperature not lower than the decomposition temperature of the crosslinking initiator and as low as possible for a long time. The increase in the degree of swelling can be achieved by suppressing the reaction rate using a polyfunctional crosslinking auxiliary having a small number of functional groups or a polymerizable vinyl monomer. In addition, reduce the amount of crosslinking initiator, use trifunctional rather than trifunctional crosslinking aids, use vinyl monomers such as methacrylate monomers or aromatic vinyl monomers, The crosslinking agent can also increase the degree of swelling by the reaction described above. However, when a crosslinking initiator and a crosslinking assistant are added excessively, the degree of crosslinking increases, but the degree of swelling decreases, and the requirements of the present invention are not satisfied. When an excessively active crosslinking initiator and crosslinking aid are used, or when high-temperature reaction conditions are used, the degree of crosslinking also increases, but the degree of swelling decreases, and the requirements of the present invention are satisfied. do not do.

On the other hand, if a crosslinking initiator and a crosslinking assistant are added to (A) while a small amount of (C) a softening agent is absorbed in advance in (A), the crosslinking reaction proceeds gently. The degree of crosslinking can be increased while suppressing the decrease. In the present invention, as a specific production method relating to the reaction system to achieve the desired degree of crosslinking and swelling, for example,

Kneading degree ^{Μ = (π 2/2)} (L / D) D 3 (N / Q)

(However, L is the extruder length (mm) in the die direction from the raw material addition section, D is the extruder barrel inner diameter (mm), Q is the discharge rate (kg / h), and N is the screw rotation speed (r pm).

1 0 X 1 0 ° ≤ M ≤ 1 0 0 0 X 1 0 °

It is important that If M is less than 10 × 10 ⁶ , dynamic crosslinking does not proceed and the degree of crosslinking is less than 50%, resulting in low mechanical strength.On the other hand, if M exceeds 1 × 100 × 10 ^D , excessive shear force Therefore, the degree of crosslinking is also less than 50%, and the mechanical strength is reduced.

In the present invention, as a specific method relating to the reaction temperature in order to achieve a desired degree of crosslinking and swelling degree, for example, (D) a one-minute half-life temperature (° C) of a crosslinking initiator as T ₁ , Below formula

Τ ₂ + 1 <Τ ₃ <Τ ₂ + 200

It is preferable to perform the melt-kneading under the melting temperature condition satisfying the following. That is, the melt kneading is performed first at a melting temperature of 2 (° C) and then at a melting temperature T ₃ (° C). In particular, in a melt extruder having a length L in the die direction starting from the raw material addition port, the extruder zone having a length of 0.1 L to 0.5 L from the raw material addition port is melted at a melting temperature T ₂ (° C ), Melt kneading is performed first, and then the extruder zone is set to a melting temperature T ₃ (° C.) to perform melt kneading. Here, in particular, it is preferred that T 1 is a 1 50 to 250 ° C, T丄又of each zone of the melting extruder T ₂ are may uniformly temperature der connexion also, or have a temperature gradient Good.

In the present invention, (C) As a specific important and preferable method for adding a softening agent to achieve a desired degree of crosslinking and swelling, one main feed portion having a different distance from a tip portion is used. When (A), (B) and (C) are melt-kneaded and dynamically cross-linked by using an extruder having Feed to the feed supply section of I can do it. Here, it is important to feed (c) by dividing it into a plurality of feed supply units. By dividing and feeding (C), the melt viscosity at the time of dynamic crosslinking in the former stage of the extruder is reduced, the reaction rate is suppressed, and the degree of swelling is increased.

The degree of swelling can be controlled by the number of divisions or the amount of addition of (C).

Various molded articles can be produced from the obtained olefin rubber composition by an arbitrary molding method. As the molding method, injection molding, extrusion molding, compression molding, blow molding, calender molding, foam molding and the like are preferably used.

Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. In these examples and comparative examples, the test methods used for evaluating various physical properties are as follows.

(1) Degree of crosslinking and degree of swelling

The weight W _{0 of the} composition is refluxed in o-dichlorobenzene 20 Om 1 for 20 hours, the solution is filtered through a filter, and the weight of the swelling composition (W ^ is measured. After vacuum drying at C, the weight (W ₂ ) is measured again, and the degree of crosslinking and the degree of swelling are calculated as follows.

Degree of crosslinking = (W ₂ / W ₀ ) X 100 (%)

Swelling degree = _Wl Zw ₂

(2) Surface hardness

Four 2 mm-thick sheets were stacked, and evaluated according to ASTM D2240 using an A type at 23 ° C.

(3) Tensile breaking strength [kgf Zcm ² ]

It was evaluated at 23 ° C according to JIS K6251.

(4) Tensile elongation at break [%]

It was evaluated at 23 ° C according to JIS K6251.

(5) Light stability

An ATLAS CI35W Weatherometer manufactured by ATLAS Electric Devices Co., USA was used as a light stability tester, and the evaluation was performed by a method based on JISK7102. The irradiation conditions were as follows: 55 ° C internal temperature, 55% humidity, no rain, xenon light (wavelength 340 nm, energy 0.30 W / m ² ) for 300 hours. After irradiation, The appearance of the sample was visually evaluated according to the following criteria.

◎ Very good.

〇 Good.

△ Good, but slightly rough.

X Overall grainy. No gloss.

(6) Thermal stability

The sheet is heated in a gear oven at 120 ° C for 100 hours, and the ratio of the value after the heating test to the initial value of the tensile breaking strength in accordance with JISK 6251 is the retention rate of the tensile breaking strength (%). Was defined as a measure of thermal stability.

(7) Bleed resistance

After left for 100 hours in an atmosphere of 120 ° C, the surface of the molded product was observed and evaluated.

A: Very good.

〇: Good.

Δ: A little oily substance adhered to the surface of the molded product.

X: A large amount of oily substance adheres to the surface of the molded product, and the stickiness is remarkable.

(8) Appearance

The surface of the molded product was observed and evaluated visually.

A: Very good.

〇: Good.

Δ: The oily substance is slightly attached to the surface of the molded product.

X: A large amount of oily substance adheres to the surface of the molded product, and the stickiness is remarkable. The following were used as each component used in Examples and Comparative Examples.

(i) Ethylene-α-olefin copolymer

1) Ethylene octene-1 copolymer (ΕΟΜ-1)

It was produced by a method using a meta-mouth catalyst described in JP-A-3-163088. The composition ratio of ethylene octene-11 in the copolymer is 72-28 by weight (referred to as ΕΟΜ-1).

2) Ethylene / Otate-1 copolymer (ΕΟΜ— 2) —②

It was prepared by a method using an ordinary Ziegler catalyst. Copolymer ethylene The composition ratio of Nocten-1 is 72/28 by weight (referred to as EOM-2).

3) Ethylene / propylene dicyclopentadiene copolymer (EPDM-1) Produced by a method using a meta-mouth catalyst described in JP-A-3-163030. The composition ratio of ethylene Z propylene Z dicycloventagen in the copolymer is 72Z 24/4 by weight (referred to as EPDM-1).

4) Ethylene Z propylene Z dicyclopentadiene copolymer (EPDM-2) It was produced by a method using a usual Ziegler catalyst. Copolymer ethylene

The composition ratio of Z propylene Z dicyclopentadiene is 72/24/4 by weight (referred to as EPDM-2).

(ii) Olefin resin

Polypropylene

Nippon Polychem Co., Ltd., isotactic polypropylene (referred to as PP)

(iii) Paraffin oil

Diana Process Oil, manufactured by Idemitsu Kosan Co., Ltd. PW-380 (referred to as MO)

(iv) Crosslinking initiator

1) Nippon Yushi Co., Ltd., 2,5-dimethyl-2,5-bis (t-butylbaroxy) hexane (trade name: Perhexa 25B) (referred to as POX-1)

2) Nippon Yushi Co., Ltd., 2,5-dimethyl-2,5-bis (t-butyl baroxy) hexine-1 3 (trade name perhexin 25 B) (referred to as POX-2)

(V) Crosslinking aid

1) Wako Pure Chemical Industries, Ltd., divinylbenzene (referred to as DVB)

2) Triallyl isocyanurate (TAIC) manufactured by Nippon Kasei Co., Ltd.

3) Ouchi Shinko Chemical Co., Ltd., N, N, -m phenylene bismaleide (PMI)

4) Methyl methacrylate (MMA) manufactured by Asahi Kasei Kogyo Co., Ltd.

5) Styrene (referred to as ST) manufactured by Asahi Kasei Kogyo Co., Ltd.

Examples 1 to 8 and Comparative Examples 1 to 4 As an extruder, a twin screw extruder (4 Omm0,

D = 47) was used. The screw used was a two-section screw with a kneading section before and after the injection port.

(A) Component ZP PZPOX—1 ZDVB / MO = 65 / 35Z0.5 / 1.0 / 45 (parts by weight) A mixture other than M〇 is first introduced into a twin-screw extruder, followed by M〇 was injected by a pump from the injection port in the center of the extruder, and melt extrusion was performed under the following conditions. The melt extrusion conditions were as follows: melt extrusion temperature 220 ⁼ C, discharge rate Q = 12 kgZh, extruder barrel inner diameter D = 25 mm, L / D = 47 when extruder length is L (mm), and screw rotation The number N = 280 rpm was set:

On the basis of the above conditions, the degree of crosslinking and the degree of swelling were controlled by adjusting the type, amount of addition, reaction temperature and reaction system of the crosslinking initiator and the crosslinking aid. Specifically, in order to increase the degree of cross-linking, the amount of the cross-linking initiator or cross-linking aid was increased, and the reaction was carried out for a long time at a temperature not lower than the decomposition temperature of the radical initiator and as low as possible. On the other hand, it is important to suppress the reaction rate to increase the degree of swelling. For example, reduction in the amount of crosslinking initiator and low-temperature reaction were performed. By incorporating P〇X and DVB into (A) while absorbing a small amount of MO in advance in (A), the degree of cross-linking was increased while suppressing the decrease in swelling.

From the rubber composition thus obtained, a sheet having a thickness of 2 mm was formed by compression molding at 200 ° C, and each mechanical property was evaluated.

The results are shown in Table 1.

table 1

Comparative example Example Comparative example Comparative example Example

1 1 2 3 2

Rubber type E OM- 1

M

Degree of crosslinking% 4 5 5 0 7 5 7 4 i 4

Special

Swelling degree 1 5 1 6 3 5 1

丄

Hardness 6 8 6 9 6 9 7 1 (U

Object Tensile breaking strength kgf / cm ² 5 0 7 1 7 0 8 0 i

丄 5

Sex

Tensile elongation at break% 1 2 0 3 9 0 3 0 0 3 4 0 ο Ζ Π U Example Example Example Example Comparative example Example Amano JUL 17 'J ^ r JlE 17 Li 3 4 5 4 6 7 8 Rubber Species E OM- 1 EOM- 2 EFDM- 1 EPDM- 2

Degree of crosslinking% 7 3 7 4 7 5 7 6 7 5 7 6 7 5

Swelling degree 2 0 3 0 4 0 4 2 1 4 1 5 1 6 Hardness 7 0 7 1 6 9 6 9 7 0 7 1 7 0

Tensile breaking strength kgf / cm ² 1 2 1 8 5 8 0 4 5 8 1 6 3 6 0

Tensile elongation at break% 4 9 0 4 4 0 4 0 0 2 8 0 4 0 0 3 8 0 3 5 0

According to Table 1, it can be seen that a composition satisfying the requirements of the degree of crosslinking and swelling of the present application is excellent in mechanical strength such as tensile breaking strength and tensile breaking elongation. Ethylene α-olefin copolymer consisting of produced ethylene and phosphorein having 3 to 20 carbon atoms, especially a copolymer of ethylene and otaten-1 produced using a meta-acene catalyst. It can be seen that it provides excellent mechanical strength.

Examples 9 to 11 and Comparative Examples 5 to 7

In Example 2, the same experiment was repeated, except that the kneading degree に従って was changed according to the following definition. The results are shown in Table 2.

^{Μ = {κ 2/2)} (L / Ό) D 3 (N / Q)

(Where, L is die direction with starting from the raw material addition unit extrusion Captain (mm), D is the extruder barrel inner diameter (m _m), Q is the discharge amount (k gZh), and N is a screw revolution speed (r pm ), Where D = 25 mm and LZD = 47.)

Table 2

Example Comparative example

9 1 0 1 1 5 6 7 Manufacturing conditions

N 300 300 2750 300 300 2800

Q 10 100 10 120 300 10

M (X10 ⁶ ) 109 11 997 9 4 1015 Degree of crosslinking (%) 7 5 6 9 5 9 5 2 4 3 4 8 Degree of swelling 1 6 2 0 8 4 2 3 8 3 Hardness 7 1 6 8 7 3 6 3 5 0 7 8 Tensile breaking strength

1 2 8 1 0 5 1 3 0 5 6 4 8 6 1 (kgf / cm ² )

Tensile elongation at break (%) 5 1 0 4 0 0 5 1 5 2 1 0 3 2 0 1 2 0 According to Table 2, by producing a range of ^{1 0 X 1 0 6 ≤M≤ 1000} X 1 0 6 kneading degree M, it can be seen that the degree of crosslinking and swelling satisfying the requirements in the present invention are achieved .

Examples 12 to 23 and Comparative Examples 8 to 9

In Example 2, the following definitions, at a melt temperature T ₂ (° C), performed first melt mixing kneading, followed except that were melt-kneaded at a melting temperature T ₃ (° C), Ri Repetitive Similar experiments I returned. Tables 3 and 4 show the results. Table 3

For P0X-1 1 = 180 80 <T ₂ <220 Τ ₂ + 1 <Τ ₃ <Τ ₂ +200

According to Ρ0Χ-2 when _{Τ! = 194 94 <Τ 2} <234 Τ 2 + 1 <Τ 3 rather T ₂ +200 Table 3, by carrying out the preparation under the following melting temperature, satisfying the requirements of the present invention It can be seen that a high degree of crosslinking and swelling is achieved.

Τ _χ : 1 minute half-life temperature of (C) (° c)

T! -1 00 <Τ 2 <! + 40

Τ + 1 <Τ <Τ 9 + 200 Table 4

According to Table 4, as a crosslinking aid, trifunctional TAIC has a higher crosslink density than bifunctional DVB or PMI, so that the degree of swelling decreases and the retention of the softener increases. It can be seen that the bleed resistance is improved.

It was also found that the trifunctional TAIC slightly reduced the appearance, but the combined use of the monofunctional monomer MMA improved the balance between appearance and bleed resistance.

Examples 24 to 26

The same experiment as in Example 2 was repeated except that 45 parts by weight of MO was divided according to the division ratio shown in Table 5. Table 5 shows the results. Table 5

According to Table 5, split feed of MO reduces the melt viscosity during dynamic bridging in the former stage of the extruder, reduces the reaction rate, and increases the degree of swelling while maintaining the degree of crosslinking. I understand.

Industrial applicability

Since the olefin rubber composition of the present invention has excellent mechanical strength, heat resistance, and oil resistance, it is used for automobile parts, automobile interior materials, airbag covers, mechanical parts, electric parts, cables, and hoses. , Belts, toys, miscellaneous goods, daily necessities, building materials, sheets, films, and other applications, and plays a major role in industry.

Claims

The scope of the claims

1. (A) 1-99 parts by weight of an ethylene-ct-olefin copolymer containing an ethylene unit and an α-olefin unit having 3 to 20 carbon atoms and (B) 1 to 99 parts by weight of an olefin resin (( A crosslinked composition containing (A) and (B) in a total amount of 100 parts by weight), wherein the degree of crosslinking of (A) is 50% or more, and the swelling of (A) An olefin rubber composition having a degree of 5 to 40.

2. The olefin-based system according to claim 1, wherein (A) is an ethylene-ct-olefin copolymer containing an ethylene unit and an α-olefin unit having 3 to 20 carbon atoms, which is produced using a meta-mouth catalyst. Rubber composition.

3. The olefin rubber composition according to claim 1 or 2, having a swelling degree of 10 to 40.

4. The olefin rubber composition according to any one of claims 1 to 3, further comprising 5 to 500 parts by weight of a softener (C).

5. The olefin rubber composition according to any one of claims 1 to 4, which is cross-linked by (D) a cross-linking initiator or (D) and (E) a cross-linking aid.

6. The olefin rubber composition according to claim 5, wherein the (E) crosslinking aid comprises a polyfunctional monomer and a monofunctional monomer.