JP2002069252A - Olefin elastomer composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an olefin elastomer composition being excellent in a melt tension, a melt elongation, mechanical strength, an appearance, a soft feeling (touch), and a scratching property. SOLUTION: The olefin elastomer composition comprises (A) 1-99 pts.wt. of an ethylene-α-olefin copolymer comprising ethylene and a 3-20C α-olefin and 1-99 pts.wt. of an olefin resin [the sum of the (A) and the (B) is 100 pts.wt.], the composition being partially or perfectly crosslinked, and X of the (A) and Y thereof being defined by the formulas: X=(W2/W0)×100(%), Y=(W2/W1), respectively, [in the formulas, the weight of a swelling crosslinked material of the (A) obtained by extracting the (A) having the weight, W0 with hot xylene makes W1, and the weight after drying the swelling crosslinked material of the (A) makes W2], and the X being 1-49% and the Y being 0.00001-0.5.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to an olefin rubber composition. More specifically, the present invention relates to an olefin rubber composition excellent in melt tension, melt elongation, mechanical strength, appearance, flexibility (touch) and scratch resistance.

[0002]

2. Description of the Related Art A rubber-like polymer such as a radically crosslinkable olefinic elastomer and an olefinic resin having no radically crosslinkable property such as PP are crosslinked while being melt-kneaded in an extruder in the presence of a radical initiator. Thermoplastic elastomer compositions by dynamic crosslinking are already known technologies and are widely used in applications such as automobile parts. As such an olefin-based elastomer, an ethylene-propylene-diene rubber (EPDM) or an olefin-based elastomer produced by using a metallocene catalyst (Japanese Patent Laid-Open No.
JP-A-120127, JP-A-9-137001), and a rheology-modified thermoplastic elastomer composition (WO98 / 32795) in which an ethylene-α-olefin copolymer and a high melting point polymer are crosslinked with a peroxide. . However, the composition has a tensile force upon melting,
Elongation, appearance, and mechanical strength are not always sufficient, and there is a demand for a rubber composition that can withstand practical use.

[0003]

SUMMARY OF THE INVENTION In view of such circumstances, the present invention has no problems as described above, namely, melt tension, melt elongation, mechanical strength, appearance, flexibility (touch) and scratch resistance. An object of the present invention is to provide a rubber composition having excellent properties.

[0004]

Means for Solving the Problems As a result of intensive studies of the rubber composition having excellent tensile strength at the time of melting, the present inventors have surprisingly found that a rubber composition having a specific crosslinked structure has a high melt tension, melt elongation, and mechanical strength. Flexibility (tactile sensation) as well as mechanical strength and appearance
The inventors have also found that the scratch resistance can be dramatically improved, and the present invention has been completed. That is, the present invention relates to (A) an ethylene / α-olefin having 3 to 20 carbon atoms.
Partially or completely crosslinked composition comprising 1 to 99 parts by weight of an α-olefin copolymer and 1 to 99 parts by weight of (B) an olefin resin [100 parts by weight in total of (A) and (B)] Olefin rubber composition characterized in that X of the (A) defined below is 1 to 49% and Y is 0.00001 to 0.5 as defined below. is there. _{X = (W 2 / W 0} ) × 100 (%) Y = W 2 / W 1 ( however, the weight W ₀ (A) is obtained by extracting hot xylene weight of the swollen crosslinked product of (A) and W _1, the weight after drying of swollen crosslinked product of the above (a) and W _2.)

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 (B) an olefin-based resin. Here, X in (A) is an index of the degree of crosslinking,
It is important that X is between 1 and 49%, preferably 1
It is 0-49%, more preferably 10-40%, and most preferably 10-30%. If X is less than 1%,
The melt viscosity is low, the melt tension is not sufficient, and not only the drawability in extrusion processing is poor, but also the mechanical strength and scratch resistance are reduced. On the other hand, if the degree of crosslinking exceeds 50%, not only does the melt tension and melt elongation decrease, but also the appearance and flexibility deteriorate. Y in (A) is an index of the crosslink density,
It is important that Y is between 0.00001 and 0.5,
It is preferably 0.00001 to 0.4, more preferably 0.00001 to 0.3, and most preferably 0.00001 to 0.3.
0001 to 0.2. The present inventors have found that only when Y is within the above range, excellent productivity, appearance, flexibility, and mechanical strength of extrusion processing are exhibited, and the present invention has been completed.

Hereinafter, each component of the present invention will be described in detail. In the present invention, (A) the ethylene / α-olefin copolymer is, for example, ethylene and having 3 to 20 carbon atoms.
Is an ethylene / α-olefin copolymer containing α-olefin. Examples of the α-olefin having 3 to 20 carbon atoms include propylene, butene-1, pentene-1, hexene-1, 4-methylpentene-1, heptene-1, octene-1, nonene-1, decene-1, Undecene-1, dodecene-1 and the like. Among them, hexene-1, 4-methylpentene-1 and octene-1 are preferred, and octene-1 is particularly preferred. Octene-1 is excellent in softening effect even in a small amount, and the obtained copolymer is excellent in mechanical strength. The ethylene / α-olefin copolymer suitably used in the present invention is preferably produced using a known metallocene catalyst or Ziegler catalyst. Generally, the metallocene catalyst is titanium,
It is composed of a cyclopentadienyl derivative of a group IV metal such as zirconium and a co-catalyst, and is not only highly active as a polymerization catalyst but also has a narrower molecular weight distribution of the obtained polymer as compared with a Ziegler-based catalyst, The distribution of the α-olefin having 3 to 20 carbon atoms as a comonomer therein is uniform.

[0007] Ethylene-α preferably used in the present invention
The olefin copolymer preferably has an α-olefin copolymerization ratio of 1 to 50% by weight, more preferably 10 to 40% by weight, and most preferably 20 to 30% by weight.
It is. If the copolymerization ratio of the α-olefin exceeds 50% by weight, the hardness, tensile strength, etc. of the composition are greatly reduced, while if it is less than 1% by weight, the hardness of the composition is high, and the mechanical strength tends to decrease. . The density of (A) is 0.8 to 0.9 g.
/ Cm ³ is preferably in the range. By using a polyolefin-based rubber having a density in this range, a thermoplastic rubber composition having excellent flexibility and low hardness can be obtained. The ethylene / α-olefin copolymer (A) used in the present invention preferably has a long-chain branch. The presence of the long-chain branch enables the density to be lower than the ratio (% by weight) of the copolymerized α-olefin without lowering the mechanical strength. Hardness and high strength rubber can be obtained. The olefin rubber having a long chain branch is described in US Pat. No. 5,278,272 and the like.

The ethylene / α-olefin copolymer (A) preferably has a DSC melting point peak at room temperature or higher. When it has a melting point peak, the form is stable in the temperature range below the melting point, the handleability is excellent, and the stickiness is small. The melt index of (A) used in the present invention is 0.01 to 100 g / 10 min (19
(0 ° C., 2.16 kg load) is preferably used, and more preferably 0.2 to 10 g / 10 min.
In the present invention, (A) contains ethylene and α-olefin units as essential components, and may contain other vinyl monomers as necessary. It is only necessary that (A) has ethylene and α-olefin units. For example, polystyrene-based, polyolefin-based, polyester-based, polyurethane-based, 1,2-polybutadiene-based, and polyvinyl chloride-based thermoplastic elastomers can be used. It also includes copolymers containing hydrogen and finally ethylene and α-olefin units in the structure.

Another preferred hydrogenated copolymer (A) is a polymer having double bonds in the main chain and side chain and / or a double bond of an unsaturated rubber comprising a random copolymer. 50% or more is hydrogenated rubber. The total double bond in the hydrogenated rubber is preferably at least 50%, more preferably at least 90%, particularly preferably at least 95%, and the remaining double bond of the main chain is at most 5%. The residual double bond in the side chain is preferably 5% or less. Specific examples of such rubbers include polybutadiene, poly (styrene-butadiene),
Rubbery polymers obtained by partially or completely hydrogenating diene rubbers such as poly (acrylonitrile-butadiene), polyisoprene, and polychloroprene;
Particularly, a hydrogenated butadiene rubber or a hydrogenated isoprene rubber is preferable.

Such a hydrogenated rubber can be obtained by partially hydrogenating the above rubber by a known hydrogenation method. For example, FLRamp, etal, J.Amer.Chem.Soc., 83,46
72 (1961) .Method of hydrogenation using triisobutylborane catalyst described in Hung Yu Chen, J. Polym. Sci. Polym. Lette
r Ed., 15,271 (1977) Hydrogenation using toluenesulfonyl hydrazide, or hydrogenation using an organic cobalt-organoaluminum catalyst or an organic nickel-organoaluminum catalyst described in JP-B-42-8704. And the like. Here, a particularly preferred method of hydrogenation is disclosed in JP-A-59-133203, JP-A-60-220147, which uses a catalyst capable of hydrogenation under mild conditions of low temperature and low pressure, or in an inert organic solvent. JP-A-62-207303 in which hydrogen is brought into contact with a bis (cyclopentadienyl) titanium compound in the presence of a catalyst comprising a hydrocarbon compound having a sodium, potassium, rubidium or cesium atom. This is the method shown in FIG. The Mooney viscosity (ML) of the hydrogenated rubber measured at 100 ° C. may be 20 to 90, and the 5% by weight styrene solution viscosity (5% SV) at 25 ° C. may be in the range of 20 to 300 centipoise (cps). preferable. A particularly preferred range is 25 to 150 cps. The endothermic peak calorie, which is an index of the crystallinity of the hydrogenated rubber, is controlled by adding a polar compound such as tetrahydrofuran or controlling the polymerization temperature. The decrease in the endothermic peak calorific value increases the amount of the polar compound or lowers the polymerization temperature,
Achieved by increasing the 1,2-vinyl bond.

(A) used in the present invention may be a mixture of a plurality of types. In such a case, it is possible to further improve the workability. In the present invention, (B) the olefin resin is polyethylene, homoisotactic polypropylene, propylene and ethylene, butene-1, pentene-1, hexene-.
And isotactic copolymer resins (including block and random) with other α-olefins such as 1. In the present invention, among (B), (B-1) a propylene random copolymer resin such as a random copolymer resin of ethylene and propylene, and (B-2) a propylene block copolymer resin or a homopolypropylene resin. Is most preferred. The appearance and mechanical strength are further improved by combining such two types of olefin resins, such as a crosslinked olefin resin and a decomposed olefin resin.

As (B-1), for example, a random copolymer resin of ethylene and propylene can be mentioned. When an ethylene component is present in the polymer main chain, it becomes a crosslinking point of a crosslinking reaction, and This shows the characteristics of the base resin. (B-2) is mainly composed of α-olefin,
It is preferable that no ethylene unit is contained in the polymer main chain. However, when an ethylene-α-olefin copolymer is present as a dispersed phase, such as a propylene-based block copolymer resin, it exhibits the properties of a decomposable olefin-based resin. (B)
May be a combination of a plurality of (B-1) and (B-2) components. The melt index of the olefin resin suitably used in the present invention is 0.1 to 100 g / 1.
Those in the range of 0 minutes (230 ° C., 2.16 kg load) are preferably used. If it exceeds 100 g / 10 minutes, the heat resistance and mechanical strength of the thermoplastic elastomer composition will be insufficient, and if it is less than 0.1 g / 10 minutes, the fluidity will be poor and the moldability will be reduced, which is not desirable. .

In 100 parts by weight of the composition comprising (A) and (B), (B) is used in a composition ratio of 1 to 99 parts by weight. Preferably 5 to 90 parts by weight, more preferably 2
0 to 80 parts by weight. If the amount is less than 1 part by weight, the fluidity and processability of the composition are reduced, and if it exceeds 99 parts by weight, the flexibility of the composition is insufficient, which is not desirable. The partially or completely crosslinked rubber composition of the present invention is preferably crosslinked with (C) a crosslinking agent. (C) contains (C-1) a crosslinking initiator as an essential component, and optionally contains (C-2) a polyfunctional monomer and (C-3) a monofunctional monomer. The above (C)
Is used in an amount of 0.01 to 10 parts by weight, preferably 0.05 to 3 parts by weight, based on 100 parts by weight of the composition comprising (A) and (B). If the amount is less than 0.01 part by weight, the crosslinking is insufficient, and if it exceeds 10 parts by weight, the appearance and mechanical strength of the composition decrease.

Here, the (C-1) crosslinking initiator includes a radical initiator such as an organic peroxide and an organic azo compound, and specific examples thereof include 1,1-bis (t-butyl). Peroxy) -3,3,5-trimethylcyclohexane,
1,1-bis (t-hexylperoxy) -3,3,5
-Trimethylcyclohexane, 1,1-bis (t-hexylperoxy) cyclohexane, 1,1-bis (t-
Butylperoxy) cyclododecane, 1,1-bis (t
-Butylperoxy) cyclohexane, 2,2-bis (t-butylperoxy) octane, n-butyl-4,
Peroxy ketals such as 4-bis (t-butylperoxy) butane and n-butyl-4,4-bis (t-butylperoxy) valerate; di-t-butyl peroxide, dicumyl peroxide, t -Butylcumyl peroxide, α, α′-bis (t-butylperoxy-m
-Isopropyl) benzene, α, α'-bis (t-butylperoxy) diisopropylbenzene, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane and 2,5-dimethyl-2,5 Dialkyl peroxides such as -bis (t-butylperoxy) hexine-3; acetyl peroxide, isobutyryl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, 3,5,5-trimethylhexa Diacyl peroxides such as noyl peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide and m-trioyl peroxide; t-butylperoxyacetate, t
-Butylperoxyisobutyrate, t-butylperoxy-2-ethylhexanoate, t-butylperoxylaurate, t-butylperoxybenzoate,
Di-t-butylperoxyisophthalate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, t-butylperoxymaleic acid, t-butylperoxyisopropyl carbonate, and cumylperoxyoctate Peroxyesters; and
Hydrogen such as t-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide and 1,1,3,3-tetramethylbutyl peroxide Peroxides can be mentioned.

Among these compounds, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, di-t-butyl peroxide, dicumyl peroxide, 2,5-dimethyl -2,5-bis (t-butylperoxy) hexane and 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3 are preferred. The component (C-1) is preferably used in an amount of 1 to 80% by weight, more preferably 10 to 50% by weight in the component (C). If the amount is less than 1% by weight, crosslinking is insufficient, and if it exceeds 80% by weight, the mechanical strength decreases.

In the present invention, one of the (C-2) polyfunctional monomers of the (C) crosslinking agent is preferably a radically polymerizable functional group as a functional group, and particularly preferably a vinyl group. The number of the functional groups is two or more, but it is effective especially in the case of having three or more functional groups in combination with (C-3). Specific examples include divinylbenzene, triallyl isocyanurate, triallyl cyanurate, diacetone diacrylamide, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate,
Trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, diethylene glycol dimethacrylate, diisopropenylbenzene, P-quinone dioxime, P,
P'-dibenzoylquinone dioxime, phenylmaleimide, allyl methacrylate, N, N'-m-phenylenebismaleimide, diallyl phthalate, tetraallyloxyethane, 1,2-polybutadiene and the like are preferably used. Particularly, triallyl isocyanurate is preferable. These polyfunctional monomers may be used in combination of two or more. (C-2) is preferably used in an amount of 1 to 80% by weight, more preferably 10 to 50% by weight in the component (C). If the amount is less than 1% by weight, crosslinking is insufficient, and if it exceeds 80% by weight, the mechanical strength decreases.

The above (C-3) used in the present invention
Is a vinyl monomer added to control the crosslinking reaction rate, preferably a radical polymerizable vinyl monomer, and an aromatic vinyl monomer, acrylonitrile, unsaturated nitrile monomer such as methacrylonitrile, etc. Body, acrylic acid ester monomer, methacrylic acid ester monomer, acrylic acid monomer, methacrylic acid monomer, maleic anhydride monomer,
And N-substituted maleimide monomers. (C-3) is preferably used in an amount of 1 to 80% by weight, more preferably 10 to 50% by weight in the component (C). If the amount is less than 1% by weight, crosslinking is insufficient, and 80% by weight
If it exceeds, the mechanical strength decreases. The (D) is preferably a paraffinic or naphthenic process oil. These are used for adjusting the hardness and flexibility of the composition.
5 to 5 parts by weight per 100 parts by weight of the composition comprising
00 parts by weight, preferably 10 to 150 parts by weight. 5
If the amount is less than 10 parts by weight, flexibility and processability are insufficient, and if it exceeds 500 parts by weight, oil bleeding becomes remarkable, which is not desirable.

The composition of the present invention can be prepared by combining (A) a specific ethylene / α-olefin copolymer, (B) an olefin resin, and (C) a softener in a specific composition ratio. The balance between the target strength, flexibility and workability is improved, and it can be preferably used. Further, the composition of the present invention, other resins to the extent that the characteristics are not impaired,
An elastomer may be added. Further, the composition of the present invention can contain an inorganic filler and a plasticizer to such an extent that its characteristics are not impaired. Examples of the inorganic filler used here include calcium carbonate, magnesium carbonate, silica, carbon black, glass fiber, titanium oxide, clay, mica, talc, magnesium hydroxide, and aluminum hydroxide. Examples of the plasticizer include phthalic acid esters such as polyethylene glycol and dioctyl phthalate (DOP). In addition, other additives, for example, organic and inorganic pigments, heat stabilizers, antioxidants, ultraviolet absorbers, light stabilizers,
Flame retardants, silicone oils, antiblocking agents, foaming agents, antistatic agents, antibacterial agents and the like are also suitably used.

For the production of the composition of the present invention, general methods such as a Banbury mixer, a kneader, a single-screw extruder, and a twin-screw extruder used in the production of ordinary resin compositions and rubber compositions are employed. It is possible to In particular, a twin-screw extruder is preferably used to achieve dynamic crosslinking efficiently. The twin-screw extruder is used to uniformly and finely disperse an olefin-based elastomer and a propylene-based resin, and to add another component to cause a crosslinking reaction, thereby continuously producing the composition of the present invention. , More suitable. In the present invention, the forms (A) and (B) are preferably finely divided forms 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 radical initiator and the crosslinking assistant may be added together with (A) and (B) from the beginning, or may be added in the middle of the extruder.
Further, (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 heated and melted and kneaded in an extruder, a cross-linking reaction is performed on (A) and (B) by using the above (C), and a cross-linking reaction is performed by further adding (D) and melt-kneading. After sufficient kneading and dispersion, take out from the extruder. Pelletized to obtain pellets of the composition of the present invention.

In the present invention, X and Y in (A) are defined as follows. After measuring the weight W ₀ of (A) in the olefin rubber composition in advance, the olefin rubber composition is refluxed in 200 ml of xylene for 20 hours, and the solution is filtered with a filter to obtain a swollen crosslinked product of (A). (At this time, even though the olefin resin (B) is crosslinked, its degree of crosslinking is small, so that it is dissolved in hot xylene and removed by filtration.) The weight (W ₁ ) of this swollen crosslinked product is measured. Next, the swelled crosslinked product (A) is vacuum-dried at 100 ° C., and the weight (W ₂ ) is measured again. Thus, X and Y are calculated as follows. X = (W ₂ / W ₀ ) × 100 (%) Y = W ₂ / W ₁ Control of X and Y is carried out by the type of radical initiator and crosslinking assistant, the amount added, the reaction temperature and the reaction system. In order to increase X, the amount of the radical initiator or the crosslinking assistant is increased, and the temperature is as low as possible above the decomposition temperature of the radical initiator.
This is achieved by performing the reaction for a long time. On the other hand, in order to decrease Y, by using a polyfunctional crosslinking auxiliary having a small number of functional groups or a radical polymerizable vinyl monomer,
The reaction rate can be suppressed. For example, reduction of the amount of radical initiator, use of a bifunctional rather than trifunctional cross-linking auxiliary agent, use of a vinyl monomer such as a methacrylate monomer or an aromatic vinyl monomer, and low-temperature reaction are performed. be able to. Excessive addition of a radical initiator and a crosslinking assistant increases X and Y, and does not satisfy the requirements of the present application. Alternatively, excessively active radical initiators, crosslinking aids, or high temperature reaction conditions also increase X and Y, and do not satisfy the requirements of the present application. By adding a small amount of (D) in advance to (A) and adding a radical initiator and a crosslinking assistant to (A), the crosslinking reaction proceeds gently, so that an increase in Y is suppressed. , X can be increased.

As a specific production method for achieving X and Y of the present invention, for example, a method satisfying the following kneading degree is preferable. ^{M = (π 2/2)} (L / D) D 3 (N / Q) 10 × 10 6 ≦ M ≦ 1000 × 10 6 where, L: die direction of extrusion PIC material added section as a base point (mm), D: extruder barrel inner diameter (mm), Q: discharge amount (kg / h), N: screw rotation speed (rpm) kneading degree ^{M = (π 2/2)} (L / D) D 3 (N / Q) Is 1
It is preferable that 0 × 10 ⁶ ≦ M ≦ 1000 × 10 ⁶ . As another specific production method for achieving X and Y of the present invention, for example, it is preferable to satisfy the melting temperature of the following relational expression. That is, first, melt-kneading is performed at a melting temperature T ₂ (° C.), and then melt-kneading is performed at a melting temperature T ₃ (° C.). 0.1 L to 0.1 L from the addition port
The extruder zone having a length of 5 L is first melt-kneaded at a melting temperature T ₂ (° C.), and then the subsequent extruder zone is melt-kneaded at a melting temperature T ₃ (° C.).

Here, it is particularly preferable that T ₁ is 150 to 250 ° C., and T ₁ or T _{2 in} each zone of the melt extruder may be a uniform temperature or have a temperature gradient. Is also good. T ₁ : One minute half-life temperature (° C.) of (C-1) peroxide T ₁ -100 <T ₂ <T ₁ +40 T ₂ +1 <T ₃ <T ₂ +200 To achieve X and Y of the present invention. The method of adding (D) is important, and as a specific manufacturing method, an extruder having one main feed portion having different distances from the tip portion and a plurality of side feedable feeding portions. Using
In melt-kneading (A), (B), (C), and (D) to perform dynamic crosslinking, it is preferable that (D) be divided into a plurality of feed supply portions and fed. Here, it is preferable that (D) is divided into a plurality of feed supply portions and fed. By dividing and feeding (D), the melt viscosity at the time of dynamic crosslinking in the former stage of the extruder decreases, the reaction rate is suppressed, and the degree of swelling increases. Y can be controlled by the number of divisions or the amount of addition in (D). The olefin rubber composition thus obtained can be used to produce various molded articles by any molding method. Injection molding, extrusion molding, compression molding, blow molding, calender molding, foam molding and the like are preferably used.

[0023]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto. In these examples and comparative examples, the test methods used for evaluating various physical properties are as follows. (1) X (%), Y After the weight W ₀ of (A) in the olefin rubber composition was measured in advance, the olefin rubber composition was treated with xylene 200
in ml refluxed for 20 hours, the solution was filtered through a filter to give a crosslinked swelling of (A), the weight (W ₁₎
Is measured. Next, the crosslinked and swollen body of (A) was
After vacuum drying at ℃, the weight (W ₂ ) is measured again. Thus, X and Y are calculated as follows. X = (W ₂ / W ₀ ) × 100 (%) Y = W ₂ / W ₁ (2) Melting test Using a capillary rheometer, Capillograph 1C / 3A manufactured by Toyo Seiki Seisaku-Sho, Ltd., melt tension and melting of the molten polymer. The elongation was measured. The take-up speed was changed under the following conditions, and the melt tension at each take-up speed was measured. At that time, the take-off speed at the time of yarn breakage was used as an index of melt elongation. Land length 10mm, orifice hole diameter 1mm, melting temperature 2
00 ° C., crosshead speed 50 mm / min. (3) Tensile breaking strength [MPa] From a T-die extruded sheet, according to JIS K6251, 2
The evaluation was performed at 3 ° C.

(4) Appearance The appearance of the sheet was evaluated based on the following criteria. ◎ Extremely good ○ Good △ Good, but somewhat rough × Overall rough. No gloss (5) Flexibility (tactile sensation) Flexibility was evaluated from the sheet skin according to the following criteria. ◎ Extremely flexible and good touch feeling ○ Good △ Good but slightly hard feeling × Hard and poor touch feeling as a whole (6) Scratch resistance Rectangular 10 mm long, 1 mm wide tip, heavy A sheet having a thickness of 300 g was dropped on the sheet from a height of 5 cm, and the sheet was visually evaluated for scratches based on the following criteria. ◎ Very good ○ Good △ Good, but noticeable scratches × Notable scratches

(7) Light stability As a light stability tester, ATLAS Electric Devices Co., USA
JIS K71 using ATLAS CI35W Weatherometer made by
02. Irradiation conditions were as follows: internal temperature of tester, 55 ° C., humidity 55%, no rain, xenon light (wavelength 340 nm, energy 0.30 W / m 2) 3
The irradiation was performed for 00 hours. After irradiation, the appearance of the sheet was visually evaluated according to the following criteria. ◎ Extremely good ○ Good △ Good, but somewhat rough × Overall rough. No gloss (8) Appearance The surface of the molded product was observed and evaluated visually. A: Very good. ：: good Δ: slightly oily substance adhered to the surface of the molded product. ×: A large amount of oily substance adhered to the surface of the molded product, and the stickiness was remarkable.

(9) Analysis of conjugated diene rubber 1) Hydrogenation rate (%) It was measured by NMR according to the following procedure. First, polybutadiene rubber before hydrogenation was dissolved in heavy chloroform, and FT-N
Chemical shift 4.7 at MR (270 mega, manufactured by JEOL)
~ 5.2 ppm (assumed to be signal C0) of 1,2-vinyl proton (= CH ₂ ) and chemical shift of 5.2 ~
From the integrated intensity of 5.8 ppm (referred to as signal D0) vinyl proton (= CH ₂ ), it was calculated by the following equation. (V) = [0.5C0 / {0.5C0 + 0.5 (D0-0.5C0)}] × 100 Next, the polybutadiene rubber after partial hydrogenation was dissolved in deuterated chloroform, and similarly by FT-NMR. , A methyl group proton (-CH) by a hydrogenated 1,2 bond having a chemical shift of 0.6 to 1.0 ppm (referred to as signal A1).
3), chemical shift 4.7-5.2 ppm (signal C1
), Non-hydrogenated 1,2-vinyl proton (= CH2), chemical shift 5.2-5.8 pp
Calculated by the following equation from the integrated intensity of m (referred to as signal D1) unhydrogenated vinyl protons (= CH ₂ ).

First, p = 0.5C0 / (0.5C1 + A1 / 3) A11 = pA1, C11 = pC1, D11 = pD1, and the hydrogenation rate of the 1,2-vinyl bond (B) (B) = [( A11 / 3) / ｛A11 / 3 + C11 /
2｝] × 100 Hydrogenation rate of 1,4-double bond (C) (C) = [｛0.5 (D0-0.5C0) -0.5 (D
11-0.5C11)｝ / 0.5 (D0-0.5C
0)] × 100 Hydrogenation rate of whole butadiene part (A) (A) = (V) × (B) / 100 + [100− (V)]
× (C) × 100 2) Microstructure Described below with the symbols defined above. 1,2-vinyl bond before hydrogenation = (V) × (B) / 1
00 (%) 1,4 bonds before hydrogenation = {100- (V)} × (C)
/ 100 (%) 1,2-vinyl bond after hydrogenation = (V) × {100- (B)} / 100 (%) 1,4-bond after hydrogenation = {100- (V)} × ｛ 1
00- (B)｝ / 100 (%)

The following components were used in Examples and Comparative Examples. (A) Ethylene / α-olefin copolymer 1) Copolymer of ethylene and octene-1 (TPE-
1) It was prepared by a method using a metallocene catalyst described in JP-A-3-1630088. The ethylene / octene-1 composition ratio of the copolymer is 72/28 (weight ratio).
(Referred to as TPE-1) 2) Copolymer of ethylene and octene-1 (TPE-
2) It was produced by a method using a usual Ziegler catalyst. The ethylene / octene-1 composition ratio of the copolymer is 72/2.
8 (weight ratio). (Referred to as TPE-2) 3) Ethylene propylene dicyclopentadiene copolymer (TPE-3) Produced by a method using a metallocene catalyst described in JP-A-3-1630088. The composition ratio of ethylene / propylene / dicyclopentadiene in the copolymer is 72/2.
4/4 (weight ratio). (Referred to as TPE-3) 4) Hydrogenated conjugated diene rubber A butadiene / n-hexane solution (butadiene concentration: 20% by weight) was used in a reactor of an autoclave with an internal volume of 10 liters and equipped with a stirrer and having a stirrer. At a rate of hr, an n-butyllithium / n-hexane solution (concentration: 5% by weight) is introduced at 70 mitter / hr,
Continuous polymerization of butadiene was carried out at a polymerization temperature of 110 ° C.
The activated polymer obtained was deactivated with methanol, 8 liters of the polymer solution was transferred to another 10 liter reactor equipped with a stirrer and a jacket and heated at a temperature of 60 ° C. as hydrogenation catalyst. 250 milliliters of 1-cyclopentadienyl) titanium / cyclohexane solution (concentration 1 milliliter / liter) and 50 milliliters of n-butyllithium solution (concentration 5 milliliter / liter)
Milliliter and a mixture obtained by mixing at 0 ° C. under a hydrogen pressure of ² kg / cm ² were added, and a hydrogen partial pressure of 3 kg / cm ² was added.
The reaction was performed for 0 minutes. To the resulting hydrogenated polymer solution was added 0.5 part of 2,6-tert-butylhydroxytoluene as an antioxidant per polymer to remove the solvent. At this time, the butadiene polymer was hydrogenated by changing the hydrogenation reaction conditions (hydrogenation pressure, hydrogenation temperature, time and amount of catalyst) to obtain a hydrogenated polymer. The results are shown in Table 2.

(B) Olefin-based resin Polypropylene (PP) Isotactic homopolypropylene manufactured by Japan Polyolefin Co., Ltd. [MFR (30 g / min) (230 according to ASTM D 1238)
(C, 2.16 kg load)] (referred to as PP) (c) Crosslinking agent 1) Crosslinking initiator (C-1) 2,5-dimethyl-2,5-bis (t-
Butylperoxy) hexane (trade name Perhexa 25)
B) (referred to as POX-1) 2) Polyfunctional monomer (C-2) Divinylbenzene (referred to as DVB) manufactured by Wako Pure Chemical Industries, Ltd. 3) Polyfunctional monomer (C-2) Nippon Kasei Triallyl isocyanurate (TA)
4) Polyfunctional monomer (C-2) N, N'-m phenylenebismaleimide (PMI) manufactured by Ouchi Shinko Chemical Co., Ltd. 5) Monofunctional monomer (C-3) Asahi Kasei Kogyo Co., Ltd., methyl methacrylate (referred to as MMA) 6) Monofunctional monomer (C-3) Asahi Kasei Kogyo Co., Ltd., styrene (referred to as ST)

(D) Paraffin oil Diana Process Oil PW-9 manufactured by Idemitsu Kosan Co., Ltd.
0 (referred to as MO) (Examples 1 to 8, Comparative Examples 1 to 5) As an extruder, a twin-screw extruder (40 mmφ, L
/ D = 47) was used. As the screw, a double screw having a kneading portion before and after the injection port was used. (A) TPE-1 / (B) PP / (C-1) POX-1
/(C-2)DVB/(D)MO=65/35/0.5
/1.0/45 (parts by weight)
The other components were introduced into a twin-screw extruder, and MO was subsequently injected from an injection port at the center of the extruder by a pump.
Melt extrusion was performed at 20 ° C. Based on the above conditions, X and Y were controlled by the type and amount of the radical initiator and the crosslinking assistant, the reaction temperature, and the reaction system. Specifically, in order to increase X, the amount of the radical initiator or the crosslinking assistant was increased, and the reaction was performed at a temperature as low as possible and longer than the decomposition temperature of the radical initiator. On the other hand, it is important to suppress the reaction rate in order to decrease Y. For example, the reaction was performed by a method of reducing the amount of a radical initiator and performing a low-temperature reaction. While absorbing a small amount of MO in advance to TPE-1, POX and DVB are converted to TP.
By mixing with E-1, X increase while suppressing increase of Y
Was increased.

From the rubber composition thus obtained, 2
2mm thick sheet is made by compression molding at 00 ℃,
Each mechanical property was evaluated. The results are shown in Table 1. According to Table 1, the composition satisfying the requirements of X and Y of the present application is:
It turns out that it is excellent in melt tension, melt elongation, tensile breaking strength, appearance, flexibility, and scratch resistance. (Examples 9 to 17) In Example 2, TPE-1 was replaced with a hydrogenated conjugated diene rubber shown in Table 2, TPE-2, TP
The same experiment was repeated except that the test was changed to E-3.
The results are shown in Table 2. According to Tables 1 and 2, as (A), an ethylene / α-olefin copolymer comprising ethylene produced by using a metallocene catalyst and an α-olefin having 3 to 20 carbon atoms and / or two When a hydrogenated rubber in which 50% or more of the total double bonds of the unsaturated rubber composed of a homopolymer and / or a random copolymer having a heavy bond is hydrogenated is used, melt tension, melt elongation, and tensile fracture It can be seen that strength, appearance, flexibility, and scratch resistance are excellent. (Examples 18 to 19) The same experiment as in Example 2 was repeated except that the component (C) was changed to the kind and amount shown in Table 3. Table 3 shows the results.

[0032]

[Table 1]

[0033]

[Table 2]

[0034]

[Table 3]

[0035]

The olefin rubber composition of the present invention has a melt tension, a melt elongation, a mechanical strength, an appearance, and flexibility (touch).
And excellent scratch resistance. The olefin rubber composition of the present invention includes automobile parts, automobile interior materials, airbag covers, mechanical parts, electric parts, cables, hoses, belts, toys, miscellaneous goods, daily necessities, building materials, sheets, films and the like. It can be widely used for various applications, and plays a large role in the industrial world.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4F070 AA06 AA12 AA13 AA15 AA16 AB11 AC32 AC40 AC45 AC48 AC56 AC63 AC65 AC66 AC94 AE02 AE08 GA05 GB08 4J002 AC03Y AC11W AE05Z BB02X BB05W BB12X BB14X BB15X0 EB02 BB15X037 EK036 EK046 EK056 EP027 ES017 ET007 EU027 EU187 FD010 FD02Z FD14Y FD147 FD156

Claims (5)

[Claims] (A) ethylene and α- having 3 to 20 carbon atoms
Partially or completely composed of 1 to 99 parts by weight of an ethylene / α-olefin copolymer composed of an olefin and (B) 1 to 99 parts by weight of an olefin resin [the total amount of (A) and (B) is 100 parts by weight] An olefin rubber composition characterized in that X of the (A) defined below is from 1 to 49% and Y is from 0.00001 to 0.5 as defined below. . _{X = (W 2 / W 0} ) × 100 (%) Y = W 2 / W 1 ( however, the weight W ₀ (A) is obtained by extracting hot xylene weight of the swollen crosslinked product of (A) and W _1, the weight after drying of swollen crosslinked product of the above (a) and W _2.) 2. An ethylene / α-olefin copolymer comprising (A) an ethylene produced by using a metallocene catalyst and an α-olefin having 3 to 20 carbon atoms, or having a double bond in a main chain and a side chain. 50% of the total double bonds of the unsaturated rubber composed of a homopolymer and / or a random copolymer
The olefin rubber composition according to claim 1, wherein the composition is at least one ethylene / α-olefin selected from hydrogenated hydrogenated rubbers. 3. X is 10-49% and Y is 0. 4%.
The olefin rubber composition according to claim 1 or 2, wherein the olefin rubber composition has a molecular weight in the range of 00001 to 0.1. 4. The olefin rubber composition according to claim 1, which is crosslinked by a crosslinking agent (C). 5. The olefin rubber composition according to claim 1, further comprising 5 to 500 parts by weight of a softener (D).