JP2000143820A - Preparation of elastomer composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a preparation process wherein an elastomer composition having superior mechanical properties is obtained. SOLUTION: In a preparation process of a partially or completely dynamically crosslinked elastomer composition comprising (A) a crosslinkable elastomer, (B) a thermoplastic resin and (C) a softener, when melt-kneading (A), (B) and (C) using an extruder having a main feeding part and multiple side-feed supplying parts located at different distances from the end for dynamic crosslinking, (C) is split-fed to multiple side-feed supplying parts.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing an elastomer composition. More specifically, the present invention relates to a method for producing an elastomer composition capable of providing an elastomer composition having excellent mechanical strength.

[0002]

2. Description of the Related Art A thermoplastic elastomer by so-called dynamic crosslinking in which a radically crosslinkable elastomer, a resin having no radical crosslinkability such as PP, and a softener are crosslinked while being melt-kneaded in an extruder in the presence of a radical initiator. The composition is
This is a known technique, and is widely used for applications such as automobile parts.

[0003] As such an elastomer composition, ethylene-propylene-diene rubber (EPDM) or an olefin elastomer produced by a metallocene catalyst (JP-A-8-120127, JP-A-9-137)
001) is known. However, the above composition does not always have sufficient mechanical strength,
There is a need for an elastomer composition that can withstand practical use.

[0004]

SUMMARY OF THE INVENTION In view of such circumstances, the present invention provides a method for producing an elastomer composition which does not have the above-mentioned problems, ie, which can provide an elastomer composition having excellent mechanical properties. The purpose is to do so.

[0005]

Means for Solving the Problems As a result of diligent studies on the improvement of an elastomer composition having excellent mechanical strength, the present inventors have surprisingly found that the mechanical strength is dramatically increased by split feed of a softener. And found that the present invention was completed. That is, the present invention relates to a method for producing a partially or completely dynamically crosslinked elastomer composition comprising (A) a crosslinkable elastomer, (B) a thermoplastic resin, and (C) a softening agent, wherein the distance from the tip is reduced. (A), (B) and (C) are melt-kneaded and dynamically crosslinked by using an extruder having one different main feed part and a plurality of side feedable supply parts. , (C) is divided into a plurality of feed supply sections and fed, and the feed is performed. In particular, it is preferable to further blend (D) a softener holding agent, (E) a crosslinking agent, and (F) a crosslinking assistant.

Hereinafter, the present invention will be described in detail. In the method of the present invention, the method of improving a composition comprising (A) a crosslinkable elastomer, (B) a thermoplastic resin, and (C) a softener is divided into (C) into a plurality of feed supply portions. It is important to feed. By feeding (C) separately, the melt viscosity at the time of dynamic crosslinking in the former stage of the extruder is lowered to improve the productivity, and also the mechanical strength of (B) is suppressed because the thermal degradation is suppressed. Have been found to be improved.

Hereinafter, each component of the present invention will be described in detail. In the present invention, (A) the crosslinkable elastomer comprises:
For example, polystyrene, polyolefin, polyester, polyurethane, 1,2-polybutadiene,
It is a polyvinyl chloride type or the like, and particularly preferably a polyolefin type thermoplastic elastomer.

Among the polyolefin-based thermoplastic elastomers (A), an ethylene / α-olefin copolymer rubber is particularly preferable, and for example, ethylene and α-olefin copolymers having 3 to 3 carbon atoms are preferred.
And ethylene-α-olefin copolymer rubber comprising 20 α-olefins. Α having 3 to 20 carbon atoms
Examples of the olefin 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. Is mentioned. 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,
The obtained copolymer has excellent mechanical strength.

The polyolefin elastomer suitably used in the present invention is preferably produced by a known metallocene catalyst or Ziegler catalyst, and more preferably produced by a metallocene catalyst. Generally, a metallocene-based catalyst is composed of a cyclopentadienyl derivative of a group IV metal such as titanium or zirconium and a co-catalyst, and is not only highly active as a polymerization catalyst, but also has a higher polymer yield than a Ziegler-based catalyst. Has a narrow molecular weight distribution, and the distribution of the comonomer α-olefin having 3 to 20 carbon atoms in the copolymer is uniform. For this reason, the polymer obtained by the metallocene catalyst method has a more uniform crosslink,
Shows excellent rubber elasticity.

The (A) polyolefin elastomer suitably used in the present invention preferably has an α-olefin copolymerization ratio of 1 to 60% by weight, more preferably 10 to 50% by weight, and most preferably. 20 to 45% by weight. When the copolymerization ratio of the α-olefin exceeds 50% by weight, the hardness, tensile strength, etc. of the composition are greatly reduced,
On the other hand, 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.
It is preferably in the range of ³ . By using a polyolefin-based elastomer having a density in this range,
A thermoplastic elastomer composition having excellent flexibility and low hardness can be obtained. The polyolefin-based elastomer 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 elastomer can be obtained. The olefin elastomer having a long chain branch is described in US Pat. No. 5,278,272.

[0012] The polyolefin-based elastomer is
It is desirable to have a melting point peak of DSC above room temperature. 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. Further, the melt index of the polyolefin-based elastomer used in the present invention is 0.01 to 100 g.
/ 10 minutes (190 ° C., 2.16 kg load) are preferably used, and more preferably 0.2 to 20 g /
10 minutes. If the amount exceeds 100 g / 10 minutes, the crosslinking property of the thermoplastic elastomer composition is insufficient, and the crosslinking rate of the thermoplastic elastomer composition is too low.
If it is less than 01 g / 10 minutes, the fluidity is poor and the processability is undesirably reduced.

(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, the thermoplastic resin (B) is not particularly limited as long as it is compatible with or homogeneously dispersed with (A). For example, polystyrene, polyphenylene ether,
Polyolefin type, polyvinyl chloride type, polyamide type,
Polyesters, polyphenylene sulfides, polycarbonates, polymethacrylates and the like can be used alone or in combination of two or more. In particular, an olefin resin such as a propylene resin is preferable as the thermoplastic resin.

Specific examples of the propylene resin most preferably used in the present invention include homo isotactic polypropylene, propylene and other α-olefins such as ethylene, butene-1, pentene-1, and hexene-1. Examples include an isotactic copolymer resin with olefin (including block and random). At least one or more thermoplastic resins (B) selected from these resins are (A) and (B)
Is used at a composition ratio of 1 to 99 parts by weight based on a total of 100 parts by weight. Preferably 5 to 90 parts by weight, more preferably 2
0 to 80 parts by weight, most preferably 20 to 70 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 propylene resin used in the present invention has a melt index of 0.1 to 100 g / 10.
Min (230 ° C., 2.16 kg load) is 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 the present invention, (C) the softener comprises (A)
And flexibility (surface hardness) of the composition comprising
The viscosity at 25 ° C. is preferably 100,000 centistokes or less. The amount of (C) is 1 to 500 parts by weight, preferably 1 to 350 parts by weight, per 100 parts by weight of the composition comprising (A) and (B).
Parts by weight, more preferably 10 to 250 parts by weight, still more preferably 20 to 200 parts by weight, most preferably 30 to 15 parts by weight.
0 parts by weight.

Examples of the softener include paraffinic,
Process oils such as naphthenes, dimethyl phthalate,
Phthalic acid esters such as diethyl phthalate and diisobutyl phthalate; phthalic acid mixed esters such as butyl benzyl phthalate; aliphatic dibasic acid esters such as diisodecyl succinate and dioctyl adipate; and glycos such as diethylene glycol dibenzoate Fatty acid esters such as methyl ester, butyl oleate, and methyl acetyl ricinoleate; epoxy plasticizers such as epoxidized soybean oil and epoxidized linseed oil; and trioctyl trimellitate and ethylphthalylethyl glycolate. Butylphthalylbutyl glycolate, tributyl acetylcitrate, chlorinated paraffin, polypropylene adipate, polyethylene sebacate, triacetin, tributyrin,
Examples thereof include toluenesulfonamide, alkylbenzene, biphenyl, partially hydrogenated t-phenyl, camphor and the like. Among the above softeners, process oils such as paraffinic and naphthenic are most preferred.

In the present invention, (D) a softener-holding agent is preferably blended, and (D) a softener-holding agent comprises (C)
Is not particularly limited as long as it is a component that suppresses bleeding and retains (C) in the composition. For example, an average particle diameter of 0.0
It is a powder having a particle size of from 0.01 to 10 μm and not melting at 250 ° C. or a compound containing an organic acid polyvalent metal salt as an essential component and further blending an organic acid as required.

The amount of (D) is preferably from 0.001 to 200 parts by weight, more preferably from 0.01 to 15 parts by weight, per 100 parts by weight of the composition comprising (A) and (B).
0 parts by weight, more preferably 0.1 to 100 parts by weight, most preferably 1 to 100 parts by weight, very preferably 1 to 5 parts by weight.
0 parts by weight. One of (D) in the present invention has an average particle diameter of 0.001 to 10 μm, and powders that do not melt at 250 ° C. include, for example, thermosetting resins, metals, metal-containing compounds, halogen-containing compounds, and nitrogen-containing compounds. , A silicon-containing compound, a reinforcing agent, a ceramic, a light stabilizer, a colorant, and the like, having an average particle diameter of 0.001 μm to 10 μm, preferably 0.01 μm to 10 μm, and more preferably 0.1 μm to 5 μm. And most preferably 0.1 μ
m to 2 μm.

As one of the powders (D), powders that have been subjected to a surface treatment are particularly preferable and have excellent mechanical strength. As the surface treatment agent, for example, an organic acid or a silane coupling agent is known. Among the above organic acids, higher fatty acids such as 2-ethylhexanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid and montanic acid are preferred.

The thermosetting resin includes a phenol resin, a melamine resin, an epoxy resin, an unsaturated polyester resin,
Furan resin, urea resin, xylene resin, silicone resin, diallyl phthalate, aramid and the like. The metal is aluminum, iron, titanium, manganese, zinc, molybdenum, cobalt, bismuth, chromium, nickel, copper,
It is a simple substance such as tungsten, tin or antimony, or a composite thereof.

The metal-containing compounds include aluminum oxide, iron oxide, titanium oxide, manganese oxide, magnesium oxide, zirconium oxide, zinc oxide, molybdenum oxide,
Cobalt oxide, bismuth oxide, chromium oxide, tin oxide,
Simple substance such as antimony oxide, nickel oxide, copper oxide, tungsten oxide, or a composite (alloy) thereof, aluminum hydroxide, magnesium hydroxide, dolomite, hydrotalcite, zeolite, calcium hydroxide, barium hydroxide, basic Hydrates of inorganic metal compounds such as magnesium carbonate, zirconium hydroxide, and tin oxide hydrate;
Zinc borate, zinc metaborate, barium metaborate, zinc carbonate, magnesium carbonate, mu calcium, calcium carbonate, barium carbonate, kaolin, montmorillonite,
Bentonite, clay, mica, talc and the like.

Examples of the halogen-containing compound include an aromatic halogen compound, a halogenated cyanurate resin, and a halogenated polyphenylene ether, and are preferably decabromodiphenyl oxide, brominated polystyrene, brominated cross-linked polystyrene, brominated polyphenylene oxide, and polydiene. Halogen-based flame retardants such as bromophenylene oxide, decabromodiphenyl oxide bisphenol condensate, and halogen-containing phosphoric acid ester.

The nitrogen-containing compounds include melamine, melam, melem, melon (product of deammonification of three to three molecules of melem at 600 ° C. or more), melamine cyanurate, melamine phosphate, succinoguanamine, And triazine skeleton-containing compounds such as poguanamine and methylglutalogamine. The silicon-containing compound is amorphous silicon dioxide, such as silica or silicone resin, or silicate.

Another preferred example of (D) in the present invention is a compound comprising an organic acid polyvalent metal salt as an essential component and further adding an organic acid as required. The organic acid polyvalent metal salt includes carboxylic acid and sulfonic acid 2A, 2B, 3
A salt of a metal element selected from the groups B, 3A, 4A, 5A, 6A, 7A, 8 and 8 is preferable, and aluminum as a metal element is most preferable.

Among the above polyvalent metal salts of organic acids, polyvalent metal salts of higher aliphatic carboxylic acids are particularly preferable, and saturated monocarboxylic acids are particularly preferable. For example, polyvalent metal salts such as 2-ethylhexanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid and montanic acid can be mentioned, among which aluminum 2-ethylhexanoate is most preferred.

The organic acid polyvalent metal salt used as (D) in the present invention exhibits excellent softener retention especially when used in combination with an organic acid. As organic acids, higher monocarboxylic acids are preferred, and oleic acid or stearic acid is most preferred. In the present invention, (E) the crosslinking agent comprises (A)
And a radical initiator used for performing dynamic cross-linking of, for example, an organic peroxide or an organic azo compound. This makes it possible to improve wear resistance, mechanical strength, heat resistance, and the like.

(E) is used in an amount of preferably 0.01 to 5 parts by weight, more preferably 0.05 to 2 parts by weight, based on 100 parts by weight of the composition comprising (A) and (B). Here, the organic peroxide which is preferably used is preferably 1 minute half-life temperature T ₁ is a 100 to 250 ° C., and more preferably 150 to 200 ° C.. Further, the crosslinking efficiency ε calculated from the hydrogen abstraction ability in the pentadecane molecule is preferably 20 to 60, and 30 to 5
More preferably, it is 0.

As a specific example of such an organic peroxide, 1,1-bis (t-butylperoxy) -3,3,3
5-trimethylcyclohexane, 1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-hexylperoxy) cyclohexane, 1,1-bis (t-butyl) Peroxy) cyclododecane, 1,1-bis (t-butylperoxy)
Cyclohexane, 2,2-bis (t-butylperoxy) octane, n-butyl-4,4-bis (t-butylperoxy) butane, n-butyl-4,4-bis (t-
Peroxyketals such as 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 Dialkyl peroxides such as 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3; acetyl peroxide, isobutyryl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide , 3,5,5-trimethylhexanoyl peroxide, benzoyl peroxide, 2,4
Diacyl peroxides such as dichlorobenzoyl peroxide and m-trioyl peroxide; t
-Butylperoxyacetate, t-butylperoxyisobutyrate, t-butylperoxy-2-ethylhexanoate, t-butylperoxylaurate, t-butylperoxy-2-ethylhexanoate
-Butylperoxybenzoate, di-t-butylperoxyisophthalate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, t-butylperoxymaleic acid, t-butylperoxyisopropyl carbonate, And peroxyesters such as cumylperoxyoctate; and t-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide and 1 And hydroperoxides such as 1,3,3-tetramethylbutyl peroxide.

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 particularly preferred.

In the present invention, a crosslinking aid (F) can be used in order to further improve the crosslinking efficiency. For example, as a crosslinking aid, divinylbenzene, triallyl isocyanurate, triallyl cyanurate, diacetone diacrylamide, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, ethylene glycol diacrylate Methacrylate, triethylene glycol dimethacrylate, diethylene glycol dimethacrylate, diisopropenylbenzene, P-quinone dioxime, P, P ^'
- dibenzoyl quinone dioxime, phenylmaleimide, allyl methacrylate, N, N ^{'-m-phenylene} bismaleimide, diallyl phthalate, tetraallyloxyethane, 1,2-polybutadiene and the like are preferably used. These crosslinking aids may be used in combination of two or more.

The crosslinking assistant (F) is used in an amount of preferably 0.01 to 5 parts by weight, more preferably 0.5 to 2 parts by weight, per 100 parts by weight of the composition comprising (A) and (B). Used in quantity. Further, in the present invention, other resins, elastomers, inorganic fillers and plasticizers can be contained to such an extent that their 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. Also,
Examples of the plasticizer include phthalic acid esters such as polyethylene glycol and dioctyl phthalate (DOP). 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 and the like are also suitably used.

The production method of the present invention comprises the steps of:
General methods such as a Banbury mixer, a kneader, a single-screw extruder, and a twin-screw extruder used for the production of the elastomer composition can be employed. 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.

The manufacturing method of the present invention goes through the following processing steps as a specific example. That is, (A) an olefin-based elastomer, (B) an olefin-based resin, (C) a part of a softening agent, if necessary, (D) a softening agent-holding agent, and (E)
After adding the cross-linking agent and the cross-linking aid (F) from the main feed section, the mixture is melt-kneaded at the former stage of the extruder to perform dynamic cross-linking, and the remaining (C) softener is added in the middle of the extruder. The division ratio of (C) is preferably from 1 to 99% by weight, more preferably from 5 to 80% by weight, most preferably from 10 to 60% by weight, and most preferably from 10 to 50% by weight. Alternatively, (A), (B), and (D) may be added from the main feed portion, and (C) may be divided and fed to a plurality of side feed supply portions from the middle of the extruder while being melt-kneaded. In this case, the division ratio of (C) is preferably the same ratio as described above.

The (A) olefin elastomer and (B) olefin resin may be partially added in the middle of the extruder. A particularly preferred melt extrusion method has a length L in the die direction with respect to the raw material addition section, and L / L
This is the case where a twin screw extruder in which D is 5 to 100 (where D is the barrel diameter) is used. The twin-screw extruder has a plurality of supply portions at a main feed portion and a side feed portion having different distances from the tip portion, and a plurality of supply portions are provided between the plurality of supply portions and the tip portion. It is preferable that a kneading portion is provided between the supply portion and the supply portion at a short distance from the distal end portion, and the length of the kneading portion is 3D to 10D, respectively.

In the present invention, the kneading portion of the twin-screw extruder is a portion for improving kneading and mixing properties.
It consists of a full flight screw part with a special mixing element, a reverse screw part and at least one of a mixing part called a kneading disk or kneading block. The full flight screw portion having the above-mentioned special mixing element is a mixing screw such as a dalmage screw, a fluxed mixing screw, a unimelt screw, a spiral barrier screw, a pin screw, a pineapple mixer, a cavity transfer mixer, or the like. Element.

The reverse screw portion has a function of suppressing resin flow and generating back pressure, and has a large kneading ability. The mixing part called the above-mentioned "nieding disk" or "nieding block" is assembled by inclining a disk which is an oval plate little by little. 90 °
The tilted combination has no propulsion, but has good kneading ability. The combination in which the screws are inclined at an angle of 30 ° to the forward screw side has a propulsive force but a small kneading ability. In addition, the disks are thick and thin. Thick ones have low propulsion and low mixing ability, but have good kneading or shearing ability. On the other hand, thinner ones have higher propulsive power and greater mixing ability, but have lower kneading ability.

Regarding the shape of the needing disk,
There is a triangular conical type three-way disc and two-way disc. 3
Since the strip disk has a shallow groove, the shearing force is excessive, but since there are many opportunities for separation and merging at the meshing portion, the distribution and mixing properties are excellent. The double disk has a smaller shear force than the double disk. The mixing and kneading of the needing disk can be controlled by the shape, angle, number of sheets, thickness and the like of the disk.

The twin-screw extruder used in the present invention may be a twin-screw co-rotating extruder or a twin-screw different-direction rotating extruder. For screw engagement,
There are a non-meshing type, a partial meshing type, and a complete meshing type, and any type may be used. In order to obtain a uniform resin at a low temperature by applying a low shear force, a screw in a different direction / partial engagement type is preferably used. When slightly large kneading is required, use the co-rotating and fully meshing type screw.
Is preferred. When even greater kneading is required, a co-rotating and fully meshing screw is preferred.

The elastomer 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.

[0041]

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) Tensile breaking strength [kgf / cm ² ] Evaluated at 23 ° C. according to JIS K6251. (2) Tensile elongation at break [%] Evaluated at 23 ° C. according to JIS K6251. (3) Compression set (C-Set) [%] A molded article is compression-molded to produce a sheet, which is specified in JIS K63.
According to No. 01, evaluation was made at 70 ° C. × 22 hours as an index of durability. The smaller the value, the better the durability. (4) Extrusion stability (quality stability) The resin composition was continuously melt-extruded for 10 hours using a melt extruder, and the tensile strength at break was measured from the composition obtained every hour, and the change in the strength was measured. And evaluated the continuous productivity (quality stability). The difference between the 10-hour maximum and minimum tensile strength at break was used as an index of extrusion stability.

The following components were used in Examples and Comparative Examples. (A) Ethylene / α-olefin copolymer Copolymer of ethylene and octene-1 (TPE-1) Produced by a method using a metallocene catalyst. The ethylene / octene-1 composition ratio of the copolymer is 72/28 (weight ratio). (Referred to as TPE-1) Copolymer of ethylene and octene-1 (TPE-2) 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) Ethylene / propylene / dicyclopentadiene copolymer (TPE-3) was produced by a method using a metallocene catalyst. The composition ratio of ethylene / propylene / dicyclopentadiene in the copolymer is 72/24/4 (weight ratio). (Referred to as TPE-3) (b) Olefin-based resin polypropylene Isotactic polypropylene (referred to as PP) manufactured by Nippon Polychem Co., Ltd. (c) Paraffin oil Diana Process Oil PW-3 manufactured by Idemitsu Kosan Co., Ltd.
80 (referred to as MO) (d) Crosslinking agent: radical initiator 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane (trade name: Perhexa 25B) manufactured by NOF CORPORATION (E) Cross-linking assistant Divinylbenzene (referred to as DVB) manufactured by Wako Pure Chemical Industries, Ltd. (f) Softener retainer calcium carbonate (CaCO3) Dowa Calfine Co., Ltd., surface-treated heavy calcium carbonate ( Aluminum 2-ethylhexanoate An aqueous solution of sodium 2-ethylhexanoate and an aqueous solution of aluminum sulfate were reacted with stirring at room temperature, filtered, washed with water, and dried to obtain aluminum 2-ethylhexanoate. (Referred to as EHA) Stearic acid Stearic acid (referred to as SA) manufactured by Wako Pure Chemical Industries, Ltd.

[0043]

EXAMPLES 1 TO 7 AND COMPARATIVE EXAMPLES 1 AND 2 A twin screw extruder (40 mm) consisting of 11 blocks having an inlet at the center of the barrel.
φ, L / D = 47,)
The mixture was melt-kneaded under the conditions shown in Table 1 at ℃ to perform dynamic crosslinking. As the screw, a double screw having a kneading portion before and after the injection port was used. That is, (A) (B) (D) (E)
(F) is mixed and added to the main feed portion (raw material addition portion), and simultaneously (C) is added to the main feed portion at a split ratio shown in Table 1, and (A) to (F) are melt-kneaded. Continue the barrel center (sixth block starting from the raw material addition section)
After adding the remaining (C), the mixture was melt-kneaded to perform dynamic crosslinking. (Referred to as manufacturing process X) The comparative example was carried out in the same manner without divisional addition.

On the other hand, in the above manufacturing process, (A)
(B) (D) (E) (F) are mixed, added to the main feed section (raw material addition section), melt-kneaded, and then (C) from the second block and the sixth block based on the raw material addition section.
Was added at a split ratio shown in Table 1, followed by melt-kneading to perform dynamic crosslinking. (Referred to as manufacturing process Y) From the elastomer composition thus obtained, 200
A sheet having a thickness of 2 mm was prepared by compression molding at ℃, and each mechanical property was evaluated. The results are shown in Table 1.

[0045]

[Table 1]

According to Table 1, the divided addition of the softener not only lowers the melt viscosity and improves the extrusion stability, but also suppresses the thermal deterioration of (B), and has excellent mechanical properties. Is found to be expressed. In particular, as (A), it can be seen that a copolymer of ethylene and octene-1 produced using a metallocene catalyst imparts excellent mechanical strength.

[0047]

The elastomer composition obtained by the process for producing an elastomer composition of the present invention has excellent mechanical properties, so that it can be used for automobile parts, automobile interior materials, airbag covers, and mechanical parts. , Electrical components, cables, hoses,
It can be widely used for applications including belts, toys, sundries, daily necessities, building materials, sheets, films, etc., and plays a large role in the industrial world.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) C08L 23/16 C08L 23/16 101/00 101/00 F term (reference) 4F070 AA04 AA12 AA13 AA16 AA18 AA22 AA32 AA47 AA50 AA52 AA54 AA58 AB09 AB11 AB16 AC06 AC07 AC13 AC14 AC15 AC16 AC20 AC22 AC23 AC32 AC33 AC39 AC42 AC43 AC45 AC50 AC56 AC65 AC66 AC75 AC76 AC80 AC82 AC84 AC86 AC87 AC88 AC89 AC92 AC94 AE02 AE08 AE30 BA02 FA03 FA17 FB06 GA05 FC06 AA03E AA03K AA04E AA45 AB01 AB03 AB07 AG01 AG08 AG16 AH05 AH17 AH26 AH53 AH59 BA01 BC01 BC12 BC37 BD05 BK02 BK13 BK33 BQ07 BQ50 4J002 AC04W AE043 AE053 BB00X BB05X BB13X05 BB13X05 BB13X05 BB13X BB14X BB13X BB13X BB13X BB13X CF00X CF214 CG00X CH07X CH074 CH084 CH124 CK02W CL00X CL064 CN01X CP034 DA077 DA087 DA097 DA107 DA117 DC007 DE067 DE077 DE087 DE097 DE107 DE117 DE127 DE137 DE147 DE237 DE247 DE267 DE287 DJ007 DJ017 DJ037 DJ047 DJ057 DK007 7 EH046 EH076 EH086 EH096 EH146 EK018 EK028 EK038 EK048 EK058 EK068 EL087 EV286 EW057 EX037 FB094 FB097 FB234 FB237 FD023 FD026 FD158 FD204 FD207

Claims (4)

[Claims] 1. A method for producing a partially or completely dynamically crosslinked elastomer composition comprising (A) a crosslinkable elastomer, (B) a thermoplastic resin, and (C) a softener,
(A), (B), and (C) are melt-kneaded using an extruder having one main feed portion having different distances from the tip portion and a plurality of side feedable feeding portions. A method for producing an elastomer composition, wherein (C) is divided into a plurality of feed supply portions and fed during dynamic crosslinking. 2. The process for producing an elastomer composition according to claim 1, further comprising (D) a softener-retaining agent. 3. The method for producing an elastomer composition according to claim 1, wherein (E) a crosslinking agent is blended. 4. A method according to claim 1, wherein (A) is ethylene and α having 3 to 20 carbon atoms.
4. The method for producing an elastomer composition according to claim 1, wherein the ethylene / α-olefin copolymer comprises an olefin, and (B) is an olefin resin.