JP2000007851A - Thermoplastic resin composition excellent in processability - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a thermoplastic resin composition excellent in mechanical strength and surface appearance and capable of stabilizing the quality due to the productivity improved by excellent processability. SOLUTION: This thermoplastic resin composition is a partially or a completely cross-linked thermoplastic resin composition comprising (A) 1-99 pts.wt. of a cross-linkable thermoplastic elastomer produced by using a metallocene-based catalyst and (B) 1-99 pts.wt. of a thermoplastic resin [the total amount of the components (A) and (B) is 100 pts.wt.]. The composition has 2.0-5.0 molecular weight distribution (Mw/Mn) which is the ratio of the weight-average molecular weight (Mw) to the number-average molecular weight (Mn) calculated by a gel permeation chromatography(GPC) of the component (A) and at least two peaks by the measurement of the molecular weight distribution according to the GPC.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a thermoplastic resin composition having excellent processability. More specifically,
The present invention relates to a thermoplastic resin composition which is excellent in mechanical strength and surface appearance, and which can stabilize quality because productivity is improved by excellent workability.

[0002]

2. Description of the Related Art In recent years, a thermoplastic resin composition, particularly a radically crosslinkable olefinic elastomer and an olefinic resin having no radically crosslinkable properties such as PP, have been extruded in the presence of a radical initiator for use in automobile parts and the like. Thermoplastic elastomer compositions by so-called dynamic crosslinking, which are crosslinked while being melt-kneaded in a medium, are widely used.

[0003] In such a thermoplastic elastomer composition, ethylene-propylene-diene rubber (EPDM) has been conventionally used as an olefin elastomer. Although EPDM is excellent in crosslinkability due to the presence of a diene component in the polymer chain, improvement in quality has been desired because of poor environmental degradation resistance. on the other hand,
JP-A-8-120127, JP-A-9-13700
No. 1 discloses a technique using an olefin elastomer produced with a metallocene catalyst. However, conventionally, metallocene-based polymerization catalysts are useful for producing polymers having a very narrow molecular weight distribution as compared with Ziegler-based catalysts, and although they are excellent in improving mechanical strength, they are inferior in processing fluidity. there were. Therefore, the composition disclosed in the above publication does not always have sufficient balance between processability and mechanical strength, and a thermoplastic resin composition that can withstand practical use is required.

[0004]

SUMMARY OF THE INVENTION In view of such circumstances, the present invention has no such problems as described above, that is, the workability,
It is an object of the present invention to provide a thermoplastic resin composition having excellent surface appearance and mechanical properties.

[0005]

The present inventors have intensively studied a thermoplastic resin composition having excellent processability and mechanical strength. As a result, the present inventors have found that the use of a crosslinkable elastomer having a specific molecular weight and a specific molecular weight distribution is surprising. It has been found that workability, surface appearance and mechanical strength are remarkably improved, and the present invention has been completed.

That is, the present invention relates to (A) 1 to 99 parts by weight of a crosslinkable elastomer produced using a metallocene catalyst and (B) 1 to 99 parts by weight of a thermoplastic resin [(A) and (B)
Is 100 parts by weight], and the weight-average molecular weight (Mw) calculated by gel permeation chromatography (GPC) of (A). ) And the number average molecular weight (Mn), the molecular weight distribution (Mw / Mn) of 2.
0 to 5.0 and at least two peaks as measured by GPC molecular weight distribution measurement, particularly the melt flow rate (AS) of (A).
TMD 1238, 230 ° C., 2.16 kg load) is 21 to 50 g / 10 minutes. Hereinafter, the present invention will be described in detail.

The composition of the present invention comprises (A) a crosslinkable elastomer and (B) a thermoplastic resin. Here, it is important that (A) is produced using a metallocene-based catalyst.
Conventionally, a metallocene-based polymerization catalyst is useful for producing a polymer having an extremely narrow copolymer composition distribution as compared with a Ziegler-based catalyst, and has an excellent effect of improving mechanical strength.

Next, (A) requires that the molecular weight distribution (Mw / Mn) by GPC be 2.0 to 5.0, preferably 2.0 to 4.0, and more preferably 2.0. ~
3.0. In the case of the above range, the balance between the workability and the mechanical strength is excellent. By using two or more kinds of (A) having different molecular weights and having at least two peaks in the molecular weight distribution measurement by GPC, the excellent balance characteristic is exhibited. One of the at least two peaks preferably has a Mw in the range of 1,000 to 100,000, more preferably 1,000.
0 to 10,000, and the other peak is 1
It is preferably in the range of from 000 to 1,000,000, more preferably in the range of from 10,000 to 500,000.

In the present invention, the melt flow rate (MFR) of (A) is preferably 21 to 50 g / 10 min, more preferably 21 to 40 g / 1.
0 minutes, most preferably 21-30 g / min. MFR
If it is 21 g / 10 minutes or more, not only the surface appearance is improved, but also the melt viscosity during processing is reduced, so that productivity is increased and quality such as mechanical strength is stabilized. On the other hand, MFR is 50
It has been found that when the amount exceeds g / min, the mechanical strength tends to decrease, and the present invention has been completed.

Hereinafter, each component of the present invention will be described in detail. In the present invention, the crosslinkable elastomer (A) is not particularly limited as long as it satisfies the above-mentioned requirements for the MFR and the molecular weight distribution. In particular, (A) is preferably an ethylene / α-olefin copolymer rubber, for example, an ethylene / α-olefin copolymer rubber composed of ethylene and an α-olefin having 3 to 20 carbon atoms.

As the α-olefin having 3 to 20 carbon atoms, for example, propylene, butene-1, pentene-1, hexene-1, 4-methylpentene-1, heptene-1, octene-1, nonene-1, decene-1 -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 crosslinkable elastomer used in the present invention is produced using a known metallocene catalyst. Generally, the metallocene catalyst is an IV catalyst such as titanium or zirconium.
It is composed of a cyclopentadienyl derivative of a group metal and a co-catalyst, and is not only highly active as a polymerization catalyst, but also has a narrower molecular weight distribution of the resulting polymer as compared with a Ziegler-based catalyst. In this case, the distribution of the α-olefin having 3 to 20 carbon atoms as a comonomer in the copolymer is uniform.

The ethylene / α-olefin copolymer (A) preferably used in the present invention preferably has an α-olefin copolymerization ratio of 1 to 50% by weight, more preferably 10 to 40% by weight. , Most preferably 20-30
% By weight. When the copolymerization ratio of the α-olefin exceeds 50% by weight, the hardness, tensile strength and the like of the composition are greatly reduced, while when it is less than 1% by weight, the mechanical strength is reduced.

The density of (A) is 0.8 to 0.9 g / cm.
It is preferably in the range of ³ . By using an olefin elastomer having a density in this range, a thermoplastic elastomer composition having excellent flexibility and low hardness can be obtained. In particular, when the following equation (a) is satisfied between the copolymerization ratio c (% by weight) and the density d (g / cm ³ ): -0.0026 × c + 0.9200 ≦ d ≦ −0.0026 × c + 0.9400- (a) The balance between the mechanical strength and the physical properties of hardness of the elastomer is excellent and more preferable. If the density d is lower than this range, the mechanical strength is insufficient, and if the density d is higher than this range, oil bleed tends to occur, which is not preferable.

The ethylene / α-olefin copolymer used in the present invention preferably has a long chain branch. Due to the presence of long-chain branching, the ratio of the copolymerized α-olefin (% by weight) without lowering the mechanical strength
As compared with the above, the density can be further reduced, and a low-density, low-hardness, high-strength elastomer can be obtained.

It is desirable that the ethylene / α-olefin copolymer 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. (A) used in the present invention is produced using a catalyst such as a metallocene catalyst.
A production method using a metallocene-based catalyst disclosed in Japanese Patent No. 088 is preferable. In order to achieve the requirement (A) of the present invention, it can be carried out by selecting a catalyst type, an amount, a polymerization temperature and a chain transfer agent. The MFR and the molecular weight distribution can be controlled by using a mixture of a plurality of (A) having the same molecular weight distribution and different average molecular weights.

In the present invention, (B) the thermoplastic resin comprises:
There is no particular limitation as long as it is compatible or uniformly dispersed with (A). For example, polystyrene-based, polyphenylene ether-based, polyolefin-based, polyvinyl chloride-based, polyamide-based, polyester-based, polyphenylene sulfide-based, polycarbonate-based, polymethacrylate-based, or a mixture of two or more of them can be used. . 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 resin selected from these resins is used in a composition ratio of 1 to 99 parts by weight. Preferably 5 to 90 parts by weight, more preferably 20
８０80 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) a softening agent can be blended as needed to improve workability. The above (C) is preferably a paraffinic or naphthenic process oil. These are used in order to adjust the hardness and flexibility of the composition, and 5 to 2 parts by weight based on 100 parts by weight of (A) and (B).
50 parts by weight, preferably 10 to 150 parts by weight are used. 5
If the amount is less than parts by weight, flexibility and workability are insufficient, and if it exceeds 250 parts by weight, oil bleeding becomes remarkable, which is not desirable.

The thermoplastic resin composition provided by the present invention comprises: (A) the specific crosslinkable elastomer described above;
By combining (B) a thermoplastic resin and (C) a softening agent at a specific composition ratio, the balance between mechanical strength, flexibility and workability is improved, and the composition can be preferably used. The thermoplastic resin composition provided by the present invention requires that the composition be partially cross-linked by a radical initiator such as an organic peroxide or a radical initiator and a crosslinking assistant. Thereby, it becomes possible to further improve the wear resistance, mechanical strength, heat resistance, and the like.

Here, specific examples of the radical initiator preferably used include 1,1-bis (t-butylperoxy) -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) hexyne-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
Hydrogens 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.

These radical initiators are (A) 100
0.02 to 3 parts by weight, preferably 0.05 to 3 parts by weight
Used in an amount of １1 part by weight. 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, as a crosslinking aid, 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 ^'- dibenzoyl quinone dioxime, phenylmaleimide, allyl methacrylate, N, ^{N'-m-phenylene} bismaleimide, diallyl phthalate, tetraallyloxyethane, 1,2-polybutadiene or the like is preferably used Can be These crosslinking aids may be used in combination of two or more.

These crosslinking assistants 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 (A). If the amount is less than 0.1 part by weight, crosslinking is insufficient, and if it exceeds 5 parts by weight, the physical properties of the composition are not improved, and an excessive amount of a crosslinking aid remains, which is not preferable. Further, other resins and elastomers may be added to the thermoplastic resin composition of the present invention to such an extent that its characteristics are not impaired.

In particular, a block copolymer composed of at least one polymer block A mainly composed of a vinyl aromatic compound and at least one polymer block B mainly composed of a conjugated diene compound, or a block copolymer of the same. The addition of a block copolymer obtained by hydrogenating the coalesced oil is preferable because the oil retention can be dramatically improved.

The block copolymer of the present invention is, for example,
-B, ABA, BABA, ABAB-
A, BABAB, (AB) ₄ Si, (BA
-B) ₄ Si, and has a _{(B-A-B) 4} Sn structure such. The polymer block mainly composed of a vinyl aromatic compound is a copolymer block of a vinyl aromatic compound containing 50% by weight or more of a vinyl aromatic compound and a conjugated diene compound and / or a homopolymer block of a vinyl aromatic compound. Show.

The polymer block mainly composed of a conjugated diene compound refers to a copolymer block of a conjugated diene compound containing at least 50% by weight of a conjugated diene compound and a vinyl aromatic compound and / or a homopolymer block of a conjugated diene compound. Show. As the vinyl aromatic compound constituting the block copolymer, one or more of styrene, methylstyrene, 1,3-dimethylstyrene, p-tert-butylstyrene and the like can be used. Among them, styrene is preferred.

As the conjugated diene compound constituting the block copolymer, one or more of butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene and the like can be used. . Among them, butadiene, isoprene and a combination thereof are preferred. As a method for producing these block copolymers, any known method may be used, for example, a method of block-polymerizing a vinyl aromatic compound and a conjugated diene compound using a polymerization initiator such as an organic lithium compound in a hydrocarbon solvent. Can be obtained by subjecting the above block copolymer to a hydrogenation reaction. The method of the hydrogenation reaction may be any known method, for example, hydrogenation can be performed in an inert solvent in the presence of a hydrogenation catalyst. The reaction conditions for hydrogenation are at least 80% of the conjugated diene compound,
Preferably, at least 90% is selected to be hydrogenated, while less than 20%, preferably less than 10%, of the vinyl aromatic compound is hydrogenated.

The number average molecular weight of the block copolymer having the above structure is 20,000 to 300,000, preferably 30.
000 to 200,000. The block copolymer of the present invention has mechanical properties as an elastomer,
It has a high oil retention ability and has the property of being crosslinked by a radical initiator. Therefore, by having the block copolymer as one component, the composition of the present invention can hold a large amount of rubber oil, and it becomes easy to obtain a low hardness composition. In the case of a dynamic crosslinking reaction,
It also functions as a crosslinkable elastomer component together with the olefinic elastomer.

The block copolymer is composed of 10 (A) and (B).
It is used in a composition ratio of 0 to 100 parts by weight with respect to 0 parts by weight. If it exceeds 100 parts by weight, the crosslinkability of the composition decreases, which is not desirable. Particularly, by adding a low molecular weight ethylene polymer having a number average molecular weight of 20,000 or less,
The molding processability of the composition, the surface texture of the molded product, and the like are remarkably improved, which is desirable.

In addition, the following polymers may be added to the composition of the present invention to such an extent that the characteristics are not impaired. Specifically, polyethylene, polybutene, polyisobutene,
Ethylene-vinyl ester copolymers such as ethylene-vinyl acetate copolymers, ethylene-unsaturated carboxylic acid ester copolymers such as ethylene-ethyl acrylate copolymers,
And ethylene-vinyl alcohol copolymer.

Further, the thermoplastic resin composition of the present invention comprises:
It is possible to contain inorganic fillers and plasticizers 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. Examples of the plasticizer include phthalic acid esters such as polyethylene glycol and dioctyl phthalate (DOP). Also, other additives, for example, organic and inorganic pigments,
Heat stabilizer, antioxidant, ultraviolet absorber, light stabilizer, flame retardant, silicone oil, anti-blocking agent, foaming agent,
Antistatic agents, antibacterial agents and the like are also preferably used.

For the production of the thermoplastic resin composition of the present invention,
General methods such as a Banbury mixer, a kneader, a single-screw extruder, a twin-screw extruder, and the like used in the production of ordinary resin compositions and elastomer compositions can be employed. In particular, a twin-screw extruder is preferably used to achieve dynamic crosslinking efficiently. The twin-screw extruder uniformly and finely disperses the crosslinkable elastomer and the thermoplastic resin,
Further adding other components to cause a crosslinking reaction,
For continuously producing the thermoplastic resin composition of the present invention,
More suitable.

Dynamic cross-linking is a processing method in which a cross-linking reaction is carried out in a kneading machine in a short time, and a cross-linking time (Tc90) which is an index of a cross-linking speed is 400 seconds or less, preferably 300 times.
A copolymer having a length of 2 seconds or less is desirable, and more preferably 2 copolymers.
00 seconds or less is desirable. Here, the crosslinking time (Tc90)
Is the time required to reach 90% of the maximum degree of crosslinking (viscosity) when adding 1.0 part by weight of dicumyl peroxide as a peroxide to an elastomer and measuring the vulcanization characteristics with a rheometer at 170 ° C. It is.

In the present invention, the form of the crosslinkable elastomer or the thermoplastic resin is preferably a finely divided form such as a pellet, powder, crumb or the like. As a specific example, the thermoplastic resin composition of the present invention can be manufactured through the following processing steps. That is, the crosslinkable elastomer and the thermoplastic resin are mixed well and then charged into a hopper of an extruder. A radical initiator and a crosslinking assistant may be added from the beginning together with a crosslinkable elastomer and a thermoplastic resin,
You may add from the middle of an extruder. The oil may be added from the middle of the extruder, or may be added separately at the beginning and during the middle. A part of the crosslinkable elastomer and the thermoplastic resin may be added in the middle of the extruder. When heated and melted and kneaded in an extruder, the elastomer and the radical initiator and the crosslinking auxiliary undergo a crosslinking reaction, and the crosslinking reaction and kneading dispersion are sufficiently performed by further adding and melting oil and kneading. Then remove from the extruder. Pellets can be obtained to obtain pellets of the thermoplastic resin composition of the present invention.

The degree of crosslinking is defined as a measure of the crosslinkability of the composition. 0.5 g of the thermoplastic resin composition of the present invention is refluxed in 200 ml of xylene for 4 hours. The solution was filtered with a quantitative filter paper, and the residue on the filter paper was quantified after vacuum drying,
It is calculated as the ratio (%) of the weight of the residue to the weight of the olefin-based elastomer in the composition. The degree of crosslinking of the thermoplastic resin composition as a preferred composition of the present invention is 30%
The above is desirable. If it is less than 30%, crosslinking is insufficient, and heat resistance such as compression set and physical properties such as rebound resilience are reduced.

From the thermoplastic resin composition thus obtained, various molded articles can be produced by any molding method. Injection molding, extrusion molding, compression molding, blow molding, calender molding, foam molding and the like are preferably used.

[0039]

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) Melt flow rate (MFR) The melt flow rate was evaluated under the conditions of 230 ° C. and a load of 2.16 kg according to ASTM D 1238.

(2) Molecular Weight Distribution The molecular weight and molecular weight distribution of the GPC apparatus and measuring method are not particularly limited, but the present inventors used the following apparatus and measuring method. 1. Equipment Waters 150C GPC 2. 2. One column SHOdex AT-807S 1 Tosoh TSK-GEL GMH-H6 2 3 in total Solvent 1,2,4-trichlorobenzene 4. Measurement temperature 140 ° C 5. Standard substance: polystyrene Further, having a peak in the molecular weight distribution is a change curve with respect to the base line in GPC measurement, and includes both a broad curve and a sharp curve. The number of peaks is defined by the number of junctions between the tangent parallel to the baseline and the curve. The weight average molecular weight of the peak is the peak top of the GPC curve, and refers to the intersection of the curve and a tangent drawn in a straight line parallel to the base line.

(3) Surface Hardness Four sheets having a thickness of 2 mm were piled up and evaluated according to ASTM D2240 using a type A in an atmosphere of 23 ° C. (4) Surface appearance hardness A sheet having a thickness of 2 mm was prepared and evaluated visually.

(5) Tensile breaking strength [kgf / cm ² ] Evaluated at 23 ° C. according to JIS K6251. (6) Tensile elongation at break [%] Evaluated at 23 ° C. according to JIS K6251. (7) Continuous productivity (quality stability) The resin composition was continuously melt-extruded for 10 hours using a twin-screw extruder, and the tensile strength at break was measured from the composition obtained every hour, and the strength was measured. From the change, continuous productivity (quality stability) was evaluated. The difference between the 10-hour maximum and minimum tensile strength at break was used as an index of continuous productivity.

The following components were used in the examples and comparative examples. (A) Crosslinkable Elastomer Copolymer of Ethylene and Octene-1 The composition ratio of ethylene / octene-1 in the copolymer is 72 /
28 (weight ratio), Mw 35000, Mn
16000, Mw / Mn = 2.2, MFR 30 and M
Copolymers having different FRs and molecular weight distributions were produced using a metallocene catalyst by controlling the amount of the metallocene catalyst and the polymerization temperature by the method described in JP-A-3-16388, and optionally mixed, Are shown in Table 1. Also,
(A) having a narrow molecular weight distribution of Mw / Mn of, for example, 2 or less
Was prepared by extracting low molecular weight components of (A) having a wide molecular weight distribution by hot xylene extraction. (B) Thermoplastic 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) Radical initiator 2,5-dimethyl-2,5-bis (t-manufactured by NOF Corporation)
Butylperoxy) hexane (trade name Perhexa 25)
B) (referred to as POX) (e) Crosslinking auxiliary divinylbenzene (referred to as DVB) manufactured by Wako Pure Chemical Industries, Ltd.

[0044]

Examples 1 to 10 and Comparative Examples 1 to 3 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. After mixing other than the paraffinic oil (MO) at the composition ratio shown in Table 1, the mixture was introduced into a twin-screw extruder (cylinder temperature 220 ° C.), and then a predetermined amount of MO was injected through an injection port at the center of the extruder. Was injected by a pump, and melt extrusion was performed for 10 hours.

From the thermoplastic resin composition thus obtained, a sheet having a thickness of 2 mm was prepared by compression molding at 200 ° C., and each mechanical property, appearance and continuous productivity were evaluated. Table 1 shows the results.

[0046]

[Table 1]

According to Table 1, the molecular weight distribution and G
It can be seen that (A) which satisfies the requirement of PC peak has excellent mechanical properties, surface appearance and continuous productivity.

[0048]

Industrial Applicability The thermoplastic resin composition of the present invention is excellent in mechanical strength and surface appearance, and is capable of stabilizing quality because of excellent workability, thereby improving productivity. The composition of the present invention can be used for automotive parts, automotive interior materials, airbag covers, mechanical parts, electrical parts, cables, hoses, belts, toys, miscellaneous goods, daily necessities, building materials, sheets, films, and other applications. It can be used widely and plays a large role in the industrial world.

Claims (6)

[Claims] 1. (A) 1 to 99 parts by weight of a crosslinkable elastomer produced using a metallocene catalyst and (B) 1 to 99 parts by weight of a thermoplastic resin [the total amount of (A) and (B) is 1
00 parts by weight], a weight-average molecular weight (Mw) and a number average molecular weight (Mw) calculated by gel permeation chromatography (GPC) of (A). A thermoplastic resin composition having a molecular weight distribution (Mw / Mn), which is a ratio with respect to the molecular weight (Mn), of 2.0 to 5.0, and having at least two peaks in GPC molecular weight distribution measurement. object. 2. The melt flow rate of (A) (ASTM D 1
The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition has a 238,230 ° C, 2.16 kg load) of 21 to 50 g / 10 minutes. 3. The method of (A), wherein Mw is determined by GPC molecular weight distribution measurement.
In the range of 1,000 to 100,000 and 10,000 to 1,
3. The thermoplastic resin composition according to claim 1, which has at least one peak in the range of 1,000,000. 4. The thermoplastic resin composition according to claim 1, wherein (A) is a copolymer comprising at least two kinds of vinyl monomers. 5. The method according to claim 1, wherein (A) is ethylene and α-α having 3 to 20 carbon atoms.
5. The thermoplastic resin composition according to claim 4, which is an ethylene / α-olefin copolymer rubber comprising an olefin. 6. The method according to claim 1, wherein (B) is an olefin resin.
6. The thermoplastic resin composition according to any one of items 1 to 5.