JPH01247440A - Thermoplastic elastomer composition - Google Patents

Abstract

PURPOSE:To obtain the title composition prevented from undergoing blocking, bleeding out, gloss staining, etc., and improved in moldability and flow property without detriment to its flame retardancy, by mixing a specified thermoplastic elastomer with a polyolefin resin. CONSTITUTION:100 pts.wt. mixture of 100-10 pts.wt. ethylene-olefin copolymer rubber (a) of a Q value (weight-average MW/number-average MW, according to gel permeation chromatography) of 2.5-8 with 0-90 pts.wt. polyolefin resin (b) of an MI of 0.1-80 is dynamically heat-treated in the presence of 0.5-20 pts.wt. softening agent component (c) selected from a peroxide-noncrosslinkable hydrocarbon type rubberlike substance or mineral oil to obtain a thermoplastic elastomer (A) of a hot xylenol-extractible gel content of 2-80wt.%, a methyl ethyl ketone-extractible content of 1-20wt.% and a cyclohexane-extractible gel content of 40-100wt.%. 100-5 pts.wt. component A is mixed with 0-95 pts.wt. polyolefin resin (B) which may be the same as or different from component (b).

Description

DETAILED DESCRIPTION OF THE INVENTION Technical Field of the Invention The present invention relates to a thermoplastic elastomer composition, and more particularly to a thermoplastic elastomer composition that has excellent moldability, flow properties, and an excellent appearance, and is free from blocking, bleed-out, matte stains, and more. The present invention relates to a thermoplastic elastomer composition that can provide a molded article that is less prone to fogging and does not have reduced flame retardancy.

Day O″l, f and d(f)+1″.

Thermoplastic elastomers have been widely used for automobile parts such as bumper parts, instrument panels, interior seats, golf club grips, swimming fins, and the like. This thermoplastic elastomer has both thermoplastic and elastic properties, and can be used for injection molding,
By extrusion molding or the like, it can be molded into a molded product with excellent heat resistance, tensile properties, weather resistance, flexibility, and elasticity.

As such a thermoplastic elastomer, for example, Japanese Patent Publication No. 53-34210 discloses a method in which 60 to 80 parts by weight of monoolefin copolymer rubber and 40 to 20 parts by weight of polyolefin plastic are dynamically partially cured. A thermoplastic elastomer is disclosed. Also, special public service in 1973
Publication No. 21021 discloses that (a) it is made of ethylene-propylene-nonconjugated polyene copolymer rubber and has a gel content of 3
0 to 90% by weight of a partially crosslinked copolymer rubber; (b)
A thermoplastic elastomer comprising a polyolefin resin is disclosed. Further, Japanese Patent Publication No. 55-18448 discloses a thermoplastic elastomer in which an ethylene-propylene copolymer rubber and a polyolefin resin are dynamically partially or completely crosslinked.

The above thermoplastic elastomer composition can be manufactured by injection molding, extrusion molding, etc. to improve heat resistance, tensile strength, weather resistance,
Although it can be molded into a molded article with excellent flexibility and elasticity, it has a problem in that it has significantly poor moldability and flow characteristics, and flow marks appear on the surface of the resulting molded article, resulting in poor appearance.

In order to solve such problems, the applicant of the present application disclosed in Japanese Patent Publication No. 56-15741 that (a) 90 to 40 parts by weight of peroxide crosslinked olefin copolymer rubber;
1)) Peroxide decomposition type olefin plastic 1
0 to 60 parts by weight (where (a) + (b) are selected to be 100 parts by weight) and (c) a peroxide non-cross-linked type A hydrocarbon-based rubbery material and/or (d) a mineral oil-based softener. A partially crosslinked thermoplastic elastomer composition is disclosed, characterized in that a mixture consisting of 5 to 100 parts by weight of an organic peroxide is dynamically heat treated in the presence of an organic peroxide.

After further intensive study, the present inventors discovered that using a polyolefin resin having a specific melt index,
A thermoplastic elastomer composition consisting of a thermoplastic elastomer having a specific boiling point R xylene extracted gel content and a specific methyl ethyl ketone extracted content and a polyolefin resin has excellent moldability and processability even when the amount of softener is small.
The inventors have discovered a scale that provides molded products with good flow characteristics and excellent appearance, and have completed the present invention.

The present invention is intended to solve the problems associated with the prior art as described above, and has improved heat resistance, tensile strength, weather resistance,
It is an object of the present invention to provide a thermoplastic elastomer composition that has excellent flexibility, elasticity, etc., and can provide a molded product with excellent moldability, flow characteristics, and excellent appearance even if the amount of softener contained is at least It is very calm.

The thermoplastic elastomer composition according to the present invention is [I]
(a) Ethylene/α-olefin copolymer rubber: 1
00 to 10 parts by weight, (b) 20 to 90 parts by weight of a polyolefin resin having a melt index of 0.1 to 80, (where (a) + (b)
) is selected to be 100 parts by weight) and at least one softening agent component selected from the following (c) and (d) (c) peroxide non-crosslinked 1i5. type hydrocarbon-based rubbery substance (d) A mixture containing mineral oil is dynamically heat-treated in the presence of a crosslinking agent, and has a hot xylene extracted gel content of 2 to 80% by weight and a methyl ethyl getone extracted content. 1-20%
It is characterized by consisting of 100 to 5 parts by weight of a thermoplastic elastomer, and 20 to 95 parts by weight of a polyolefin resin.

The thermoplastic elastomer according to the present invention as described above has excellent heat resistance, tensile strength, weather resistance, flexibility, elasticity, etc., and contains at least the amount of a softener, and has excellent moldability and flow characteristics. A molded product with excellent appearance can be obtained.

The thermoplastic elastomer composition according to the present invention will be specifically explained.

The thermoplastic elastomer composition according to the present invention is [I]
A mixture consisting of fa) ethylene/α-olefin copolymer rubber, fb) polyolefin resin, and (c) peroxide non-crosslinked hydrocarbon rubber material (d) mineral oil is dynamically mixed in the presence of a crosslinking agent. It consists of a specific thermoplastic elastomer obtained by heat treatment and [1] polyolefin resin, and each component will be explained below.

(a) Ethylene α, a raw material for thermoplastic elastomer
-Olefin copolymer rubbers include, for example, ethylene-propylene copolymer rubber, ethylene-10-pyrene-
Ethylene and 3 carbon atoms, such as non-conjugated diene ternary or multi-component copolymer rubber, ethylene-butadiene copolymer rubber, ethylene-1-butene copolymer rubber, ethylene-1-butene-non-conjugated diene multi-component rubber, etc. -14 α-olefins as a main component or a mixture thereof. Among these, ethylene-propylene copolymer rubber and ethylene-propylene-diene terpolymer rubber are preferred.

Here, the non-conjugated diene is dicyclopentadiene, 1
．． It means 4-hexadiene, cyclooctadiene, methylenenorbornene, 5-ethylidene-2-norbornene, etc., and in the present invention, among these, ternary one having dicyclopentadiene or 5-ethylidene-2-norbornene as the third component Copolymer or dicyclopentadiene and 5
A quaternary copolymer containing both components of -ethylidene-2 and norbornene is preferred.

Mooney viscosity [WL,
(100°C)] is usually 10 to 180.14, preferably 40 to 140, and its iodine value (degree of unsaturation) is preferably 16 or less.

In the present invention, the amount of each compositional unit contained in these copolymer rubbers is such that in the 1-olefin portion, the ratio of ethylene/α-olefin units is 90/10 to 50150, preferably 80/20 to 60/ A ratio of 40 (molar ratio) is particularly desirable.

1-olefin (Koteshin+α-olefin) unit 7″
'The m-position of the non-conjugated diethylene (in the case of ternary or multi-component copolymers) is usually 98/2 to 90/10, preferably 97,
,...3 to 94/6 (molar ratio).

Such (aJ ethylene/α-olefin copolymer rubber) has Qlti (weight average molecular weight,/number average molecule M) measured by gel permeation method < GPC method.
is preferably 2.5 to 8.

By using fa) ethylene/α-olefin copolymer rubber with a QσC of 2.5 to 8, heat can be applied to produce molded products with even better moldability and flow characteristics, as well as an excellent appearance. A plastic elastomer composition is obtained.

The Q value was measured as follows according to "Gel Permeation Chromatography" written by Takeuchi and published by Marukubi.

(1) Using standard polystyrene with a known molecular weight (monodisperse polystyrene manufactured by Toyo Soda Co., Ltd.), molecule IM and its G
P C (Get Parneation Chron)
atograph) counts and molecular weights M and E
Phase 11 of V (Elution + uie)] Plot the calibration curve. The concentration of Bpi is 0.02 parts or more.

(2) GP (Take the GPC pattern of the sample using the Jtll standard method, and find M using the above (1). The sample preparation conditions and GPC measurement conditions at that time are as follows.

Sample Preparation (a) Aliquot the sample into an Erlenmeyer flask together with 0-dichlorobenzene to give a concentration of 0.04%.

(b) Add anti-aging agent 2 to the Erlenmeyer flask containing the sample.
0.1% by weight of 6-tart-butyl-p-cresol is added to the polymer solution.

(c) Heat the Erlenmeyer flask to 140°C and stir for about 30 minutes to dissolve.

(iv) Thereafter, it is filtered through a 1μ Millipore filter at 135°C to 140°C.

(e) Apply the P solution to GPC.

GPC measurement conditions It was conducted under the following conditions.

(B) Equipment 200 type (B) Column manufactured by Waters Co., Ltd. S-type (Mix type) manufactured by Toyo Soda (C) Sample 12 m1 (D) Temperature 135'C (E) Flow rate 1 ml/min ( f) Total number of theoretical plates of column 2X104 to 4X10' (b) Polyolefin resin to be mixed with ethylene/α-olefin copolymer rubber during dynamic heat treatment: ethylene, propylene, butene-1, hexene-1, 4-
Homopolymers of 1-olefins such as methyl-1-pentene, copolymers of two or more thereof, or copolymers of α-olefins with up to 15 mol% of other polymerizable monopolymers, such as ethylene- Vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-methacrylic acid copolymer, ethylene-methyl methacrylate copolymer, etc. Examples include certain resinous polymeric substances. Among these, melt index (ASTM-D-1238-65
T) is 0.1 to 80 g/10 min (230°C), especially 5
A polyolefin resin having a crystallinity of ~20 g/10 minutes and a crystallinity of 40% or more as determined by X-ray diffraction measurement is preferably used.

Among these, preferred polyolefin resin (b) is a melt index of 0.1 to 50 r/10 min (2
30°C) and a crystallinity of 40% or more, peroxide-decomposed polyolefin resin (a polyolefin that is thermally decomposed by mixing with peroxide and kneading under heat to reduce the molecular weight and increase the fluidity of the resin) resins), specifically isotactic polypropylene, copolymers of propylene and 15 mol% or less of other α-olefins,
For example, propylene-ethylene block copolymer, propylene-1-butene copolymer, propylene-1-hexene copolymer, and propylene-4-methyl-1-pentene copolymer have a melt index of 0.1 to 50 tr/
A time of 10 minutes is preferable from the viewpoint of flow characteristics of the thermoplastic elastomer obtained.

In addition, as ib) polyolefin resins, the above-mentioned peroxide decomposition type polyolefin resins and peroxide crosslinked polyolefin resins (polyolefin resins that are crosslinked by mixing with peroxide and kneading under heating to reduce the fluidity of the resin), such as Density 0.910~
0.940 low, medium, and high density polyethylene in a weight ratio of 10010 to 30/70, especially 80/20 to 20/80.
It is preferable to use a mixture obtained by mixing the above because it has excellent moldability.

Next, in the preparation of the thermoplastic elastomer, (c) peroxide non-crosslinked hydrocarbon-based rubbery substances to be blended as necessary include polyisobutylene, butyl rubber, propylene-ethylene copolymer containing 50 mol% or more of propylene. Hydrocarbon-based rubbery substances such as composite rubber, propylene-1-butene copolymer rubber, atactic polypropylene, etc., which are crosslinked and do not reduce fluidity even when mixed with peroxide and kneaded under heating are used. . Among these, polyisobutylene rubber, butyl rubber and propylene-1-butene copolymer rubber are most preferred.

(d) Mineral oil is usually used to weaken the intermolecular forces of rubber during roll processing, making processing easier, and assisting in the dispersion of carbon black, white carbon, etc., or hardening of vulcanized rubber. High-boiling point petroleum fractions are used to reduce stiffness and increase flexibility or elasticity. Specifically, paraffinic, naphthenic, or aromatic mineral oils are used.

''-Each component is used in the appropriate proportions as shown below.

(a) Ethylene/α-olefin copolymer rubber is 10
0~10@weight part preferably 90~20 heavy view part soba stone (i
l) The polyolefin resin is used in an amount of 0 to 90 parts by weight, preferably 10 to 80 parts by weight,
) is used in such proportions that the total weight of the ingredients is 100 parts by weight.

Also, peroxide non-crosslinked hydrocarbon rubber material (c)
and /' or mineral oil (d) is a thermoplastic elastomer 1 to
In order to improve the flow characteristics, that is, the moldability of the polymer composition, the above fc) and 7/mana is 0 above (d)
．． It is blended in an amount of 5 to 20 parts by weight, preferably 0.5 to 10 parts by weight, more preferably 0.5 parts by weight or more and less than 5 parts by weight.

When used in an amount less than 1 part by weight, for example 1 to 4.9 parts by weight, the moldability and fluidity of the resulting thermoplastic elastomer composition are good, but the molded articles obtained from the composition are Fronking, bleeding,
Phenomena such as gloss, stains, and fogging are hardly observed, and the flame retardant properties of molded products are also improved.

To prepare the thermoplastic elastomer in the present invention,
(a) Ethylene/α-olefin copolymer rubber, (b
l polyolefin resin, and (c) peroxide non-crosslinked rubber and/or ((1) mineral oil softener,
A blend made by mixing in the proportions above! T! 110
About 0.01 to 2 parts by weight or more than 0 parts by weight
．． 0.03 to 1.0%, more preferably 0.05 to 0.0%.
5% by weight of a crosslinking agent may be blended and dynamically heat treated to effect partial or complete crosslinking.

Dynamic heat treatment here means kneading in a molten state. In this case, the kneading device may be an open type device such as a mixing roll or a Banbury mixer 1.
Closed equipment such as extruders, kneaders or continuous mixers may be used.

The kneading is preferably carried out in a non-release type device, preferably in an inert gas atmosphere such as nitrogen or carbon dioxide, and the temperature is usually 150 to 280°C, preferably 170 to 240°C. , kneading time is usually 1 to 20
minutes, preferably 1 to 10 minutes.

Crosslinking agents used for partial or complete crosslinking include organic peroxides, sulfur, phenolic vulcanizing agents,
Oximes, polyamines, etc. are used, and among these, organic peroxides and phenolic vulcanizing agents are preferred from the viewpoint of the physical properties of the thermoplastic elastomer obtained.

As the phenolic vulcanizing agent, an alkylphenol formaldehyde resin, a triazine-formaldehyde resin, and a melamine-polmaldehyde resin can be used.

Examples of organic peroxides include dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane, and 2,5-dimethyl-2,5-bis(tert-butylperoxide).
butylperoxy)hexyne-3,1,3-bis(tQ
rt-butylperoxyisopropyl)benzene, 1.
1-bis(tcr[-butylperoxy)-3,3,
5-1-limethylcyclohexane, n-butyl-4,4
-bis(tart-butylperoxy)valerate, dibenzoyl peroxide, tert-butylperoxybenzoate, etc. can be used. Among these, bisperoxide compounds are preferred because they have low odor and high scorch stability, and particularly 1,3-bis(tert) compounds are preferred.
-butylperoxyisopropyl)benzene is most suitable.

In addition, when performing partial or complete crosslinking, crosslinking aids such as p-quinonedioxime, p,p'-dibenzoylquinonedioxime, or divinylbenzene (DVB) are used.
By blending polyfunctional vinyl monomers such as diethylene glycol methacrylate and polyethylene diglycol methacrylate, a more uniform and mild crosslinking reaction can be achieved, so it is preferable to blend these crosslinking aids or polyfunctional vinyl monomers. In particular, divinylbenzene (DVB) is most preferred because it has a homogeneous crosslinking effect upon heat treatment and can yield a thermoplastic elastomer with well-balanced fluidity and physical properties.

The blending amount of divinylbenzene (DVB) is 100% of the composition.
0.05 to 2 parts by weight, preferably 0.1 to 2 parts by weight
It is 1.5 parts by weight.

The partially or fully crosslinked thermoplastic elastomer thus obtained usually has a hot xylene extracted gel content of 2 to 80% by weight, preferably 5 to 60% by weight, measured by the method described below. .

The thermal xylene extracted gel content is measured as follows. That is, sample pellets (size of each pellet = 3
11+×311IIX31w+) to about 0.3,
This weight is defined as the initial weight (X).

Next, this sample pellet was immersed in 80 ml of boiling IIIJ# silane in a closed container for 5 hours, filtered through a 325 mesh screen, the residue on the screen was air-dried, and then vacuumed at 80°C for 5 hours. Dry and let the amount of this dry residue be the final type i (Y).

If the thermoplastic elastomer contains thermally xylene-insoluble fillers, pigments, etc., subtract the weight of these thermally xylene-insoluble fillers, pigments, etc. from the weight of the sample pellet and the weight of the dry residue. Let the weights obtained be the first Tomoshige M (X) and the final type jt (Y), respectively.

From these initial weights (X) and final mold jt (Y),
The thermal xylene extracted gel content is determined by the following formula.

Final form Ji (Y) 1 silene extracted gel content (%) =
X 100 initial weight i (X) Also, the partially or completely crosslinked thermoplastic elastomer thus obtained has a hot xylene extracted gel content of 2 to 80% by weight as described above, and the following: The gel content extracted by cyclohexane measured as follows is 40% by weight or more, preferably 70 to 100% by weight, more preferably 70 to 99.5% by weight, particularly preferably 80 to 96% by weight. desirable.

Here, the measurement of the cyclohexane-extracted gel content is performed as follows. Sample pellet of thermoplastic elastomer (
Size of each pellet: 1am x 1g x 0.5mm) approx. 10
0# was weighed and immersed in 30 cc of cyclohexane in a closed container at 23°C for 48 hours, and then the sample was taken out and dried.

If the thermoplastic elastomer contains cyclohexane-insoluble fillers, pigments, etc., subtract the weight of all cyclohexane-insoluble fillers, pigments, and other substances other than the polymer components from the weight of this dry residue. The corrected final weight after drying (Y), while the weight of cyclohexane-soluble components other than the ethylene/α-olefin copolymer (e.g., mineral oil, plasticizer, and cyclohexane-soluble rubber components) and If the thermoplastic elastomer contains cyclohexane-insoluble fillers, pigments, etc., the corrected initial Weight (X)
shall be.

From these values, the cyclohexane extracted gel content is determined by the following formula.

Furthermore, the partially or completely crosslinked thermoplastic elastomer obtained as described above has a methyl ethyl ketone extractable content of 1 to 20
% by weight, preferably 2-15% by weight, more preferably 5-15% by weight
It is 10% by weight.

Here, the measurement of the methyl ethyl ketone extract is carried out as follows. Thermoplastic elastomer sample pellets approximately 100+w (size of each pellet: 1+m x 1 city x 0.
5) was weighed and immersed in 30 CC of methyl ethyl ketone at 23°C for 48 hours in a sealed container.
If the sample is taken out and dried, and the thermoplastic elastomer contains fillers, pigments, etc. that are insoluble in methyl ethyl ketone, the weight of this dry residue is determined to include all insoluble fillers, pigments, etc. other than the polymer component. The corrected final form i (Y) after drying is obtained by subtracting the others.
On the other hand, if the thermoplastic elastomer contains methyl ethyl ketone insoluble filler, face v1, etc., the weight of the insoluble filler, face f, °1, etc. is subtracted from the weight of the sample pellet. , corrected initial flat day (X>
shall be.

From these values, the methyl ethyl ketone extract is determined by the following formula.

Corrected 1 weight (X) - Corrected i endstone (Y
) Extraction content (%)・□×100 Corrected initial flat The thermoplastic elastomer according to the present invention has the above-mentioned 2
having a hot xylene extracted gel content of ~80% by weight and a methyl ethyl ketone extractable content of 1 to 20% by weight, and 40 to
Since the thermoplastic elastomer composition preferably has a content of 100% by weight, the resulting thermoplastic elastomer composition has excellent moldability and flow properties even when the need for softeners is low, and provides molded articles with excellent appearance. -Can be done.

Furthermore, in the present invention, the polyolefin resin (n) to be mixed as necessary after the dynamic heat treatment includes resins similar to the polyolefin resin (fly) added during the dynamic heat treatment, such as ethylene, propylene, butene-1, hexene, etc. - A homopolymer of 1-olefin such as 1,4-methyl-1-pentene, a copolymer of two or more thereof, or a copolymer of α-olefin and 15 mol% or less of another polymerizable monomer. Coalescing, such as ethylene-vinyl 1v acid copolymer, ethylene-acrylic acid copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-methacrylic acid copolymer, ethylene-methacrylic acid A resinous polymeric substance such as a methyl copolymer is used. Melt index of these polyolefin resins (n) (A S T M ~ D-1238-65
T, 190'C1 However, in the case of propylene polymers, the temperature (230°C) is preferably 5 to 100 t/I 0 min, particularly 10 to 50 g/10 min, during and after dynamic heat treatment. When adding a polyolefin resin to both, the polyolefin resin (b) and the polyolefin resin (II) may be of the same type or different types.

The thermoplastic elastomer composition according to the present invention may further contain carbon black, clay, talc, calcium carbonate, heavy calcium carbonate, kaolin, diatomaceous earth, silica, alumina, asbestos, graphite, glass fiber, etc. Fillers or antioxidants such as phenyl-α-naphthylamine, 2,6-di-tert-butylphenol, tetrakis [methylene (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], weathering agents, heat stabilizers, 11 Combustion agents, antistatic agents, and other additive ingredients can be blended.

These fillers or additives may be added at the AgJ stage of the thermoplastic elastomer, or may be added after preparation when it is made into a molded article.

The thermoplastic elastomer composition according to the present invention can be molded using molding equipment used for ordinary thermoplastic polymers, and is suitable for extrusion molding, calendar molding, and especially injection molding. This thermoplastic elastomer composition also uses a specific ethylene-α-olefin copolymer rubber and has specific boiling xylene extractable gel content, methyl ethyl ketone extractable content, and preferably cyclohexane extractable gel content. Because of this, it has excellent rubber properties such as heat resistance, weather resistance, tensile properties, flexibility, and rebound resilience.
In addition, it has good fluidity and excellent moldability, so when it is made into a large, thick molded product, a product with a good appearance without flow marks or whiskers can be obtained.

Such thermoplastic elastomers are used in body panels, bumper parts, sight shields, automotive parts such as steering wheels, footwear such as shoe soles and sandals, electrical parts such as electric wire coverings, connectors, and cap plugs, and golf club greens and y It is used for applications such as baseball bat grips, swimming fins, underwater eyewear, gas nets, waterproof cloth, garden hoses, belts, etc., but is especially used for large thick products such as parts of bumpers. suitable for

The present invention will be explained by examples, but the present invention is not limited to these examples in any way unless the gist of the invention is exceeded.

The moldability and basic physical properties of the compositions in Examples were evaluated by the following methods.

A thermoplastic elastomer was produced in the following manner using the following components.

(Component A) Ethylene/propylene/ethylidenenorbornene ternary copolymer rubber: ethylene unit/propylene unit (molar ratio) near 8/22, iodine value 15, Mooney viscosity (ML, , 121°C) 1+4 61, Q value , 3.0) (Component B) Isotactic polypropylene resin; Melt index 25 g/10 minutes (230°C) (Component C) Low density polyethylene: ethylene content 97 mol%, α-olefin content 3 mol% (density 0. 920, M
FR16g/10min 190°C) (Component F) naphthenic process oil (component C) 20% by weight of 1,3-bis(tert-butylperoxyisopropyl)benzene, 30% by weight of divinylbenzene and 50% by weight of paraffinic mineral oil A mixture consisting of 20 parts by weight of the above (component A), 1 part by weight of 60 parts (component B), (
After kneading 20 parts by weight of component (c) and 4.5 parts by weight of component (F) in a Banbury mixer at 180° C. under a nitrogen atmosphere for 5 minutes, the resulting kneaded product was cut into a square pellet shape using a sheet cutter.

To 100 parts by weight of this square pellet, 1 double foot part (component c) was kneaded in a Henschel mixer and extruded at 220°C in a nitrogen atmosphere using an extruder to obtain a thermoplastic elastomer containing 10.5% by weight of xylene extracted gel. .

Table 1 shows the physical properties of the thermoplastic elastomer thus obtained.

Each physical property value should be measured as follows.

MFR: ASTM D-1238 (230°C110
minutes).

Initial bending modulus: Measured in accordance with ASTM D-790.

Torsional rigidity: Measured in accordance with ASTM D-1043.

Shore D hardness +Measured in accordance with ASTM D-2240.

Shore A hardness: Measured in accordance with JIS K-6301.

Permanent elongation: Measured according to JIS K-6301.

Spiral flow: Equipment I S-3OP (manufactured by Toshiba) Conditions: Mold: Spiral mold (T: 2.5 cities) Resin temperature: 210°C Injection pressure = 1st 800kIr/Sake 2nd 640kg/cd Mold temperature: In Example 1, component (8), component B) and component ([) were used in the proportions shown in Table 1, and component (G)
except that the components and amounts of were used in the proportions shown in Table 1, and instead of component (c), the components shown in component D) or component (E) were used in the proportions shown in Table 1. Example 1
I did the same thing.

The results are shown in Table 1.

In addition, the butyl rubber as (component 0) had a Mooney viscosity ML (100° C.) of 45 and a degree of un1+4 saturation of 1.0 mol %. In addition, the propylene-ethylene rubber as ([component)] has a propylene content of 59 mol%, an ethylene content of 41 mol%, and an MFR (230 mol%).
'C) was 0.4r/10 minutes.

Claims (1)

[Scope of Claims] 1) [I] (a) Ethylene/α-olefin copolymer rubber: 100 to 10 parts by weight, (b) Polyolefin resin having a melt index of 0.1 to 80: 0 to 90 Parts by weight, (where (a) + (b
) is selected to be 100 parts by weight) and at least one softener component selected from the following (c) and (d): 0.5 to 20 parts by weight (c) peroxide non-crosslinked hydrocarbon rubber Substance (d) is obtained by dynamically heat-treating a mixture containing mineral oil in the presence of a crosslinking agent, and has a hot xylene extracted gel content of 2 to 80% by weight and a methyl ethyl ketone extracted content of 1 to 20% by weight. A thermoplastic elastomer composition comprising 100 to 5 parts by weight of a thermoplastic elastomer and 0 to 95 parts by weight of [II] polyolefin resin. 2) Gel permeation chromatography method (GP) of the (a) ethylene/α-olefin copolymer rubber
The thermoplastic elastomer composition according to claim 1, which has a Q value (weight average molecular weight/number average molecular weight) measured by method C) in the range of 2.5 to 8. 3) [I] The thermoplastic elastomer composition according to claim 1, wherein the cyclohexane-extracted gel content of the thermoplastic elastomer is 40 to 100% by weight.