JP5055072B2 - Method for producing thermoplastic elastomer composition and molded body - Google Patents

Description

  The present invention relates to a thermoplastic elastomer composition and use thereof, and more particularly to a thermoplastic elastomer composition excellent in mechanical strength, rubber elasticity or transparency and use thereof.

Polypropylene is inexpensive and has excellent rigidity, moisture resistance, and heat resistance, and is therefore used in a wide range of applications such as automotive materials and household appliance materials. On the other hand, polyolefins having flexibility and transparency have been desired as the trend of desoftening vinyl chloride has increased due to problems such as environmental hormones and dioxins. Under such circumstances, polypropylene is softened by blending polypropylene with an ethylene / α-olefin copolymer or propylene / α-olefin copolymer (Patent Document 1). The blend is inferior in rubber elasticity. Furthermore, a crosslinked thermoplastic elastomer composition called TPV is excellent in flexibility and rubber elasticity (Patent Document 2), but is inferior in mechanical strength and lacks transparency. In addition, a system in which a styrene elastomer is added to PP (Patent Document 3) is flexible and transparent but expensive, and therefore has limited applications.
Japanese Patent Laid-Open No. 10-212382 JP-A-52-0663353 Japanese Patent Laid-Open No. 7-048485

The present invention is intended to solve the problems associated with the prior art as described above, and provides a method for producing a thermoplastic elastomer composition excellent in mechanical strength and rubber elasticity or excellent in transparency. The purpose is that.

The present invention is derived from α-olefin having 1 to 98 parts by weight of isotactic polypropylene (A), 45 to 89 mol% of propylene component, 10 to 25 mol% of ethylene component, and optionally 4 to 20 carbon atoms. Propylene / ethylene (.alpha.-olefin) random copolymer (B) containing 2 to 99 parts by weight of component unit in an amount of 0 to 30 mol% [total of (A) and (B) is 100 parts by weight], propylene・ Ethylene (.alpha.-olefin) random copolymer (B) is cross-linked , and ethylene and C3-C20 alpha-olefin with respect to a total of 100 parts by weight of (A) and (B). And an ethylene / α-olefin / nonconjugated polyene copolymer rubber (C) comprising 2 to 1900 parts by weight of a propylene / ethylene (• α-olefin) random copolymer (B) and ethylene / - to provide a method for producing a thermoplastic elastomer composition olefin-nonconjugated polyene copolymer rubber component (C) to produce a thermoplastic elastomer composition is crosslinked.

The manufacturing method of the 1st thermoplastic elastomer composition is 1-40 weight part of isotactic polypropylene (A), 45-89 mol% of propylene components, 10-25 mol% of ethylene components, and carbon number as needed. To 100 parts by weight of a composition obtained by mixing 60 to 99 parts by weight of propylene / ethylene (.alpha.-olefin) random copolymer (B) containing 4 to 20 α-olefin-derived component units in an amount of 0 to 30 mol%. Further, by mixing and cross-linking 2 to 1900 parts by weight of ethylene / α-olefin / non-conjugated polyene copolymer rubber (C) composed of ethylene, an α-olefin having 3 to 20 carbon atoms and a non-conjugated polyene, tactic polypropylene (a) 1 to 40 parts by weight, the propylene component 45-89 mol%, the ethylene component 10 to 25 mol%, optionally carbon Propylene-ethylene (- alpha-olefin) random copolymer comprising an amount of a component unit 0-30 mol% from 4-20 alpha-olefin (B) a 60 to 99 parts by weight comprises [and (A) (B ) Is 100 parts by weight], the propylene / ethylene (.α-olefin) random copolymer (B) is cross-linked, and ethylene is added to 100 parts by weight of the total of (A) and (B). , Including 2 to 1900 parts by weight of an ethylene / α-olefin / nonconjugated polyene copolymer rubber (C) composed of an α-olefin having 3 to 20 carbon atoms and a nonconjugated polyene, and propylene / ethylene (• α-olefin) random A thermoplastic comprising producing a thermoplastic elastomer composition in which a copolymer (B) and an ethylene / α-olefin / non-conjugated polyene copolymer rubber (C) component are crosslinked. It is a manufacturing method of the elastomer composition.
The method for producing the second thermoplastic elastomer composition includes 1 to 40 parts by weight of isotactic polypropylene (A), 45 to 89 mol% of the propylene component, 10 to 25 mol% of the ethylene component, and optionally carbon number. To 100 parts by weight of a composition obtained by mixing 60 to 99 parts by weight of propylene / ethylene (.alpha.-olefin) random copolymer (B) containing 4 to 20 α-olefin-derived component units in an amount of 0 to 30 mol%. Further, ethylene / α-olefin / nonconjugated polyene copolymer rubber (C) 2 comprising 5 to 1900 parts by weight of the isotactic polypropylene (A) and ethylene, an α-olefin having 3 to 20 carbon atoms and a nonconjugated polyene. by crosslinking by mixing 1900 parts by weight, 1 to 40 parts by weight of isotactic polypropylene (a), the propylene component 4 Propylene / ethylene (• α-olefin) random containing ˜89 mol%, ethylene component in an amount of 10 to 25 mol%, and optionally containing 0 to 30 mol% of a component unit derived from an α-olefin having 4 to 20 carbon atoms copolymer (B) 60 to 99 parts by weight include [(a) and total 100 parts by weight of (B)], the propylene-ethylene (- alpha-olefin) random copolymer (B) has been crosslinked Further, an ethylene / α-olefin / non-conjugated polyene copolymer rubber comprising ethylene, an α-olefin having 3 to 20 carbon atoms and a non-conjugated polyene (100 parts by weight of the total of (A) and (B)) ( C) Including 2 to 1900 parts by weight, the propylene / ethylene / (α-olefin) random copolymer (B) and the ethylene / α-olefin / non-conjugated polyene copolymer rubber (C) component are crosslinked. A method for producing a thermoplastic elastomer composition characterized by the production of the thermoplastic elastomer composition are.

The method for producing the thermoplastic elastomer composition according to the present invention can produce a thermoplastic elastomer composition excellent in mechanical strength, rubber elasticity or transparency. Moreover, the thermoplastic elastomer composition obtained by the method for producing the thermoplastic elastomer composition according to the present invention is suitable for automobile parts, skin materials or sealing materials.

Hereinafter, the thermoplastic elastomer composition according to the present invention will be specifically described.
Isotactic polypropylene (A)
In the present invention, a propylene polymer having the following characteristics is used. The propylene polymer may be a homopolypropylene, a propylene / α-olefin random copolymer, or a propylene block copolymer as long as it has the following characteristics. Homopolypropylene or propylene-α olefin random copolymer.

  The melt flow rate (MFR; ASTM D1238, 230 ° C., 2.16 kg load) of the isotactic polypropylene (A) used in the present invention is 0.01 to 400 g / 10 minutes, preferably 0.5 to 90 g / 10. Minutes. The melting point obtained by DSC measurement is 120 ° C. or higher, preferably 130 ° C. or higher, and more preferably 150 ° C. or higher.

  From such an MFR value isotactic polypropylene (A), it is possible to obtain a propylene polymer composition which is excellent in fluidity and capable of molding a large product. A composition formed from isotactic polypropylene having an MFR value exceeding 400 g / 10 min may be inferior in impact resistance (IZ impact strength).

  When the isotactic polypropylene (A) is a propylene / α-olefin random copolymer, the α-olefin is preferably selected from ethylene and / or an α-olefin having 4 to 20 carbon atoms. It is preferable to contain 3 to 7 mol%, preferably 0.3 to 6 mol%, more preferably 0.3 to 5 mol%.

  In addition, the normal temperature n-decane soluble component content of the propylene polymer was obtained by immersing 5 g of a sample (propylene polymer) in 200 cc of boiling n-decane for 5 hours and then cooling to room temperature to precipitate a solid phase. Can be obtained by back-calculating from the solid phase weight measured after drying with a G4 glass filter.

  The isotactic polypropylene (A) used in the present invention as described above can be produced by various methods. For example, it can be produced using a stereoregular catalyst. Specifically, it can be produced using a catalyst formed from a solid titanium catalyst component, an organometallic compound catalyst component, and, if necessary, an electron donor. Specific examples of the solid titanium catalyst component include titanium trichloride or a titanium trichloride composition supported on a carrier having a specific surface area of 100 m @ 2 / g or more, or magnesium, halogen, electron donation. Examples include a solid titanium catalyst component supported on a carrier having a body (preferably an aromatic carboxylic acid ester or an alkyl group-containing ether) and titanium as essential components, and these essential components having a specific surface area of 100 m @ 2 / g or more. It can also be produced with a metallocene catalyst. Of these, the latter solid titanium catalyst component is particularly preferred.

  The organometallic compound catalyst component is preferably an organoaluminum compound. Specific examples of the organoaluminum compound include trialkylaluminum, dialkylaluminum halide, alkylaluminum sesquihalide, and alkylaluminum dihalide. The organoaluminum compound can be appropriately selected according to the type of titanium catalyst component used.

  As the electron donor, an organic compound having a nitrogen atom, a phosphorus atom, a sulfur atom, a silicon atom, or a boron atom can be used, and preferably, an ester compound and an ether compound having the above atoms are used. .

  Such a catalyst may be further activated by a technique such as co-grinding, or an olefin as described above may be prepolymerized.

  The isotactic polypropylene (A) of the present invention is 1 to 98 weights per 100 weight parts of the total amount of isotactic polypropylene (A) and propylene / ethylene (.α-olefin) random copolymer (B). Parts, preferably 5 to 85 parts by weight, more preferably 10 to 70 parts by weight.

Propylene / ethylene (α-olefin) random copolymer (B)
The propylene / ethylene (.α-olefin) copolymer (B) used in the present invention has a propylene component of 45 to 89 mol%, preferably 45 to 80 mol%, preferably 50 to 75 mol%, and an ethylene component. 10 to 25 mol%, preferably 10 to 23 mol%, more preferably 12 to 23 mol%, and optionally 0 to 30 mol% of the component unit (a) derived from an α-olefin having 4 to 20 carbon atoms, Preferably, it contains 0 to 25 mol%, more preferably 0 to 20 mol%.

Specific examples of the α-olefin having 4 to 20 carbon atoms include 1-butene, 4-methylpentene-1, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1 -Undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-nonadecene, 1-eicosene, 9-methyldecene-1, 11-methyldodecene-1, 12-ethyl And tetradecene-1. Of these, 1-butene and 1-octene are preferable.
These α-olefins are used alone or in combination of two or more.

  The propylene / ethylene (• α-olefin) random copolymer (B) containing propylene, an ethylene component and, if necessary, an α-olefin component having 4 to 20 carbon atoms in such an amount is obtained from isotactic polypropylene and The resulting propylene polymer composition tends to exhibit sufficient transparency, flexibility, heat resistance, and scratch resistance.

  Such propylene / ethylene (• α-olefin) random copolymer (B) has an intrinsic viscosity [η] measured in decalin at 135 ° C. of usually 0.01 to 10 dl / g, preferably 0.05 to It is desirable to be in the range of 10 dl / g. When the intrinsic viscosity [η] of the propylene / ethylene (.α-olefin) random copolymer (B) is within the above range, weather resistance, ozone resistance, heat aging resistance, low temperature characteristics, dynamic fatigue resistance It becomes a propylene / ethylene (• α-olefin) random copolymer with excellent properties.

  This propylene / ethylene (.α-olefin) random copolymer (B) was measured at 23 ° C. using a JIS No. 3 dumbbell in accordance with JIS K6251 with a span interval of 30 mm and a pulling speed of 30 mm / min. The stress at 100% strain (M100) is 4 MPa or less, preferably 3 MPa or less, more preferably 2 MPa or less. When the propylene / ethylene (.α-olefin) random copolymer (B) is in such a range, the flexibility, transparency and rubber elasticity are excellent.

  The propylene / ethylene (• α-olefin) random copolymer (B) has a crystallinity of 20% or less, preferably 0 to 15%, as measured by X-ray diffraction. The propylene / ethylene (.α-olefin) random copolymer (B) has a single glass transition temperature, and the glass transition temperature Tg measured by a differential scanning calorimeter (DSC) is usually −10 ° C. or lower. It is desirable that the temperature be in the range of −15 ° C. or lower. When the glass transition temperature Tg of the propylene / ethylene (.α-olefin) random copolymer (B) is within the above range, the cold resistance and the low temperature characteristics are excellent.

This propylene / ethylene (.α-olefin) random copolymer (B) has a heat of fusion ΔH of 30 J / in the presence of a melting point (Tm, ° C.) in the endothermic curve of a differential scanning calorimeter (DSC). The following relational expression holds for the relationship between the C3 content (mol%) and the heat of fusion ΔH (J / g).
ΔH <345Ln (C3 content mol%)-1492, where 76 ≦ C3 content (mol%) ≦ 90

  The molecular weight distribution measured by GPC (Mw / Mn, polystyrene conversion, Mw: weight average molecular weight, Mn: number average molecular weight) is 4.0 or less, preferably 3.0 or less, more preferably 2.5 or less. Is preferred.

  The propylene / ethylene (• α-olefin) random copolymer (B) as described above may be partially graft-modified with a polar monomer. Examples of polar monomers include hydroxyl group-containing ethylenically unsaturated compounds, amino group-containing ethylenically unsaturated compounds, epoxy group-containing ethylenically unsaturated compounds, aromatic vinyl compounds, unsaturated carboxylic acids or their derivatives, vinyl ester compounds, chlorides. Vinyl etc. are mentioned.

The modified propylene / ethylene (• α-olefin) random copolymer is obtained by graft polymerization of a polar monomer to the propylene / ethylene (• α-olefin) random copolymer (B) as described above. When the above-mentioned polar monomer is graft-polymerized to the propylene / ethylene (• α-olefin) random copolymer (B), the polar monomer is a propylene / ethylene (• α-olefin) random copolymer ( B) It is usually used in an amount of 1 to 100 parts by weight, preferably 5 to 80 parts by weight, based on 100 parts by weight. This graft polymerization is usually carried out in the presence of a radical initiator.
As the radical initiator, an organic peroxide or an azo compound can be used.

  The radical initiator can be used as it is mixed with the propylene / ethylene (.α-olefin) random copolymer (B) and the polar monomer, but can also be used after being dissolved in a small amount of an organic solvent. . Any organic solvent that can dissolve the radical initiator can be used without particular limitation.

  Further, when the polar monomer is graft-polymerized to the propylene / ethylene (• α-olefin) random copolymer (B), a reducing substance may be used. When a reducing substance is used, the graft amount of the polar monomer can be improved.

  Graft modification of the propylene / ethylene (.alpha.-olefin) random copolymer (B) with a polar monomer can be carried out by a conventionally known method. For example, propylene / ethylene (.alpha.-olefin) random copolymer (B ) Is dissolved in an organic solvent, and then a polar monomer and a radical initiator are added to the solution, and the reaction is carried out at a temperature of 70 to 200 ° C., preferably 80 to 190 ° C., for 0.5 to 15 hours, preferably 1 to 10 hours. Can be performed.

  Also, using propylene / ethylene (• α-olefin) random copolymer by reacting propylene / ethylene (• α-olefin) random copolymer (B) and polar monomer without solvent using an extruder, etc. A coalescence (B) can also be manufactured. This reaction is preferably carried out usually at a temperature not lower than the melting point of the propylene / ethylene (.α-olefin) random copolymer (B), specifically at a temperature of 120 to 250 ° C., usually for 0.5 to 10 minutes.

  The modified amount of the modified propylene / ethylene (α-olefin) random copolymer thus obtained (the graft amount of the polar monomer) is usually 0.1 to 50% by weight, preferably 0.2 to 30% by weight. More preferably, the content is 0.2 to 10% by weight.

  When the above-mentioned modified propylene / ethylene (• α-olefin) random copolymer is contained in the propylene polymer composition of the present invention, the propylene polymer composition is excellent in adhesion and compatibility with other resins. In some cases, the wettability of the surface of the molded body obtained from the product is improved.

  The propylene / ethylene (.alpha.-olefin) random copolymer (B) of the present invention is 100 weights in total of isotactic polypropylene (A) and propylene / ethylene (.alpha.-olefin) random copolymer (B). 2 to 99 parts by weight, preferably 15 to 95 parts by weight, and more preferably 30 to 70 parts by weight with respect to parts.

Ethylene / α-olefin / non-conjugated polyene copolymer rubber (C)
The ethylene / α-olefin / non-conjugated polyene copolymer rubber (C) used in the present invention is a rubber comprising ethylene, an α-olefin having 3 to 20 carbon atoms and a non-conjugated polyene.

Specific examples of the α-olefin having 3 to 20 carbon atoms include propylene, 1-butene,
4-methylpentene-1,1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene 1-heptadecene, 1-nonadecene, 1-eicosene, 9-methyldecene-1, 11-methyldodecene-1, 12-ethyltetradecene-1, and the like. Among them, propylene, 1-butene,
4-methylpentene-1, 1-hexene and 1-octene are preferred. Particularly preferred is propylene.

These α-olefins are used alone or in combination of two or more.
Further, as the non-conjugated polyene, specifically,
1,4-hexadiene, 3-methyl-1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 4,5-dimethyl-1,4-hexadiene, 7- Linear unconjugated dienes such as methyl-1,6-octadiene, 8-methyl-4-ethylidene-1,7-nonadiene, 4-ethylidene-1,7-undecadiene;
Methyltetrahydroindene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene-2-norbornene, 5-vinylidene-2-norbornene, 6-chloromethyl-5-isopropenyl-2-norbornene Cyclic non-conjugated dienes such as 5-vinyl-2-norbornene, 5-isopropenyl-2-norbornene, 5-isobutenyl-2-norbornene, cyclopentadiene, norbornadiene;
2,3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, 2-propenyl-2,2-norbornadiene, 4-ethylidene-8-methyl-1,7-nanodiene, etc. A triene etc. are mentioned and it can use even 2 or more types. Of these, 2-ethylidene-2-norbornene and 5-vinyl-2-norbornene are preferred.

The ethylene / α-olefin / non-conjugated polyene copolymer rubber (C) used in the present invention is derived from (1) (a) a unit derived from ethylene and (b) an α-olefin having 3 to 20 carbon atoms. The unit is included in a molar ratio of 40/60 to 95/5, preferably 60/40 to 80/20, more preferably 65/35 to 75/25 [(a) / (b)]. .

The iodine value as an index of the amount of the non-conjugated polyene component of the ethylene / α-olefin / non-conjugated polyene copolymer rubber (C) used in the present invention is 1 to 50, preferably 5 to 40, more preferably 10 ~ 30. Moreover, in the total amount of components of a nonconjugated diene amount, it is 2 to 20 weight% in (C) component.

The ethylene / α-olefin / non-conjugated polyene copolymer rubber (C) used in the present invention has an intrinsic viscosity of 1.0 to 10.0 dl / g, preferably 1 as measured in decalin at 135 ° C.
. 5 to 8.0 dl / g.

The ethylene / α-olefin / non-conjugated polyene copolymer (C) used in the present invention may be a so-called oil-extended rubber in which a softener, preferably a mineral oil softener, is blended in the production.
Examples of the mineral oil softener include conventionally known mineral oil softeners such as paraffin process oil.

The Mooney viscosity [ML] of ethylene / α-olefin / non-conjugated polyene copolymer rubber (C)
_{1 + 4} (100 ° C.)] is usually 10 to 250, preferably 30 to 150.

The ethylene / α-olefin / non-conjugated polyene copolymer rubber (C) as described above can be produced by a conventionally known method.

  Further, if necessary, an ethylene / α-olefin copolymer rubber different from (A) and (B) may be blended.

The α-olefin composing the ethylene / α-olefin copolymer rubber is ethylene / α-
This is the same as the α-olefin constituting the olefin / non-conjugated polyene copolymer rubber. The ethylene / α-olefin copolymer rubber has a constitutional unit content (ethylene content) derived from ethylene of 50 mol% or more, usually 50 to 90 mol%, preferably 60 to 85 mol%, and has a carbon atom number. The content of structural units derived from 3 to 20 α-olefin (α-olefin content) is 50 mol% or less, usually 50 to 10 mol%, preferably 40 to 15 mol%.

  The ethylene / α-olefin / non-conjugated polyene copolymer rubber (C) of the present invention is a total amount of 100 wt.% Of isotactic polypropylene (A) and propylene / ethylene (• α-olefin) random copolymer (B). 2 to 1900 parts by weight, preferably 10 to 1000 parts by weight, and more preferably 50 to 500 parts by weight with respect to parts. When the amount of the ethylene / α-olefin / non-conjugated polyene copolymer rubber (C) is 1900 parts by weight or more, the extrudability may deteriorate and the productivity may deteriorate.

  The thermoplastic elastomer composition according to the present invention comprises the above component (A) and component (B), or a blend comprising component (A), component (B) and component (C) in the presence of a crosslinking agent. It can be prepared by dynamic heat treatment.

  For example, 1 to 40 parts by weight of isotactic polypropylene (A) and 45 to 89 mol% of a propylene component, 10 to 25 mol% of an ethylene component, and optionally a component unit derived from an α-olefin having 4 to 20 carbon atoms Is added to 100 parts by weight of a composition obtained by mixing 60 to 99 parts by weight of a propylene / ethylene (.α-olefin) random copolymer (B) containing 0 to 30% by mole of isotactic polypropylene (A) 5 to By mixing 1900 parts by weight and crosslinking, 1 to 98 parts by weight of isotactic polypropylene (A) and 2 to 99 parts by weight of the propylene / ethylene (• α-olefin) random copolymer (B) are included. [The total of (A) and (B) is 100 parts by weight], a thermoplastic elastomer group in which the propylene / ethylene (• α-olefin) random copolymer (B) is crosslinked It is possible to manufacture things.

  Further, ethylene is further added to 100 parts by weight of a composition obtained by mixing 1 to 40 parts by weight of isotactic polypropylene (A) and 60 to 99 parts by weight of the propylene / ethylene (.alpha.-olefin) random copolymer (B). By mixing and cross-linking 2 to 1900 parts by weight of ethylene / α-olefin / non-conjugated polyene copolymer rubber (C) composed of an α-olefin having 3 to 20 carbon atoms and a non-conjugated polyene, (B) 2 to 1900 parts by weight of ethylene / α-olefin / non-conjugated polyene copolymer rubber (C) with respect to a total of 100 parts by weight of propylene / ethylene (• α-olefin) random copolymer (B ) And an ethylene / α-olefin / non-conjugated polyene copolymer rubber (C) component can be produced.

In addition, 100 parts by weight of a composition obtained by mixing 1 to 40 parts by weight of isotactic polypropylene (A) and 60 to 99 parts by weight of the propylene / ethylene (• α-olefin) random copolymer (B) is further added to isotactic. By mixing and crosslinking the tic polypropylene (A) 5 to 1900 parts by weight and the ethylene / α-olefin / non-conjugated polyene copolymer rubber (C) 2 to 1900 parts by weight, the (A) and (B) Of ethylene / α-olefin / non-conjugated polyene copolymer rubber (C) 2 to 1900 parts by weight, and propylene / ethylene (• α-olefin) random copolymer (B) and ethylene. A thermoplastic elastomer composition in which the α-olefin / non-conjugated polyene copolymer rubber (C) component is crosslinked can be produced.
Here, “dynamically heat-treating” means kneading in a molten state (hereinafter the same).

  In the present invention, the component (A), the component (B), and the component (A), the component (B), or the components (A) and (B) are further added in the presence of a crosslinking agent. You may adjust by carrying out "dynamic heat processing."

   In the above production method and the production method using the thermoplastic elastomer composition (D) described later, 1 to 40 parts by weight of isotactic polypropylene (A) and propylene / ethylene (• α-olefin) random copolymer (B ) In the composition obtained by mixing 60 to 99 parts by weight, in the endothermic curve in the differential scanning calorimeter (DSC), the maximum peak of the melting point (Tm, ° C) exists at 100 ° C or higher, and the heat of fusion is 5 to 40 It is preferably in the range of / g.

  A composition in which 1 to 40 parts by weight of isotactic polypropylene (A) and 60 to 99 parts by weight of propylene / ethylene (.α-olefin) random copolymer (B) are mixed is preferably obtained by melt press molding. The haze in the obtained 1 mm sheet is 30% or less.

A composition in which 1 to 40 parts by weight of isotactic polypropylene (A) and 60 to 99 parts by weight of propylene / ethylene (.alpha.-olefin) random copolymer (B) are mixed is a styrene or ethylene block copolymer. It is a composition that does not contain a polymer, and preferably satisfies the following ( a ), ( b ), ( c ), and ( d ).

(A) in dynamic viscoelasticity measurement at torsion mode (10 rad / s), a peak of loss tangent (tan [delta) in the range of -25 ° C. to 25 ° C., and is a value of 0.5 or more,
( B ) The ratio G ′ (20 ° C./G ′ (100 ° C.)) of the storage elastic modulus G ′ (20 ° C.) and G ′ (100 ° C.) obtained from the dynamic viscoelasticity measurement is 5 or less ( c ) Needle penetration temperature (° C.) measured according to JIS K7196 is 100 ° C. to 168 ° C. ( d ) 100% strain is applied at 30 mm between chucks and at a pulling speed of 30 mm / min. The residual strain after 10 minutes of loading is 20% or less.

Crosslinking agent Examples of the crosslinking agent used in the present invention include organic peroxides, sulfur, sulfur compounds,
Examples thereof include phenolic vulcanizing agents such as phenol resins, among which organic peroxides are preferably used.

Specific examples of organic peroxides include dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexane, and 2,5-dimethyl-2. ,Five-
Di (tert-butylperoxy) hexyne-3, 1,3-bis (tert-butylperoxyisopropyl) benzene, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, n-butyl- 4,4-bis (tert-butylperoxy) valerate, benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, tert-butyl peroxybenzoate, tert-butyl perbenzoate, tert-butyl peroxyisopropyl carbonate, diacetyl Peroxide, lauroyl peroxide, tert-
Examples include butyl cumyl peroxide.

Among them, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne-3 in terms of odor and scorch stability 1,3-bis (tert-butylperoxyisopropyl) benzene, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane and n-butyl-4,4-bis (tert-butylperoxy) ) Valerate is preferred, with 1,3-bis (tert-butylperoxyisopropyl) benzene being most preferred.

  This organic peroxide is 0.01 to 15 parts by weight, preferably 100 parts by weight of the total amount of isotactic polypropylene (A) and propylene / ethylene (• α-olefin) random copolymer (B), preferably It is used at a ratio of 0.03 to 12 parts by weight. When the organic peroxide is used in the above ratio, a thermoplastic elastomer composition in which component (B) and component (C) are crosslinked is obtained, and a molded article having sufficient heat resistance, tensile properties and rubber elasticity is obtained. . Moreover, this composition is excellent in moldability.

Crosslinking aid In the present invention, in the crosslinking treatment with the organic peroxide, sulfur, p-quinonedioxime, p, p'-dibenzoylquinonedioxime, N-methyl-N, 4-dinitrosoaniline, nitrobenzene , Diphenylguanidine, trimethylolpropane-N, N'-m-phenylenedimaleimide and other crosslinking aids, or divinylbenzene, triallyl cyanurate, eletin glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylol Polyfunctional methacrylate monomers such as propane trimethacrylate and allyl methacrylate, and polyfunctional vinyl monomers such as vinyl butyrate or vinyl stearate can be blended. By such a compound, a uniform and mild crosslinking reaction can be expected. In particular, in the present invention, when divinylbenzene is used,
Ease of handling, isotactic polypropylene (A), propylene / ethylene (• α-olefin) random copolymer (B), and optionally ethylene / α-olefin / non-conjugated polyene copolymer Good compatibility with the combined rubber (C), solubilizing organic peroxides, and acting as a dispersion aid for organic peroxides. Therefore, the crosslinking effect by heat treatment is uniform, and the balance between fluidity and physical properties. Most preferred because a good composition is obtained.

Softener A softener may be added as a fluidity or hardness adjusting agent during dynamic crosslinking.

Specifically, petroleum-based softeners such as process oil, lubricating oil, paraffin, liquid paraffin, polyethylene wax, polypropylene wax, petroleum asphalt, and petroleum jelly;
Coal tar softeners such as coal tar and coal tar pitch;
Fatty oil softeners such as castor oil, linseed oil, rapeseed oil, soybean oil, coconut oil;
Tall oil;
Sub, (Factis);
Waxes such as beeswax, carnauba wax, lanolin;
Fatty acids and fatty acid salts such as ricinoleic acid, palmitic acid, stearic acid, barium stearate, calcium stearate, zinc laurate;
Naphthenic acid;
Pine oil, rosin or derivatives thereof;
Synthetic polymer materials such as terpene resin, petroleum resin, coumarone indene resin, atactic polypropylene;
Ester softeners such as dioctyl phthalate, dioctyl adipate, dioctyl sebacate;
Examples thereof include microcrystalline wax, liquid polybutadiene, modified liquid polybutadiene, liquid polyisoprene, terminal-modified polyisoprene, hydrogenated terminal-modified polyisoprene, liquid thiocol, and hydrocarbon-based synthetic lubricating oil. Among these, petroleum softeners, particularly process oils are preferably used.

The dynamic heat treatment in the present invention is preferably performed in a non-open type apparatus, and is preferably performed in an inert gas atmosphere such as nitrogen or carbon dioxide.

The kneading temperature is usually 150 to 280 ° C, preferably 170 to 240 ° C. The kneading time is usually 1 to 20 minutes, preferably 3 to 10 minutes. The applied shear force is
The shear rate is 10 to 100,000 sec-1, preferably 100 to 50,000 sec-1.

As a kneading apparatus, a mixing roll, an intensive mixer (for example, a Banbury mixer, a kneader), a single-screw or twin-screw extruder can be used, and a non-open type apparatus is preferable.

Additives In the thermoplastic elastomer composition according to the present invention, additives such as slip agents, nucleating agents, fillers, antioxidants, weathering stabilizers, colorants, and the like are impaired as necessary. It can mix | blend in the range which is not.

Examples of the nucleating agent include non-melting type and melting type crystallization nucleating agents, and these can be used alone or in combination of two or more. Non-melting crystallization nucleating agents include inorganic substances such as talc, mica, silica, aluminum, brominated biphenyl ether, aluminum hydroxydi-p-tert-butylbenzoate (TBBA), organophosphate, rosin crystallization Nucleating agents, substituted triethylene glycol terephthalate and Terylene &
Nylon fiber and the like, and particularly hydroxy-di-p-tert-butylbenzoic acid aluminum salt, methylene bis (2,4-di-tert-butylphenyl) phosphate sodium salt, 2,2′-methylene bis (4,6- Di-tert-butylphenyl) sodium phosphate and rosin crystallization nucleating agent are desirable. Melting crystallization nucleating agents include dibenzylidene sorbitol (DBS), substituted DBS, lower alkyl dibenzylidene sorbitol (PDTS).
), And the like.

Examples of the slip agent include fatty acid amide, silicone oil, glycerin, wax, and paraffinic oil.

Examples of the filler include conventionally known fillers, specifically, carbon black, clay, talc, calcium carbonate, kaolin, diatomaceous earth, silica, alumina, graphite, glass fiber and the like.

  The thermoplastic elastomer composition of the present invention is prepared by “dynamically heat-treating” the following thermoplastic elastomer composition (D) into a composition obtained by previously melt-kneading the components (A) and (B). May be.

Thermoplastic elastomer composition (D)
The thermoplastic elastomer composition (D) used in the present invention is obtained by mixing the above-mentioned isotactic polypropylene (A) and ethylene / α-olefin / non-conjugated polyene copolymer rubber (C) to produce ethylene / α-olefin / It is a thermoplastic elastomer composition in which at least a part of the non-conjugated polyene copolymer rubber (C) is crosslinked.

  As the isotactic polypropylene (A), the above-mentioned isotactic polypropylene (A) is used, and a homopolypropylene or a propylene block copolymer is preferable.

  The melt flow rate (MFR; ASTM D1238, 230 ° C., 2.16 kg load) of the isotactic polypropylene (A) used here is preferably 0.5 to 90 g / 10 min.

  Examples of the ethylene / α-olefin / non-conjugated polyene copolymer rubber (C) used herein include the above-described ethylene / α-olefin / non-conjugated polyene copolymer rubber (C).

  Isotactic polypropylene (A) and ethylene / α-olefin / nonconjugated polyene copolymer rubber (C) are used in proportions of isotactic polypropylene (A) and ethylene / α-olefin / nonconjugated polyene copolymer rubber. 10 to 80 parts by weight of isotactic polypropylene (A), preferably 15 to 60 parts by weight, and 90% of ethylene / α-olefin / non-conjugated polyene copolymer rubber (C) with respect to 100 parts by weight of the total of (C). It is desirable to be -20 parts by weight, preferably 85-40 parts by weight. When the proportion of isotactic polypropylene (A) and ethylene / α-olefin / non-conjugated polyene copolymer rubber (C) is within the above range, the thermoplastic resin is excellent in flexibility and rubber elasticity and excellent in molding. An elastomer composition is obtained.

  The thermoplastic elastomer composition (D) used in the present invention is prepared by “dynamically heat-treating” the component (A) and the component (C) in the presence of the above-described crosslinking agent.

  Moreover, you may mix | blend crystalline polyolefin resin other than a component (A) as needed at the time of dynamic bridge | crosslinking. Specific examples of suitable raw material olefins for such crystalline polyolefin resins include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, and 2-methyl-1-propene. , 3-methyl-1-pentene, 4-methyl-1-pentene, 5-methyl-1-hexene and the like, and α-olefins having 2 to 20 carbon atoms, preferably 2 to 12 carbon atoms, are mentioned. These α-olefins are used alone or in combination of two or more.

The polymerization mode may be random type or block type, and any polymerization mode can be adopted as long as a resinous material is obtained.

  Such a crystalline polyolefin resin has a melt flow rate (MFR: ASTM D 1238-65T, 230 ° C., 2.16 kg load) usually 0.01 to 100 g / 10 min, preferably 0.05 to 50 g / 10 min. It is desirable to be in the range.

  Crystalline polyolefin resin may be used independently and may be used in combination of 2 or more type. Although there is no restriction | limiting in particular as said crystalline polyolefin resin, Polyethylene etc. can be illustrated.

  Furthermore, the thermoplastic elastomer composition (D) does not impair the purpose of the present invention with additives such as the above-mentioned softeners, slip agents, nucleating agents, fillers, weathering stabilizers, and colorants as necessary. It can mix | blend in the range.

  For example, the thermoplastic elastomer composition of the present invention is obtained by “dynamically heat-treating” the thermoplastic elastomer composition (D) and the composition obtained by previously melt-kneading the components (A) and (B). It is done. “Dynamic heat treatment” can be performed by the method described above.

  The thermoplastic elastomer composition (D) of the present invention comprises 1 to 40 parts by weight of isotactic polypropylene (A) and 60 to 99 parts by weight of propylene / ethylene (• α-olefin) random copolymer (B). 5 to 1900 parts by weight, preferably 10 to 1000 parts by weight, and more preferably 50 to 500 parts by weight with respect to 100 parts by weight.

The thermoplastic elastomer composition according to the present invention has a gel content of 0.5 to 95% by weight treated in xylene at 140 ° C. for 24 hours. When the gel content is within this range, a thermoplastic elastomer composition excellent in rubber elasticity, particularly permanent elongation at ordinary temperature and compression set at high temperature, can be obtained.

  The thermoplastic elastomer composition according to the present invention can prepare a thermoplastic elastomer molded body by various molding methods such as extrusion molding, press molding, injection molding, and calendar molding.

  In addition, the thermoplastic elastomer molded body according to the present invention is not particularly limited in its usage, but it is used for automobile parts, especially automobile skin materials and seal members, or building material parts, particularly seal materials and gasket materials, Suitable for electrical parts and daily necessities.

  According to the present invention, isotactic polypropylene (A) and propylene component are 45 to 89 mol%, ethylene component is 10 to 25 mol%, and component units derived from α-olefin having 4 to 20 carbon atoms as necessary. Propylene / ethylene (.alpha.-olefin) random copolymer (B) containing 0 to 30 mol%, or (A) and (B) and ethylene.alpha.-olefin / non-conjugated polyene copolymer rubber ( C), a thermoplastic elastomer composition in which a propylene / ethylene (.alpha.-olefin) random copolymer (B) and an ethylene.alpha.-olefin / nonconjugated polyene copolymer rubber (C) component are crosslinked. , Excellent in mechanical strength, rubber elasticity, or transparency.

EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited at all by these Examples.

[Synthesis Example 1]
Synthesis of Propylene / Ethylene / Butene Copolymer (B-1) After charging 917 ml of dry hexane, 85 g of 1-butene and triisobutylaluminum (1.0 mmol) in a 2000 ml polymerization apparatus sufficiently purged with nitrogen at room temperature. The temperature inside the polymerization apparatus was raised to 65 ° C., and the pressure inside the system was increased to 0.77 MPa with propylene, and then the system pressure was adjusted to 0.78 MPa with ethylene. Next, a toluene solution in which 0.002 mmol of dimethylmethylene (3-tert-butyl-5-methylcyclopentadienyl) fluorenylzirconium dichloride and 0.6 mmol of methylaluminoxane (produced by Tosoh Finechem) in contact with aluminum were contacted. Was added to the polymerization vessel, polymerization was carried out for 20 minutes while maintaining the internal temperature at 65 ° C. and the internal pressure at 0.78 MPa with ethylene, and 20 ml of methanol was added to terminate the polymerization. After depressurization, the polymer was precipitated from the polymerization solution in 2 L of methanol and dried under vacuum at 130 ° C. for 12 hours. The obtained polymer was 60.4 g, intrinsic viscosity [η] was 1.81 dl / g, glass transition temperature Tg was −27 ° C., ethylene content was 13 mol%, butene content was 19 The molecular weight distribution measured by GPC (Mw / Mn))) was 2.4. Further, a clear melting peak could not be confirmed for the heat of fusion by DSC measurement.
The methods for measuring intrinsic viscosity [η], DSC measurement (glass transition temperature (Tg) and melting point (Tm)), and molecular weight distribution (Mw / Mn) are as follows.

A composition in which isotactic polypropylene (A) and propylene / ethylene / butene copolymer (B-1) are mixed. Isotactic polypropylene (A-1) [MFR (ASTM D 1238, 230 ° C., 2.16 kg load) ): 3 g / 10 min] 15 parts by weight and 85 parts by weight of the propylene / ethylene / butene copolymer (B-1) obtained in Synthesis Example 1 were used in an extruder [Part No. KTX-46, Kobe Steel Co., Ltd. ), Cylinder temperature: C1 to C2 ; 120 ° C, C3 to C4 ; 140 ° C, C5 to C6 ; 180 ° C, C7 to C8 ; 200 ° C, C9 to C14 ; 220 ° C, die temperature: 210 ° C, screw rotation speed : 400 rpm, extrusion rate: 60 kg / h], kneading was carried out to obtain pellets of a composition in which (A) and (B) were mixed. The obtained composition was evaluated according to the following method. The results are shown in Table 1.

[Intrinsic viscosity [η]]
Measurements were made at 135 ° C. in decalin.

[Glass transition temperature (Tg) and melting point (Tm)]
An endothermic curve of DSC is obtained, and the temperature at the maximum peak position is defined as Tm. In the DSC measurement, the sample was packed in an aluminum pan, heated to 200 ° C. at 100 ° C./min, held at 200 ° C. for 10 minutes, then decreased to −150 ° C. at 10 ° C./min at 100 ° C./min, and then It calculated | required from the endothermic curve at the time of heating up at 10 degree-C / min.

[Mw / Mn]
GPC (gel permeation chromatography) was used and measured at 140 ° C. with an orthodichlorobenzene solvent.

[Dynamic viscoelasticity measurement]
Using RDS-II made by Rheometric Co., measured at 10HZ from -100 ° C to 100 ° C at a rate of temperature rise of 2 ° C / min in a torsion mode (twist) between 10mm in width and 38mm in length. The values of loss tangent tan δ and storage modulus G ′ were obtained.

[Needle penetration temperature (℃)]
In accordance with JIS K7196, using a test piece with a thickness of 1 mm, a pressure of 2 kg / cm 2 was applied to a flat indenter of 1.8 mmφ at a heating rate of 5 ° C./min, and the needle entry temperature (° C.) was calculated from the TMA curve. Asked.

[Residual strain];
A dumbbell piece with a length of 50 mm (L0), a width of 5 mm, and a 1 mm thick dumbbell piece is given a strain of 30 mm between the marked lines at a pulling speed of 30 mm / min. Measure length (L). Residual strain (%) = [(L-30) / 30] × 100.

[Haze (%)]
Using a test piece having a thickness of 1 mm, measurement was performed with a digital turbidimeter “NDH-20D” manufactured by Nippon Denshoku Industries Co., Ltd.

  The thermoplastic elastomer compositions obtained in the following examples and comparative examples were subjected to hardness, tensile strength, tensile elongation, permanent elongation, and compression set according to the following methods.

(1) Hardness As for hardness, Shore A hardness was measured in accordance with JIS K6253.
(Measurement conditions) A sheet was prepared by a press molding machine, and the scale was read immediately after contact with the pressing needle using an A-type measuring instrument.

(2) Tensile strength and elongation In accordance with JIS K6251, a tensile test was performed under the following conditions, and the tensile strength and elongation at break were measured.
(Test conditions) A sheet was prepared by a press molding machine, and a JIS No. 3 test piece was punched out under the conditions of a tensile speed of 500 mm / min.

(3) Permanent Elongation (Test Conditions) A sheet was prepared by a press molding machine, a JIS No. 3 test piece was punched and stretched 100% and held for 10 minutes, and the residual strain after 10 minutes of load removal was defined as permanent elongation.

(4) Compression set The compression set was measured according to JIS K6262.
(Measurement conditions) A cylindrical test piece having a diameter of 29 mm and a height of 12.5 mm was molded by an injection molding machine, and the compression rate was 25% and the conditions were 70 ° C. and 24 hours.

(5) Samples were 100g collected gel content Thermoplastic elastomer composition, samples xylene 140 ° C. This was cut into strips 0.5 mm × 0.5 mm × 0.5 mm, was immersed for 24 hours, the sample Is taken out on a filter paper and dried in a vacuum dryer at room temperature for 24 hours or more until a constant weight is obtained. From the weight of the dry residue, filler, filler, the amount obtained by subtracting the weight of xylene insoluble components such as pigments and "final weight". On the other hand, the amount obtained by adding the weights of the propylene / ethylene / α-olefin random copolymer (B) and the ethylene / α-olefin / non-conjugated polyene copolymer rubber (C) is defined as “initial weight”. The gel content was determined by the following formula.
Gel content (% by weight ) = “final weight (Y)” / “initial weight (X)” × 100

[ Reference Example 1]
15 parts by weight of isotactic polypropylene (A-1) [MFR (ASTM D 1238, 230 ° C., 2.16 kg load): 3 g / 10 min] and the propylene / ethylene / butene copolymer obtained in Synthesis Example 1 (B-1) 85 parts by weight,
As a crosslinking agent, 0.3 part by weight of an organic peroxide [manufactured by NOF Corporation, trade name: Perhexa 25B]
0.3 parts by weight of divinylbenzene as a crosslinking aid and 0.1 parts by weight of a phenolic antioxidant [Nippon Ciba Geigy Co., Ltd., trade name: Irganox 1010] as an antioxidant;
Are sufficiently mixed with a Henschel mixer, and an extruder [product number KTX-46, manufactured by Kobe Steel, cylinder temperature: C1 to C2; 120 ° C, C3 to C4; 140 ° C, C5 to C6; 180 ° C, C7 to C8. Kneading at 200 ° C., C9 to C14; 220 ° C., die temperature: 210 ° C., screw rotation speed: 400 rpm, extrusion rate: 60 kg / h] to obtain pellets of a thermoplastic elastomer composition.
The obtained thermoplastic elastomer composition was evaluated according to the method described above. The results are shown in Table 2.

[ Reference Example 2]
In the same manner as in Reference Example 1, except that 5 parts by weight of isotactic polypropylene (A-1) and 95 parts by weight of propylene / ethylene / butene copolymer (B-1) were changed in Reference Example 1, A pellet of the plastic elastomer composition was obtained.
The obtained thermoplastic elastomer composition was evaluated according to the method described above. The results are shown in Table 2.

[ Reference Example 3]
Except for changing the 65 parts by weight 35 parts by weight of propylene-ethylene-butene copolymer (B-1) an isotactic polypropylene (A-1) in Reference Example 1, in the same manner as in Reference Example 1, the thermal A pellet of the plastic elastomer composition was obtained.
The obtained thermoplastic elastomer composition was evaluated according to the method described above. The results are shown in Table 2.

[ Reference Example 4]
Kneaded at isotactic polypropylene in Reference Example 1 (A-1) 15 parts by weight of propylene-ethylene-butene copolymer (B-1) 85 parts by weight of the extruder [the same manner as in Reference Example 1 was mixed A composition was obtained. A thermoplastic elastomer composition is prepared by kneading 100 parts by weight of this composition, 15 parts by weight of isotactic polypropylene (A-1), a crosslinking agent, a crosslinking assistant, and an antioxidant in the same manner as in Reference Example 1. Pellets were obtained.
The obtained thermoplastic elastomer composition was evaluated according to the method described above. The results are shown in Table 2.

[Example 1 ]
100 parts by weight of the mixed composition of Reference Example 4 and oil-extended ethylene / propylene / 5-ethylidene-2-norbornene copolymer rubber (C-1) [ethylene content: 57 wt%, diene content: 7.3 wt%, Mooney viscosity [ML _{1 + 4} (125 ° C.)] 74, oil extended amount: 100 parts by weight of rubber, 40 parts by weight of paraffinic process oil (made by Idemitsu Kosan Co., Ltd., trade name PW-380)] 230 parts by weight In the same manner as in Reference Example 1, a pellet of a thermoplastic elastomer composition was obtained.
The obtained thermoplastic elastomer composition was evaluated according to the method described above. The results are shown in Table 2.

[Example 2 ]
Except for changing in Example 1 oil-extended ethylene-propylene-5-ethylidene-2-norbornene copolymer rubber (C-1) to 1500 parts by weight, in the same manner as in Example 1, the thermoplastic elastomer composition Pellets were obtained.
The obtained thermoplastic elastomer composition was evaluated according to the method described above. The results are shown in Table 2.

[Example 3 ]
And mixed 100 parts by weight of the composition of Example 4, further isotactic polypropylene (A-1) 15 parts by weight of the Example 1 oil-extended ethylene-propylene-5-ethylidene-2-norbornene copolymer rubber (C -1) In the same manner as in Reference Example 1, 230 parts by weight of a thermoplastic elastomer composition pellet was obtained.
The obtained thermoplastic elastomer composition was evaluated according to the method described above. The results are shown in Table 2.

[Example 4 ]
Except for changing 1000 parts by weight of the isotactic polypropylene (A-1) of Example 3 and 1500 parts by weight of the oil-extended ethylene / propylene / 5-ethylidene-2-norbornene copolymer rubber (C-1), In the same manner as in Example 3 , pellets of a thermoplastic elastomer composition were obtained.
The obtained thermoplastic elastomer composition was evaluated according to the method described above. The results are shown in Table 2.

[ Reference Example 5]
100 parts by weight of the mixed composition of Reference Example 4 and 230 parts by weight of the thermoplastic elastomer composition (D-1) prepared below were melt-kneaded using an extruder to obtain pellets of the thermoplastic elastomer composition.
The obtained thermoplastic elastomer composition was evaluated according to the method described above. The results are shown in Table 2.

Thermoplastic elastomer composition (D-1)
30 parts by weight of isotactic polypropylene (A-2) [MFR (ASTM D 1238, 230 ° C., 2.16 kg load): 15 g / 10 min] and the oil-extended ethylene / propylene / 5-ethylidene-2- of Example 1 70 parts by weight of norbornene copolymer rubber (C-1) and a crosslinking agent, a crosslinking aid, and an antioxidant are kneaded in the same manner as in Example 1, and 10 parts by weight of the paraffinic process oil of Example 1 Was injected into the cylinder to obtain pellets of the thermoplastic elastomer composition (D-1).

[Comparative Example 1]
In Reference Example 1, pellets of a thermoplastic elastomer composition were obtained in the same manner except that the crosslinking agent and the crosslinking aid were not used.
The obtained thermoplastic elastomer composition was evaluated according to the method described above. The results are shown in Table 2.

[Comparative Example 2]
In Example 1 , pellets of a thermoplastic elastomer composition were obtained in the same manner except that a crosslinking agent and a crosslinking aid were not used.
The obtained thermoplastic elastomer composition was evaluated according to the method described above. The results are shown in Table 2.

[Comparative Example 3]
The thermoplastic elastomer composition (D-1) obtained in Example 5 was evaluated according to the method described above. The results are shown in Table 2.

Claims (10)

1 to 40 parts by weight of isotactic polypropylene (A) and 45 to 89 mol% of the propylene component, 10 to 25 mol% of the ethylene component, and 0 component units derived from an α-olefin having 4 to 20 carbon atoms as necessary. In addition to 100 parts by weight of a composition obtained by mixing 60 to 99 parts by weight of propylene / ethylene (.α-olefin) random copolymer (B) in an amount of ˜30 mol%, ethylene, and an α-olefin having 3 to 20 carbon atoms. And 1 to 40 parts by weight of isotactic polypropylene (A) by mixing 2 to 1900 parts by weight of ethylene / α-olefin / nonconjugated polyene copolymer rubber (C) composed of non-conjugated polyene and crosslinking. The propylene component is 45 to 89 mol%, the ethylene component is 10 to 25 mol%, and the component unit derived from the α-olefin having 4 to 20 carbon atoms is optionally 0 to 0 mole% of the amount including propylene-ethylene (- alpha-olefin) random copolymer (B) to 60 to 99 parts by weight include [(A) and total 100 parts by weight of (B)], the propylene-ethylene (- [alpha] -olefin) random copolymer (B) is crosslinked, and further, ethylene, C3-C20 [alpha] -olefin and non-conjugated polyene with respect to a total of 100 parts by weight of (A) and (B). 2 to 1900 parts by weight of an ethylene / α-olefin / non-conjugated polyene copolymer rubber (C) comprising propylene / ethylene / (α-olefin) random copolymer (B) and ethylene / α-olefin / non A method for producing a thermoplastic elastomer composition, comprising producing a thermoplastic elastomer composition in which a conjugated polyene copolymer rubber (C) component is crosslinked. 1 to 40 parts by weight of isotactic polypropylene (A) and 45 to 89 mol% of the propylene component, 10 to 25 mol% of the ethylene component, and 0 component units derived from an α-olefin having 4 to 20 carbon atoms as necessary. The isotactic polypropylene (A) 5 to 1900 is further added to 100 parts by weight of a composition obtained by mixing 60 to 99 parts by weight of propylene / ethylene (.α-olefin) random copolymer (B) in an amount of ˜30 mol%. By mixing 2 to 1900 parts by weight of ethylene / α-olefin / non-conjugated polyene copolymer rubber (C) composed of parts by weight and ethylene, an α-olefin having 3 to 20 carbon atoms and a non-conjugated polyene, and crosslinking, 1-40 parts by weight of isotactic polypropylene (a), from 45 to 89 mol% of propylene component, the ethylene component 10 to 25 mol% 60-99 parts by weight comprising a propylene-ethylene (- alpha-olefin) random copolymer comprising an amount of 0 to 30 mol% of constituent units derived from the alpha-olefin having 4 to 20 carbon atoms (B) as required [ The total of (A) and (B) is 100 parts by weight], the propylene / ethylene (• α-olefin) random copolymer (B) is crosslinked, and the total of (A) and (B) is 100. Including 2 to 1900 parts by weight of ethylene / α-olefin / non-conjugated polyene copolymer rubber (C) composed of ethylene, an α-olefin having 3 to 20 carbon atoms and a non-conjugated polyene with respect to parts by weight, propylene / ethylene ( · A thermoplastic elastomer composition in which an α-olefin) random copolymer (B) and an ethylene · α-olefin · non-conjugated polyene copolymer rubber (C) component are crosslinked. Method for producing a thermoplastic elastomer composition characterized.   A composition obtained by mixing 1 to 40 parts by weight of the isotactic polypropylene (A) and 60 to 99 parts by weight of the propylene / ethylene (.alpha.-olefin) random copolymer (B) is a differential scanning calorimeter (DSC). In the endothermic curve in (1), the maximum peak of the melting point (Tm, ° C) is present at 100 ° C or higher, and the heat of fusion is in the range of 5 to 40 J / g. A process for producing a thermoplastic elastomer composition.   It was obtained by melt press molding of a composition in which 1 to 40 parts by weight of the isotactic polypropylene (A) and 60 to 99 parts by weight of the propylene / ethylene (• α-olefin) random copolymer (B) were mixed. The method for producing a thermoplastic elastomer composition according to claim 1 or 2, wherein a haze in a 1 mm sheet is 30% or less. A composition in which 1 to 40 parts by weight of the isotactic polypropylene (A) and 60 to 99 parts by weight of the propylene / ethylene (• α-olefin) random copolymer (B) are mixed together is a styrene-based or ethylene-based block copolymer. The thermoplastic elastomer composition according to claim 1 or 2, wherein the composition does not contain a polymer and satisfies the following (a), (b), (c), and (d): Manufacturing method.
(A) In dynamic viscoelasticity measurement (10 rad / s) in torsion mode, it has a loss tangent (tan δ) peak in the range of −25 ° C. to 25 ° C., and the value is 0.5 or more,
(B) Ratio G ′ (20 ° C./G ′ (100 ° C.)) of storage elastic modulus G ′ (20 ° C.) and G ′ (100 ° C.) obtained from the dynamic viscoelasticity measurement is 5 or less ( c) Needle penetration temperature (° C.) measured in accordance with JIS K7196 is 100 ° C. to 168 ° C. (d) 100% strain is applied at 30 mm between chucks and at a pulling speed of 30 mm / min. The residual strain after 10 minutes of loading is 20% or less.   Use of 0.01 to 15 parts by weight of a crosslinking agent with respect to 100 parts by weight of the composition (A) + (B) or 100 parts by weight of the composition (A) + (B) + (C). The method for producing a thermoplastic elastomer composition according to claim 1 or 2, wherein   The molded object which consists of a thermoplastic elastomer composition manufactured by the manufacturing method of the thermoplastic elastomer composition of Claim 1 or Claim 2.   The molded article according to claim 7, wherein the molded article is an automotive part.   It is a skin material, The molded object of Claim 7 characterized by the above-mentioned.   It is a sealing material, The molded object of Claim 7 characterized by the above-mentioned.