JP2000226480A - Propylene resin composition and molded product thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide, from a composition, a molded product that is excellent in balance of transparency, impact resistance and surface hardness and especially, from a crosslinking composition that is excellent not only in the balance, but also in abrasion resistance and oil resistance. SOLUTION: The propylene resin composition comprises [I] an ethylene polymer which is made of ethylene, at least one α-olefin having 4 to 20 carbon atoms, a diene and/or triene, has an intrinsic viscosity ranging from 0.01 to 10 dl/g on measurement in decalin at 135 deg.C, a Mw/Mn of 4 or below when measured by GPC, an ethylene content of 30 to 70 mole % and a total content of the diene and/or triene of 0.1 to 10 mole %, and has no crystal melting peak observed by a DSC method, and [II] a propylene resin contained at a specified ratio. This composition may be heated in the presence of a crosslinking agent or subjected to irradiation with an electron beam in the presence or absence of a crosslinking agent, thereby crosslinking the ethylene polymer [I]. The molded product is made of the composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a propylene-based resin composition obtained by mixing an ethylene-based polymer with polypropylene, and a molded product thereof.

[0002]

BACKGROUND OF THE INVENTION Polypropylene is excellent in rigidity, hardness, heat resistance, etc., can be easily formed into a desired shape by various molding methods such as injection molding, calender molding, extrusion molding, and is inexpensive. Therefore, it is widely used in a wide range of applications, such as housing for home appliances, film applications, containers, automotive interior applications, automotive exterior applications such as fenders, bumpers, side moldings, mudguards, mirror covers, and general miscellaneous goods. I have.

In addition, depending on such various uses, polypropylene is mixed with polyethylene or a rubber component such as polyisobutylene, polybutadiene, amorphous or low-crystalline ethylene / 1-butene copolymer (EBR), or the like. Although a polypropylene composition imparted with flexibility and impact resistance is also known, there is a problem in that rigidity and surface hardness are reduced by compounding a rubber component.

Recently, a method has been proposed in which an ethylene / α-olefin copolymer is added to a propylene resin to improve transparency, flexibility and impact resistance. (JP-A-8-269263). However, in this method, although the impact resistance is improved, there is a problem that the surface hardness is greatly reduced. Further, in this composition, since the ethylene / α-olefin copolymer does not contain a diene, a triene, or the like as a component thereof, it is difficult to obtain a crosslinked product, and there is a problem in abrasion resistance and oil resistance. .

[0005] The present inventors have conducted intensive studies in view of such a situation. As a result, when a specific ethylene polymer is used as a modifier for a propylene resin, the transparency, impact resistance and surface hardness are balanced. A propylene-based resin composition capable of producing an excellent molded article was obtained, and a molded article obtained by crosslinking this composition was also found to be excellent in abrasion resistance and oil resistance, and completed the present invention. .

[0006]

SUMMARY OF THE INVENTION The object of the present invention is to solve the problems associated with the prior art as described above, and to provide a molded article having an excellent balance of transparency, impact resistance and surface hardness. It is an object of the present invention to provide a propylene-based resin composition capable of producing a molded article excellent in balance between impact resistance and surface hardness, and also excellent in wear resistance and oil resistance, and a molded article thereof.

[0007]

SUMMARY OF THE INVENTION A propylene resin composition according to the present invention comprises [I] ethylene and one or more kinds of carbon atoms having 4 to 20 carbon atoms.
Having an intrinsic viscosity [η] in the range of 0.01 to 10 dl / g, measured in decalin at 135 ° C., and a GPC
Molecular weight distribution (Mw / Mn) is 4 or less, the ethylene content is 30 to 70 mol%, the total content of diene and / or triene is 0.1 to 10 mol%, and the DSC method 1 to 90 parts by weight of an ethylene-based polymer in which no crystal melting peak is observed, and 99 to 10 parts by weight of a [II] propylene-based resin (components [I] and [II])
Is 100 parts by weight).

At least one of the α-olefins having 4 to 20 carbon atoms constituting the ethylene polymer [I] is 1-butene, 1-hexene, 4-methyl-1-pentene,
It is preferably selected from the group consisting of octene, 1-decene, 1-dodecene and 1-eicosene.

The diene constituting the ethylene polymer [I] includes dicyclopentadiene, 1,4-hexadiene, cyclooctadiene, 1,6-octadiene, 7-methyl
At least one diene selected from the group consisting of -1,6-octadiene, methylene norbornene, ethylidene norbornene, butadiene and isoprene is preferred.

The trienes constituting the ethylene polymer [I] include 4-ethylidene-8-methyl-1,7-nonadiene, 4-ethylidene-1,7-undecadiene and 4,8-
At least one triene selected from the group consisting of dimethyl-1,4,8-decatriene is preferred. Among them, 4-ethylidene-1,7-undecadiene which is a non-conjugated triene is particularly preferred.

The ethylene polymer [I] includes a transition metal complex (a) represented by the following formula (I) or (II):
A copolymer prepared by using a metallocene-based catalyst, which comprises an ionized ionic compound (b), one or more compounds selected from an organoaluminum compound (c) and an alumoxane (d), is preferred.

[0012]

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In the formulas (I) and (II), M is Ti, Z
r, Hf, Rn, Nd, Sm or Ru, and Cp1
And Cp2 are cyclopentadienyl groups bound M and [pi, indenyl group, a fluorenyl group or a derivative group thereof, X ¹ and X ² are anionic ligand or a neutral Lewis base ligand Y is a ligand containing a nitrogen atom, an oxygen atom, a phosphorus atom, or a sulfur atom, and Z is a C, O, B, S, Ge, Si or Sn atom or a atom containing these atoms. It is a group to do. The stereoregularity index [M ₅ ] of the n-decane-insoluble portion at 64 ° C. of the propylene-based resin [II] is desirably 0.970 to 0.995.

The propylene resin composition according to the present invention comprises:
It is desirable that the ethylene polymer [I] be cross-linked by heating in the presence of a cross-linking agent, or by irradiating with an electron beam in the presence or absence of a cross-linking agent.

The molded article according to the present invention is characterized by comprising the propylene resin composition according to the present invention as described above. The molded article according to the present invention includes a molded article made of a non-crosslinked type propylene resin composition and a molded article made of a crosslinked type propylene resin composition, and a balance of transparency, impact resistance and surface hardness. Is better and better. Among the molded articles according to the present invention, a molded article composed of a crosslinked type propylene-based resin composition has excellent balance of transparency, impact resistance and surface hardness, as well as oil resistance,
Excellent wear resistance.

[0016]

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the propylene-based resin composition and the molded product thereof according to the present invention will be specifically described.

The propylene resin composition according to the present invention comprises:
It is a thermoplastic elastomer composition containing an ethylene-based polymer [I] and a propylene-based resin [II], and can be roughly classified into a non-crosslinked type and a crosslinked type.

First, each component forming the propylene resin composition according to the present invention will be described. Ethylene Polymer [I] The ethylene polymer [I] used in the present invention comprises ethylene, one or more α-olefins having 4 to 20 carbon atoms, and diene and / or triene.
A ternary or higher random copolymer in which no crystal melting peak is observed by the method. Here, “the crystal melting peak is not observed by the DSC method” means that the heat of fusion of the maximum peak in the endothermic curve is 2.0 J / g or less, and the ethylene-based polymer [I] is amorphous. Is a random copolymer, that is, an elastomer.

In the present invention, since the ethylene polymer [I] in which no crystal melting peak is observed by the DSC method is used, a propylene resin composition excellent in whitening resistance can be obtained. 4 to 4 carbon atoms constituting the ethylene polymer [I]
Specific examples of the α-olefin of 20 include 1-butene, 1-hexene, 3-methyl-1-pentene, and 3-ethyl-1-
Penten, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-eicosene and the like. Among them, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-
Octene, 1-decene, 1-dodecene and 1-eicosene are preferred, and 1-butene, 1-hexene, 4-methyl-1-pentene and 1-octene are particularly preferred. In the present invention, when two or more α-olefins having 4 to 20 carbon atoms are used, at least one of them is 1-butene, 1-hexene, 4-
It is preferably selected from the group consisting of methyl-1-pentene, 1-octene, 1-decene, 1-dodecene and 1-eicosene.

The ethylene content of the ethylene polymer [I] varies depending on the type of α-olefin having 4 to 20 carbon atoms, but is usually 30 to 70 mol%, preferably 35 to 70 mol%.
It is desirable that the content be from about 68 to about 68 mol%, more preferably from about 40 to about 65 mol%. When the α-olefin having 4 to 20 carbon atoms is 1-butene, the ethylene content is preferably 3
The content is 0 to 60 mol%, more preferably 30 to 55 mol%. When the number of carbon atoms is 1-octene, it is preferably 35 to 70 mol%, more preferably 40 to 65 mol%.
Mol%.

Examples of the diene constituting the ethylene polymer [I] include 1,4-pentadiene, 1,5-hexadiene, 1,4-hexadiene, 1,4-octadiene and 1,5-pentadiene. Octadiene, 1,6-octadiene, 1,7-octadiene, cyclooctadiene, methylenenorbornene, ethylidene norbornene, vinylnorbornene, dicyclopentadiene, 7-methyl-1,6-octadiene, 4-ethylidene-8-
Non-conjugated dienes such as methyl-1,7-nonadiene; conjugated dienes such as butadiene and isoprene; Among them, dicyclopentadiene, 1,4-hexadiene, cyclooctadiene, methylene norbornene, ethylidene norbornene, butadiene and isoprene are preferred.

The above-mentioned dienes can be used alone or in combination of two or more. Specific examples of the triene constituting the ethylene-based polymer [I] include 6,10-dimethyl-1,5,9-undecatriene and 4,8-
Dimethyl-1,4,8-decatriene, 5,9-dimethyl-1,4,8-
Decatriene, 6,9-dimethyl-1,5,8-decatriene, 6,
8,9-trimethyl-1,5,8-decatriene, 6-ethyl-10-methyl-1,5,9-undecatriene, 4-ethylidene-1,6,-
Octadiene, 7-methyl-4-ethylidene-1,6-octadiene, 4-ethylidene-8-methyl-1,7-nonadiene (EM
ND), 7-methyl-4-ethylidene-1,6-nonadiene, 7-
Ethyl-4-ethylidene-1,6-nonadiene, 6,7-dimethyl
-4-ethylidene-1,6-octadiene, 6,7-dimethyl-4-
Ethylidene-1,6-nonadiene, 4-ethylidene-1,6-decadiene, 7-methyl-4-ethylidene-1,6-decadiene, 7-
Methyl-6-propyl-4-ethylidene-1,6-octadiene, 4-ethylidene-1,7-nonadiene, 8-methyl-4-ethylidene-1,7-nonadiene, 4-ethylidene-1,7-undecanediene And conjugated trienes such as 1,3,5-hexatriene. Among them, 4,8-dimethyl-
1,4,8-decatriene, 4-ethylidene-8-methyl-1,7-
Nonadiene (EMND) is preferred.

The above-mentioned trienes can be used alone or in combination of two or more. Further, a triene and a diene can be used in combination. The diene and / or the ethylene polymer [I]
Alternatively, the total content of triene is 0.1 to 10 mol%, preferably 0.1 to 8 mol%, more preferably 0.1 to 6 mol%.
It is preferable that the iodine value is 5 to 80,
Preferably, it is 5 to 60, more preferably 5 to 50.

The ethylene polymer [I] used in the present invention has an intrinsic viscosity [η] measured at 135 ° C. in decalin of usually 0.01 to 10 dl / g, preferably 0.05 to 10 dl / g. Is desirably within the range.
When the intrinsic viscosity [η] of the ethylene polymer [I] is within the above range, a propylene resin composition having excellent properties such as abrasion resistance and oil resistance can be obtained.

This ethylene polymer [I] has a molecular weight distribution (Mw / Mn, in terms of polystyrene, Mw: weight average molecular weight, Mn: number average molecular weight) measured by GPC.
It is preferably 4.0 or less. When the Mw / Mn of the ethylene-based polymer [I] is in the above range, the propylene-based resin is excellent in compatibility with the propylene-based resin [II] and can produce a molded article having excellent scratch resistance and impact resistance. It is preferable because a composition can be obtained.

[ Production of Ethylene Polymer [I]] The ethylene polymer [I] used in the present invention comprises, for example, ethylene, at least one α-olefin having 4 to 20 carbon atoms, diene, And / or triene in the presence of a metallocene catalyst shown below.

Such metallocene catalysts include transition metal complexes (a) represented by the following formulas (I) and (II):

[0028]

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[In the formulas (I) and (II), M is Ti, Z
r, Hf, Rn, Nd, Sm or Ru, and Cp1
And Cp2 are cyclopentadienyl groups bound M and [pi, indenyl group, a fluorenyl group or a derivative group thereof, X ¹ and X ² are anionic ligand or a neutral Lewis base ligand Y is a nitrogen atom,
A ligand containing an oxygen atom, a phosphorus atom, or a sulfur atom, wherein Z is C, O, B, S, Ge, Si or Sn
It is an atom or a group containing these atoms. ]When,
At least one catalyst system comprising at least one compound selected from the following components (b), (c) and (d) is used. (B): a compound that reacts with the transition metal M in the component (a) to form an ionic complex (also referred to as an ionized ionic compound) (c): an organoaluminum compound (d): alumoxane.

First, the transition metal complex (a) represented by the following formula (I) used in the present invention will be described. <Transition metal complex (a)>

[0031]

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In the formula (I), M is Ti, Zr, Hf, R
n, Nd, Sm or Ru, preferably Ti, Z
r or Hf, Cp1 and Cp2 are a cyclopentadienyl group, an indenyl group, a fluorenyl group or a derivative thereof bonded to M by π, X ¹ and X ² are an anionic ligand or A neutral Lewis base ligand wherein Z is C, O, B, S, Ge, Si or S
It is an n atom or a group containing these atoms.

In the formula (I), the linking group Z is preferably C, O,
It is preferably one atom selected from B, S, Ge, Si, and Sn, and this atom may have a substituent such as an alkyl group or an alkoxy group, and the substituents of Z are mutually bonded. To form a ring. Of these, Z is preferably selected from O, Si and C.

Cp1 and Cp2 are ligands which coordinate to the transition metal, and include cyclopentadienyl group, indenyl group,
4,5,6,7-tetrahydroindenyl group, a ligand having a cyclopentadienyl skeleton such as a fluorenyl group,
The ligand having a cyclopentadienyl skeleton may have a substituent such as an alkyl group, a cycloalkyl group, a trialkylsilyl group, and a halogen atom.

X ¹ and X ² are anionic ligands or neutral Lewis base ligands, and specifically include a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group, an aryloxy group and a sulfone group. acid-containing group (-SO ₃ Ra, however, Ra
Is an alkyl group, an alkyl group substituted with a halogen atom,
An aryl group, an aryl group substituted with a halogen atom, or an aryl group substituted with an alkyl group. ), A halogen atom, a hydrogen atom and the like.

In the following, M is zirconium, and
A metallocene compound containing two ligands having a cyclopentadienyl skeleton is exemplified. Cyclohexylidene-bis (indenyl) dimethyl zirconium, cyclohexylidene-bis (indenyl) zirconium dichloride, isopropylidene-bis (indenyl) zirconium dichloride, isopropylidene (cyclopentadienyl-fluorenyl) zirconium dichloride, diphenylsilylene-bis (Indenyl) zirconium dichloride, methylphenylsilylene-bis (indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-1
-Indenyl) zirconium dichloride, rac-dimethylsilylene-bis (4,7-dimethyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2,4,
7-trimethyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2,4,6-trimethyl-1
-Indenyl) zirconium dichloride, rac-dimethylsilylene-bis (4-phenyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4-phenyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene -Bis (2-methyl-4- (α-naphthyl) -1-indenyl) zirconium dichloride, ra
c-Dimethylsilylene-bis (2-methyl-4- (β-naphthyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4- (1-anthryl)-
1-indenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) fluorenylzirconium dichloride, isopropyl (cyclopentadienyl-1-fluorenyl) hafnium dichloride, isopropyl (cyclopentadienyl-1-fluorenyl) zirconium dichloride, diphenyl Methylene (cyclopentadienyl) fluorenyl zirconium dichloride and the like.

In addition, metallocene compounds in which zirconium metal is replaced with titanium metal or hafnium metal in the above compounds can also be exemplified. The metallocene compounds as described above can be used alone or in combination of two or more.

The metallocene compound as described above is
It can also be used by being supported on a particulate carrier. As such a particulate carrier, specifically, SiO ₂ , Al ₂
O ₃ , B ₂ O ₃ , MgO, ZrO ₂ , CaO, TiO ₂ ,
Inorganic carriers such as ZnO, SnO ₂ , BaO, and ThO, and organic carriers such as polyethylene, polypropylene, poly-1-butene, poly-4-methyl-1-pentene, and styrene-divinylbenzene copolymer can be used. These particulate carriers can be used alone or in combination of two or more.

In the present invention, not only the fiber metal compound (metallocene compound) represented by the above formula (I) but also the transition metal compound (metallocene compound) represented by the following formula (II)
Can also be used.

[0040]

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In the formula (II), M is a transition metal of Group 4 of the periodic table or a lanthanide series, and specifically, Ti,
Zr, Hf, Rn, Nd, Sm, and Ru, preferably Ti, Zr, and Hf, and Cp1 represents a cyclopentadienyl group, an indenyl group, a fluorenyl group, or a derivative thereof, which is π-bonded to M. X ¹ and X
² is an anionic ligand or a neutral Lewis base ligand, Y is a ligand containing a nitrogen atom, an oxygen atom, a phosphorus atom, or a sulfur atom, and Z is carbon, oxygen, Sulfur, boron or an element of Group 14 of the periodic table (eg, silicon, germanium or tin), preferably any of carbon, oxygen and silicon; Z may have a substituent; Y may form a condensed ring.

More specifically, Cp1 is a ligand which coordinates to a transition metal, and has a cyclopentadienyl skeleton such as a cyclopentadienyl group, an indenyl group, a fluorenyl group or a derivative group thereof. And
The ligand having a cyclopentadienyl skeleton may have a substituent such as an alkyl group, a cycloalkyl group, a trialkylsilyl group, and a halogen atom.

Z is C, O, B, S, Ge, S
i is an atom selected from Sn, Z is an alkyl group,
There may be a substituent such as an alkoxy group, and the substituents of Z may be bonded to each other to form a ring.

X ¹ and X ² are anionic ligands or neutral Lewis base ligands, which may be the same or different from each other, are hydrogen atoms or halogen atoms, or have up to 20 carbon atoms. A hydrocarbon group, a silyl group or a germyl group containing an atom, a silicon atom or a germanium atom.

Specific examples of the compound represented by the formula (II) include (t-butylamido) dimethyl (fluorenyl) silanetitaniumdimethyl, (dimethyl (t-butylamido) (tetramethyl-η ⁵ -cyclopentane) Dienyl)
(Silylene) titanium dichloride, ((t-butylamide)
(Tetramethyl-η ⁵ -cyclopentadienyl) -1,2-ethanediyl) titanium dichloride, (dimethyl (phenylamide) (tetramethyl-η ⁵ -cyclopentadienyl)
(Silylene) titanium dichloride, (dimethyl (t-butylamide) (tetramethyl-η ⁵ -cyclopentadienyl) silylene) titanium dimethyl, (dimethyl (4-methylphenylamide) (tetramethyl-η ⁵ -cyclopentadienyl) silylene) titanium dichloride, (dimethyl (t-butylamido) (eta ⁵ - cyclopentadienyl) silylene) titanium dichloride, (tetramethyl (t-butylamido)
(Tetramethyl-η ⁵ -cyclopentadienyl) disilylene) titanium dichloride.

In the present invention, as the olefin polymerization catalyst, the above-mentioned metallocene catalyst is preferably used. Next, a metallocene-based catalyst is formed. (B): a compound that reacts with the transition metal M in the component (a) to form an ionic complex (that is, an ionized ionic compound); (c): an organoaluminum compound; And (d): alumoxane (aluminum oxy compound) will be described.

<(B) Ionized ionic compound> (b)
The ionized ionic compound (a) is a compound that reacts with the transition metal M in the transition metal complex component to form an ionic complex. Examples of the (b) ionized ionic compound include a Lewis acid and an ionized ion. Compounds, borane compounds and carborane compounds.

As the Lewis acid, a compound represented by BR ₃ (wherein R is a fluorine atom, a phenyl group which may have a substituent such as a methyl group or a trifluoromethyl group or a fluorine atom). For example, trifluoroboron, triphenylboron, tris (4-fluorophenyl) boron, tris (3,5-difluorophenyl)
Boron, tris (4-fluoromethylphenyl) boron,
Tris (pentafluorophenyl) boron, tris (p-
And tris (o-tolyl) boron and tris (3,5-dimethylphenyl) boron.

Examples of the ionic compound include trialkyl-substituted ammonium salts, N, N-dialkylanilinium salts, dialkylammonium salts, and triarylphosphonium salts. Specifically, the trialkyl-substituted ammonium salts include, for example, triethylammonium tetra (phenyl) boron, tripropylammonium tetra (phenyl) boron, tri (n-butyl) boron.
And ammonium tetra (phenyl) boron. Examples of the dialkyl ammonium salt include di (1-propyl) ammonium tetra (pentafluorophenyl) boron and dicyclohexylammonium tetra (phenyl) boron. Further, examples of the ionic compound include triphenylcarbenium tetrakis (pentafluorophenyl) borate, N, N-dimethylaniliniumtetrakis (pentafluorophenyl) borate, and ferrocenium tetra (pentafluorophenyl) borate.

As the borane compound, decaborane (1
4), bis [tri (n-butyl) ammonium] nonaborate, bis [tri (n-butyl) ammonium] decaborate, bis [tri (n-butyl) ammonium] bis (dodecahydride dodecaborate) nickelate (II
And salts of metal borane anions such as I).

Examples of the carborane compound include 4-carbanonaborane (14), 1,3-dicarbanonaborane (13) and bis [tri (n-butyl) ammonium] bis (undecahydride-7-carboundecaborate). Salts of metal carborane anions such as nickelate (IV) are exemplified.

The above-mentioned (b) ionized ionic compounds can be used alone or in combination of two or more. The (d) organic aluminum oxy compound or (b) ionized ionic compound can be used by being supported on the above-mentioned particulate carrier.

In forming the catalyst, the following (c) organoaluminum compound may be used together with (d) the organoaluminum oxy compound and / or (b) the ionized ionic compound.

<(C) Organoaluminum compound> (c)
As the organoaluminum compound, a compound having at least one Al-carbon bond in a molecule can be used. Such compounds include, for example, organoaluminum compounds represented by the following general formula.

(R ¹ ) mAl (O (R ² )) nHpXq (wherein R ¹ and R ² may be the same or different, and usually have 1 to 15, preferably 1 to 1 carbon atoms)
X is a halogen atom, m is 0 <m ≦ 3, n is 0 ≦ n <3, p is 0 ≦ p <3, and q is 0
≦ q <3, and m + n + p + q
= 3. )

<(D) Organoaluminum oxy compound (alumoxane)> The (d) organoaluminum oxy compound may be a conventionally known aluminoxane or benzene as exemplified in JP-A-2-78687. It may be an insoluble organic aluminum oxy compound.

The conventionally known aluminoxane (alumoxane) is specifically represented by the following general formula.

[0058]

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In the formula, R is a hydrocarbon group such as a methyl group, an ethyl group, a propyl group and a butyl group, preferably a methyl group, an ethyl group, and particularly preferably a methyl group. m is an integer of 2 or more, preferably 5 to 40.

Here, the aluminoxane has the formula (OAl (R
¹⁾⁾ alkyloxy aluminum units (here represented by alkyloxy aluminum units and formula represented by (OAl (R ^2)), R ¹ and R ² are the same hydrocarbon group as R, R ¹ and R ² represents a different group.).

The (d) organic aluminum oxy compound may contain a small amount of an organic compound component of a metal other than aluminum. In the present invention, the above-mentioned metallocene-based catalyst is preferably used as the catalyst (olefin-based catalyst) for producing the ethylene-based polymer [I]. In some cases, a conventionally known metallocene-based catalyst other than the metallocene-based catalyst is used. It is also possible to use (1) a titanium-based catalyst comprising a solid titanium catalyst component and an organoaluminum compound, and (2) a vanadium-based catalyst comprising a soluble vanadium compound and an organoaluminum compound.

In the present invention, ethylene, an α-olefin such as 1-butene, and a diene and / or a triene are usually copolymerized in a liquid phase in the presence of the above-mentioned metallocene catalyst. In this case, a hydrocarbon solvent is generally used, but propylene may be used as the solvent. This copolymerization can be carried out by either a batch method or a continuous method.

When the copolymerization is carried out by a batch method using a metallocene catalyst, the concentration of the transition metal complex (metallocene compound) in the polymerization system is usually 0.00005 to 1 / liter of polymerization volume. It is used in an amount of 1 mmol, preferably 0.0001-0.5 mmol.

(D) The organoaluminum oxy compound (alumoxane) has a molar ratio (Al / M) of the aluminum atom (Al) to the transition metal atom (M) in the metallocene compound (a) of 1 to 10,000, preferably 10-5
000 is used.

(B) The ionized ionic compound is (a)
It is used in an amount such that the molar ratio of the (b) ionized ionic compound to the metallocene compound ((b) / (a)) is 0.5 to 20, preferably 1 to 10.

When (c) an organoaluminum compound is used, the amount of polymerization is usually about 0 per liter of polymerization volume.
５5 mmol, preferably about 0-2 mmol.

The copolymerization reaction is usually carried out at a temperature of -20 to 15
0 ° C, preferably 0 to 120 ° C, more preferably 0 to
In the range of 100 ° C., the pressure exceeds 0 and is ~ 80 kg / cm
² , preferably above 0 and up to 50 kg / cm ² .

The reaction time (average residence time when the copolymerization is carried out by a continuous method) varies depending on conditions such as the catalyst concentration and the polymerization temperature, but is usually 5 minutes to 3 hours, preferably 10 minutes. ~ 1.5 hours.

The above-mentioned propylene, ethylene, carbon atom 4
The α-olefin and the diene (or triene) -derived component-based copolymerizing monomer are supplied to the polymerization system in such amounts that the above-mentioned ethylene-based polymer [I] is obtained. At the time of copolymerization, a molecular weight regulator such as hydrogen can be used.

As described above, propylene, ethylene,
When a monomer for copolymerization of a component derived from an α-olefin having 4 to 20 carbon atoms and a diene (or triene) is copolymerized, an ethylene-based polymer [I] is generally obtained as a polymerization solution containing the same. This polymerization liquid is processed by a conventional method,
An ethylene polymer [I] is obtained.

In the present invention, the ethylene polymer [I] is used in an amount of 1 to 90 parts by weight, preferably 10 to 90 parts by weight, based on 100 parts by weight of the total amount of the ethylene polymer [I] and the propylene resin [II]. To 90 parts by weight, more preferably 20 to 80 parts by weight.

Propylene resin [II] The propylene resin [II] used in the present invention has a melt flow rate (MFR; ASTM D 1238, 230 ° C, 2.16 kg load) of 0.1 to 200 g / 10 min. And more preferably 0.1 to 100 g / 10 min.

Further, 64 of the propylene resin [II]
The amount of n-decane-insoluble components is usually 99.9 to 80% by weight.
And preferably 99.9 to 90% by weight. Specifically, the n-decane-insoluble component at 64 ° C. of the propylene-based resin [II] is dissolved in 5 g of a sample (propylene-based resin) by immersing it in 200 cc of boiling n-decane for 5 hours and then cooling to 64 ° C. Then, the precipitated solid phase can be obtained by filtering off the precipitated solid phase with a G4 glass filter and drying the solid phase (insoluble component).

The boiling heptane-insoluble component of the n-decane-insoluble component at 64 ° C. has a stereoregularity index [M ₅ ] obtained by the following formula (1) of 0.970 to 0.995. It is desirable that the value of the stereoregularity index [M ₃ ] obtained by the equation (2) is 0.0020 to 0.0050.

The stereoregularity index [M ₅ ] of the boiling heptane-insoluble component is determined by the P mmmm, Pw, Sαγ, Sαδ ⁺ , Tmm in the ¹³ C-NMR spectrum of the boiling heptane-insoluble component.
It is obtained from the absorption intensity of δ ⁺ δ ^{+ by} the following equation (1),
Pentad isotacticity [M _5] is, Pmmrm in ¹³ C-NMR spectrum, Pmrmr, Pmrrr, Prmrr, Prmmr , Prr
rr, Pw, Sαγ, Sαδ ⁺ , and Tδ ⁺ δ ⁺ are obtained from the absorption intensity according to the following equation (2).

[0076]

(Equation 1)

(Where, [Pmmmm] is the absorption intensity derived from the methyl group of the third unit at the site where 5 units of propylene units are continuously bonded isotactically, and [Pw] is the methyl group of the propylene unit. [Sαγ] is a secondary carbon in the main chain, one of the two tertiary carbons closest to the secondary carbon is in the α-position, and the other is in the γ-position. [Sαδ ⁺ ]: a secondary carbon in the main chain, one of the two tertiary carbons closest to the secondary carbon is α And [Tδ ⁺ δ ⁺ ] is the tertiary carbon in the main chain, and the other is the tertiary carbon in the main chain. One of the two tertiary carbons closest to the quaternary carbon is at the δ-position or at a position away from the δ-position, It is the absorption intensity derived from a tertiary carbon, such as in the position away from the position or [delta] position [delta].)

[0078]

(Equation 2)

[Pw], [Sαγ], [Sαδ ⁺ ] and [Tδ ⁺ δ ⁺ ] are the same as those in the above formula (1). ) Specifically described above propylene resin [II], such as (stereoregularity index used for the evaluation of the stereoregularity of the boiling n- heptane-insoluble component) [M ^5] and [M ^3].

When the propylene resin [II] is a propylene homopolymer, the insoluble component can be represented, for example, by the following formula (A).

[0081]

Embedded image

3 in 5 chains of propylene units represented by
Derived from the methyl group of the unit (eg Me ³ , Me ⁴ )
The absorption intensity in the ¹³ C-NMR spectrum was defined as Pmmmm, and all the methyl groups (Me ¹ , Me ² , M
When the absorption intensity derived from e ³ · · ·) and Pw, the stereoregularity of the boiling heptane-insoluble component represented by the above formula (A) is determined from the ratio of the Pmmmm and Pw, i.e. formula (1A) The value can be evaluated.

[0083]

(Equation 3)

Further, the propylene-based resin [II] may have a structural unit derived from an olefin other than the propylene unit,
For example, when a small amount of ethylene units is contained, the insoluble component is
For example, it can be expressed as the following equation (B-1) or (B-2). The formula (B-1) shows the case where one ethylene unit is contained in the propylene unit chain, and the formula (B-1)
-2) shows a case where an ethylene unit chain composed of two or more ethylene units is included in the propylene unit chain.

[0085]

Embedded image

In such a case, a methyl group other than the methyl group at the third unit in the five chains of propylene units (the above formula (B-
In (1) and (B-2), Me ⁴ , Me ⁵ , Me ⁶ and M
e ⁷ ) The absorption intensity derived from
It should be excluded in principle. However, since the absorption of these methyl groups is observed overlapping with the absorption of other methyl groups, it is difficult to quantify.

Therefore, the boiling n-
In the case where the heptane-insoluble component is represented by the formula (B-1), the secondary carbon in the ethylene unit, which is bonded to the tertiary carbon (C ^a ) in the propylene unit ( C ¹ )
The absorption intensity (Sαγ) in the ¹³ C-NMR spectrum and the secondary carbon (C ³ ) in the propylene unit, which is bonded to the secondary carbon (C ² ) in the ethylene unit This is excluded using the absorption intensity (Sαγ) derived from

That is, among the secondary carbons in the main chain, one of two tertiary carbons (C ^a or C ^b ) closest to the secondary carbon (C ¹ or C ³ ) is the α-position. And the other (C
^b or C ^a ) is twice the absorption intensity (Sαγ) derived from the secondary carbon such that it is at the γ-position and subtracted from Pw to obtain methyl other than the methyl unit of the third unit in the five chains of propylene units. Exclude the absorption intensity from the groups (Me ⁴ , Me ⁵ , Me ⁶ and Me ⁷ ).

When the boiling n-heptane insoluble component of the propylene resin [II] is represented by the formula (B-2),
¹³ C derived from a secondary carbon (C ⁴ ) which is a secondary carbon in an ethylene unit chain composed of two or more ethylene units and is bonded to a tertiary carbon (C ^d ) in a propylene unit
The absorption intensity (Sαδ ⁺ ) in the NMR spectrum and the secondary carbon in the propylene unit which is bonded to the secondary carbon (C ⁵ ) in the chain of two or more ethylene units.
This is excluded by using the absorption intensity (Sαδ ⁺ ) derived from the graded carbon (C ⁶ ).

That is, one of the secondary carbons in the main chain (C ^d or C ^e ) is the α-position among the two tertiary carbons closest to the secondary carbon (C ⁴ or C ⁶ ). And the other (C
^e or C ^d ) is obtained by subtracting twice the absorption intensity (Sαδ ⁺ ) derived from a secondary carbon such that S or C ^d ) is located at the δ position or a position farther from the δ position from Pw to obtain 3 out of 5 propylene units in 5 chains. Methyl groups other than the methyl group in the unit (Me ⁴ , M
e ⁵ , Me ⁶ and Me ⁷ ) are excluded.

Therefore, the stereoregularity of the boiling n-heptane-insoluble component of the propylene resin [II] represented by the above formulas (B-1) and (B-2) is determined by the value obtained from the following formula (1B). Can be evaluated.

[0092]

(Equation 4)

Further, the boiling n-
The heptane-insoluble component contains a small amount of ethylene units, and
When one propylene unit is contained in the ethylene unit chain, the insoluble component can be represented, for example, by the following formula (C).

[0094]

Embedded image

In such a case, if the above formula (1B) is applied as it is, five methyl groups to be excluded (Me ⁴ , M ⁴
e ⁵ , Me ⁶ , Me ⁷ and Me ⁸ ), because there are four methyl groups corresponding to Sαγ or Sαδ ⁺ , methyl groups other than the central methyl group in the five chains of propylene units are Since three more are excluded, further correction is required.

Therefore, this is corrected using the absorption intensity in the ¹³ C-NMR spectrum derived from the tertiary carbon in the propylene unit contained in the ethylene unit chain. That is, the tertiary carbon in the main chain, and one of the two tertiary carbons (C ^f , C ^g ) closest to the tertiary carbon (C ^f ) is located at the δ-position or at a position away from the δ-position And triple the absorption intensity (Tδ ⁺ δ ⁺ ) derived from the tertiary carbon (C ⁷ ) in which the other (C ^g ) is at the δ-position or at a position farther from the δ-position. To correct this.

Accordingly, the stereoregularity of the boiling n-heptane insoluble component of the propylene resin [II] can be evaluated by the value of the stereoregularity index [M ₅ ] obtained by the above equation (1).

The expressions (1A) and (1B) are
It is not different from equation (1), and is regarded as a special case of equation (1). Note that the above correction may not be necessary depending on the constituent unit other than the propylene unit contained in the boiling n-heptane-insoluble component.

In the above equation (2) for obtaining the stereoregularity index [M ₃ ], [Pmmrm], [Pmrmr], [Pmrrr],
[Prmrr], [Prmmr] and [Prrrr] have a structure in which three of the methyl groups of five consecutive propylene units in the propylene unit chain are oriented in the same direction and two in the opposite direction (hereinafter referred to as “M ₃ ), which indicates the absorption intensity derived from the methyl group of the third unit in five chains of propylene units having a “ ₃ structure”). That is, the value of the stereoregularity index [M ₃ ] obtained by the above (2) indicates the ratio of the M ₃ structure in the propylene unit chain.

The propylene resin [I] used in the present invention
Boiling n- heptane insoluble component I], the value of stereoregularity index determined by the above formula (1) [M _5] is 0.970～
Since the value of the stereoregularity index [M ₃ ] of the boiling n-heptane insoluble component obtained by the above equation (2) is in the range of 0.0020 to 0.0050, the extremely long meso Chains (propylene unit chains in which the α-methyl carbons are oriented in the same direction).

The value of [M ₃ ] is preferably 0.00
23 to 0.0045, more preferably 0.0025 to
0.0040. Generally propylene resin [II]
Is that the smaller the value of the stereoregularity index [M ₃ ], the longer the meso-chain. However, when the value of the stereoregularity index [M ₅ ] is extremely large and the value of the stereoregularity index [M ₃ ] is extremely small, if the value of the stereoregularity index [M ₅ ] is almost the same, When the value of the regularity index [M ₃ ] is larger, the meso-chain may be longer.

For example, comparing a propylene resin having the following structure (a) with a propylene resin having the structure (b), the propylene resin represented by the structure (a) having the M ₃ structure is has a long mesochain than the propylene-based resin represented by the structure having no M ₃ structure (ii). (However, each of the following structures (a) and (b) consists of 1003 propylene units)

[0103]

Embedded image

A propylene-based compound represented by the above structure (a)
Stereoregularity index of resin [M_Five] Is 0.986.
Of the propylene resin represented by the above structure (b).
Body regularity index [M_Five] Is 0.985 and the structure
Propylene resin represented by (a) and structure (b)
Of stereoregularity of propylene resin expressed by
[M_Five] Are almost equal. However,
M_ThreePropylene represented by structure (a) having a structure
In resins, the propylene units in the meso chain are average
497 units, M_ThreeStructure without structure (b)
In the propylene-based resin represented by
The average propylene unit is 250 units. Ie
Stereoregularity index [M_FivePropylene with an extremely large value of
In the system resin, r (race) contained in the propylene unit chain
Since the ratio of the structure represented by mo) becomes extremely small, r
(Racemo) is a concentrated propyle structure
Resin (M _ThreePropylene resin having a structure)
(Racemo) is a propyle with a dispersed structure
Resin (M_ThreePropylene resin without a structure)
It will have long meso chains.

The stereoregularity index values [M ₅ ] and [M ₃ ] as described above are determined by the peak intensity or the peak intensity based on each structure of ¹³ C-NMR of the boiling n-heptane insoluble component measured as follows. It can be determined from the sum of the peak intensities.

According to ¹³ C-NMR, 0.35 g of the insoluble component is dissolved by heating in 2.0 ml of hexachlorobutadiene.
This solution was filtered through a glass filter (G2), and 0.5 ml of deuterated benzene was added.
The sample is charged into an R tube, and ¹³ C-NMR measurement is performed at 120 ° C. using a GX-500 type NMR measurement device manufactured by JEOL Ltd. The number of integration is 10,000 or more.

The n-decane-insoluble component at 64 ° C. of the propylene-based resin [II] is generally 80% by weight or more, preferably 85% by weight or more, based on the amount of the boiling n-heptane-insoluble component as described above.
More preferably 90% by weight or more, even more preferably 93% by weight.
% By weight, particularly preferably 94% by weight or more.

The boiling n-heptane insoluble component was obtained as an extraction residue by Soxhlet extraction of 1.5 g of the n-decane insoluble component at 64 ° C. with n-heptane for 6 hours or more.
The boiling n-heptane insoluble component amount is calculated on the assumption that the n-decane soluble component at 64 ° C. is also soluble in boiling n-heptane.

In the present invention, the crystallinity of the boiling n-heptane insoluble component is desirably 60% or more, preferably 65% or more, and more preferably 68% or more. The degree of crystallinity is determined by using a press sheet obtained by forming a sample into a square plate having a thickness of 1 mm using a pressure molding machine at 180 ° C. and immediately cooling with water, using a rotor flex RU300 manufactured by Rigaku Corporation.
It can be determined by measuring using a measuring device (output: 50 kV, 250 mA). As a measuring method at this time, a transmission method is used, and the measurement is performed while rotating the sample.

In the present invention, the n-decane-insoluble component at 64 ° C. of the propylene-based resin [II] as described above may be made of homopolypropylene or propylene and other olefins as long as the above-mentioned properties are satisfied. And a copolymer of

Examples of other olefins include ethylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-hexadecene, and 4-methyl-1 Α-olefins such as pentene; vinyl compounds such as vinylcyclopentene, vinylcyclohexane and vinylnorbornane; vinyl esters such as vinyl acetate; unsaturated organic acids such as maleic anhydride and derivatives thereof.

Of these, it is desirable to use a homopolypropylene. The polypropylene component forming the n-decane-insoluble component at 64 ° C. includes, for example, 3-methyl-1-butene, 3,3-dimethyl-1-butene, and 3-methyl-1-butene.
Pentene, 3-methyl-1-hexene, 3,5,5-trimethyl-1
A homopolymer or a copolymer such as hexene, vinylcyclopentene, vinylcyclohexane or vinylnorbornane may be contained as a prepolymer formed, for example, by prepolymerization; It is preferable to contain the compound in an amount of about ppm to 3% by weight because the crystallization rate increases.

The propylene resin [II] as described above is
One type may be used alone, or two or more types may be used in combination. The propylene resin [II] as described above is 10 to 99 parts by weight, preferably 10 to 90 parts by weight, based on 100 parts by weight of the total amount of the ethylene polymer [I] and the propylene resin [II]. More preferably, 20 to 80
Used in parts by weight.

Crosslinking Agents Crosslinking agents used as necessary in the present invention include organic peroxides and sulfur compounds, among which organic peroxides are preferably used.

Examples of the organic peroxide include dicumyl peroxide, di-t-butyl peroxide,
-t-butylperoxy-3,3,5-trimethylcyclohexane, t-butylhydroperoxide, t-butylcumyl peroxide, benzoyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxide Oxine) Hexin-3, 2,5-
Dimethyl-2,5-di (benzoylperoxy) hexane,
2,5-dimethyl-2,5-mono (t-butylperoxy) -hexane, α, α′-bis (t-butylperoxy-m-isopropyl) benzene and the like. Among them, dicumyl peroxide, di-t-butyl peroxide, di-t-
Butyl peroxy-3,3,5-trimethylcyclohexane is preferably used.

In the present invention, the organic peroxide is selected from the group consisting of the ethylene polymer [I] and the propylene resin [II].
For a total amount of 100 parts by weight, 0.01 to 2 parts by weight,
Preferably 0.01 to 1 part by weight, more preferably 0.1 to 1 part by weight.
It is used in a proportion of from 0.01 to 0.5 parts by weight.

When the organic peroxide is used in the above ratio, a molded article (crosslinked product) having excellent balance of transparency, impact resistance and surface hardness, and excellent wear resistance and oil resistance can be produced. A propylene-based resin composition is obtained.

When an organic peroxide is used as a crosslinking agent, it is preferable to use a crosslinking assistant together. Specific examples of such a crosslinking aid include sulfur; quinone dioxime compounds such as p-quinone dioxime; methacrylate compounds such as polyethylene glycol dimethacrylate; allyl compounds such as diallyl phthalate and triallyl cyanurate. Compounds; other maleimide compounds; divinylbenzene, and the like.

The cross-linking assistant is the above-mentioned ethylene polymer [I]
And 0.01 to 5 parts by weight, preferably 0.01 to 2 parts by weight, per 100 parts by weight of the total amount of
Parts by weight, more preferably 0.01 to 1 part by weight.

Specific examples of the sulfur compound used as the crosslinking agent include sulfur, sulfur chloride, sulfur dichloride, morpholine disulfide, alkylphenol disulfide, tetramethylthiuram disulfide, selenium dimethyldithiocarbamate and the like. Among them, sulfur is preferably used.

The sulfur compound is used in an amount of 0.1 to 10 parts by weight, preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the total amount of the ethylene polymer [I] and the propylene resin [II].
To 8 parts by weight, more preferably 0.1 to 6 parts by weight. When the sulfur compound is used in the above ratio, the propylene resin composition is excellent in balance of transparency, impact resistance and surface hardness, and can produce a molded article (crosslinked product) having excellent wear resistance and oil resistance. Things are obtained.

When a sulfur compound is used as a crosslinking agent, it is preferable to use a vulcanization accelerator in combination. As such a vulcanization accelerator, specifically, N-cyclohexyl
-2-benzothiazolesulfenamide, N-oxydiethylene-2-benzothiazolesulfenamide, N, N-diisopropyl-2-benzothiazolesulfenamide,
Thiazole compounds such as 2-mercaptobenzothiazole, 2- (2,4-dinitrophenyl) mercaptobenzothiazole, 2- (2,6-diethyl-4-morpholinothio) benzothiazole, dibenzothiazyldisulfide; diphenylguanidine; Guanidine compounds such as triphenylguanidine, diornitrile guanidine, orthonitrile biguanide, diphenylguanidine phthalate; acetaldehyde-aniline reactant, butyraldehyde-
Aldehyde derivatives such as aniline condensate, hexamethylenetetramine, acetaldehyde ammonia or aldehyde-ammonia compounds; imidazoline compounds such as 2-mercaptoimidazoline; thiocarbanilide, diethylthiourea, dibutylthiourea, trimethylthiourea, diorthotolylthiourea Thiourea-based compounds such as tetramethylthiuram monosulfide, tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide, pentamethylenethiuram tetrasulfide and the like; zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate, di-n -Zinc butyldithiocarbamate, zinc ethylphenyldithiocarbamate, butylphenyldithiocarbamate Zinc, sodium dimethyl dithiocarbamate, dimethyl dithiocarbamate selenium, dithio acid salt-based compounds such as dimethyl dithiocarbamate tellurium; dibutyl Ruki xanthate-based compounds such as Santo Gen zinc; and zinc oxide can be mentioned.

These vulcanization accelerators contain a total amount of 10 parts of the above-mentioned ethylene polymer [I] and propylene resin [II].
It is used in an amount of 0.1 to 20 parts by weight, preferably 0.1 to 10 parts by weight, based on 0 parts by weight.

Other Components The propylene resin composition of the present invention may contain, if necessary,
Inorganic filler, organic filler, nucleating agent, weather stabilizer, heat stabilizer, antistatic agent, anti-slip agent, anti-blocking agent, anti-fogging agent, lubricant, pigment, dye, plasticizer, softener, anti-aging agent In addition, additives such as a hydrochloric acid absorbent, an antioxidant and the like can be blended within a range that does not impair the object of the present invention. Further, other synthetic resins can be blended in a small amount without departing from the object of the present invention.

[Inorganic filler and organic filler] As the inorganic filler, specifically, fine powder talc, kaolinite,
Natural silicic acid or silicates such as calcined clay, bilophilite, sericite, wollastonite, precipitated calcium carbonate, heavy calcium carbonate, carbonates such as magnesium carbonate, hydroxides such as aluminum hydroxide and magnesium hydroxide, Oxides such as zinc oxide, zinc oxide and magnesium oxide, hydrous calcium silicate, hydrous aluminum silicate, hydrous silicic acid, silicic acid and other synthetic silicic acids or silicates, etc .; powdery fillers such as mica; flake-like fillers such as mica; Magnesium sulfate whisker, calcium titanate whisker, aluminum borate whisker, sepiolite, P
Fibrous fillers such as MF (Processed Mineral Fiber), zonotolite, potassium titanate, and elestadite; and balun-like fillers such as glass balun and fly ash balun can be used.

In the present invention, of these, talc is preferably used, and particularly, fine powder talc having an average particle size of 0.01 to 10 μm is preferably used. The average particle size of talc can be measured by a liquid phase sedimentation method.

The inorganic filler used in the present invention, especially talc, may be untreated or may be surface-treated in advance. Examples of the surface treatment include, specifically, chemical or physical treatment using a treating agent such as a silane coupling agent, a higher fatty acid, a fatty acid metal salt, an unsaturated organic acid, an organic titanate, a resin acid, or polyethylene glycol. Is mentioned. When talc subjected to such a surface treatment is used, a propylene-based resin composition excellent in weld strength, coatability, and moldability can be obtained.

The above-mentioned inorganic fillers may be used alone.
Alternatively, two or more kinds can be used in combination. In the present invention, together with such an inorganic filler, an organic filler such as high styrenes, lignin, and recycled rubber can also be used.

Preparation of Propylene Resin Composition The propylene resin composition according to the present invention can be prepared by any conventionally known method.

For example, the non-crosslinked propylene resin composition according to the present invention is obtained by extruding the ethylene polymer [I], the propylene resin [II] and, if necessary, the above-mentioned additives such as the inorganic filler. It can be prepared by melt-kneading using a kneading device such as a kneader, a twin-screw kneader, a kneader, a Banbury mixer, and a roll.

The crosslinked type propylene resin composition according to the present invention comprises an ethylene polymer [I], a propylene resin [II], a crosslinking agent, and if necessary, the crosslinking aid,
Additives such as a vulcanization accelerator and an inorganic filler are usually added at 100 to 250 ° C., preferably 150
It can be obtained by melt-kneading at ~ 250 ° C.

The crosslinked propylene resin composition according to the present invention comprises an ethylene polymer [I], a propylene resin [II], and, if necessary, a crosslinking agent, a crosslinking assistant, and a vulcanization accelerator. Additives such as the inorganic filler, melt-kneaded using an extruder, into pellets obtained by granulation,
An electron having an energy of 0.1 to 10 MeV, preferably 0.3 to 2 MeV is absorbed by an absorbed dose of 0.1 to 50 Mr.
ad, preferably from 1 to 30 Mrad.

The propylene resin composition according to the present invention comprises:
Usually, after kneading the above components in a kneading device such as an extruder,
The kneaded material is used after being formed into pellets. When preparing the propylene-based resin composition, the order in which the above components are added to the kneading apparatus is not limited, and may be simultaneous or separate.

Molded Article The molded article according to the present invention includes a non-crosslinked type molded article and a crosslinked type molded article. Each of these molded bodies can be manufactured using a conventionally known method.

[0135]

According to the propylene resin composition of the present invention, a specific ethylene polymer is blended in a specific ratio with a propylene resin, so that the balance of transparency, impact resistance and surface hardness is improved. An excellent molded article can be provided. Among them, the crosslinked propylene-based resin composition according to the present invention can provide a molded article that is not only excellent in balance of transparency, impact resistance and surface hardness, but also excellent in abrasion resistance and oil resistance. .

The molded product according to the present invention is excellent in the above-mentioned various properties.

[0137]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

The tests for haze, Izod impact strength (IZ), Rockwell hardness (HR), spring hardness, oil resistance and abrasion resistance in the examples and the like were performed according to the following methods.

(1) Haze [Preparation of Sheet] On a press plate, an aluminum sheet having a thickness of 0.1 mm, a polyethylene terephthalate (PET) sheet, and an aluminum sheet having a thickness of 1 mm and having a center cut into a 15 cm × 15 cm square were prepared. The samples were spread in this order, and a 22 g sample (polymer) was placed at the center (the cut-out portion). Next, a PET sheet, an aluminum plate, and a press plate are further stacked in this order.

Next, the sample sandwiched between the press plates was
After placing in a hot press at 00 ° C and preheating for about 7 minutes, pressurize (50 kg) to remove air bubbles in the sample.
/ cm ² -G) Repeat the depressurization operation several times. Then finally 10
The pressure is increased to 0 kg / cm ² -G, and the mixture is heated under pressure for 2 minutes. After depressurization, the press plate is taken out of the press machine, transferred to another press machine in which the press-bonded portion is kept at 0 ° C., pressurized and cooled at 100 kg / cm ² -G for 4 minutes, depressurized, and a sample is taken out. Thus, a sheet having a uniform thickness of 1 mm was obtained.

[ Measurement of Haze] The press sheet having a thickness of 1 mm obtained as described above was measured for haze [%] using a digital turbidimeter “NDH-20D” manufactured by Nippon Denshoku Industries Co., Ltd. did.

(2) Izod Impact Strength (IZ) Izod impact strength (IZ) was measured at 23 ° C. using a 1/4 inch thick test piece (post notch) in accordance with ASTM D256. .

(3) Rockwell hardness (HR) Rockwell hardness (HR) was measured using a square plate having a thickness of 2 mm, a length of 120 mm and a width of 130 mm in accordance with ASTM D785.

(4) Spring Hardness The spring hardness is measured according to JIS described in JIS K6301.
It was measured by the A type method.

(5) Oil resistance According to JIS K 6258, 336 hours at 50 ° C.
The volume change rate ΔV after immersion in JIS No. 3 oil was measured, and this volume change rate ΔV was used as an index of oil resistance.

(6) Wear Resistance In accordance with JIS K 7204, the amount of wear was measured under the conditions of a worn wheel CS-17, a load of 1000 g, 60 rpm, and 1,000 revolutions, and this wear amount was used as an index of wear resistance. .

Further, the melting point (Tm), intrinsic viscosity [η] and Mw / M of the olefin polymer in Examples and Comparative Examples
n was measured by the following method or condition. (1) Melting point (Tm) The endothermic curve of DSC was determined, and the temperature at the maximum peak position was determined as Tm.
And

Using a differential scanning calorimeter (DSC), the sample was packed in an aluminum pan, heated to 200 ° C. at 100 ° C./min, kept at 200 ° C. for 5 minutes, and then charged at −15 ° C. at 10 ° C./min.
It was determined from an endothermic curve when the temperature was decreased to 0 ° C. and then increased at a rate of 10 ° C./min. (2) Intrinsic viscosity [η] Intrinsic viscosity [η] was measured in decalin at 135 ° C. (3) Mw / Mn Mw / Mn was measured using GPC (gel permeation chromatography) in an orthodichlorobenzene solvent,
It was measured at 140 ° C.

[0149]

[Production Example 1] [Preliminary contact between zirconium compound A and methylalumoxane, preparation of catalyst solution] A predetermined amount of zirconium compound A (rac-dimethylsilylene-bis (2,7-
Dimethyl-4-phenyl-1-indenyl) zirconium dichloride) and a toluene solution of methylalumoxane (1.2 mg atom /
was mixed by stirring for 30 minutes at room temperature in a dark place to prepare a toluene solution in which the zirconium compound A and methylalumoxane were dissolved.

The Zr concentration of this toluene solution was 0.004
Mmol / ml, and the concentration of methylalumoxane is 1.2 milligram atoms / ml in terms of aluminum atoms.
It is.

Next, hexane having a volume 5 times the volume of toluene was added to this toluene solution under stirring to prepare a catalyst solution having the following Zr concentration and methylalumoxane concentration, and this was polymerized. Used as a reaction catalyst.

Zr concentration: 0.00067 mmol / ml
(0.67 mmol / liter) Methylalumoxane concentration (converted to Al atom): 0.1.
20 mmol / ml (200 mmol / liter) [Polymerization] Ethylene, 1-butene, and 5-ethylidene-2-norbornene were continuously reacted with a 15-liter stainless steel polymerization vessel equipped with a stirring blade. Was copolymerized as follows.

First, 3.185 liters / hour of dehydrated and purified hexane, 0.015 liters / hour of the above-obtained catalyst solution, and a hexane solution of triisobutaluminum (concentration: 17 mmol) were introduced into the polymerization reactor from the top of the polymerization reactor. / Liter), and a hexane solution (concentration: 0.15 liter / liter) of 5-ethylidene-2-norbornene (hereinafter also referred to as ENB) at a rate of 1.5 liter / hour.
Each was fed continuously.

In addition, ethylene was fed from the upper part of the polymerization reactor at a rate of 1 hour / hour.
50 liters and 280 liters per hour of 1-butene were continuously supplied. The copolymerization reaction was carried out at 90 ° C. and the average residence time was 1 hour (that is, the polymerization scale was 5 liters).

On the other hand, a small amount of methanol was added to the polymerization solution extracted from the lower part of the polymerization vessel to stop the polymerization reaction.
After separating the copolymer from the solvent by steam stripping, under conditions of 100 ° C. and reduced pressure (100 mmHg),
Dry for 24 hours.

As described above, ethylene / 1-butene
ENB random copolymer was obtained in an amount of 108 g per hour. The obtained random copolymer has a constitutional unit derived from ethylene and a constitutional unit derived from 1-butene in 5 units.
2/48 (molar ratio). It also contained units derived from ethylidene norbornene (ENB) in an amount of 2.3 mol%.

The iodine value of this random copolymer is 16
And the intrinsic viscosity [η] measured in 135 ° C. decalin
Was 1.9 dl / g.

[0158]

[Production Example 2] [Polymerization] Ethylene, 1-octene, and dicyclopentadiene were continuously copolymerized as follows using a 15-liter stainless steel polymerization vessel equipped with stirring blades. Was.

First, 3.185 liters / hour of dehydrated and purified hexane, 0.015 liters / hour of the same catalyst solution as used in Production Example 1, and hexane of triisobutylaluminum were introduced into the polymerization reactor from the top of the polymerization reactor. A solution (concentration of 17 mmol / l) was 0.3 liter / hour, and a hexane solution of dicyclopentadiene (hereinafter also referred to as DCPD) (concentration: 0.15 liter / liter) was added at an hourly rate.
5 liters were each fed continuously.

In addition, ethylene was fed from the upper part of the polymerization reactor at a rate of 2 hours / hour.
00 liters and 1-octene were continuously supplied at 4.5 liters per hour. The copolymerization reaction was carried out at 90 ° C. and the average residence time was 1 hour (that is, the polymerization scale was 5 liters).

On the other hand, a small amount of methanol was added to the polymerization solution extracted from the lower part of the polymerization vessel to stop the polymerization reaction.
After separating the copolymer from the solvent by steam stripping, under conditions of 100 ° C. and reduced pressure (100 mmHg),
Dry for 24 hours.

As described above, an ethylene / 1-octene / DCPD random copolymer was obtained in an amount of 80 g / h. The obtained random copolymer has a structural unit derived from ethylene and a structural unit derived from 1-octene,
62/38 (molar ratio). In addition, structural units derived from dicyclopentadiene (DCPD) are described in 2.
It was contained in an amount of 5 mol%.

The iodine value of this random copolymer is 16
And the intrinsic viscosity [η] measured in 135 ° C. decalin
Was 1.8 dl / g.

[0164]

Example 1 75 parts by weight of homopolypropylene (Grand Polypro; J105) manufactured by Grand Polymer Co., Ltd. and the ethylene / 1-butene / 5-ethylidene-2-norbornene random copolymer obtained in Production Example 1 (ethylene/
1-butene (molar ratio) = 52/48, 5-ethylidene-2-norbornene content = 2.3 mol%, iodine value = 16, Mw
/Mn=2.1, intrinsic viscosity [η] = 1.9 dl / g, T
g = -60.1 ° C .; hereinafter, sometimes abbreviated as EB-ENB)) and 25 parts by weight thereof are mixed with a Henschel mixer and melt-kneaded at 200 ° C. using an extruder with a pelletizer.
Granulation was performed to obtain pellets of a non-crosslinked propylene resin composition.

Using the pellets of the obtained propylene-based resin composition, tests were conducted according to the above-mentioned method for haze, Rockwell hardness (HR) and Izod impact strength (IZ). As a result, the haze of this composition was 22
%, The Rockwell hardness (HR) was 55, and the test piece did not break for Izod impact strength (IZ).

[0166]

Example 2 In Example 1, E was obtained in Production Example 1.
Instead of B-ENB, the ethylene
1-octene-dicyclopentadiene random copolymer (ethylene / 1-octene (molar ratio) = 62/38, dicyclopentadiene content = 2.5 mol%, iodine value = 1
6, Mw / Mn = 2.0, intrinsic viscosity [η] = 1.8 dl
/ G, Tg = −72 ° C .; hereinafter, may be abbreviated as EO-DCPD) to obtain pellets of a non-crosslinked propylene-based resin composition in the same manner as in Example 1.

Using the obtained pellets of the propylene-based resin composition, tests were conducted according to the above-mentioned method for haze, Rockwell hardness (HR) and Izod impact strength (IZ). As a result, the haze of this composition was 28
%, Rockwell hardness (HR) was 60, and the test piece did not break for Izod impact strength (IZ).

[0168]

Example 3 30 parts by weight of homopolypropylene (trade name: Grand Polypro; J105) manufactured by Grand Polymer Co., Ltd. and 70 parts by weight of EB-ENB obtained in Production Example 1 were mixed with a Henschel mixer and extruded with a pelletizer. The mixture was melt-kneaded at 200 ° C. and granulated to obtain pellets of the propylene-based resin composition.

Next, 100 parts by weight of the propylene resin composition pellets and perhexin 25B (trade name; Nippon Oil & Fats Co., Ltd.) were used as a crosslinking agent in a tumbler blender.
Was added, and 0.3 parts by weight of divinylbenzene (DVB) was added as a crosslinking aid, and the crosslinking agent and the crosslinking aid were uniformly attached to the pellet surface.

Next, using an extruder with a pelletizer,
The pellets were again melt-kneaded at 210 ° C. and granulated to obtain pellets of a crosslinked propylene-based resin composition.
Using the pellets of the obtained propylene-based resin composition, haze, Izod impact strength (IZ), spring hardness,
A test was conducted for oil resistance (ΔV) and abrasion resistance (abrasion amount) according to the above-described method. As a result, the haze of this composition was 21%, the Izod impact strength was not broken, the spring hardness was 75, and ΔV was 110.
% And the amount of wear was 5 mg.

[0171]

Example 4 In Example 3, the E obtained in Production Example 1 was used.
EO-DC obtained in Production Example 2 instead of B-ENB
Except that PD was used, a pellet of a crosslinked type propylene-based resin composition was obtained in the same manner as in Example 3.

Using the obtained pellets of the propylene-based resin composition, haze, Izod impact strength (IZ), spring hardness, oil resistance (ΔV), and abrasion resistance (abrasion amount) were used.
Was tested in accordance with the above method. As a result, the haze of this composition was 18%, the Izod impact strength (IZ) was not broken, and the spring hardness was 7%.
8, ΔV was 100%, and the wear amount was 5 mg.

[0173]

Comparative Example 1 In Example 1, E obtained in Production Example 1 was used.
Instead of B-ENB, an ethylene / 1-butene random copolymer (ethylene / 1-butene (molar ratio) = 53/47,
Intrinsic viscosity [η] = 2.9 dl / g, Mw / Mn = 2.
Except for using 1), a pellet of a non-crosslinked type propylene-based resin composition was obtained in the same manner as in Example 1.

Using the obtained pellets of the propylene-based resin composition, tests were carried out in accordance with the above-mentioned methods for haze, Rockwell hardness (HR) and Izod impact strength (IZ). As a result, the haze of this composition was 30
%, The Rockwell hardness (HR) was 50, and the Izod impact strength was 400 J / m.

[0175]

Comparative Example 2 In Example 3, E obtained in Production Example 1 was used.
Instead of B-ENB, an ethylene / 1-butene random copolymer (ethylene / 1-butene (molar ratio) = 53/47,
Intrinsic viscosity [η] = 2.9 dl / g, Mw / Mn = 2.
Except for using 1), a pellet of a crosslinked propylene-based resin composition was obtained in the same manner as in Example 3.

Using the pellets of the obtained propylene resin composition, haze, Izod impact strength (IZ), spring hardness, oil resistance (ΔV) and abrasion resistance (abrasion amount) were used.
Was tested in accordance with the above method. As a result, the haze of this composition was 23%, the Izod impact strength (IZ) was not broken, and the spring hardness was 5%.
5, the ΔV was 290%, and the abrasion amount was 10 mg.

[0177]

[Table 1]

[0178]

[Table 2]

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 23/18 C08L 23/18 (72) Inventor Seiji Ota 6-chome Waki, Waki-machi, Kuga-gun, Yamaguchi Prefecture 1-2 1-2 Mitsui Chemicals, Inc. (72) Keiji Okada 1-2-2 Waki, Waki-cho, Kuga-gun, Yamaguchi Prefecture Mitsui Chemicals Inc. (72) Koji Yoshii, Kuga-gun, Yamaguchi Prefecture 6-2 1-2 Waki, Wakicho F-term (reference) in Mitsui Chemicals, Inc. BA01B BB00B BB01B BC12B BC13B BC15B BC24B BC25B CA17A CA17B CA17C CB95B EB02 EB05 EB07 EB09 EB10 EB11 EB12 EB13 EB14 EB16 EB18 EB26 EC04 EC05 FA02 GA04 GA06 GA14 GA15 GA19 GA2 1

Claims (9)

[Claims] (1) An intrinsic viscosity [η] of ethylene, one or more α-olefins having 4 to 20 carbon atoms, and a diene and / or triene measured in decalin at 135 ° C. In the range of 0.01 to 10 dl / g,
The molecular weight distribution (Mw / Mn) measured by GPC is 4 or less, the ethylene content is 30 to 70 mol%, the total content of diene and / or triene is 0.1 to 10 mol%, and the DSC Ethylene polymer in which no crystal melting peak is observed by the method: 1 to 90 parts by weight;
I] Propylene resin: 99 to 10 parts by weight (component [I]
And the total amount of [II] is 100 parts by weight). 2. The ethylene polymer [I], wherein at least one of the α-olefins having 4 to 20 carbon atoms is 1-butene, 1-hexene, 4-methyl-1-pentene, 1-butene.
The propylene resin composition according to claim 1, wherein the propylene resin composition is selected from the group consisting of octene, 1-decene, 1-dodecene, and 1-eicosene. 3. The diene constituting the ethylene polymer [I] is dicyclopentadiene, 1,4-hexadiene, cyclooctadiene, 1,6-octadiene, 7-methyl-1,6-diene.
The propylene-based resin composition according to claim 1, wherein the propylene-based resin composition is at least one diene selected from the group consisting of octadiene, methylene norbornene, ethylidene norbornene, butadiene, and isoprene. 4. The triene constituting the ethylene polymer [I] is 4-ethylidene-8-methyl-1,7-nonadiene,
4-ethylidene-1,7-undecadiene and 4,8-dimethyl
The propylene-based resin composition according to claim 1, wherein the propylene-based resin composition is at least one triene selected from the group consisting of -1,4,8-decatriene. 5. The transition metal complex (a) wherein the ethylene-based copolymer (A) is represented by the following formula (I) or (II):
And a metallocene-based catalyst comprising at least one compound selected from the group consisting of an ionized ionic compound (b), an organoaluminum compound (c) and an alumoxane (d). A propylene-based resin composition according to any one of claims 1 to 4, characterized by the following: [In the formulas (I) and (II), M is Ti, Zr, Hf, R
n, Nd, Sm or Ru; Cp1 and Cp2 are a cyclopentadienyl group, an indenyl group, a fluorenyl group or a derivative group thereof bonded to M by π, X ¹ and X ² are anionic A ligand or a neutral Lewis base ligand, Y is a ligand containing a nitrogen atom, an oxygen atom, a phosphorus atom, or a sulfur atom, and Z is C, O, B, S, Ge , Si or Sn atom or a group containing these atoms. ]. 6. The propylene-based resin [II] having a stereoregularity index [M ₅ ] of 0.970 to 64 ° C. in an n-decane-insoluble portion.
The propylene-based resin composition according to claim 1, wherein the propylene-based resin composition is 0.995. 7. The method according to claim 1, wherein the propylene resin composition is heated in the presence of a cross-linking agent to cross-link the ethylene polymer [I]. Propylene resin composition. 8. The propylene resin composition is irradiated with an electron beam in the presence or absence of a crosslinking agent to crosslink the ethylene polymer [I]. A propylene-based resin composition according to any one of the above. 9. A molded article comprising the propylene-based resin composition according to claim 1.