JP2003342425A - Polyolefin resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyolefin resin composition which gives a melt having a high melt tension and is excellent in stability when molded. <P>SOLUTION: The polyolefin resin composition comprises 1-99 wt.% of a polyolefin resin (A) and 99-1 wt.% of a copolymer (B), where the copolymer (B) is obtained by copolymerizing ethylene and/or an α-olefin with a vinyl compound represented by the formula: CH<SB>2</SB>=CH-R, the substituent R having a steric parameter Es of at most -1.64 and a steric parameter B1 of at least 1.53. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a polyolefin resin composition. More specifically, the present invention relates to a polyolefin resin composition having a large melt tension of the melt and excellent stability during molding.

[0002]

2. Description of the Related Art Molding of a polyolefin resin is usually performed in a state where the polyolefin resin is heated and melted and the polyolefin resin flows. As a method for molding a polyolefin resin, conventionally, a blown film molding method, a T-die cast film molding method, a direct blow molding method, an injection blow molding method, an extrusion molding method for extruding a polyolefin resin into various shapes, a calender molding method. Known are roll molding, vacuum / pressure molding, foam molding, spinning and the like.

When a polyolefin resin is molded by using these molding methods, it cannot be molded unless the melt tension of the melt of the polyolefin resin is large to some extent.
Molding may be difficult or molding conditions may be limited, and in some cases, the molded product may be defective. For example, in the case of the blown film molding method, the bubbles of the melt during molding become unstable, or the melt sags (drawdown), resulting in uneven thickness or width in the obtained film, and It may be uniform. Further, in the case of the foam molding method, there are cases in which foam breakage occurs, a large expansion ratio cannot be obtained, or the sizes of the foam cells become uneven. In the situation as described above, further improvement in melt tension of the melt of the polyolefin resin and stability at the time of molding is desired, and for example, a method of broadening the molecular weight distribution of the polyolefin resin has been proposed (for example, patents Reference 1.).

[0004]

[Patent Document 1] Japanese Unexamined Patent Publication No. 5-230136

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a polyolefin resin composition having a large melt tension of the melt and excellent stability during molding.

[0006]

That is, the present invention provides a polyolefin resin composition containing 1 to 99% by weight of a polyolefin resin (A) and 99 to 1% by weight of a copolymer (B), The copolymer (B) is ethylene and / or
Alternatively, the present invention relates to a polyolefin resin composition, which is a copolymer obtained by copolymerizing an α-olefin and the following vinyl compound. Vinyl compound: CH
₂ = CH-R, the steric parameter Es of the substituent R
Is −1.64 or less, and the steric parameter B1 of the substituent R is 1.53 or more.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The polyolefin resin (A) used in the present invention means a thermoplastic resin containing 50 to 100% by weight of at least one structural unit derived from an olefin having 2 to 12 carbon atoms. .

The polyolefin resin (A) is, for example, a homopolymer of ethylene or α-olefin, an ethylene / α-olefin copolymer, a propylene / α-olefin copolymer, an ethylene / propylene / α-olefin copolymer. Examples thereof include polymers and copolymers of ethylene with α-olefins and / or polyunsaturated compounds such as conjugated dienes and non-conjugated dienes. Further, as polyolefin resins (A) other than the above, unsaturated carboxylic acids such as ethylene and acrylic acid, methacrylic acid, maleic acid and the like, copolymers of their esterified products and acid anhydrides, and vinyl esters such as ethylene and vinyl acetate. Examples of the copolymer with the class, increase of melt tension of the melt, from the viewpoint of stability during processing,
It is preferably an ethylene / α-olefin copolymer.
Further, these polyolefin resins (A) may be used alone or in combination of two or more kinds.

Α used for polyolefin resin (A)
-As olefins, propylene, butene-1, pentene-1, hexene-1, heptene-1, octene-
1, nonene-1, decene-1, 4-methylpentene-
1,4-methylhexene-1 and the like, preferably α-olefin having 3 to 12 carbon atoms, more preferably propylene, butene-1, hexene-1, 4-methylpentene-1, octene-1. And more preferably propylene, butene-1, hexene-1, octene-1.
Is. These α-olefins may be used alone or in combination of two or more.

Examples of polyunsaturated compounds are divinylbenzene, norbornadiene, dicyclopentadiene,
1,5-hexadiene, 1,7-octadiene, 1,9
-Decadiene, vinyl norbornene, vinyl cyclohexene, ethylidene norbornene and the like can be mentioned, with preference given to divinylbenzene, norbornadiene and dicyclopentadiene.

The homopolymer used as the polyolefin resin (A) is polyethylene, polypropylene, polybutene-1, poly-4-methyl-pentene-1.
And the like, and polyethylene and polypropylene are preferable.

Examples of the propylene / α-olefin copolymer include propylene / butene-1 copolymer and propylene / α-olefin copolymer.
4-methylpentene-1 copolymer, propylene / hexene-1 copolymer, propylene / octene-1 copolymer and the like can be mentioned, preferably propylene and carbon number 4-12.
Is a copolymer with α-olefin, more preferably a propylene / butene-1 copolymer or a propylene / hexene-1 copolymer.

Examples of the ethylene / propylene / α-olefin copolymer include ethylene / propylene / butene-1 copolymer and ethylene / propylene / 4-methylpentene-
1 copolymers, ethylene / propylene / hexene-1 copolymers, ethylene / propylene / octene-1 copolymers, and the like, and preferably ethylene and propylene and an α-olefin having 4 to 12 carbon atoms. It is a copolymer, more preferably an ethylene / propylene / butene-1 copolymer or an ethylene / propylene / hexene-1 copolymer.

As the copolymer of ethylene and α-olefin and / or polyunsaturated compound such as conjugated diene and non-conjugated diene, ethylene / propylene / divinylbenzene copolymer, ethylene / propylene / norbornadiene copolymer, Examples thereof include an ethylene / propylene / dicyclopentadiene copolymer, and an ethylene / propylene / divinylbenzene copolymer is preferable.

Specific examples of the ethylene / α-olefin copolymer include, for example, ethylene / propylene copolymer,
Ethylene / Butene-1 Copolymer, Ethylene / Pentene-
1 copolymer, ethylene / hexene-1 copolymer, ethylene / heptene-1 copolymer, ethylene / octene-1 copolymer, ethylene / nonene-1 copolymer, ethylene / decene-1 copolymer, Ethylene-4-methylpentene-1
Copolymers, ethylene-4-methylhexene-1 copolymers and the like can be mentioned, preferably a copolymer of ethylene and an α-olefin having 3 to 12 carbon atoms, more preferably an ethylene / propylene copolymer, Ethylene / butene-1 copolymer, ethylene / hexene-1 copolymer, ethylene / octene-1 copolymer, ethylene-4-methylpentene-
1 copolymer, more preferably an ethylene / propylene copolymer, an ethylene / butene-1 copolymer, an ethylene / hexene-1 copolymer, and an ethylene / octene-1 copolymer.

The density of the ethylene / α-olefin copolymer used in the polyolefin resin composition of the present invention is 870 from the viewpoint of preventing the stickiness of the molded product and the strength of the molded product.
To 970 Kg / m ³ , preferably 875 to 940
Kg / m ³ , more preferably 880 to 935 Kg
/ M ³ .

The melt flow rate of the ethylene / α-olefin copolymer is usually 0.01 to 100 g / 10 minutes, and is 0.1 from the viewpoint of preventing an increase in extrusion load, strength of the molded product and moldability. -30 g / 10 minutes, preferably 0.5-20 g / 10 minutes, more preferably 0.8.
It is -10 g / 10 minutes.

Examples of the method for producing the ethylene / α-olefin copolymer include a method for producing a copolymer by using a known polymerization catalyst. Known catalysts include
Examples thereof include Ziegler-Natta catalysts and metallocene catalysts, with metallocene catalysts being preferred. Known polymerization methods include, for example, a solution polymerization method, a slurry polymerization method, a high pressure ionic polymerization method, a gas phase polymerization method and the like.

The copolymer (B) used in the present invention is a copolymer obtained by copolymerizing ethylene and / or α-olefin with the following vinyl compound, and the following vinyl compound has a bulky substituent group. It is a vinyl compound having. Vinyl compound: A vinyl compound represented by CH ₂ ═CH—R, the steric parameter Es of the substituent R is −1.64 or less, and the steric parameter B1 of the substituent R is 1.53 or more.

The three-dimensional parameters Es and B1 mentioned here
Is a parameter (Es represents a three-dimensional spread and B1 represents a two-dimensional spread) representing the steric bulkiness of a substituent, and is a document (C. Hansch and A. Leo:
"Exploring QSAR Fundament
als and Applications in Ch
emissary and Biology "Chapt
er3 (ACS Professional Ref.
Rence Book, Washington, DC (1
995)).

In Table 1, the solid parameter Es is -1.64.
And the steric parameter B1 of the substituent R is 1.
Examples of the vinyl compound are 53 or more.

[0022]

[Table 1]

For reference, the steric parameters of some vinyl compounds having non-bulky substituents are shown in Table 2.

[0024]

[Table 2]

As the vinyl compound of the copolymer (B) used in the present invention, a vinyl compound having a bulkier substituent is more preferably used. The steric parameter Es of the substituent R is preferably -4.65 to -1.70.
, More preferably -3.00 to -1.72, still more preferably -2.80 to -1.75, and most preferably -2.10 to -1.75.
The steric parameter B1 of the substituent R is preferably 1.53 to 2.90, more preferably 1.7.
0 to 2.70, more preferably 1.91 to 2.
Thirty. If the steric parameter Es is too large or the steric parameter B1 is too small, the molding stability, elastic recovery property and delayed recovery property may be poor. Also,
From the viewpoint of thermal stability, the vinyl compound of the copolymer (B) is preferably a vinyl compound in which the substituent R is a hydrocarbon group, and more preferably a vinyl compound in which the substituent R is a saturated hydrocarbon group. is there.

The vinyl compound used in the present invention preferably has no branched structure other than the carbon atom at the 3-position. The term “branched structure” as used herein refers to a structure in which the molecular skeleton is not linear and has a skeleton branched through a tertiary or quaternary carbon atom. Such a vinyl compound is easier to synthesize than a vinyl compound having a plurality of branched structures.

The vinyl compound used in the present invention is more preferably a vinyl compound having a tertiary carbon atom at the 3-position and a structure having no branched structure other than the carbon atom at the 3-position.

The vinyl compound used in the present invention is more preferably one in which the substituent R is a secondary alkyl group or a tertiary alkyl group.

The secondary alkyl group or tertiary alkyl group referred to herein is preferably a secondary alkyl group having 3 to 20 carbon atoms or a tertiary alkyl group having 4 to 20 carbon atoms. R
May be a cycloalkyl group, in which case it is preferably a 3- to 16-membered cycloalkyl group, and more preferably a 3- to 10-membered cycloalkyl group.

Specific examples of such vinyl compounds include vinylcyclopropane, vinylcyclobutane, vinylcyclopentane, vinylcyclohexane, vinylcycloheptane, vinylcyclooctane, 3-methyl-1-butene, 3-methyl-1-pentene, 3-methyl-1-hexene, 3-methyl-1-heptene, 3-methyl-1-octene, 3,3-dimethyl-1-butene, 3,3-dimethyl-1-pentene, 3,3-dimethyl- 1-hexene, 3,3-dimethyl-1-heptene, 3,3-dimethyl-1-octene, 3,4-dimethyl-1-pentene,
3,4-dimethyl-1-hexene, 3,4-dimethyl-
1-heptene, 3,4-dimethyl-1-octene, 3,
5-dimethyl-1-hexene, 3,5-dimethyl-1-
Heptene, 3,5-dimethyl-1-octene, 3,6-
Dimethyl-1-heptene, 3,6-dimethyl-1-octene, 3,7-dimethyl-1-octene, 3,3,4-
Trimethyl-1-pentene, 3,3,4-trimethyl-
1-hexene, 3,3,4-trimethyl-1-heptene, 3,3,4-trimethyl-1-octene, 3,4
4-trimethyl-1-pentene, 3,4,4-trimethyl-1-hexene, 3,4,4-trimethyl-1-heptene, 3,4,4-trimethyl-1-octene, 5-vinyl-2- Norbornene, 1-vinyl adamantane, 4
-Vinyl-1-cyclohexene and the like can be mentioned.

More preferred vinyl compounds are vinylcyclopentane, vinylcyclohexane, vinylcycloheptane, vinylcyclooctane, 5-vinyl-2-norbornene, 3-methyl-1-butene, 3-methyl-1-pentene and 3-. Methyl-1-hexene, 3,3-dimethyl-1-butene, 3,3-dimethyl-1-pentene, 3,
4-dimethyl-1-pentene, 3,5-dimethyl-1-
It is hexene, 3,3,4-trimethyl-1-pentene, or 3,4,4-trimethyl-1-pentene. More preferred vinyl compound is vinylcyclohexane,
Vinyl norbornene, 3-methyl-1-butene, 3-methyl-1-pentene, 3,3-dimethyl-1-butene,
3,4-dimethyl-1-pentene, or 3,3,4-
Trimethyl-1-pentene, and a particularly preferred vinyl compound is vinylcyclohexane or 3,3-dimethyl-1-butene.

Α-of the copolymer (B) used in the present invention
As the olefin, the above-mentioned polyolefin resin (A)
The same ones as the α-olefin of the ethylene-α-olefin copolymer used as can be used.

The copolymer (B) used in the present invention is a copolymer obtained by copolymerizing ethylene, α-olefin, a vinyl compound having a bulky substituent, and at least one addition-polymerizable monomer. May be Examples of the addition-polymerizable monomer include cyclic olefins having 3 to 20 carbon atoms, vinylidene compounds, diene compounds, and vinyl compounds other than the vinyl compound having a bulky substituent used in the copolymer (B). You can

Specific examples of such cyclic olefins include:
Cyclobutene, cyclopentene, cyclohexene, cyclooctene, 3-methylcyclopentene, 4-methylcyclopentene, 3-methylcyclohexene, 2-norbornene, 5-methyl-2-norbornene, 5-ethyl-
2-norbornene, 5-butyl-2-norbornene, 5
-Phenyl-2-norbornene, 5-benzyl-2-norbornene, 2-tetracyclododecene, 2-tricyclodecene, 2-tricycloundecene, 2-pentacyclopentadecene, 2-pentacyclohexadecene, 8-
Methyl-2-tetracyclododecene, 8-ethyl-2-
Tetracyclododecene, 5-acetyl-2-norbornene, 5-acetyloxy-2-norbornene, 5-methoxycarbonyl-2-norbornene, 5-ethoxycarbonyl-2-norbornene, 5-methyl-5-methoxycarbonyl-2. -Norbornene, 5-cyano-2-norbornene, 8-methoxycarbonyl-2-tetracyclododecene, 8-methyl-8-methoxycarbonyl-2-
Examples thereof include tetracyclododecene and 8-cyano-2-tetracyclododecene. More preferred cyclic olefins are cyclopentene, cyclohexene, cyclooctene, 2-norbornene, 5-methyl-2-norbornene, 5-phenyl-2-norbornene, 2-tetracyclododecene, 2-tricyclodecene and 2-tricyclo. Undecene, 2-pentacyclopentadecene, 2-pentacyclohexadecene, 5-acetyl-2-norbornene, 5-acetyloxy-2-norbornene, 5-methoxycarbonyl-2-norbornene, 5-methyl-5-
Methoxycarbonyl-2-norbornene or 5-cyano-2-norbornene, particularly preferably 2-norbornene or 2-tetracyclododecene.
These may be used alone or in combination of two or more.

Specific examples of the vinylidene compound include:
Isobutene, 2-methyl-1-butene, 2-methyl-1
-Pentene, 2-methyl-1-hexene, 2-methyl-
1-heptene, 2-methyl-1-octene, 2,3-dimethyl-1-butene, 2,3-dimethyl-1-pentene, 2,3-dimethyl-1-hexene, 2,3-dimethyl-1- Heptene, 2,3-dimethyl-1-octene,
2,4-dimethyl-1-pentene, 2,4,4-trimethyl-1-pentene and the like can be mentioned. Particularly preferred vinylidene compounds are isobutene, 2,3-dimethyl-1-butene, or 2,4,4-trimethyl-1-pentene. These may be used alone or in combination of two or more.

Specific examples of the diene compound include 1,
3-butadiene, 1,4-pentadiene, 1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene, 1,5-cyclooctadiene, 2,5-norbornadiene, dicyclopentadiene, 5-vinyl- 2-norbornene, 5-allyl-2-norbornene, 4-vinyl-1-cyclohexene, 5-ethylidene-2-norbornene and the like can be mentioned. A particularly preferred diene compound is 1,
4-pentadiene, 1,5-hexadiene, 2,5-norbornadiene, dicyclopentadiene, 5-vinyl-
2-norbornene, 4-vinyl-1-cyclohexene,
Alternatively, it is 5-ethylidene-2-norbornene. These may be used alone or in combination of two or more.

Specific examples of vinyl compounds other than the vinyl compound having a bulky substituent used in the copolymer (B) include methyl vinyl ether, ethyl vinyl ether, acrylic acid, methyl acrylate, ethyl acrylate, methyl methacrylate, Examples thereof include acrylonitrile and vinyl acetate. These may be used alone or in combination of two or more.

In the copolymer (B) used in the present invention, the copolymer composition of the vinyl compound having a bulky substituent can be in a wide range such as 0.1 to 99 mol%. The copolymerization composition of the vinyl compound is preferably 1 to 90 mol%, more preferably 5 to 90 mol%, and further preferably 1 from the viewpoint of transparency and processability.
0 to 90 mol%, particularly preferably 15 to 85 m
ol%. However, the total composition of the copolymer (B) is 10
It is 0 mol%. The copolymerization composition of the vinyl compound is
^It can be easily obtained by a conventional method using a ¹ H-NMR spectrum or a ¹³ C-NMR spectrum.

The copolymer (B) used in the present invention is derived from a vinyl compound having a bulky substituent in the polymer skeleton (including branched polymer chains in the polymer molecular chain). There are secondary carbon atoms and tertiary carbon atoms. Further, in the case of a copolymer of ethylene and a vinyl compound having a bulky substituent, a secondary carbon atom derived from ethylene is also present, and in the case of a copolymer of α-olefin such as propylene, α-olefin. There are also secondary and tertiary carbon atoms of origin. A structure in which tertiary carbon atoms are separated from each other by one methylene group, a structure separated by two methylene groups, or a structure separated by three methylene groups, depending on the sequence in the polymer skeleton,
There may be structures separated by 4 or more methylene groups. The polymer structure is determined by ¹³ C-NMR spectrum. Copolymer (B) used in the present invention
Has, in its skeleton, a structure in which carbon atoms substituted by a substituent R derived from a vinyl compound having a bulky substituent are separated from each other by preferably 3 methylene groups, and more preferably 1 methylene. It has a structure separated by a group. A copolymer having such a structure is preferable because it has excellent flexibility.

From the viewpoint of weather resistance, the copolymer (B) used in the present invention does not contain a double bond in all the molecular structures (including the substituent R) of the polymer except the terminal of the copolymer. Is preferred. A copolymer containing a double bond in the molecular structure of the polymer is also inferior in thermal stability and may cause problems such as generation of fish eyes due to gelation during molding.

The molecular weight distribution (Mw / Mn) represented by the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the copolymer (B) used in the present invention is mechanical strength and transparency. From the viewpoint of, it is preferably 1.5 to 4.0, more preferably 1.5 to 3.5, and particularly preferably 1.5 to 3.0.

Further, the copolymer (B) used in the present invention
From the viewpoint of mechanical strength, the weight average molecular weight (Mw) of
It is preferably 5,000 to 1,000,000, more preferably 10,000 to 500,000,
Particularly preferably, it is 20,000 to 400,000.

The intrinsic viscosity [η] of the copolymer (B) used in the present invention is preferably 0. 0 from the viewpoint of mechanical strength.
2-10.0 dl / g, more preferably 0.2
5 to 6.0 dl / g, particularly preferably 0.3 to
It is 5.0 dl / g.

The method for producing the copolymer (B) used in the present invention is, for example, in the presence of a catalyst obtained by contacting trityl borate and triisobutylaluminum or methylalumoxane with ethylene and / or Alternatively, there may be mentioned a method of copolymerizing an α-olefin and a vinyl compound having a bulky substituent. At that time, ethylene, α-olefin, the input amount of a vinyl compound having a bulky substituent, the polymerization conditions such as the polymerization temperature and the polymerization time are appropriately changed to obtain copolymers having different copolymerization compositions and molecular weights. be able to.

Regarding the content of the polyolefin resin (A) and the copolymer (B) in the polyolefin resin composition of the present invention, the content of the polyolefin resin (A) is 1 to 9.
9% by weight, the content of the copolymer (B) is 99 to 1% by weight, preferably the content of the polyolefin resin (A) is 50 to 95% by weight, and the copolymer (B) is Is 50 to 5% by weight, more preferably the content of polyolefin resin (A) is 60 to 90% by weight, and the content of copolymer (B) is 40 to 10% by weight. . When the content of the polyolefin resin (A) is too small (the content of the copolymer (B) is too large), the appearance of the molded product using the obtained resin composition may be poor, and the polyolefin resin If the content of (A) is too large (the content of the copolymer (B) is too small), the melt tension may decrease and the molding stability may be poor. However, the total amount of the polyolefin resin (A) and the copolymer (B) is 10
It is 0% by weight.

The polyolefin resin composition of the present invention contains
If necessary, other resin components and additives such as stabilizers, lubricants, antistatic agents, processability improvers and antiblocking agents may be added.

Examples of the stabilizer include 2,6-di-t.
-Butyl-p-cresol (BHT), tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane (trade name: IRG
ANOX 1010, manufactured by Ciba Specialty Chemicals), n-octadecyl-3- (4'-hydroxy-3,5'-di-t-butylphenyl) propionate (trade name: IRGANOX 1076, Ciba Specialty Chemicals) Stabilizers such as bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite and tris (2,4-di-t-butylphenyl) phosphite. Etc.

Examples of the lubricant include higher fatty acid amides and higher fatty acid esters, and examples of the antistatic agent include glycerin esters of fatty acids having 8 to 22 carbon atoms, sorbitan acid esters, polyethylene glycol esters and the like. Examples of the processability improver include fatty acid metal salts such as calcium stearate and fluororesins.

The antiblocking agents include inorganic antiblocking agents and organic antiblocking agents, and the inorganic antiblocking agents include, for example, silica, calcium carbonate, talc, etc., organic antiblocking agents. Examples thereof include crosslinked polymethylmethacrylate, crosslinked poly (methylmethacrylate-styrene) copolymer, crosslinked silicone, and crosslinked polystyrene powder. Organic blocking inhibitors are preferred.

Examples of the method for producing the polyolefin resin composition of the present invention include known mixing methods. For example, a method of melt-kneading the polyrefin resin (A) and the copolymer (B) used in the present invention and the like. Can be mentioned.

As a method of mixing other resins and additives such as a stabilizer, a lubricant, an antistatic agent, a processability improving agent and an antiblocking agent which are blended as necessary, known methods can be mentioned. For example, a method of previously melt-kneading a resin composition comprising the polyolefin resin (A) and the copolymer (B) used in the present invention, the polyolefin resin (A) or the copolymer (B) used in the present invention Dry blending, and a method of preparing a master batch of at least one other resin or additive and dry blending.

[0052]

EXAMPLES The present invention will be described below with reference to examples and comparative examples, but the present invention is not limited to these examples. The physical properties of the resin composition composed of the polyolefin resin (A) and the copolymer (B) used in the examples were measured according to the following methods.

(1) Melt flow rate (unit: g / 1
0 minutes) Measured according to the method specified in JIS K6760. The load was 2.16 kg and the temperature was 190 ° C. (2) Melt tension (unit: cN) Using a melt tension tester manufactured by Toyo Seiki Seisakusho,
A molten resin extruded from an orifice having a diameter of 2.09 mmφ and a length of 8 mm was wound up at a winding rate of 40 rpm / min by a piston at 150 ° C. and a descent rate of 5.5 mm / min, and the tension was measured. (3) Intrinsic viscosity ([η], unit: dl / g) The intrinsic viscosity [η] was measured at 135 ° C. using tetralin as a solvent using an Ubbelohde viscometer. (4) Copolymer composition of vinylcyclohexane unit in polymer (unit: mol%) The copolymer composition of vinylcyclohexane unit in the polymer is ¹³
It was determined by C-NMR analysis. ¹³ C-NMR apparatus: DRX600 manufactured by BRUKER Co., Ltd. Measurement solvent: 4: 1 (volume ratio) mixed solution of orthodichlorobenzene and orthodichlorobenzene-d4 Measurement temperature: 135 ° C. (5) Density Measured according to the method specified in JIS K6760 did.

Polyolefin resin (A) used in the examples
And the copolymer (B) are shown below. (I) Polyolefin resin (A) (A-1): ethylene-hexene-1 copolymer Sumikasen EFV402 (manufactured by Nippon Evolue Co., Ltd.,
Sold by Sumitomo Chemical Co., Ltd., density 915 kg / m ³ , melt flow rate 4.0 g / 10 min (A-2): ethylene-hexene-1 copolymer Sumikasen E FV205 (manufactured by Nippon Evolue Co., Ltd.,
Sold by Sumitomo Chemical Co., Ltd., density 923 kg / m ³ , melt flow rate 2.0 g / 10 minutes)

(II) Copolymer (B) (B-1): Ethylene / vinylcyclohexane copolymer (1) Synthesis method In a 5000 ml autoclave substituted with argon, vinylcyclohexane (117 g) and dehydrated toluene (1618) were added.
g was added. After raising the temperature to 50 ° C, 0.8MP of ethylene
a. Toluene solution of methylalumoxane [MMAO manufactured by Tosoh Akzo Co., Ltd., Al atom conversion concentration 6wt
%] 14.7 ml, followed by isopropylidene bis (indenyl) zirconium dichloride 10.8 m
What was dissolved in 10.8 ml of dehydrated toluene was added. After stirring the reaction solution for 35 minutes, the reaction solution was added with methanol 6
It was thrown into 000 ml and the precipitated white solid was collected by filtration. The solid was washed with methanol and dried under reduced pressure, and as a result, 292.6 g of a polymer was obtained. Hereinafter, this polymer is referred to as (B-1). (2) Physical properties Obtained ethylene / vinylcyclohexane copolymer (B
The intrinsic viscosity [η] of -1) was 0.90 dl / g, and the copolymer composition of vinylcyclohexane was 12 mol%.

(B-2): Ethylene / vinylcyclohexane copolymer (2) Synthesis method The above ethylene / vinylcyclohexane copolymer (B-
In the synthesis of 1), vinylcyclohexane 117 g was added to 1116 g, dehydrated toluene 1618 g was added to 507 g, and
Ethylene 0.8 MPa to 0.1 MPa, methylalumoxane toluene solution 14.7 ml to 31.0 ml,
A solution of isopropylidene bis (indenyl) zirconium dichloride (10.8 mg) dissolved in dehydrated toluene (10.8 ml) was dissolved in isopropylidenebis (indenyl) zirconium dichloride (21.6 mg) and dehydrated toluene (21.6 mg).
Polymerization was carried out in the same manner as in the above-mentioned ethylene-vinylcyclohexane copolymer (B-1) except that the stirring time was changed to 90 minutes for 35 minutes, and 425.5 g of a polymer was obtained. It was Hereinafter, this polymer is referred to as (B-2). (2) Physical properties Obtained ethylene / vinylcyclohexane copolymer (B
-2) had an intrinsic viscosity [η] of 0.38 dl / g and a vinylcyclohexane copolymer composition of 77 mol%.

Examples 1 to 3 and Comparative Examples 1 and 2 The polyolefin resins (A) and copolymers (B) in the amounts shown in Table 1 were used at 150 ° C. using a Labo Plastomill apparatus manufactured by Toyo Seiki. Kneading was performed for 5 minutes to obtain a resin composition. The results of melt flow rate and melt tension of the obtained resin composition are shown in Table 3.

[0058]

[Table 3]

Examples 1 to 3 satisfying the requirements of the present invention are
It can be seen that the melt tension is high. On the other hand, Comparative Example 1 in which the copolymer (B) which is a requirement of the present invention was not used, and the copolymer (B) which is a requirement of the present invention
It can be seen that Comparative Example 2 in which the ethylene-hexene-1 copolymer which is not used has a low melt tension.

[0060]

As described in detail above, according to the present invention, it is possible to obtain a polyolefin resin composition having a large melt tension of the melt and excellent stability during molding. Also,
The resin composition of the present invention is also excellent from the viewpoint of reducing the load on the extruder and the strength of the molded product.

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Claims (4)

[Claims] 1. A polyolefin resin (A) in an amount of 1 to 99% by weight.
And 99 to 1% by weight of a copolymer (B), wherein the copolymer (B) is obtained by copolymerizing ethylene and / or α-olefin with the following vinyl compound. A polyolefin resin composition, which is the obtained copolymer. Vinyl compound: CH ₂ =
CH-R, and the steric parameter Es of the substituent R is-.
Stereo parameter B of 1.64 or less and the substituent R
A vinyl compound in which 1 is 1.53 or more. 2. The substituent R of the vinyl compound is a secondary alkyl group or a tertiary alkyl group.
The polyolefin resin composition described. 3. The polyolefin resin composition according to claim 1 or 2, wherein the vinyl compound is vinylcyclohexane. 4. The polyolefin resin (A) is ethylene
The polyolefin resin composition according to claim 1, which is an α-olefin copolymer.