JP2001213923A - Polyolefin composition and its manufacturing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyolefin composition which gives a polypropylene film having a low heat sealing temperature and a wide hot tack temperature range and to provide a polymer suitable as a starting material of this composition. SOLUTION: The polyolefin composition comprises 5-95 wt.% of a polypropylene and 5-95 wt.% of a propylene//propylene/olefin block copolymer, where the propylene//propylene/olefin block copolymer comprises 20-95 wt.% of a segment A comprising a polymer composed mainly of propylene obtained in the presence of a catalyst system for olefin polymerization comprising a specific supported metallocene catalyst and 80-5 wt.% of a segment B comprising a propylene/olefin random copolymer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel polyolefin composition. More specifically, the present invention relates to a composition comprising polypropylene and a novel propylene // propylene / olefin block copolymer.
It has the characteristic that the hot tack strength is strong in a wide temperature range. Further, the propylene // propylene / olefin block copolymer constituting the present invention is obtained as a copolymer having a preferable particle shape by producing the propylene // propylene / olefin block copolymer by a process including a gas phase polymerization using a specific supported catalyst system. be able to.

[0002]

2. Description of the Related Art Hitherto, polypropylene has been widely used as a thermoplastic molding material having excellent rigidity, heat resistance, transparency and the like. Since this polypropylene is inferior in flexibility and impact resistance, in the field where flexibility and impact resistance are required, usually, a soft rubber component is blended with polypropylene for use. In particular, in the field of files, improvement of low-temperature heat sealability is required for the purpose of improving productivity during processing, specifically, improving high-speed processing.

[0003] JP-A-8-208909 discloses that 5-95% by weight of polypropylene and 5 to 5% of 1-butene unit are used.
It is disclosed that a polypropylene composition comprising 5 to 95% by weight of a propylene / 1-butene elastomer containing 0 mol% is excellent in flexibility and impact resistance, and also excellent in heat resistance and heat sealability. I have.

Japanese Patent Application Laid-Open No. 9-268241 discloses that 40 to 95% by weight of polypropylene and 5 to 1-butene unit are used.
40 mol% and 5 to 40 mol% of ethylene units,
And a propylene / ethylene / 1-butene elastomer 5 in which the amount of 1-butene units is larger than the amount of ethylene units.
Molded article obtained from a composition consisting of
It describes that it is excellent in transparency and excellent in flexibility.

[0005] When a soft rubber component is blended with polypropylene as described above, a polypropylene composition having improved flexibility and impact resistance can be obtained. However, a polypropylene composition which does not sufficiently satisfy the low-temperature heat-sealing performance required in the field of files. Did not. In addition, propylene / 1-
A butene-based elastomer and a propylene / ethylene / 1-butene-based elastomer can be obtained as a particulate polymer, particularly, for a low-melting elastomer used for the purpose of improving flexibility and impact resistance, or an amorphous elastomer. Difficult, production is generally by solution polymerization, and production in processes involving gas phase polymerization has generally been difficult.

[0006] Therefore, a polypropylene composition which can be produced in the form of particles by a process including a gas phase polymerization, whereby an elastomer capable of improving the low-temperature heat sealing performance of a film obtained by processing the polypropylene can be produced by blending with polypropylene. The development of was desired.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide a polyolefin composition and a method for producing the same, wherein the elastomer to be blended is granular, and a film exhibiting excellent low-temperature heat sealing performance can be obtained. And

[0008]

Means for Solving the Problems The present inventors have made intensive studies to achieve the above object, and as a result, have found that a polyolefin composition obtained by blending polypropylene with a specific propylene // propylene / olefin block copolymer. The product can be used to obtain a film having an excellent low-temperature heat sealability when used, and the block copolymer has a particle shape by a process including a gas phase polymerization method using a specific catalyst system. And found that the present invention was completed.

[0009] The present invention relates to a propylene // segment comprising an A segment composed of a propylene-based polymer and a B segment composed of a propylene / olefin / random copolymer.
A propylene / olefin block copolymer,
The A segment is 20 to 20 parts by weight based on the weight of the block copolymer.
95 to 5% by weight of a propylene // propylene / olefin block copolymer containing 95% by weight and a B segment in the range of 80 to 5% by weight based on the weight of the block copolymer.
And a propylene // propylene / olefin block copolymer comprising: (1) a metallocene-supported catalyst (1) obtained by performing the following steps (a) to (c): I) or the following (a) to
In the presence of an olefin polymerization catalyst system comprising a metallocene-supported catalyst (II) obtained by performing the step (d) and an organoaluminum compound, propylene alone or a mixture of olefins other than propylene and propylene A polymerization step of producing an A segment composed of a propylene-based polymer having a weight ratio of olefin units other than propylene units / propylene units in the polymer chain of 0/100 to 30/70, and (2) ) In the presence of a propylene-based polymer including the olefin polymerization catalyst system from the first polymerization step, a mixture of olefins other than propylene and propylene is copolymerized, and propylene units in the polymer chain /
The weight ratio of olefin units other than propylene is 5 / 95-
A second polymerization step of generating a B segment composed of a 95/5 propylene / olefin random copolymer, which is a block copolymer obtained by sequentially performing a polyolefin composition. (A) a step of reacting an organic transition metal compound having two crosslinked π-electron conjugated ligands with an aluminoxane in an inert solvent; (b) a reaction product produced in the step (a) and an inorganic fine particle carrier Is contacted at a temperature of 85 to 150 ° C. in the presence of an inert solvent. (C) A slurry containing the solid product produced in the step (b) is reacted with an aliphatic hydrocarbon at a temperature of −50 to 50 ° C. (D) contacting the metallocene-supported catalyst obtained in the step (c) with the olefin to prepolymerize the olefin, whereby 0.01 to 100 kg of olefin reserve per kg of the metallocene-supported catalyst; Step of supporting polymer

Another aspect of the present invention is to provide an A segment comprising a propylene-based polymer and propylene / olefin.
A propylene // propylene / olefin block copolymer comprising a B segment comprising a random copolymer, wherein the A segment is 20 to 95% by weight based on the weight of the block copolymer and the B segment is a block copolymer. A propylene // propylene / olefin block copolymer containing from 80 to 5% by weight based on the weight of the combined product;
A method for producing a polyolefin composition comprising 5% by weight and 5 to 95% by weight of polypropylene, comprising:
A metallocene-supported catalyst (I) obtained by performing the following steps (a) to (c) or a metallocene-supported catalyst (II) obtained by performing the following steps (a) to (d): Propylene alone or a mixture of olefins other than propylene and propylene in the presence of an olefin polymerization catalyst system consisting of olefin and an organoaluminum compound, and the weight ratio of olefin units other than propylene / propylene units in the polymer chain (1) a first polymerization step for producing an A segment consisting of a propylene-based polymer having a ratio of 0/100 to 30/70, and (2) a propylene-based polymer containing an olefin polymerization catalyst system from the first polymerization step. In the presence, a mixture of an olefin other than propylene and propylene is copolymerized, and a propylene unit in the polymer chain / an olefin unit other than propylene A second polymerization step for producing a B segment composed of a propylene / olefin random copolymer having a weight ratio of 5/95 to 95/5 is sequentially performed to produce a propylene // propylene / olefin block copolymer. , The propylene // propylene / olefin.
5 to 95% by weight of a block copolymer and polypropylene 9
5 to 5% by weight of a polyolefin composition. (A) a step of reacting an organic transition metal compound having two crosslinked π-electron conjugated ligands with an aluminoxane in an inert solvent; (b) a reaction product produced in the step (a) and an inorganic fine particle carrier Is contacted at a temperature of 85 to 150 ° C. in the presence of an inert solvent. (C) A slurry containing the solid product produced in the step (b) is reacted with an aliphatic hydrocarbon at a temperature of −50 to 50 ° C. (D) contacting the metallocene-supported catalyst obtained in the step (c) with the olefin to prepolymerize the olefin, whereby 0.01 to 100 kg of olefin reserve per kg of the metallocene-supported catalyst; Step of supporting polymer

[0011]

DETAILED DESCRIPTION OF THE INVENTION The polyolefin composition of the present invention comprises 5-95% by weight of polypropylene and propylene //
A polyolefin composition comprising 95 to 5% by weight of a propylene / olefin block copolymer, preferably 10 to 90% by weight of polypropylene,
/ Propylene / olefin block copolymer 90-1
0% by weight, particularly preferably 30 to 70% by weight of polypropylene and propylene // propylene / olefin block copolymer 7
It is a polyolefin composition comprising 0 to 30% by weight.

As the polypropylene constituting the polyolefin composition of the present invention, conventionally known polypropylenes are widely used. The polypropylene may be a propylene homopolymer or a random copolymer or a block copolymer of propylene containing another olefin unit in an amount of 50% by weight or less and another olefin. . Among these, a random copolymer of propylene and another olefin is preferably used.

The other olefin forming a random copolymer or a block copolymer of propylene and another olefin is, specifically, a propylene having 2 carbon atoms other than propylene.
To 20 alpha-olefins, such as ethylene, 1-butene, 1-pentene, 1-hexene, 1-heptene,
-Octene, 1-decene, 1-dodecene, 1-hexadecene, 4-methyl-1-pentene and the like. Further, two or more of these olefins may be used simultaneously.

[0014] The polypropylene preferably used in the present invention has a melting point of 100 to 165 ° C, particularly preferably 12 to 165 ° C.
0-165 ° C. Among the polypropylenes having such a melting point, it is desirable that the polypropylene has a melting point higher than the melting point of the A segment constituting the propylene // propylene / olefin block copolymer described later. 30 to 0.1 ° C from the melting point of the A segment
Those having a high melting point are preferable, and those having a high melting point of 10 to 0.1 ° C are particularly preferable.

The polypropylene has an MFR of preferably 0.1 to 400 g / 10 min, particularly preferably 1 to 1 when measured under the conditions of 230 ° C. and a load of 21.8 N.
00g / 10 min, and the molecular weight distribution (Mw / Mn) is
It is suitably in the range from 1.5 to 15, particularly preferably from 4 to 10.

As the polypropylene used in the present invention, a polypropylene produced by a known method using a conventionally known solid titanium catalyst component is preferable. Further, a polypropylene obtained by using a metallocene compound catalyst component can also be used.

The propylene // propylene / olefin block copolymer used in the present invention may be a propylene homopolymer having a weight ratio of olefin units other than propylene / propylene unit of 0/100 to 30/70 in the polymer chain or A weight ratio of propylene unit / olefin unit other than propylene in the polymer chain of the A segment composed of a propylene-based polymer which is a propylene / olefin random copolymer and propylene / olefin. It consists of a B segment composed of a random copolymer, and the weight ratio of A segment / B segment is 20/80.
９５95/5. Preferably, its intrinsic viscosity in 135 ° C. tetralin is between 0.1 and 12 dl / g.

This block copolymer is an AB-type block copolymer in which an A segment and a B segment are bonded by a covalent bond, and a polymer of an A segment and a B segment in which there is no chemical bond between both segments. It may be a mixture or a mixture thereof.

The olefins other than propylene constituting the A segment and the B segment are each independently ethylene, 1-butene, 1-pentene, 1-pentene,
Linear monoolefins such as hexene, 1-octene, 1-decene, 1-dodecene, 3-methyl-1-butene,
Branched monoolefins such as 4-methyl-1-pentene and 2-methyl-1-pentene, cyclopentene, cyclohexene, norbornene, 5-methyl-2-norbornene, 5-ethyl-2-norbornene, phenylnorbornene, indanyl Cyclic olefins such as norbornene, 1,3-butadiene, isoprene, 1,4-hexadiene, 1,7-octadiene, 1,9-decadiene, 4-
Chain polyenes such as methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 7-methyl-1,6-octadiene, dicyclopentadiene, 5-methylene-2-norbornene, 5-ethylidene- Cyclic polyenes such as 2-norbornene, styrenes such as styrene, vinylnaphthalene and α-methylstyrene, 5- (N,
There are substituted olefins such as (N-diisopropylamino) -1-pentene and 4-trimethylsiloxy-1,6-heptadiene, and polyene derivatives, and furthermore, olefins such as vinylcyclohexane, vinyl chloride, methyl methacrylate, and ethyl acrylate. Examples thereof include polymerizable vinyl compounds, and these can be used in combination of two or more. Among these, the use of ethylene and / or 1-butene is particularly preferred.

The A segment of the propylene // propylene / olefin block copolymer includes propylene homopolymer, propylene / ethylene random copolymer, propylene / 1-butene random copolymer,
Alternatively, a propylene / ethylene / 1-butene / ternary random copolymer is preferably used. Preferably, the melting point is 100 ° C to 165 ° C, more preferably, 110 ° C to 1 ° C.
A propylene-based polymer at 55 ° C, particularly preferably in the range of 110 ° C to 140 ° C, is used.

The B segment of the propylene // propylene / olefin block copolymer described above may be a propylene / 1-butene random copolymer or 2.9.
Propylene / ethylene / 1-butene random copolymer containing ethylene units of not more than 5% by weight is suitably used.
7.1 to 84.9% by weight, 0.1 to 2.
A propylene / ethylene / 1-butene random copolymer containing 9% by weight and 15 to 60% by weight of 1-butene unit is preferably used.

When the A segment is a copolymer of propylene and an olefin, the olefin constituting the A segment and the olefin constituting the B segment may be the same or different from each other. Are preferably propylene / 1-butene random copolymers, and the propylene / 1-butene random copolymer of the B segment further contains ethylene units in a range not exceeding 2.9% by weight. Are preferred.

The preferred method for producing the propylene // propylene / olefin block copolymer used in the present invention is as follows. That is, (A)
A production method comprising a step and a step (B), wherein the step (A) is carried out in the presence of a catalyst system for olefin polymerization comprising a metallocene-supported catalyst and an organoaluminum compound, or in the presence of 0 per kg of a metallocene-supported catalyst. .01-100k
g olefin prepolymer is polymerized with propylene alone in the presence of an olefin polymerization catalyst system consisting of a preactivated catalyst consisting of particulates supported on the metallocene-supported catalyst and an organoaluminum compound, or This is a first polymerization step in which a mixture of propylene and an olefin other than propylene is polymerized to form an A segment composed of a propylene-based polymer, and the subsequent step (B) is a catalyst for olefin polymerization from the first polymerization step. This is a second polymerization step in which propylene and an olefin other than propylene are copolymerized in the presence of a propylene-based polymer including the system to generate a B segment composed of the propylene / olefin random copolymer.

As used herein, the term "preactivation" as used in reference to a catalyst refers to the various activities of the catalyst with respect to the polymerization of olefins, including the polymerization of propylene, for example, the amount of olefin polymerized per unit weight of the active ingredient of the catalyst. Means that the polymerization activity represented by the formula (1) and the activity affecting the stereoregularity and crystallinity of the resulting olefin polymer are activated before the main polymerization of the olefin.

The term "prepolymerization" of olefins is
To pre-activate the catalyst, prepolymerizing a small amount of olefin in the presence of the catalyst prior to the main polymerization of the olefin, and the term "olefin prepolymer" refers to
It means an olefin polymer that has been prepolymerized prior to the main polymerization of the olefin.

The metallocene-supported catalyst used in the present invention includes an organic transition metal compound having two π-electron conjugated ligands cross-linked to each other, a so-called cross-linked metallocene compound (hereinafter referred to as a “cross-linked metallocene compound”) and an aluminoxane. And a solid product supported on an inorganic fine particle carrier, containing 0.01 to 5% by weight of a transition metal derived from a crosslinked metallocene compound and 0.1 to 50% by weight of aluminum derived from an aluminoxane. And the molar ratio of aluminum / transition metal in the metallocene-supported catalyst is 1
Solid particles in the range of ~ 1,000.

The transition metal content and the aluminum / transition metal molar ratio in the metallocene-supported catalyst both affect the olefin polymerization activity. If the content of the transition metal is too small, practical olefin polymerization activity cannot be obtained,
Further, even if it is larger than necessary, the polymerization activity corresponding thereto cannot be obtained. If the content of the transition metal in the metallocene-supported catalyst is in the range of 0.01 to 5% by weight, practically sufficient olefin polymerization activity can be obtained, but the content of the transition metal is 0.03 to 2% by weight.
Is preferably within the range. On the other hand, the content of aluminum is 0.1 to 50% by weight, preferably 1 to 40% by weight.
And the molar ratio of aluminum / transition metal is 1 to 1.0.
00, preferably 5 to 700, more preferably 10 to
It is adjusted to the range of 500.

The above-mentioned metallocene-supported catalyst has a unique peak at a position of 1426 cm -1 in its infrared absorption spectrum. A catalyst having such a unique peak and having a high peak intensity has a high olefin polymerization activity.
The infrared absorption spectrum of the metallocene-supported catalyst,
An FTIR device with a resolution of 4 cm ^-1 or more (eg, Nicolet 60S)
XR type) and can be measured by a diffuse reflection method.

The above metallocene-supported catalyst comprises: (a) a step of reacting a crosslinked metallocene compound with an aluminoxane in an inert solvent; (b) a reaction product produced in the step (a) and an inorganic fine particle carrier, 85 to 85 in the presence of an inert solvent
(C) contacting the slurry containing the solid product produced in step (b) with a temperature of −50 to 50 ° C.
Washing at least twice with an aliphatic hydrocarbon at a temperature of ° C.

In the present invention, the pre-activation of the metallocene-supported catalyst is carried out in the step (d) following the above step (c) by reacting the metallocene-supported catalyst obtained in the step (c) with the olefin. Contacting to prepolymerize the olefin, and further supporting 0.01 to 100 kg of the olefin prepolymer per 1 kg of the metallocene-supported catalyst. The catalyst thus preactivated is
It is called a preactivation catalyst.

The metallocene compound used for the metallocene-supported catalyst and the preactivation catalyst is represented by the following general formula (1)
It is represented by

Embedded imageIn the formula, M represents a transition metal, and p represents the valence of the transition metal.
And X may be the same or different, and each is hydrogen
Represents an atom, a halogen atom or a hydrocarbon group; ¹And
And R^TwoMay be the same or different.
Π-electron conjugated ligand, and Q represents two π-conjugated ligands.
Electron conjugated ligand R¹And R^TwoAnd a divalent group that crosslinks

In the general formula (1), as the transition metal represented by M, for example, Y, Sm, Zr, Ti, Hf, V, N
b, Ta and Cr, with preferred transition metals being Y, Sm, Zr, Ti or Hf, more preferably Zr or Hf. In the general formula (1), π-cyclopentadienyl structure, η-benzene structure, η-cycloheptatrienyl structure and η-cycloocta are represented by π electron conjugated ligands represented by R ¹ and R ^2. A ligand having a tetraene structure is exemplified, and a particularly preferred ligand is a ligand having an η-cyclopentadienyl structure.

As the ligand having an η-cyclopentadienyl structure, for example, a cyclopentadienyl group, an indenyl group, an indenyl hydride group, a fluorenyl group and the like can be mentioned. These groups are halogen, alkyl,
It may be further substituted with a hydrocarbon group such as aryl, aralkyl, alkoxy and aryloxy, a silyl group containing a hydrocarbon group such as a trialkylsilyl group, and a chain or cyclic alkylene group.

In the general formula (1), the group that bridges R ¹ and R ² represented by Q is not particularly limited as long as it is a divalent group.
For example, a linear or branched alkylene group, an unsubstituted or substituted cycloalkylene group, an alkylidene group,
Examples include an unsubstituted or substituted cycloalkylidene group, an unsubstituted or substituted phenylene group, a silylene group, a dialkyl-substituted silylene group, a germyl group, and a dialkyl-substituted germyl group.

Examples of the above bridged metallocene compound include dimethylsilylene (3-t-butylcyclopentadienyl) (fluorenyl) zirconium dichloride,
Dimethylsilylene (3-t-butylcyclopentadienyl) (fluorenyl) hafnium dichloride, rac-
Ethylenebis (indenyl) zirconium dimethyl, r
ac-ethylenebis (indenyl) zirconium dichloride, rac-dimethylsilylenebis (indenyl) zirconium dimethyl, rac-dimethylsilylenebis (indenyl) zirconium dichloride, rac-dimethylgermylbis (indenyl) zirconium dimethyl, rac-dimethylgermylbis (Indenyl) zirconium dichloride,

Rac-ethylenebis (tetrahydroindenyl) zirconium dimethyl, rac-ethylenebis (tetrahydroindenyl) zirconium dichloride,
rac-dimethylsilylenebis (tetrahydroindenyl) zirconium dimethyl, rac-dimethylsilylenebis (tetrahydroindenyl) zirconium dichloride, rac-dimethylgermylbis (tetrahydroindenyl) zirconium dimethyl, rac-dimethylgermylbis (tetrahydroindenyl) ) Zirconium dichloride, rac-dimethylsilylenebis (2-methyl-
4,5,6,7-tetrahydroindenyl) zirconium dichloride, rac-dimethylsilylenebis (2-methyl-4,5,6,7-tetrahydroindenyl) zirconium dimethyl, rac-dimethylgermylbis (2-methyl -4,5,6,7-tetrahydroindenyl) zirconium dichloride, rac-dimethylgermylbis (2
-Methyl-4,5,6,7-tetrahydroindenyl) zirconium dimethyl, rac-ethylenebis (2-methyl-4,5,6,7-tetrahydroindenyl) hafnium dichloride,

Rac-dimethylsilylenebis (2-methyl-4-phenylindenyl) zirconium dichloride, rac-dimethylsilylenebis (2-methyl-4-
Phenylindenyl) zirconium dimethyl, rac-
Dimethylgermylbis (2-methyl-4-phenylindenyl) zirconium dichloride, rac-dimethylgermylbis (2-methyl-4-phenylindenyl) zirconium dimethyl, rac-dimethylsilylenebis (2-methyl-4- Phenylindenyl) hafnium dichloride, rac-dimethylsilylenebis (2-methyl-4-naphthylindenyl) zirconium dimethyl, r
ac-dimethylsilylenebis (2-methyl-4-naphthylindenyl) hafnium dichloride, rac-dimethylgermylbis (2-methyl-4-naphthylindenyl) zirconium dimethyl, rac-dimethylgermylbis (2-methyl- 4-naphthylindenyl) hafnium dichloride, rac-dimethylsilylenebis (2-methyl-4,5-benzoindenyl) zirconium dichloride, rac-dimethylsilylenebis (2-methyl-
4,5-benzoindenyl) zirconium dimethyl, r
ac-dimethylgermylbis (2-methyl-4,5-benzoindenyl) zirconium dichloride, rac-dimethylgermylbis (2-methyl-4,5-benzoindenyl) zirconium dimethyl, rac-dimethylsilylenebis ( 2-methyl-4,5-benzoindenyl) hafnium dichloride, rac-dimethylsilylenebis (2-ethyl-4-phenylindenyl) zirconium dichloride, rac-dimethylsilylenebis (2-ethyl-4-phenylindenyl) Zirconium dimethyl,
rac-dimethylgermylbis (2-ethyl-4-phenylindenyl) zirconium dichloride, rac-dimethylsilylenebis (2-ethyl-4-phenylindenyl) hafnium dichloride, rac-dimethylsilylenebis (2-methyl-4 , 6-Diisopropylindenyl) zirconium dichloride, rac-dimethylsilylenebis (2-methyl-4,6-diisopropylindenyl) zirconium dimethyl, rac-dimethylgermylbis (2-methyl-4,6-diisopropylindenyl) Zirconium dichloride, rac-dimethylsilylenebis (2-methyl-4,6-diisopropylindenyl) hafnium dichloride,

Dimethylsilylene (2,4-dimethylcyclopentadienyl) (3 ', 5'-dimethylcyclopentadienyl) titanium dichloride, dimethylsilylene (2,4-dimethylcyclopentadienyl) (3', 5 ′
-Dimethylcyclopentadienyl) zirconium dichloride, dimethylsilylene (2,4-dimethylcyclopentadienyl) (3 ', 5'-dimethylcyclopentadienyl) zirconium dimethyl, dimethylgermil (2,
4-dimethylcyclopentadienyl) (3 ', 5'-dimethylcyclopentadienyl) zirconium dichloride, dimethylgermyl (2,4-dimethylcyclopentadienyl) (3', 5'-dimethylcyclopentadienyl) ) Zirconium dimethyl, dimethylsilylene (2,4
-Dimethylcyclopentadienyl) (3 ', 5'-dimethylcyclopentadienyl) hafnium dichloride, dimethylsilylene (2,4-dimethylcyclopentadienyl) (3', 5'-dimethylcyclopentadienyl) hafnium Dimethyl, dimethylsilylene (2,3,5-trimethylcyclopentadienyl) (2 ', 4', 5'-trimethylcyclopentadienyl) titanium dichloride,
Dimethylsilylene (2,3,5-trimethylcyclopentadienyl) (2 ', 4', 5'-trimethylcyclopentadienyl) zirconium dichloride, dimethylsilylene (2,3,5-trimethylcyclopentadienyl)
(2 ', 4', 5'-trimethylcyclopentadienyl)
Zirconium dimethyl, dimethyl gel mill (2,3,5-
Trimethylcyclopentadienyl) (2 ', 4', 5'-
Trimethylcyclopentadienyl) zirconium dichloride, dimethylgermyl (2,3,5-trimethylcyclopentadienyl) (2 ', 4', 5'-trimethylcyclopentadienyl) zirconium dimethyl, dimethylsilylene (2,3 , 5-trimethylcyclopentadienyl)
(2 ', 4', 5'-trimethylcyclopentadienyl)
Hafnium dichloride, dimethylsilylene (2,3,5-
Trimethylcyclopentadienyl) (2 ', 4', 5'-
Trimethylcyclopentadienyl) hafnium dimethyl, rac-dimethylsilylenebis (2-methyl-4-
Phenyldihydroazulenyl) zirconium dichloride, rac-dimethylsilylenebis (2-ethyl-4-
Phenyldihydroazulenyl) zirconium dichloride.

Among the above bridged metallocene compounds, particularly preferred compounds are dimethylsilylene (3-t-butylcyclopentadienyl) (fluorenyl) zirconium dichloride and rac-dimethylsilylenebis (2-methyl-4-phenylindenyl). ) Zirconium dichloride, rac-dimethylgermylbis (2-methyl-4-
Phenylindenyl) zirconium dichloride, rac
-Dimethylgermylbis (2-methyl-4-phenylindenyl) zirconium didichloride, rac-dimethylsilylenebis (2-methyl-4-naphthylindenyl) zirconium dichloride, rac-dimethylgermylbis (2-methyl- 4-naphthylindenyl) zirconium dichloride, rac-dimethylsilylenebis (2
-Methyl-4,5-benzoindenyl) zirconium dichloride, rac-dimethylgermylbis (2-methyl-4,5-benzoindenyl) zirconium dichloride, rac-dimethylsilylenebis (2-ethyl-4-
Phenylindenyl) zirconium dichloride, rac
-Dimethylgermylbis (2-ethyl-4-phenylindenyl) zirconium dichloride, rac-dimethylsilylenebis (2-methyl-4,6-diisopropylindenyl) zirconium dichloride, rac-dimethylgermylbis (2-methyl -4,6-diisopropylindenyl) zirconium dichloride, dimethylsilylene (2,4-dimethylcyclopentadienyl) (3 ', 5'
-Dimethylcyclopentadienyl) zirconium dichloride, dimethylsilylene (2,4-dimethylcyclopentadienyl) (3 ', 5'-dimethylcyclopentadienyl) zirconium dimethyl, dimethylgermil (2,
4-dimethylcyclopentadienyl) (3 ', 5'-dimethylcyclopentadienyl) zirconium dichloride, dimethylgermyl (2,4-dimethylcyclopentadienyl) (3', 5'-dimethylcyclopentadienyl) ) Zirconium dimethyl, dimethylsilylene (2,4
-Dimethylcyclopentadienyl) (3 ', 5'-dimethylcyclopentadienyl) hafnium dichloride, dimethylsilylene (2,4-dimethylcyclopentadienyl) (3', 5'-dimethylcyclopentadienyl) hafnium Dimethyl, dimethylsilylene (2,3,5-trimethylcyclopentadienyl) (2 ', 4', 5'-trimethylcyclopentadienyl) zirconium dichloride, dimethylsilylene (2,3,5-trimethylcyclopentadienyl) ) (2 ', 4', 5'-trimethylcyclopentadienyl) zirconium dimethyl, dimethylgermyl (2,3,5-trimethylcyclopentadienyl)
(2 ', 4', 5'-trimethylcyclopentadienyl)
Zirconium dichloride, dimethylgermil (2,3,5
-Trimethylcyclopentadienyl) (2 ', 4', 5 '
-Trimethylcyclopentadienyl) zirconium dimethyl, dimethylsilylene (2,3,5-trimethylcyclopentadienyl) (2 ', 4', 5'-trimethylcyclopentadienyl) hafnium dichloride, dimethylsilylene (2,3 , 5-trimethylcyclopentadienyl)
(2 ', 4', 5'-trimethylcyclopentadienyl)
Hafnium dimethyl, rac-dimethylsilylene bis (2-methyl-4-phenyldihydroazulenyl) zirconium dichloride.

The most preferred bridged metallocene compounds are dimethylsilylene (2,3,5-trimethylcyclopentadienyl) (2 ', 4', 5'-trimethylcyclopentadienyl) zirconium dichloride, dimethylgermil ( 2,3,5-trimethylcyclopentadienyl)
(2 ', 4', 5'-trimethylcyclopentadienyl)
Zirconium dichloride, dimethylsilylene (2,3,5
-Trimethylcyclopentadienyl) (2 ', 4', 5 '
-Trimethylcyclopentadienyl) hafnium dichloride, as well as rac-dimethylsilylene (2-methyl-4-phenylindenyl) zirconium dichloride.

The meso compound corresponding to the above-mentioned racemic compound may be used in a state of being contained in the racemic compound if it is a small amount of 5 mol% or less.

In the step (a), the aluminoxane to be reacted with the bridged metallocene compound is represented by the following general formula:
It is represented by [1] or [2].

Embedded imageWhere each R^ThreeMay be the same or different, each
Represents a hydrocarbon group having 1 to 6, preferably 1 to 4 carbon atoms.
And q is an integer of 4 to 30, preferably 6 to 30,
Particularly preferably, it is an integer of 8 to 30. General formula [1] and
In [2], R ^ThreeAre, for example, a methyl group,
Chill, propyl, butyl, isobutyl, pliers
Alkyl group such as benzyl group, hexyl group, allyl group, 2-methyl
Realyl, propenyl, isopropenyl, 2-me
Alkenyl such as tyl-1-propenyl group and butenyl group
Group, cyclopropyl group, cyclobutyl group, cyclopent
And cycloalkyl groups such as cyclohexyl group, aryl
And an alkyl group is preferred.
And a methyl group is particularly preferred.

As the aluminoxane, a commercially available aluminoxane solution dissolved in an organic solvent can be used.
The aluminoxane can also be prepared under various known conditions, and the following preparation method can be specifically exemplified. A method in which a trialkylaluminum, for example, trimethylaluminum, triisobutylaluminum or a mixture thereof is directly reacted with water in an organic solvent such as toluene or ether. A method in which a trialkylaluminum such as trimethylaluminum, triisobutylaluminum or a mixture thereof is reacted with a salt having water of crystallization such as copper sulfate hydrate or aluminum sulfate hydrate. Moisture impregnated in silica gel, etc.,
A method in which a trialkylaluminum, for example, trimethylaluminum or triisobutylaluminum is reacted individually, simultaneously or sequentially. Further, even if unreacted trialkylaluminum remains in the aluminoxane obtained by these methods, there is no particular problem.

In the step (a), in an inert solvent, -50 to
Under a temperature condition of 100 ° C., preferably 0 to 50 ° C., 10 to 1,000 mol, preferably 20 to 500 mol, of aluminum atom per 1 mol of the bridged metallocene compound.
The moles of aluminoxane are reacted for 1 minute to 10 hours, preferably 3 minutes to 5 hours to obtain a reaction product.

The use of an inert solvent is preferable in that the reaction proceeds uniformly and efficiently. The amount of the inert solvent used is not particularly limited, but is usually 10 to 10,000 liters, preferably 10 to 1 liter, per 1 mol of the metallocene compound.
It is about 000 liters. As the inert solvent used in the above reaction, for example, aromatic hydrocarbons such as benzene, toluene, xylene, cumene, butane, tetramethylbutane, pentane, ethylpentane, trimethylpentane, hexane, methylhexane, ethylhexane, dimethylhexane , Heptane, methylheptane, octane,
Aliphatic hydrocarbons such as nonane, decane, hexadecane and octadecane, cyclopentane, methylcyclopentane,
Alicyclic hydrocarbons such as cyclohexane and cyclooctane,
Alternatively, there may be mentioned halogenated hydrocarbons obtained by substituting the above aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons with halogens, and mixed solvents thereof. Further, ethers such as ethyl ether and tetrahydrofuran can also be used. A preferred inert solvent is an aromatic hydrocarbon. Alternatively, a commercially available solvent of an aluminoxane solution may be used as it is, or may be used in addition to other aromatic hydrocarbons.

In the step (b) following the step (a),
The reaction product obtained in the step (a) and the inorganic fine particle carrier, in the presence of the inert solvent used in the step (a),
By contacting at a temperature of 85 to 150 ° C., a solid product in which the reaction product is supported on an inorganic fine particle carrier is obtained. In this contact reaction, an inert solvent can be added as needed.

The inorganic fine particle carrier to be brought into contact with the reaction product obtained in the step (a) is an inorganic compound or a mixture thereof and has a particle diameter of 5 to 300 μm, preferably 10 to 300 μm.
It is a granular or spherical solid fine particle of up to 200 μm. These inorganic particulate carriers have a specific surface area of 50 to
1,000m ² / g, preferably 100~700m ² / g
And the pore volume is preferably in the range of 0.3 to 2.5 m ³ / g.

As the inorganic fine particle carrier, metal oxide,
For example, SiO_Two, Al_TwoO_Three, MgO, TiO_Two, ZnO,
Mixtures or composite oxides thereof are preferred,
SiO as main component_TwoOr Al_TwoO_ThreeThe carrier containing
Particularly preferred. As a more specific inorganic compound, SiO 2
_Two, Al_TwoO_Three, MgO, SiO_Two-Al_TwoO_Three, SiO _Two−
MgO, SiO_Two-TiO_Two, SiO_Two-Al_TwoO_Three-Mg
O, etc., and especially SiO._TwoIs preferred.

Prior to use, the inorganic fine particle carrier is usually used at 100 to 1,000 ° C., preferably at 300 to 1,000 ° C.
The one fired at 900 ° C, particularly preferably 400 to 900 ° C, is used. The amount of water adsorbed on the surface of the inorganic fine particle carrier after calcination is 0.1% by weight or less, preferably 0.01% by weight or less, and the surface hydroxyl group content is 1.0% by weight or more, preferably 1.5 to 4.5%. 0% by weight, more preferably 2.0 to
It is in the range of 3.5% by weight. Further, these inorganic fine particle carriers may be subjected to a contact treatment with an organic aluminum compound and / or a halogen-containing silicon compound before use.

The ratio of the reaction product obtained in the step (a) to the inorganic fine particle carrier is 1 to 1,000 kg, preferably 5 to 500 kg, per 1 mol of transition metal atom in the reaction product. It is. The amount of the inert solvent used is from 10 to 10,000 per mole of transition metal atom in the reaction product.
Liter, preferably 10 to 1,000 liter.

The contact condition between the reaction product obtained in the step (a) and the inorganic fine particle carrier is 85 to 150 ° C., preferably 90 to 130 ° C., particularly preferably 95 to 120 ° C. 5 minutes to 100 hours, preferably 10 minutes to
50 hours. Particularly, the temperature condition is an important factor. By bringing the catalyst into contact within the above temperature range, a catalyst for olefin polymerization having high polymerization activity can be obtained, and by using this catalyst, propylene having a high bulk density and good particle properties can be obtained. / Propylene / olefin block copolymer can be obtained.

In the following step (c), the solid product containing the inert solvent obtained in step (b) is washed at least twice with an aliphatic hydrocarbon at a temperature of -50 to 50 ° C. Thereby, a metallocene-supported catalyst comprising a solid product in which a reaction product of a crosslinked metallocene compound and an aluminoxane is supported on an inorganic fine particle carrier is obtained. Examples of the aliphatic hydrocarbon used for washing include the aliphatic hydrocarbons exemplified as the inert solvent and a mixed solvent thereof. Preferably, n-hexane, isopentane or a mixture thereof is used.

As a method for washing the solid product obtained in the step (b), for example, after completion of the step (b), a slurry comprising an inert solvent and the solid product is filtered, centrifuged or decanted. A method of separating the inert solvent and washing the obtained solid product with an aliphatic hydrocarbon,
(b) After completion of the step, after adding the aliphatic hydrocarbon to the slurry comprising the inert solvent and the solid product, the mixed solvent comprising the inert solvent and the aliphatic hydrocarbon is separated by the same means as described above. And a method in which the obtained solid product is washed with an aliphatic hydrocarbon. Here, the latter is the more preferred method.

The washing conditions for the solid product are as follows: 1 kg of the inorganic particulate carrier per washing, 1 to 50 aliphatic hydrocarbons.
Using 0 liter, preferably 10 to 100 liters, at a temperature of -50 to 50 ° C, preferably -30 to 40 ° C, particularly preferably -30 to 30 ° C, in the aliphatic hydrocarbon after washing. The washing is repeated until the metallocene compound is no longer eluted. It is sufficient to wash at least two times, usually four times or more, but not limited thereto. The washing temperature condition is an important factor. By washing in the above temperature range, a catalyst for olefin polymerization having a high polymerization activity can be obtained, and by using this catalyst, propylene having high bulk specific gravity and good particle properties can be obtained. A propylene / olefin block copolymer is obtained.

The metallocene-supported catalyst prepared by the above method can be used as a usual catalyst for olefin polymerization carried out by a gas phase polymerization method or a bulk polymerization method. As the polymerization catalyst, the propylene of the present invention //
It is suitably used for producing a propylene / olefin block copolymer.

Subsequent to the above step (c), as the step (d), the olefin is prepolymerized by bringing the metallocene-supported catalyst obtained in the step (c) into contact with the olefin, and the olefin is prepolymerized. By performing the step of further supporting 0.01 to 100 kg of the olefin prepolymer, a particulate preactivation catalyst in which the metallocene supported catalyst is coated with the olefin prepolymer can be prepared.

As the olefin prepolymer supported on the preactivation catalyst, olefins having 2 to 20 carbon atoms, for example, ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 2-methyl -1-pentene, 1-hexene, 1-octene, 1-decene, 1-
Examples thereof include homopolymers such as dodecene and copolymers thereof, and particularly preferred are ethylene homopolymer, propylene homopolymer, and olefin copolymer mainly composed of ethylene or propylene. In addition, these olefin prepolymers preferably have an intrinsic viscosity [η] measured in decalin at 135 ° C. in the range of 0.1 to 10 dl / g, and more preferably 0.2 to 7 dl / g. is there.

The prepolymerization of the olefin is preferably carried out by (c)
The olefin is introduced into a slurry in which the metallocene-supported catalyst obtained in the step is dispersed in an aliphatic hydrocarbon. As a slurry in which the metallocene-supported catalyst is dispersed in an aliphatic hydrocarbon, the solid product obtained in the final stage of the step (c) may be used without separating the solid product from the aliphatic hydrocarbon, and The solid product once separated from the aliphatic hydrocarbon may be used by dispersing it again in the same aliphatic hydrocarbon. The prepolymerization of olefins can be carried out in the liquid phase using the olefin itself to be polymerized as a solvent or in the gas phase without using a solvent.However, polymerization of a small amount of olefins is controlled and uniform polymerization is performed. Is preferably carried out in the presence of an aliphatic hydrocarbon.

[0059] Preliminary polymerization of olefins carried out in aliphatic hydrocarbons, to the supported metallocene catalyst 1 kg, aliphatic hydrocarbons 0.005～5M ^3, preferably in a slurry consisting of 0.01～1M ^3, 0.01 to 1,000 of olefin
kg, preferably 0.1-500 kg, -50-1
The polymerization is carried out at a temperature of 00 ° C., preferably 0 to 50 ° C., for 1 minute to 50 hours, preferably 3 minutes to 20 hours.

In the above-mentioned olefin prepolymerization, since the reaction product of the cross-linked metallocene compound and the aluminoxane is supported on the metallocene-supported catalyst, it is newly represented by an organoaluminum compound such as a trialkylaluminum or aluminoxane. There is no particular need to add a co-catalyst, but it can be added if desired. These cocatalysts were added in an amount of 1,000 aluminum atoms per mole of transition metal atoms in the metallocene-supported catalyst.
It is preferable to keep it in the range of 0 mol or less, preferably 500 mol or less. The olefin prepolymerization may be performed in the presence of hydrogen to control the molecular weight of the resulting olefin prepolymer.

The pre-activated catalyst obtained above is kept in a slurry state in which the prepolymerization of the olefin has been completed, or after the prepolymerization of the olefin has been completed, washed with an aliphatic hydrocarbon, and then re-used in the aliphatic hydrocarbon. In a suspended state or in a state where an aliphatic hydrocarbon is separated and dried, it can be used for general olefin polymerization by a slurry polymerization method, a gas phase polymerization method, and a bulk polymerization method. As a catalyst system for olefin polymerization, it is suitably used in the production of the propylene // propylene / olefin block copolymer of the present invention.

The propylene // propylene / olefin block copolymer constituting the present invention is obtained by firstly, in a first polymerization step, an olefin polymerization catalyst obtained by combining the metallocene-supported catalyst with an organic aluminum compound, In the presence of an olefin polymerization catalyst in which an activation catalyst and an organoaluminum compound are combined, propylene alone or a mixture of propylene and an olefin other than propylene is polymerized to form an A segment comprising a propylene-based polymer. Is generated. At this time, the ratio of the A segment is propylene // propylene / olefin.
The amount of polymerization is adjusted so as to be 20 to 95% by weight based on the weight of the random copolymer.

The organoaluminum compound constituting the catalyst system for olefin polymerization is a compound represented by the following general formula. AlR ⁴ _s R in _{^{5 t X 3- (s + t}} ) Equation, R ⁴ and R ^5, carbon atoms each independently 1 to 1
0 represents a hydrocarbon group such as an alkyl group, a cycloalkyl group or an aryl group; an alkoxy group; a phenyl group which may have a substituent such as a fluorine atom, a methyl group or a trifluorophenyl group; and X represents a halogen atom And s and t
Is an arbitrary integer satisfying 0 <s + t ≦ 3.

Examples of the organoaluminum compound represented by the above general formula include, for example, trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, tri-aluminum.
trialkylaluminums such as n-octylaluminum; dialkylaluminum halides such as dimethylaluminum chloride, dimethylaluminum bromide, diethylaluminum chloride and diisopropylaluminum chloride; methylaluminum sesquichloride, ethylaluminum sesquichloride, ethylaluminum sesquibromide, isopropylaluminum sesquibromide Examples thereof include alkylaluminum sesquihalides such as chloride and the like, and mixtures of two or more thereof. A preferred organoaluminum compound is a trialkylaluminum.

The amount of the organoaluminum compound to be used is 1 to 5,000 mol, preferably 5 to 3,000 mol, particularly preferably 10 to 3,000 mol, as Al atoms in the organoaluminum compound, per mol of the transition metal atom in the catalyst system. ~ 1,000
Range of moles.

The amount of the metallocene-supported catalyst or preactivated catalyst used is 1 × 10 ⁻¹⁰ to 1 × 10 ⁻³ mol, preferably 1 × 10 ⁻¹⁰ mol, in terms of transition metal atoms in the catalyst system, per liter of polymerization volume. It is 1 × 10 ^-9 to 1 × 10 ^-4 mol. By setting the amount of the catalyst in the above range, an efficient and controlled polymerization reaction rate of olefin can be maintained.

The term “polymerization volume” refers to the volume of the liquid phase portion in the polymerization vessel in the case of polymerization by the liquid phase method, and the volume of the gas phase portion in the polymerization vessel in the case of polymerization by the gas phase method. means.

The polymerization conditions in the first polymerization step are as described above.
In the presence of the olefin polymerization catalyst, the polymerization temperature is 20 to 12
0 ° C., preferably in the range of 40 to 100 ° C., the polymerization pressure is
Atmospheric pressure to 9.9 MPa, preferably 0.59 to 5.0 M
Pa range. Also, if necessary, molecules such as hydrogen
Using the amount regulator, the intrinsic viscosity of the A segment [η] _A
Can be adjusted to a desired value.

Following the first polymerization step, in the second polymerization step, propylene and an olefin other than propylene are copolymerized in the presence of the propylene-based polymer including the olefin polymerization catalyst system from the first polymerization step. Polymerize,
A B segment comprising the propylene / olefin random copolymer is generated. At this time, the amount of polymerization is adjusted so that the ratio of the B segment is 80 to 5% by weight based on the weight of the propylene // propylene / olefin block copolymer.

The polymerization conditions in the second polymerization step are such that the polymerization temperature is in the range of 20 to 120 ° C., preferably 40 to 100 ° C., and the polymerization pressure is atmospheric pressure to 9.9 MPa, preferably 0.1 to 1.9 MPa.
The range is from 59 to 5.0 MPa. Further, similarly to the first polymerization step, the intrinsic viscosity [η] _B of the B segment can be adjusted to a desired value by using a molecular weight modifier such as hydrogen as necessary.

Propylene // propylene / olefin
The ratio (weight) of the A segment and the B segment in the block copolymer can be adjusted by adjusting the polymerization time, polymerization pressure, or polymerization temperature in each of the first polymerization step and the second polymerization step, and further, by adjusting the second polymerization step. In the polymerization step, it can be adjusted by a known method such as a carbon monoxide method or a method using a polymerization activity regulator for a catalyst such as hydrogen sulfide.

After the first polymerization step and the second polymerization step are performed as described above, the unreacted monomer, the molecular weight regulator and the polymerization activity regulator are separated from the polymerization system, and the catalyst is deactivated and necessary. By separating the solvent accordingly, a particulate propylene // propylene / olefin block copolymer can be obtained.

In the first polymerization step and the second polymerization step, known olefin polymerization processes including a gas phase method can be used. For example, the first polymerization step is a bulk polymerization method using an olefin such as propylene itself as a solvent,
A process in which the polymerization step is performed in a gas phase method in which the polymerization step is performed in a gas phase olefin, or a process in which both the first polymerization step and the second polymerization step are performed in a gas phase method. In particular, by employing a gas phase method in both the first polymerization step and the second polymerization step, the desired propylene // propylene / olefin block copolymer can be produced more efficiently, and good particle properties and An excellent copolymer having both physical properties can be obtained. The first polymerization step and the second polymerization step may be performed using a common one-vessel polymerization vessel,
Each may be carried out using one or more polymerization vessels. Further, any polymerization system of a batch system, a semi-continuous system or a continuous system may be adopted.

The propylene // propylene / olefin block copolymer thus obtained may optionally contain an antioxidant, an ultraviolet absorber, an antistatic agent, a nucleating agent,
Lubricant, flame retardant, anti-blocking agent, coloring agent, organic filler, various additives such as inorganic filler, further blended various synthetic resins, melt-kneaded, molded into pellets,
It is used as a raw material for the polyolefin composition of the present invention.

Another aspect of the present invention is to produce a propylene // propylene / olefin block copolymer as described above, which comprises from 95 to 5% by weight, based on the weight of the composition,
This is a method for producing a polyolefin composition, in which polypropylene is blended in a range of 5 to 95% by weight.

The method of blending polypropylene with a propylene // propylene / olefin block copolymer includes the following methods. (1) Dry blending of powdery polypropylene with particulate propylene // propylene / olefin block copolymer And (2) a method of melt-kneading polypropylene and a propylene // propylene / olefin block copolymer using an extruder, a kneader or the like.

The polyolefin composition of the present invention is excellent in low-temperature heat sealability and has a wide hot tack temperature range, so that it can be suitably used as a sealant for cast films or biaxially stretched films. An excellent film can be obtained.

[0078]

The present invention will be described below more specifically with reference to examples and comparative examples. The evaluation methods and measurement conditions performed in Examples and Comparative Examples are shown below. (1) ZY: polymerization activity of catalyst (unit: g · polymer / g)
-Zr) The amount (g) of the produced polymer per 1 g of Zr atoms in the crosslinked metallocene compound was calculated from the amount of the metallocene-supported catalyst or the preactivated catalyst used and the amount of the produced polymer. (2) BD: bulk density of produced polymer (unit: kg / m ³ ) (3) [η]: intrinsic viscosity (unit: dl / g) Automatic viscosity measuring device (AVS2 type, manufactured by Mitsui Toatsu Co., Ltd.) )
The measurement was performed at 135 ° C. using tetralin as a solvent. (4) MFR: melt flow rate (unit: g / 10)
Min.) According to JIS K7210, condition 14 in Table 1
(21.8N, 230 ° C). (5) 1-butene content: Measured by ¹³ C-NMR. (6) B segment content: Calculated assuming that a portion eluted at 50 ° C. or less by temperature rising elution fractionation (TREF) using o-dichlorobenzene as a solvent is a B segment. (7) Tm: melting point (unit: ° C.) Differential scanning calorimeter (D
Using u-Pont's DSC-220), the sample (10 mg) packed in an aluminum pan was heated to 230 ° C., kept at 230 ° C. for 10 minutes, and then cooled to −60 ° C. at a rate of 20 ° C./min. After cooling, holding at −60 ° C. for 10 minutes, and then heating at a rate of 20 ° C./min, a peak value of an endothermic curve obtained was obtained. (8) Molecular weight distribution (Mw / Mn): gel permeation chromatograph (GPC-150, manufactured by Waters)
135) using o-dichlorobenzene as a solvent.
Measured in ° C. (9) Heat sealing temperature: two films having a width of 5 mm are overlapped so that the sealant layers face each other, a sealing pressure of 0.1 MPa, a sealing time of 1 sec, and a sealing width of 10 m.
Under the conditions of m, heat sealing was performed at various sealing temperatures. 90 ° peel strength (unit: N / 1) of the obtained test piece
5 mm) was measured using a tensile tester. 3N / 15m
The lowest sealing temperature at which a peel strength of at least m was obtained was taken as the heat sealing temperature of the sample. (10) 172 gf hot tack temperature width: width 75 mm, restoring force is 111, 172, 273 and 317 gf /, respectively.
inch each spring plate is bent by hand in a U-shape so that both ends in the width direction are in contact with each other, and the length around it is 270 mm.
The film having a width of 75 mm was covered so that the sealant face was on the inside, and the film ends 10 mm protruding from the spring were overlapped with each other. The overlapped portion is sealed with a seal bar adjusted to a predetermined temperature at a pressure of 0.1 MPa for 0.8 seconds, and then the force that bends the spring is released, and the restoring force of the spring is applied to the seal portion. Loaded. If the seal portion is still kept with a width of 7 mm or more against this restoring force, the hot tack property is judged to be passed, and the restoring of the spring plate having the highest restoring force among those judged to be passed. Force was expressed as the hot tack strength of the film at the seal temperature. The above operation was performed by changing the temperature of the seal bar (unit:
gf / inch). The temperature range in which the hot tack strength was 172 gf / inch or more was defined as the 172 gf hot tack temperature range. The wider this temperature range is, the wider the processing temperature range is, and a suitable film is obtained.

<Production Example> (1) Production of Metallocene-Supported Catalyst A toluene solution of methylaluminoxane (concentration: 3 mol / l, trade name: trade name) was placed in a 2 liter glass reactor equipped with a stirrer and purged with nitrogen gas. 0.58 liter of PMAO (manufactured by Tosoh Akzo) (1.74 in terms of Al atom)
Mol), and chiral dimethylsilylene (2,3,5-trimethylcyclopentadienyl) (2 ', 4', 5'-trimethylcyclopentadienyl) as a bridged metallocene compound
Zirconium dichloride and its meso form, dimethylsilylene (2,3,5-trimethylcyclopentadienyl)
6.89 mmol of a mixture with (2 ′, 3 ′, 5′-trimethylcyclopentadienyl) zirconium dichloride (meso content: 1 mol%) was added, and the mixture was reacted by stirring at 25 ° C. for 30 minutes. Thus, a reaction product of a metallocene compound and an aluminoxane was obtained. Subsequently, 50 g of silica (trade name: SYLOPOL (R) 948, manufactured by Grace Davison) having an average particle size of 51 μm, which was previously calcined at 750 ° C. for 8 hours under reduced pressure, was charged into the reactor at 110 ° C. for 90 minutes. With stirring and holding, a contact reaction between the reaction product and silica was carried out to obtain a slurry containing the solid product in which the reaction product was supported on silica. The reactor was cooled to −20 ° C., 1 liter of n-hexane was added, the mixture was stirred for 10 minutes, and then allowed to stand.
The solvent was separated and removed by decantation. Subsequently, while maintaining the reactor at −20 ° C., n-hexane 1
Of a metallocene compound and an aluminoxane, and the solid product (metallocene) in which the reaction product of the metallocene compound and the aluminoxane is supported on silica is repeatedly washed four times to separate and remove the solvent by decantation. Supported catalyst). Further, 1 liter of n-hexane was charged into the reactor, and the metallocene-supported catalyst was dispersed in n-hexane to form a slurry. A part of the metallocene-supported catalyst / n-hexane slurry was sampled, the solvent was removed, and the metallocene-supported catalyst obtained by drying under reduced pressure was analyzed. As a result, 0.40 wt. % And 13.9% by weight of Al derived from methylaluminoxane. The molar ratio of aluminum to transition metal in the metallocene supported catalyst was 117. Further, no massive catalyst having a particle size of 350 μm or more was observed.

(2) Production of Preactivated Catalyst A metallocene-supported catalyst / n obtained in (1) was placed in a glass reactor equipped with a stirrer having an inner volume of 2 liter and purged with nitrogen gas.
The hexane slurry was transferred and the reactor temperature was adjusted to 0 ° C. While stirring and maintaining the same temperature, propylene gas was supplied at a supply rate of 53.2 mmol / min for 60 minutes to perform prepolymerization, and the produced propylene homopolymer was converted to the metallocene-supported catalyst obtained in (1). Supported. During this prepolymerization, unreacted propylene gas was discharged outside the reactor. After the scheduled reaction time, the supply of propylene gas was stopped, and the temperature of the reactor was raised to 25 ° C.
The gas phase of the reactor was replaced with nitrogen gas. After separating and removing the solvent from the reaction mixture by decantation, 1 liter of n-hexane was added, and the mixture was stirred for 5 minutes, and a washing operation of removing n-hexane by decantation was repeated 5 times. Further, 1 liter of n-hexane was charged, and the preactivated catalyst was dispersed in n-hexane to form a slurry. This preactivated catalyst / n-hexane slurry was filtered to remove the solvent, and then dried under reduced pressure at 25 ° C. to obtain a preactivated catalyst composed of solid particles. As a result of analyzing the obtained pre-activated catalyst, it was found that polypropylene having an intrinsic viscosity of 1.2 dl / g per 1 g of the metallocene-supported catalyst was 0.1%.
74 g was carried.

(3) Production of propylene / 1-butene // propylene / 1-butene block copolymer After replacing a 50-liter stainless steel polymerization vessel equipped with a stirrer with nitrogen, 11.8 kg of liquefied propylene was added. 2.5 kg of liquefied 1-butene and 27.0 mmol of triethylaluminum were added, and the mixture was stirred at 50 ° C. for 10 minutes. Next, the preactivated catalyst 2.2782 obtained in (2)
g was added, and the polymerization reaction was carried out for 40 minutes while maintaining the internal temperature of the polymerization vessel at 40 ° C. After the polymerization time has elapsed, the unreacted mixed monomer is discharged out of the system, and the temperature of the polymerization vessel is cooled to 25 ° C., and then a part (210.1 g) of the reaction product is extracted to obtain propylene corresponding to the A segment. A sample of the / 1-butene copolymer was used. Subsequently, 13.5 mmol of triethylaluminum was added to the polymerization reactor having the reaction product in the reactor, the internal temperature was raised to 50 ° C., and propylene / 1- was adjusted to maintain the internal pressure of the polymerization reactor at 0.6 MPa. Butene mixed gas (molar ratio: propylene / 1-butene = 27/7)
3) was supplied, and gas phase polymerization of propylene / 1-butene was performed for 75 minutes. After the polymerization time has elapsed, propylene / 1-
The supply of the butene mixed gas was stopped, unreacted gas was discharged out of the system, and the temperature of the polymerization reactor was cooled to 25 ° C., after which the granular reaction product (propylene / 1-butene // propylene / 1-butene) was cooled. -Block copolymer: YB-1) 543
1 g was obtained. After the polymerization was completed, the inside of the open polymerization vessel was observed. As a result, neither the presence of the bulk polymer nor the adhesion of the polymer to the polymerization vessel wall was found. The obtained propylene /
The 1-butene // propylene / 1-butene block copolymer (YB-1) has a 1-butene content of 47.8% by weight, a BD of 440 kg / m ³ , and an intrinsic viscosity ([η] _W ). 1.60 dl / g, Tm of 122.8 ° C. and 66.9
° C. As a result of TREF measurement, the obtained propylene / 1-butene // propylene / 1-butene block copolymer had an A segment of 46.5% by weight and a B
The segment was 53.5% by weight. The 1-butene content in the A segment was 14.1% by weight. Also,
The 1-butene content in the B segment was calculated to be 77.1% by weight. Further, the polymerization activity (YZ) of the catalyst is 1.
It was 1 × 10 ⁶ g · polymer / g · Zr. Propylene / 1-butene // propylene / 1 under the same conditions as above
The production of the butene-block copolymer was repeated three times, and using the obtained polymer, the “heat sealing temperature” and “17
2g hot tack temperature range "was measured.

(4) Mixing of additives The propylene / 1-butene // propylene / 1-butene block copolymer (YB-1) obtained in the above (3)
100 parts by weight, calcium stearate 0.05
Parts by weight, tetrakis (methylene (3,5-di-t-butyl-4-hydroxy-hydrocinnamate)) methane 0.05 part by weight, and tris (2,4-di-t-butylphenyl) -phosphate 0.1% by weight
Using a twin screw extruder with a screw diameter of 20 mm, a melting temperature of 2
The mixture was extruded at 00 ° C. to obtain a pellet-like propylene / 1-butene // propylene / 1-butene block copolymer composition (YC-1).

<Comparative Production Example> (1) Production of Propylene / 1-Butene Random Copolymer After replacing a 50 L stainless steel polymerization vessel equipped with a stirrer with nitrogen, 20 L of n-hexane and 1 L -2.5 kg of butene was added, and 25 mmol of triisobutylaluminum was added. Then, the internal temperature was raised to 50 ° C, and propylene gas was supplied to raise the internal pressure of the polymerization reactor to 0.6 MPa. Next, after adding 25 mmol of triethylaluminum and 0.125 mmol of a titanium catalyst supported on magnesium chloride in terms of Ti atoms, propylene gas was supplied so as to keep the internal pressure of the polymerization vessel at 0.6 MPa. For 30 minutes. After the elapse of the polymerization time, unreacted gas was released, and the reaction solution was poured into a large amount of methanol to recover a polymer. The polymer was dried at 110 ° C. for 12 hours under reduced pressure, and 820 g of propylene / 1-butene.
A random copolymer (YB-2) was obtained. The obtained propylene / 1-butene random copolymer (YB-2)
The 1-butene content was 31% by weight and the Tm was 110 ° C. The production of the propylene / 1-butene random copolymer was repeated 5 times under the same conditions as above, and the “heat seal temperature” and “172 gf hot tack temperature range” were measured using the obtained polymer.

Further, based on 100 parts by weight of the propylene / 1-butene random copolymer (YB-2) obtained in the above (1), 0.05 parts by weight of calcium stearate,
Tetrakis (methylene (3,5-di-t-butyl-4-
Hydroxy-hydrocinnamate)) 0.05 parts by weight of methane and 0.1% by weight of tris (2,4-di-t-butylphenyl) -phosphate are compounded, and a twin-screw extruder having a screw diameter of 20 mm is used. The mixture was extruded at a melting temperature of 200 ° C. to obtain a pellet-like propylene / 1-butene random copolymer composition (YC-2).

<Example 1> [Preparation of polyolefin composition] 30 parts by weight of the propylene / 1-butene // propylene / 1-butene block copolymer composition (YC-1) obtained in Production Example 1 , Crystalline polypropylene (manufactured by Chisso Corporation, grade name: XP)
M7700, MFR = 5.0, melting point = 125 ° C., Mw /
(Mn = 4.0) was melt-kneaded at 230 ° C. to obtain a pellet of the polyolefin composition (YD-1). [Production of Biaxially Stretched Multilayer Film] Using a two-layer co-extrusion sheet molding machine with a T die, the polyolefin composition (YD-1) prepared above was supplied to an extruder for a surface layer, and a crystalline polypropylene (Chisso ( Grade name: HF11
70, melting point: 160 ° C.) to the extruder for the substrate layer,
Co-extrusion was performed at an extrusion temperature of 250 ° C and a cooling temperature of 30 ° C to form a two-layer sheet. This two-layer sheet is stretched 5 times in the machine direction using a roll-type stretching machine at a preheating temperature of 115 ° C and a stretching temperature of 123 ° C.
The film was stretched 9 times in the transverse direction using a tenter-type stretching machine at 0 ° C. and a stretching temperature of 160 ° C., and further subjected to 8% stress relaxation at an annealing temperature of 170 ° C. to obtain a biaxially stretched two-layer film. In the obtained biaxially stretched two-layer film, the thickness of the surface layer (sealant layer) was 1 μm, and the thickness of the base material layer was 24 μm. The physical properties of the biaxially stretched two-layer film were measured,
Table 1 shows the measurement results.

<Comparative Example 1> [Preparation of polyolefin composition] Comparative Example 1 was repeated in place of the propylene / 1-butene // propylene / 1-butene block copolymer composition (YC-1) obtained in Production Example. 30 parts by weight of the propylene / 1-butene random copolymer composition (YC-2) obtained in Production Example and crystalline polypropylene (manufactured by Chisso Corporation, grade name: XPM7700,
MFR = 5.0, melting point = 125 ° C., Mw / Mn = 4.
0) 70 parts by weight were melt-kneaded at 230 ° C. to obtain pellets of the polyolefin composition (YD-2). [Production of Biaxially Stretched Multilayer Film] Biaxial stretching was performed in the same manner as in Example 1 except that the polyolefin composition (YD-2) was used instead of the polyolefin composition (YD-1) used in Example 1. A two-layer film was prepared, and the physical properties of the film were measured. Table 1 shows the measurement results.

Comparative Example 2 [Production of Biaxially Stretched Multilayer Film] In place of the polyolefin composition (YD-1) used in Example 1, crystalline polypropylene (manufactured by Chisso Corporation, grade name: XPM770)
0, MFR = 5.0, melting point = 125 ° C., Mw / Mn =
A biaxially stretched two-layer film was prepared in the same manner as in Example 1 except that only 4.0) was used, and the physical properties of the film were measured. Table 1 shows the measurement results.

[0088]

[Table 1]

[0089]

The polyolefin composition of the present invention has excellent low-temperature heat-sealing properties and a wide hot-tack temperature range, so that it can be suitably used especially as a sealant for cast films or biaxially stretched films. A film having excellent properties can be obtained. Further, since the propylene // propylene / olefin block copolymer used in the present invention is obtained as a particulate polymer, it can be produced by various processes including a gas phase method.

 ──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Yasuhiro Shiraishi 5-1, Goi Kaigan, Ichihara-shi, Chiba Chisso Petrochemical Co., Ltd. Polymer Research Laboratory (72) Inventor Tsutomu Shioda 1-5-1 Goi Kaigan, Ichihara-shi, Chiba Chisso Petrochemical Co., Ltd. Polymer Research Laboratory F term (reference) 4J002 BB12X BB14X BP02W GG02 4J026 HA02 HA04 HA27 HA35 HA43 HB02 HB04 HB27 HB35 HB45 HB48 HE01 4J028 AA01A AB00A AB01A AC01A AC10A AC28A01B01 AC39A01B ACB BB03B BC15B BC16B BC19B BC25A CA24A CA25A CA27A CA28A CA29A DA01 DA02 DA03 DA04 EA02 EB03 EB04 ED01 ED02 ED03 ED04 FA04 GA09 GB01

Claims (8)

[Claims] 1. A propylene // propylene / olefin block copolymer comprising an A segment composed of a propylene-based polymer and a B segment composed of a propylene / olefin random copolymer, wherein the A segment is a block copolymer. 20 to 95% by weight based on the weight of the copolymer, and 80% of the B segment based on the weight of the block copolymer.
Propylene // propylene / olefin block copolymer containing 95 to 5% by weight and polypropylene of 5 to 95% by weight.
The propylene / olefin block copolymer is (1)
A metallocene-supported catalyst (I) obtained by performing the following steps (a) to (c) or a metallocene-supported catalyst (II) obtained by performing the following steps (a) to (d): Propylene alone or a mixture of olefins other than propylene and propylene in the presence of an olefin polymerization catalyst system comprising an organoaluminum compound, and the weight ratio of olefin units other than propylene / propylene units in the polymer chain (1) a first polymerization step for producing an A segment consisting of a propylene-based polymer having a ratio of 0/100 to 30/70, and (2) a propylene-based polymer containing an olefin polymerization catalyst system from the first polymerization step. In the presence, a mixture of an olefin other than propylene and propylene is copolymerized, and a propylene unit in the polymer chain / an olefin unit other than propylene The second polymerization step is sequentially executed block copolymer obtained by the polyolefin compositions to produce a B segment weight ratio of propylene / olefin random copolymer 5/95 to 95/5. (A) a step of reacting an organic transition metal compound having two crosslinked π-electron conjugated ligands with an aluminoxane in an inert solvent; (b) a reaction product produced in the step (a) and an inorganic fine particle carrier Is contacted at a temperature of 85 to 150 ° C. in the presence of an inert solvent. (C) A slurry containing the solid product produced in the step (b) is reacted with an aliphatic hydrocarbon at a temperature of −50 to 50 ° C. (D) contacting the metallocene-supported catalyst obtained in the step (c) with the olefin to prepolymerize the olefin, whereby 0.01 to 100 kg of olefin reserve per kg of the metallocene-supported catalyst; Step of supporting polymer 2. The polyolefin composition according to claim 1, wherein the polyolefin composition comprises 10 to 90% by weight of polypropylene and 90 to 10% by weight of a propylene // propylene / olefin block copolymer. 3. The polyolefin composition according to claim 1, wherein the polyolefin composition comprises 30 to 70% by weight of polypropylene and 70 to 30% by weight of a propylene // propylene / olefin block copolymer. 4. A propylene // propylene / olefin.
When the B segment of the block copolymer is propylene / 1-
The polyolefin according to claim 1, wherein the polyolefin is a butene binary random copolymer or a propylene / ethylene / 1-butene ternary random copolymer containing 2.9% by weight or less of ethylene units. Composition. 5. A propylene // propylene / olefin.
The melting point of the A segment of the block copolymer is 110 to 14
The polyolefin composition according to claim 1, wherein the temperature is in the range of 0 ° C. 6. A propylene // propylene / olefin block copolymer comprising an A segment composed of a propylene-based polymer and a B segment composed of a propylene / olefin random copolymer, wherein the A segment is a block copolymer. 20 to 95% by weight based on the weight of the copolymer
And the B segment are 80 to 80% by weight of the block copolymer.
A method for producing a polyolefin composition, comprising 95 to 5% by weight of a propylene // propylene / olefin block copolymer containing 5% by weight, and 5 to 95% by weight of a polypropylene, wherein (1) metallocene-supported catalyst (I) obtained by performing steps a) to (c) or metallocene-supported catalyst (II) obtained by performing steps (a) to (d) below;
In the presence of an olefin polymerization catalyst system consisting of and an organoaluminum compound, propylene alone or a mixture of propylene other than propylene and propylene is polymerized,
A first polymerization step of generating an A segment composed of a propylene-based polymer having a weight ratio of olefin units other than propylene / propylene unit in the polymer chain of 0/100 to 30/70, and (2) first polymerization A mixture of olefins other than propylene and propylene is copolymerized in the presence of a propylene-based polymer including the olefin polymerization catalyst system from the step, and the weight ratio of propylene units / olefin units other than propylene in the polymer chain Is 5 / 95-95 /
5, a second polymerization step for producing a B segment comprising a propylene / olefin random copolymer is sequentially performed to produce a propylene // propylene / olefin block copolymer, and the propylene // propylene / olefin. A method for producing a polyolefin composition, comprising blending 5 to 95% by weight of a block copolymer with 95 to 5% by weight of a polypropylene. (A) a step of reacting an organic transition metal compound having two crosslinked π-electron conjugated ligands with an aluminoxane in an inert solvent; (b) a reaction product produced in the step (a) and an inorganic fine particle carrier Is contacted at a temperature of 85 to 150 ° C in the presence of an inert solvent. The slurry containing the solid product produced in the steps (c) and (b) is reacted with (D) contacting the metallocene-supported catalyst obtained in the step (c) with the olefin to prepolymerize the olefin, whereby 0.01 to 100 kg of olefin reserve per kg of the metallocene-supported catalyst; Step of supporting polymer 7. A propylene // propylene / olefin.
The method for producing a polyolefin composition according to claim 6, wherein in the production of the block copolymer, the second polymerization step is performed by a gas phase polymerization method. 8. A propylene // propylene / olefin.
In the production of the block copolymer, the first polymerization step and the second polymerization step are both performed by a gas phase polymerization method,
A method for producing the polyolefin composition according to claim 6.