JPH10279632A - Modified olefin (co)polymer composition, production thereof, and modified olefin (co)polymer molding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a compsn. which has improved melt strengths (expressed by melt tension, etc.) and crystallization temp. and is excellent in moldability (such as high-speed productivity) by exposing an ethylene-olefin (co)polymer compsn. contg. high-mol.-wt. polyethylene dispersed therein as fine particles having specified particle sizes to an ionizing radiation and then heating the compsn. SOLUTION: This compsn. contains 0.01-5.0 pts.wt. high-mol.-wt. polyethylene which is an ethylene homopolymer or an ethylene-olefin copolymer having an ethylene unit content of at least 50 wt.% and has an intrinsic viscosity (135 deg.C, tetralin) of 15-100 dl/g and 100 pts.wt. olefin (co)polymer other than the high- mol.-wt. polyethylene. The high-mol.-wt. polyethylene exists in the compsn. as fine particles with a number average particle size of 1-5,000 nm. The ionizing radiation is pref. an electron beam, and a suitable dose is 0.1-1,000 kGy.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a modified olefin.
The present invention relates to a (co) polymer composition, a modified olefin (co) polymer composition molded article, and the composition and a method for producing the composition molded article. More specifically, the modified olefin (co) has high melt strength such as melt tension and crystallization temperature, and has excellent moldability.
The present invention relates to a polymer composition, a molded article of a modified olefin (co) polymer composition having excellent physical properties such as rigidity and heat resistance, and a method for producing the same.

[0002]

2. Description of the Related Art Polypropylene, high density polyethylene,
Polyolefins such as linear low-density polyethylene are widely used in various molding fields because they have excellent mechanical properties, chemical resistance and the like, and are extremely useful in balance with economic efficiency. However, due to low melt tension and low crystallization temperature, not only are moldability such as hollow molding, foam molding, and extrusion molding inferior, but also the high-speed productivity of molded articles is limited in other various molding methods. Has occurred.

As a method for increasing the melt tension and the crystallization temperature of polypropylene, a method of reacting polypropylene with an organic peroxide and a crosslinking aid in a molten state (JP-A-59-93711, JP-A-61-93711) 15275
4) a method of producing a gel-free polypropylene having a free-end long-chain branch by reacting a semi-crystalline polypropylene with a peroxide having a low decomposition temperature in the absence of oxygen (JP-A-2-298536). No.) is disclosed.

Further, a method of irradiating a semi-crystalline polypropylene with an electron beam in the absence of oxygen to obtain a gel having no free-end long-chain branch and containing no gel (Japanese Patent Laid-Open No. 2-29)
No. 8536).

As other methods for improving melt viscoelasticity such as melt tension, there have been proposed a composition containing polyethylene or polypropylene having different intrinsic viscosities or molecular weights, and a method for producing such a composition by multi-stage polymerization. ing.

For example, ultra high molecular weight polypropylene 2
A method in which 30 parts by weight is added to 100 parts by weight of ordinary polypropylene and extruded in a temperature range from a melting point to 210 ° C.
(JP-B-61-28694), an extruded sheet made of a two-component polypropylene having a limiting viscosity ratio of 2 or more and different molecular weights obtained by a multistage polymerization method (JP-B 1-12).
No. 770), polyethylene having a high viscosity average molecular weight of 1
A polyethylene composition comprising three kinds of polyethylenes having different viscosity average molecular weights, including 10 to 10% by weight, a melt kneading method,
Alternatively, a method of producing by a multi-stage polymerization method (Japanese Patent Publication No. Sho 62)
No. 61057), using a highly active titanium / vanadium solid catalyst component, a limiting viscosity of 20 by a multistage polymerization method.
A method for polymerizing polyethylene in which ultra-high molecular weight polyethylene of dl / g or more is polymerized at 0.05 to less than 1% by weight (Japanese Patent Publication No. 5-79683), 1-butene and 4-methyl-
Polymerization of ultra-high-molecular-weight polyethylene having an intrinsic viscosity of 15 dl / g or more by a multistage polymerization method using a highly active titanium catalyst component preliminarily polymerized with 1-pentene and a specially arranged polymerization reactor, in an amount of 0.1 to 5% by weight. And the like (Japanese Patent Publication No. 7-8890).

Further, propylene is polymerized using a prepolymerized catalyst in which ethylene and a polyene compound are prepolymerized to a supported titanium-containing solid catalyst component and an organoaluminum compound catalyst component to produce polypropylene having a high melt tension. (Japanese Unexamined Patent Publication (Kokai) No. 5-222212)
No. 2) and a similar catalyst component, and prepolymerization is performed solely with ethylene, and an ethylene / α-olefin copolymer having a high melt tension using an ethylene-containing prepolymerization catalyst containing a polyethylene having an intrinsic viscosity of 20 dl / g or more. A method for producing a united product (Japanese Patent Application Laid-Open No. 4-55410) is disclosed.

As described above, in the various compositions proposed conventionally and their production methods, although a certain improvement in the melt tension is recognized, the odor due to the crosslinking aid, the organic peroxide, and the crystallization remain. There are points to be improved such as the activation temperature, thermal stability, and electron beam irradiation efficiency.

In a multistage polymerization method in which a process for producing a high-molecular-weight polyolefin is incorporated into a usual olefin (co-) polymerization process in the main polymerization, an olefin (co) polymerization for producing a trace amount of the high-molecular-weight polyolefin is carried out. Difficulty in controlling the volume and the need for low polymerization temperatures to produce polyolefins of sufficiently high molecular weight require process modifications and also reduce the productivity of the final polyolefin composition .

In the method of prepolymerizing a polyene compound, it is necessary to separately prepare a polyene compound,
In addition, in the method of prepolymerizing polyethylene, the dispersibility of the prepolymerized polyethylene in the finally obtained polyolefin composition is not uniform, and further improvement is required in terms of the stability of the polyolefin composition.

As a method for improving the rigidity, heat resistance and the like of the propylene polymer, a molded article made of a propylene polymer obtained by copolymerizing propylene and alkenylsilane is irradiated with ionizing radiation. A method of obtaining a molded article of a propylene-based polymer having excellent heat resistance and rigidity (Japanese Patent Application Laid-Open No. 3-50239) has been proposed.

As described above, in the prior art, polyolefins such as propylene-based polymers are insufficiently improved in melting strength such as melt tension, crystallization temperature, heat resistance and rigidity. In addition, there are problems to be solved in that the irradiation efficiency of ionizing radiation is insufficient, the problem of odor and thermal stability, and the necessity of comonomer other than olefin are required. In addition, when producing such a polyolefin, it is required to improve the productivity.

[0013]

SUMMARY OF THE INVENTION The present invention relates to a hollow molding,
Foam molding, suitable for extrusion molding, and olefin (co) polymer composition having a high melt tension and a high crystallization temperature capable of exhibiting high-speed productivity even in various other molding methods,
Modified olefin (co) polymer obtained by irradiating with ionizing radiation and having improved melting strength and crystallization temperature represented by melt tension, etc., and further excellent moldability such as high-speed productivity An object of the present invention is to provide a composition, a molded article of a modified olefin (co) polymer composition excellent in physical properties such as heat resistance and rigidity, and a method for producing the same.

[0014]

Means for Solving the Problems The present inventors have conducted intensive studies to achieve the above object, and as a result, have found that a small amount of a polyolefin for the purpose of (co) polymerization having a specific intrinsic viscosity and a specific Olefin with high melt tension and high crystallization temperature obtained by subjecting olefin to (co) polymerization using a catalyst pre-activated by supporting a small amount of polyolefin having high intrinsic viscosity
By irradiating the (co) polymer composition with ionizing radiation, the modified olefin excellent in moldability by further improving the melting strength and crystallization temperature represented by the melt tension and the like (co)
The present inventors have found that a polymer composition and a molded article of a modified olefin (co) polymer composition having excellent physical properties such as heat resistance and rigidity can be obtained, and have completed the present invention.

The first invention of the present invention relates to a modified olefin (co)
A polymer composition, (a) an ethylene homopolymer or an ethylene-olefin copolymer containing 50% by weight or more of ethylene polymerized units, wherein the intrinsic viscosity [η _E ] measured with tetralin at least 135 ° C. 0.01 to 5.0 parts by weight of high molecular weight polyethylene in the range of 15 to 100 dl / g, and (b) 100 parts by weight of an olefin (co) polymer other than the high molecular weight polyethylene, (c) and the high molecular weight polyethylene Is an olefin (co) polymer composition that is finely dispersed as fine particles having a number average particle diameter in the range of 1 to 5000 nm. A) a polymer composition.

In the composition of the present invention, the ionizing radiation is preferably at least one selected from γ-rays and electron beams, and the dose of the ionizing radiation is preferably in the range of 0.1 to 1000 KGy.

In the composition of the present invention, the high-molecular-weight polyethylene preferably has a number-average particle diameter of 10 to 500 nm. In the composition of the present invention, the intrinsic viscosity [η] of the olefin (co) polymer composition measured with tetralin at 135 ° C. is preferably in the range of 0.2 to 10 dl / g.

In the composition of the present invention, the olefin (co) polymer other than the high molecular weight polyethylene may be a propylene homopolymer or a propylene polymer unit in an amount of 50% by weight.
It is preferable that at least one selected from the propylene-olefin copolymers contained above.

In the composition of the present invention, the high-molecular-weight polyethylene fine particles are preferably added before or during olefin (co) polymerization.

In the composition of the present invention, the olefin (co) polymer is at least one polymer selected from a propylene homopolymer and a propylene-olefin copolymer containing 50% by weight or more of propylene polymerized units. The relationship between the melt tension (MS) of the modified olefin (co) polymer composition at 230 ° C. and the intrinsic viscosity [η _T ] measured at 135 ° C. is represented by the following formula (Formula 3). It is preferred to have.

[0021]

Embedded image in log (MS)> 4.24 × log [η T] -0.950 The compositions of the present invention, the olefin (co) polymer, a propylene homopolymer or a propylene polymerization unit A propylene-olefin copolymer containing 50% by weight or more, and a modified olefin (co) polymer composition of 230% or more.
C. and the intrinsic viscosity [η] measured at 135 ° C.
_T ] preferably has a relationship represented by the following formula (Formula 4).

[0022]

Embedded image 4.24xlog [η _T ] +0.40> log (MS)> 4.24xlog
[η _T ] -0.950 In the composition of the present invention, the olefin (co) polymer has an ethylene homopolymer or an ethylene polymerized unit of 50.
It is preferable that the ethylene-olefin copolymer is contained in an amount of at least 1% by weight.

In the composition of the present invention, at least one stabilizer selected from the group consisting of a phenolic antioxidant and a phosphorus antioxidant is added to 100 parts by weight of the modified olefin (co) polymer composition. Is preferably added in an amount of 0.001 to 2 parts by weight.

In the composition of the present invention, the olefin (co) polymer other than high molecular weight polyethylene is a propylene homopolymer or a propylene-olefin copolymer containing 50% by weight or more of propylene polymerized units, Metal compound catalyst component, 0.01 to 1 mole of transition metal atom
1,000 moles of the periodic table (1991 edition) per group of organometallic compounds (AL1) and transition metal atoms of a metal selected from the group consisting of metals belonging to Group 1, Group 2, Group 12 and Group 13
In the presence of a polyolefin production catalyst comprising a combination of 0 to 500 mol of an electron donor (E1), and a preactivation catalyst containing polyethylene supported on the catalyst, propylene alone or propylene and a carbon number of 2 to It is preferably produced by subjecting this (co) polymerization with 12 other olefins.

In the composition of the present invention, the preactivated catalyst is selected from the group consisting of metals belonging to Groups 1, 2, 12, and 13 of the Periodic Table (1991 edition). The total amount of the metal organometallic compound (AL2) and the metal organometallic compound (AL1) contained in the preactivation catalyst is 0.05 to 5,000 mol per mol of transition metal atom in the preactivation catalyst, and an electron donor. Olefin book (co) polymerization catalyst further containing (E2) in addition to the electron donor (E1) contained in the preactivated catalyst and further containing 0 to 3,000 mol per mol of transition metal atom in the preactivated catalyst Propylene alone or propylene and other olefins having 2 to 12 carbon atoms in the presence of
(Co) polymerization is preferred.

In the composition of the present invention, the preactivated catalyst may contain 135 g / g of the transition metal compound catalyst component.
Intrinsic viscosity [η _A ] measured in tetralin at 15 ° C is 15-100dl
It is preferable to carry 0.01 to 5,000 g of polyethylene in the range of / g.

[0027] In the composition of the present invention, the preactivated catalyst may contain 135 g / g of the transition metal compound catalyst component.
Propylene homopolymer or a propylene-olefin copolymer containing 50% by weight or more of a propylene homopolymer or a propylene polymerization unit having an intrinsic viscosity [η _B ] of less than 15 dl / g measured in tetralin at 0.01 ° C., 0.01 to 100 g, Further, it is preferable to support 0.01 to 5,000 g of polyethylene having an intrinsic viscosity [η _A ] of 15 to 100 dl / g measured in tetralin at 135 ° C.

In the composition of the present invention, a propylene homopolymer other than high-molecular-weight polyethylene or a propylene-olefin copolymer containing 50% by weight or more of propylene polymerized units contains propylene or propylene and another olefin ( Preferably, the catalyst is produced with a catalyst amount of 0.01 to 1,000 mmol in terms of transition metal atoms in the catalyst per liter of (co) polymerization volume.

In the composition of the present invention, the olefin (co) polymer other than the high-molecular-weight polyethylene is a) a propylene homopolymer or 50
A propylene-olefin copolymer containing at least 0.01% by weight of a transition metal compound catalyst component, and from 0.01 to 1,000 mol per mol of transition metal atom of the Periodic Table (1991 edition), Groups 1 and 2.
Consisting of a combination of an organometallic compound of a metal selected from the group consisting of metals belonging to Group 12, Group 12 and Group 13 (AL1) and 0 to 500 moles of an electron donor (E1) per mole of transition metal atom In the presence of a polyolefin production catalyst, and a preactivation catalyst containing polyethylene supported on this catalyst, propylene alone or propylene
(Co) polymers produced by subjecting (co) polymerizing other olefins to (b) to (b), and b) a propylene homopolymer or propylene
It is preferably a mixture of a propylene-olefin copolymer containing at least 10% by weight.

In the composition of the present invention, the heating temperature is preferably in the range of 60 to 350 ° C. More preferably, it is in the range of 80 to 300 ° C. The preferred heating time is about 1 minute to 2 hours. By this heat treatment,
Radicals generated by the ionizing radiation treatment can be eliminated. If the radicals remain, the polymer is likely to deteriorate, but if the radicals are eliminated, the polymer will be stabilized.

Next, the process for producing the modified olefin (co) polymer composition of the present invention is described in the Periodic Table (1991 edition) of 0.01 to 1,000 mol per 1 mol of the transition metal compound catalyst component and transition metal atom.
Group 1, Group 2, Organometallic compounds of metals selected from the group consisting of metals belonging to Group 12 and Group 13 (AL1) and 0 to 500 moles of electron donor (E1 ), And a titanium-containing solid catalyst component supported on this catalyst in an amount of 0.
Intrinsic viscosity measured in tetralin between 135g and 01g-5,000g
In the presence of a preactivated catalyst containing polyethylene consisting of an ethylene homopolymer or an ethylene-olefin copolymer containing 50% by weight or more of ethylene polymerized units, where [η] is 15 to 100 dl / g, (Co) polymerization to produce an olefin (co) polymer composition, further irradiating the composition with ionizing radiation, followed by heat treatment.

In the above method, the olefin to be (co) polymerized is propylene alone or an olefin having 2 to 12 carbon atoms, and the olefin (co) polymer is not less than 50% by weight of propylene homopolymer or propylene polymerized unit. It is preferably a copolymer of the contained propylene and an olefin having 2 to 12 carbon atoms.

In the above method, the preactivated catalyst may further comprise a) an organoaluminum compound (AL1) contained in the preactivated catalyst per 1 mol of transition metal atoms in the preactivated catalyst.
0.05 to 5,000 mol of organoaluminum compound in total
(AL2), and b) a total of 0 to 1 mol of the transition metal atom in the preactivated catalyst and the electron donor (E1) contained in the preactivated catalyst.
Preferably, 3,000 moles of the electron donor (E2) are added.

In the above method, the amount of the catalyst is preferably from 0.01 to 1,000 mmol per 1 liter of the olefin (co) polymerization volume in terms of titanium atoms in the catalyst. Further, in the above method, the intrinsic viscosity [η _B ] measured in tetralin at 135 ° C. per 1 g of the transition metal compound catalyst component supported on the catalyst in addition to polyethylene in addition to the preactivated catalyst has a value of 15 dl / g. A polypropylene which is a small propylene homopolymer or a propylene-olefin copolymer containing at least 50% by weight of propylene polymerized units
(B) It is preferable to contain 0.01 to 100 g.

In the above method, the amount of the catalyst is preferably 0.01 to 1,000 mmol per 1 liter of the (co) polymerized olefin in terms of transition metal atoms in the catalyst.

In the above method, a) the catalyst component of the transition metal compound and 0.01 to 1,000 per mol of the transition metal atom.
Periodic Table of the Mole (1991 edition) Groups 1, 2, 12 and
Organometallic compound (AL1) of a metal selected from the group consisting of metals belonging to Group 13 and 0 to 500 per mole of transition metal atom
The olefin was (co) polymerized in the presence of a catalyst for the production of a polyolefin comprising a combination of a molar electron donor (E1) and the intrinsic viscosity [η] measured in tetralin at 135 ° C. was 15d.
a preliminary (co) polymerization step for producing 0.01 g to 100 g of polyolefin (B) smaller than 1 / g per 1 g of the transition metal compound catalyst component; b) subsequent (co) polymerization of the olefin and measurement in tetralin at 135 ° C A pre-activated (co) polymerization step of producing 0.01 g to 5,000 g of polyolefin (A) having an intrinsic viscosity [η] of 15 to 100 dl / g per 1 g of the transition metal compound catalyst component. C) Polyolefin (B) and In the presence of a preactivated catalyst for olefin (co) polymerization obtained by a method in which polyolefin (A) is supported on a transition metal compound catalyst component,
It is preferred that the main component (co) polymerization of 2 to 12 olefins be performed.

Further, in the above method, a) 0.01 to 1,00 parts per mole of the transition metal compound catalyst component and the transition metal atom.
0 moles of the periodic table (1991 edition) per group of organometallic compounds (AL1) and transition metal atoms of a metal selected from the group consisting of metals belonging to Group 1, Group 2, Group 12 and Group 13 0-5
The olefin was (co) polymerized in the presence of a polyolefin-producing catalyst comprising a combination of 00 moles of the electron donor (E1), and had an intrinsic viscosity [η] of 1 measured at 135 ° C. in tetralin.
Preliminary (co) polymerization step of producing 0.01 g to 100 g of polyolefin (B) smaller than 5 dl / g per 1 g of the transition metal compound catalyst component, followed by (co) polymerization of the olefin, 135 ° C
Intrinsic viscosity [η] measured in tetralin of 15 to 100 dl / g
1 g of the transition metal compound catalyst component
Including a pre-activated (co) polymerization step of producing 0.01 g to 5,000 g per polyolefin (B) and polyolefin
(A) a pre-activated catalyst for olefin (co) polymerization obtained by a method in which the component is supported on a transition metal compound catalyst component; Periodic table of 0.05 to 5,000 mol in total with the organometallic compound (AL1) of the metal contained in the activation catalyst
(1991 edition) Organometallic compounds of metals selected from the group consisting of metals belonging to Group 1, Group 2, Group 12 and Group 13 (A
L2), and c) a total of 0 to 3,000 moles of electron donation with respect to 1 mole of transition metal atoms in the preactivation catalyst and the electron donor (E1) contained in the preactivation catalyst for olefin (co) polymerization. The olefin is preferably (co) polymerized in the presence of an olefin (co) polymerization catalyst comprising the isomer (E2).

In the above method, the olefin is
After (co) polymerization, irradiate with ionizing radiation, and then
After the heat treatment, it is preferable to further add 0.01 to 2 parts by weight of at least one stabilizer selected from a phenolic antioxidant and a phosphorus antioxidant.

In the above method, the heating temperature is 60-35.
Preferably it is in the range of 0 ° C. More preferably, 8
It is in the range of 0-300 ° C. The preferred heating time is from 1 minute to 2 minutes.
About an hour. By this heat treatment, radicals generated by the ionizing radiation treatment can be eliminated. If the radicals remain, the polymer is likely to deteriorate, but if the radicals are eliminated, the polymer will be stabilized.

Further, based on 100 parts by weight of the modified olefin (co) polymer composition obtained by the above-mentioned production method, the olefin (co) polymer obtained by a known method is further added to 0 to 10,000 parts by weight. Range mixing can also be performed.

A mixture of the modified olefin (co) polymer composition of the present invention and an olefin (co) polymer may also be used. Next, the modified olefin (co) polymer composition molded article of the present invention is the modified olefin according to any of the above.
A molded article obtained from the (co) polymer composition. As a molding method, any known method may be adopted.

The molded article of the modified olefin (co) polymer composition of the present invention is (a) an ethylene homopolymer or an ethylene-olefin copolymer containing 50% by weight or more of ethylene polymer units, and Intrinsic viscosity [η _E ] measured with tetralin at 135 ° C. is 0.01 to 5.0 parts by weight of a high-molecular-weight polyethylene having a range of 15 to 100 dl / g, and (b) an olefin (co) polymer other than the high-molecular-weight polyethylene is 100. Parts by weight, (c) and the high-molecular-weight polyethylene has a number-average particle diameter of 1 to 5000 nm, and is present as a finely dispersed fine particle as an olefin (co) polymer. A modified olefin (co) polymer composition molded article obtained by irradiating with ionizing radiation can also be obtained.

As described above, according to the present invention, a high-molecular-weight polyethylene is formed by pre-polymerization, and this is added during the main polymerization of an olefin such as polypropylene, and the high-molecular-weight polyethylene is added to a polyolefin such as polypropylene. The olefin (co) polymer composition, which is finely dispersed as fine particles, is irradiated with ionizing radiation, and subsequently heat-treated to modify the strength and crystallinity at the time of melting represented by the melt tension and the like. Further improve the
Modified olefin (co) polymer composition excellent in moldability such as high-speed productivity, and heat-resistant, modified olefin (co) polymer composition molded articles excellent in physical properties such as rigidity and methods for producing them Can be provided.

[0044]

BEST MODE FOR CARRYING OUT THE INVENTION In the specification of the present invention, the term "polyolefin" refers to an olefin homopolymer having 2 to 12 carbon atoms, an olefin random copolymer containing two or more olefin polymer units, and an olefin. The terms “olefin” and “ethylene (co) polymer” are defined as olefin-based (co) polymers including block copolymers. Ethylene homopolymer, ethylene-olefin containing 50% by weight or more of ethylene polymerized units. An ethylene-based (co) polymer including a random copolymer and an ethylene-olefin block copolymer, and the term "polypropylene" refers to a propylene homopolymer and a propylene-containing polymer containing at least 50% by weight of propylene polymerized units. Olefin random copolymers and propylene-olefin block copolymers Means pyrene-based (co) polymer.

The term "polyolefin composition" means a mixture of different polyolefins such as polymerized units, molecular weight, randomness, block units and the like. The modified olefin (co) polymer composition and the molded article of the modified olefin (co) polymer composition of the present invention are suitable for hollow molding, foam molding, extrusion molding, and high-speed productivity in various other molding methods. An olefin (co) polymer composition having a high melt tension and a high crystallization temperature capable of exhibiting, once produced, and then provided with a step of irradiating the olefin (co) polymer composition with ionizing radiation It can be obtained by:

The pre-irradiated olefin (co) polymer composition is treated with an olefin (co) polymerization catalyst by using a preactivated catalyst obtained by performing a preactivation specific to the present invention and an olefin (co) polymerization catalyst. The preactivated catalyst, the preactivated catalyst for olefin (co) polymerization, the olefin (co) polymerization, and the olefin
The (co) polymer composition and the like will be described in detail.

The term "pre-activation" means that the activity of the polyolefin-producing catalyst for increasing the molecular weight is pre-activated before the main (co) polymerization of the olefin is carried out. By pre-activated (co) polymerization of the olefin in the presence of and supporting on a catalyst.

The preactivated catalyst for olefin (co) polymerization of the present invention is a polyolefin comprising a catalyst component of a transition metal compound conventionally used for the production of polyolefin, an organometallic compound, and an electron donor optionally used. The catalyst is preactivated by supporting a small amount of a polyolefin for the purpose of main (co) polymerization having a specific intrinsic viscosity and a small amount of a polyolefin having a specific high intrinsic viscosity on a production catalyst.

In the preactivated catalyst for olefin (co) polymerization of the present invention, any of the known catalyst components mainly composed of the transition metal compound catalyst component proposed for polyolefin production may be used as the transition metal compound catalyst component. Can also be used. Among them, a solid catalyst component is suitably used in industrial production.

As the solid catalyst component, a titanium-containing solid catalyst component containing a titanium trichloride composition as a main component (Japanese Patent Publication No.
-3356, JP-B-59-28573, JP-B-63-66323, etc.) and titanium containing titanium tetrachloride as a magnesium compound and containing titanium, magnesium, halogen, and an electron donor as essential components. Containing supported catalyst components (JP-A-62-104810, JP-A-62-104811, JP-A-62-10848)
No. 12, JP-A-57-63310, JP-A-5-63310
7-63311, JP-A-58-83006, JP-A-58-138712, etc., and any of these can be used.

Further, a transition metal compound having at least one π-electron conjugated ligand usually called a metallocene can also be used as a transition metal catalyst component. At this time, the transition metal is preferably selected from Zr, Ti, Hf, V, Nb, Ta, and Cr.

As the π-electron conjugated ligand, specifically, η-
A ligand having a cyclopentadienyl structure, an η-benzene structure, an η-cycloptatetrienyl structure, or an η-cyclooctatetraene structure may be mentioned, and particularly preferred is an η-cyclopentadienyl structure. Ligand.

The ligand having an η-cyclopentadienyl structure includes, for example, a cyclopentadienyl group, an indenyl group, a fluorenyl group and the like. These groups include hydrocarbon groups such as alkyl groups, aryl groups and aralkyl groups, silicon-substituted hydrocarbon groups such as trialkylsilyl groups, halogen atoms, alkoxy groups, aryloxy groups, linear and cyclic alkylene groups, and the like. It may be replaced.

When the transition metal compound contains two or more π-electron conjugated ligands, two of the π-electron conjugated ligands are linked to each other by an alkylene group, a substituted alkylene group, a cycloalkylene group, a substituted cycloalkylene group. It may be crosslinked via an alkylene group, a substituted alkylidene group, a phenylene group, a silylene group, a substituted dimethylsilylene group, a germyl group, or the like.

In this case, the transition metal catalyst component has at least one π-electron ligand as described above, a hydrocarbon group such as an alkyl group, a cycloalkyl group, an aryl group, and an aralkyl group, and a silicon-substituted group. It may have a hydrocarbon group, an alkoxy group, an aryloxy group, a substituted sulfonato group, an amidosilylene group, an amidoalkylene group and the like. In addition, 2 such as amide silylene group or amide alkylene group
The valence group may be bonded to a π-electron conjugated ligand.

As described above, π which is usually called metallocene
The transition metal compound catalyst component having at least one electron conjugated ligand can be further used by being supported on a particulate carrier. Such a particulate carrier is an inorganic or organic compound having a particle diameter of 5 to 300 μm.
m, preferably 10-200 μm granular or spherical fine particle solid is used. Among them, inorganic compounds used alone include SiO ₂ , Al ₂ O ₃ , MgO,
TiO ₂ , ZnO and the like or a mixture thereof are mentioned. Among them, those containing SiO ₂ or Al ₂ O ₃ as a main component are preferable.

The organic compounds used for the carrier include ethylene, propylene, 1-butene, 4-methyl-1-
Examples thereof include polymers or copolymers of α-olefins having 2 to 12 carbon atoms, such as pentene, and polymers or copolymers of styrene or styrene derivatives.

As the organometallic compound (AL1), the periodic table
1st, 2nd, 12th and 13th (1991)
A compound having an organic group of a metal selected from the group consisting of metals belonging to the group, for example, an organic lithium compound, an organic sodium compound, an organic magnesium compound, an organic zinc compound, an organic aluminum compound, and the like, the transition metal compound catalyst component and They can be used in combination.

In particular, the general formula AlR ¹ _p R ² _q X
_{(3- (p + q))} (wherein, R ¹ and R ² are the same or different of a hydrocarbon group such as an alkyl group, a cycloalkyl group, and an aryl group and an alkoxy group; X represents a halogen atom;
p and q each represent a positive number satisfying 0 <p + q ≦ 3).

Specific examples of the organoaluminum compound include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, tri-i-butylaluminum, tri-n-hexylaluminum, tri-i-aluminum. Hexyl aluminum,
Trialkylaluminum such as tri-n-octylaluminum, diethylaluminum chloride, di-n-propylaluminum chloride, di-i-butylaluminum chloride, dialkylaluminum monohalide such as diethylaluminum bromide, diethylaluminum iodide, and diethylaluminum hydride Dialkylaluminum hydrides, alkylaluminum sesquihalides such as ethylaluminum sesquichloride, monoalkylaluminum dihalides such as ethylaluminum dichloride, and other alkoxyalkylaluminums such as diethoxymonoethylaluminum. Alkyl aluminum and dialkyl aluminum monohalides are used. These organoaluminum compounds are:
Not only seeds but also two or more kinds can be used in combination.

As the organometallic compound (AL1),
Aluminoxane compounds can also be used. Aluminoxane is an organoaluminum compound represented by the following general formula (Formula 5) or (Formula 6).

[0062]

Embedded image

[0063]

Embedded image

In the above formula, R ³ is a hydrocarbon group having 1 to 6, preferably 1 to 4 carbon atoms, and specifically, a methyl group, an ethyl group, a propyl group, a butyl group, an isobutyl group,
Alkyl groups such as pentyl group and hexyl group, allyl group, 2
-Methylallyl group, propenyl group, isopropenyl group,
Compounds such as alkenyl groups such as 2-methyl-1-propenyl group and butenyl group, cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group and cyclohexyl group, and aryl groups are exemplified. Among these, an alkyl group is particularly preferred, and each R ³ may be the same or different. Also, p is an integer of 4 to 30, preferably 6 to 30, and particularly preferably 8 to 30.
It is.

Another compound as the organometallic compound (AL1) is a boron-based organometallic compound. This boron-based organometallic compound is obtained by reacting a transition metal compound with an ionic compound containing a boron atom.

The transition metal compound used at this time may be the same as the transition metal compound catalyst component used in producing the preactivated catalyst for olefin (co) polymerization, but is preferably used. Is a transition metal compound catalyst component having at least one π-electron conjugated ligand usually referred to as a metallocene described above.

Specific examples of the ionic compound containing a boron atom include triethylammonium tetrakis (pentafluorophenyl) borate, n-butylammonium tetrakis (pentafluorophenyl) borate, and triphenyltetrakis (pentafluorophenyl) borate. Examples include ammonium, methyl anilium tetrakis (pentafluorophenyl) borate, dimethyl anilium tetrakis (pentafluorophenyl) borate, and trimethyl anilium tetrakis (pentafluorophenyl) borate.

The boron-based organometallic compound can also be obtained by contacting a transition metal compound with a boron atom-containing Lewis acid. As the transition metal compound used at this time, it is possible to use the same transition metal compound catalyst component used when producing the preactivated catalyst for olefin (co) polymerization, but preferably used as described above. And a transition metal compound catalyst component having at least one π-electron conjugated ligand usually referred to as a metallocene.

As the boron atom-containing Lewis acid, a compound represented by the following general formula (Formula 7) can be used.

[0070]

Embedded image BR ⁴ R ⁵ R ⁶ (wherein R ⁴ , R ⁵ and R ⁶ are each independently a phenyl which may have a substituent such as a fluorine atom, a methyl group or a trifluorophenyl group) Or a fluorine atom.) Specific examples of the compound represented by the above general formula include tri (n-butyl) boron, triphenylboron, tris [3,5-bis (trifluoromethyl) phenyl] Boron, tris [4-fluoromethyl) phenyl] boron,
Tris (3,5-difluorophenyl) boron, tris (2,4,6-trifluorophenylboron, tris (pentafluorophenyl) boron and the like are mentioned, and tris (pentafluorophenyl) boron is particularly preferred.

The electron donor (E1) is used as needed for the purpose of controlling the production rate and / or stereoregularity of the polyolefin. Examples of the electron donor (E1) include ethers, alcohols, esters, aldehydes, fatty acids, ketones, nitriles,
Amine, amide, urea and thioureas, isocyanates, azo compounds, phosphines, phosphites, hydrogen sulfide and thioethers, neoalcohols, etc. Examples include organic compounds having atoms, silanols, and organic silicon compounds having a Si—O—C bond in the molecule.

As ethers, dimethyl ether,
Diethyl ether, di-n-propyl ether, di-n-butyl ether, di-i-amyl ether, di-n-pentyl ether, di-n-hexyl ether, di-i-hexyl ether, di-n-octyl ether , Di-i-octyl ether, di-n-dodecyl ether, diphenyl ether,
Ethylene glycol monoethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, etc.,
Alcohols include methanol, ethanol, propanol, butanol, pentanol, hexanol,
Octanol, 2-ethylhexanol, allyl alcohol, benzyl alcohol, ethylene glycol, glycerin and the like, and phenols such as phenol, cresol, xylenol, ethylphenol, naphthol and the like.

Examples of the esters include methyl methacrylate, methyl formate, methyl acetate, methyl butyrate, ethyl acetate, vinyl acetate, n-propyl acetate, i-propyl acetate, butyl formate, amyl acetate, and n-butyl acetate. Octyl acetate, phenyl acetate, ethyl propionate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, 2-ethylhexyl benzoate, methyl toluate, ethyl toluate, methyl anisate, Monocarboxylic acid esters such as ethyl anisate, propyl anisate, phenyl anisate, ethyl cinnamate, methyl naphthoate, ethyl naphthoate, propyl naphthoate, butyl naphthoate, 2-ethylhexyl naphthoate, and ethyl phenylacetate , Diethyl succinate, diethyl methylmalonate, butyl maleate Aliphatic polycarboxylic acid esters such as diethyl lonate, dibutyl maleate and diethyl butyl maleate, monomethyl phthalate, dimethyl phthalate, diethyl phthalate, di-n-propyl phthalate, mono-n-butyl phthalate , Di-n-butyl phthalate,
Diisobutyl phthalate, di-n-heptyl phthalate, di-2-ethylhexyl phthalate, di-n-octyl phthalate,
Diethyl isophthalate, dipropyl isophthalate, dibutyl isophthalate, di-2-ethylhexyl isophthalate, diethyl terephthalate, dipropyl terephthalate,
Aromatic polycarboxylic acid esters such as dibutyl terephthalate and diisobutyl naphthalenedicarboxylate are exemplified.

The aldehydes include acetaldehyde, propionaldehyde, benzaldehyde and the like, and the carboxylic acids include formic acid, acetic acid, propionic acid, butyric acid,
Monocarboxylic acids such as oxalic acid, succinic acid, acrylic acid, maleic acid, valeric acid, and benzoic acid and acid anhydrides such as benzoic anhydride, phthalic anhydride, and tetrahydrophthalic anhydride are used as ketones such as acetone, methyl ethyl ketone,
Examples thereof include methyl isobutyl ketone and benzophenone.

Examples of the nitrogen-containing compound include nitriles such as acetonitrile and benzonitrile, methylamine, diethylamine, tributylamine, triethanolamine, β- (N, N-dimethylamino) ethanol, pyridine, quinoline, α-picoline, 2,4,6-trimethylpyridine, 2,2,5,6-tetramethylpiperidine, 2,2,
Amines such as 5,5-tetramethylpyrrolidine, N, N, N ', N'-tetramethylethylenediamine, aniline, dimethylaniline, formamide, hexamethylphosphoric triamide, N, N, N', N ', N "-pentamethyl-N '
amides such as -β-dimethylaminomethylphosphoric triamide, octamethylpyrophosphoramide, N, N, N ',
Examples include ureas such as N'-tetramethylurea, isocyanates such as phenyl isocyanate and toluyl isocyanate, and azo compounds such as azobenzene.

Examples of the phosphorus-containing compound include phosphines such as ethyl phosphine, triethyl phosphine, tri-n-octyl phosphine, triphenyl phosphine, and triphenyl phosphine oxide; dimethyl phosphite;
phosphines such as -n-octyl phosphine, triphenyl phosphine, triphenyl phosphine oxide, etc .; Phytos are exemplified.

Examples of the sulfur-containing compound include thioethers such as diethylthioether, diphenylthioether and methylphenylthioether, ethylthioalcohol,
n-propylthioalcohol, thioalcohols such as thiophenol, and the like, and further, as an organosilicon compound, trimethylsilanol, triethylsilanol,
Silanols such as triphenylsilanol, trimethylmethoxysilane, dimethyldimethoxysilane, methylphenyldimethoxysilane, diphenyldimethoxysilane, methyltrimethoxysilane, vinyltrimethoxysilane, phenyltrimethoxysilane, trimethylethoxysilane, dimethyldiethoxysilane, diisopropyl Dimethoxysilane, diisobutyldimethoxysilane, diphenyldiethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, butyltriethoxysilane, phenyltriethoxysilane, ethyltriisopropoxysilane, vinyltriacetoxysilane, cyclopentylmethyl Dimethoxysilane, cyclopentyltrimethoxysilane, dicyclopentyldimethoxysilane Emissions, cyclohexylmethyl dimethoxysilane, cyclohexyl trimethoxysilane, dicyclohexyl dimethoxysilane, organic silicon compound having Si-O-C bonds in the molecule such as 2-norbornyl methyl dimethoxy silane.

These electron donors can be used alone or as a mixture of two or more. In the preactivated catalyst for olefin (co) polymerization of the present invention, the polyolefin (A) is 15 to 100 dl / g, preferably 1 to 100 dl / g.
It has an intrinsic viscosity [η] measured in tetralin at 135 ° C. in the range of 7-50 dl / g. Polyolefin (A)
Is a homopolymer of an olefin having 2 to 12 carbon atoms or a copolymer thereof, and preferably has a homopolymer of ethylene or propylene or a polymerization unit of ethylene or propylene of 50% by weight or more, preferably 70% by weight or more. More preferably 90% by weight or more of ethylene-olefin copolymer or propylene-olefin copolymer, more preferably ethylene homopolymer or ethylene polymerized unit is 50% by weight or more, preferably 70% by weight or more, The ethylene-olefin copolymer is more preferably 90% by weight or more.

If the intrinsic viscosity [η] of the polyolefin (A) is too small, the melt tension and the crystallization temperature of the polyolefin composition finally obtained by the (co) polymerization become insufficient. Although there is no particular upper limit for the intrinsic viscosity [η],
If the intrinsic viscosity [η] difference from the finally obtained polyolefin composition is too large, dispersion of the polyolefin (A) in the polyolefin composition becomes poor, and as a result, the melt tension may become insufficient. From the viewpoint of production efficiency, the upper limit is preferably limited to about 100 dl / g. Further, it is necessary to increase the intrinsic viscosity [η] of the polyolefin (A) in tetralin at 135 ° C. to 15 dl / g. Is preferably 50% by weight or more of an ethylene-olefin copolymer.

The density of the polyolefin (A) is not particularly limited, but is preferably about 880 to 980 g / liter. The supported amount of polyolefin (A) per gram of the transition metal compound catalyst component is 0.01 to 5,000.
0 g, preferably 0.05 to 2,000 g, more preferably 0.1 to 1,000 g. When the amount supported per 1 g of the transition metal compound catalyst component is less than 0.01 g, the effect of improving the melt tension and the crystallization temperature of the polyolefin composition finally obtained by the main (co) polymerization of the olefin is insufficient, and If the amount is more than 5,000 g, not only the improvement of those effects will not be remarkable, but also the homogeneity of the finally obtained polyolefin composition may deteriorate, which is not preferable.

The olefin to be (co) polymerized as polyolefin (A) includes ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 4-methyl-1-pentene, 3 -Methyl-1-pentene and the like, and among them, ethylene, propylene, 1-butene and 4-methyl-1-pentene are more preferred.

On the other hand, the polyolefin (B) is a polyolefin of the same kind as the polyolefin for the purpose of main (co) polymerization, having an intrinsic viscosity [η] of less than 15 dl / g measured in tetralin at 135 ° C. The polyolefin (B) is a component that imparts dispersibility of the polyolefin (A) in the finally obtained polyolefin composition. In this sense, the intrinsic viscosity [η] is the intrinsic viscosity of the polyolefin (A). [Η]
It is preferably smaller and larger than the intrinsic viscosity [η] of the obtained polyolefin composition.

On the other hand, the supported amount of polyolefin (B) per g of the transition metal compound catalyst component is 0.01 to 100 g,
In other words, 0.0 based on the polyolefin composition obtained.
A range of 01 to 1% by weight is preferred. Polyolefin
If the amount of (B) supported is small, the dispersibility of the polyolefin (A) in the target polyolefin composition becomes insufficient, and if it is too large, the dispersibility of the polyolefin (A) in the polyolefin composition becomes saturated. And even olefins
This leads to a reduction in the production efficiency of the pre-activated catalyst for (co) polymerization.

The preactivated catalyst for olefin (co) polymerization of the present invention comprises a combination of the above-mentioned catalyst component of a transition metal compound containing at least a titanium compound, an organometallic compound (AL1) and an electron donor (E1) used as required. In the presence of a catalyst for the production of polyolefin consisting of, the (olefin) pre- (co) polymerization step of pre- (co) polymerizing the olefin for the purpose of polymerization to form polyolefin (B),
A pre-activation polymerization step of (co) polymerizing to produce the polyolefin (A), which is produced by a pre-activation treatment in which the transition metal compound catalyst component carries the polyolefin (B) and the polyolefin (A).

In this preactivation treatment, 0.01 to 1,000 mol, preferably 0.05 to 500 mol, of the transition metal compound catalyst component containing a titanium compound, and preferably 0.05 to 500 mol, per mol of the transition metal in the catalyst component. 0 to 500 mol per 1 mol of the transition metal in the compound (AL1) and the catalyst component,
Preferably, 0 to 100 moles of the electron donor (E1) are used in combination as a catalyst for producing a polyolefin.

The polyolefin production catalyst is present in an amount of 0.001 to 5,000 mmol, preferably 0.01 to 1,000 mmol, as transition metal atoms in the catalyst component, per liter of olefin polymerization volume. In the absence of a solvent or in a solvent up to 100 liters per 1 g of the transition metal compound catalyst component, 0.01 to 500 g of the olefin for the purpose of (co) polymerization is supplied and preliminarily (co) polymerized to prepare the transition metal compound. 0.01 to 100 g per 1 g of catalyst component
Of polyolefin (A), and then 0.01 to 10,000 g of olefin is supplied and (co) polymerized to produce 0.01 to 5,000 g of polyolefin (A) per 1 g of the transition metal compound catalyst component. As a result, the polyolefin (B) and the polyolefin (A) are coated and supported on the transition metal compound catalyst component. In the present specification, the term `` polymerization volume '' means the volume of the liquid phase portion in the polymerization vessel in the case of liquid phase polymerization, and the volume of the gas phase portion in the polymerization vessel in the case of gas phase polymerization. I do. The amount of the transition metal compound used as the catalyst component is an efficient and controlled (co) polyolefin (A).
In order to maintain the polymerization reaction rate, the above range is preferable. On the other hand, if the amount of the organometallic compound (AL1) is too small, the (co) polymerization reaction rate becomes too slow, and even if it is too large, a corresponding increase in the (co) polymerization reaction rate cannot be expected. The residue of the organometallic compound (AL1) is undesirably increased in the polyolefin composition obtained in (1). Further, if the amount of the electron donor (E1) is too large, the (co) polymerization reaction rate is reduced. If the amount of the solvent used is too large, not only a large reaction vessel is required, but also it is difficult to efficiently control and maintain the (co) polymerization reaction rate.

The pre-activation treatment includes, for example, aliphatic hydrocarbons such as butane, pentane, hexane, heptane, octane, isooctane, decane and dodecane; alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclohexane; It can be performed in a liquid phase using an aromatic hydrocarbon such as xylene or ethylbenzene, an inert solvent such as a gasoline fraction or a hydrogenated diesel oil fraction, or an olefin itself as a solvent. It can also be done in phase.

The preactivation treatment may be carried out in the presence of hydrogen, but the intrinsic viscosity [η] is 15 to 100 dl /
In order to produce g of a high molecular weight polyolefin (A), it is preferable not to use hydrogen.

In the pre-activation treatment, the conditions for the pre- (co) polymerization of the olefin for the purpose of the (co) polymerization are polyolefin.
(B) is 0.01 to 1 per gram of the transition metal compound catalyst component.
As long as it is a condition for producing 00 g, usually -40 to 10
It is carried out at a temperature of 0 ° C. under a pressure of 0.1 to 5 MPa for 1 minute to 24 hours. The conditions for the preactivation (co) polymerization with an olefin are as follows: the polyolefin (A) is used in an amount of 0.01 to 5,000 g, preferably 0.05, per gram of the transition metal compound catalyst component.
~ 2,000g, more preferably 0.1 ~ 1,000g
The amount is not particularly limited as long as the condition is such that the amount is formed in the amount of 0.1 to 4,000. 1
The pressure is from 1 to 24 MPa, preferably from 5 to 18 hours, more preferably from 10 to 12 hours under a pressure of from 5 to 5 MPa, preferably from 0.2 to 5 MPa, more preferably from 0.3 to 5 MPa.

Further, after the preactivation treatment, addition polymerization with an olefin for the purpose of (co) polymerization is carried out by a transition metal compound catalyst for the purpose of suppressing a decrease in main (co) polymerization activity due to the preactivation treatment. 0.01 to 10 per gram of component
The reaction may be performed with a reaction amount of 0 g of the olefin. in this case,
The amount of the organometallic compound (AL1), electron donor (E1), solvent, and olefin used is based on the pre-activation with olefin.
The (co) polymerization can be carried out within the same range as in the (co) polymerization, but 0.005 to 10 mol, preferably 0.1 to 10 mol per mol of transition metal atom.
It is preferably carried out in the presence of from 01 to 5 mol of electron donor. The reaction is carried out at a temperature of -40 to 100 ° C and a pressure of 0.1 to 5 MPa for 1 minute to 24 hours.

The organometallic compound (A) used for the addition polymerization
As for L1), the electron donor (E1), and the type of the solvent, those similar to those used in the preactivated (co) polymerization with olefin can be used, and the olefin used for the main (co) polymerization is used.

The intrinsic viscosity [η] of the polyolefin formed by the addition polymerization is in a range smaller than the intrinsic viscosity [η] of the polyolefin (A), and is finally incorporated as a part of the polyolefin after the main (co) polymerization. Can be

Next, the preactivated catalyst for olefin (co) polymerization of the present invention can be used as it is or with an additional organometallic compound (A
L2) and an electron donor (E2), together with an olefin having 2 to 12 carbon atoms to obtain a target polyolefin composition (co).
It can be used for polymerization.

The olefin main (co) polymerization catalyst of the present invention is
Preactivated catalyst for olefin (co) polymerization, olefin
The total (AL) of the organometallic compound (AL2) and the organometallic compound (AL1) in the olefin (co) polymerization preactivation catalyst per mole of the transition metal atom in the (co) polymerization preactivation catalyst.
1 + AL2) in the range of 0.05 to 3,000 mol, preferably 0.1 mol.
1 to 1,000 moles and 1 mole of the transition metal atom in the preactivated catalyst for olefin (co) polymerization, and
2) is 0 to 5,000 mol, preferably 0 to 3,000 mol, in total (E1 + E2) with the electron donor (E1) in the preactivated catalyst for olefin (co) polymerization.

Content of organometallic compound (AL1 + AL2)
Is too small, the (co)
If the polymerization reaction rate is too slow, on the other hand, even if it is excessively large, the (co) polymerization reaction rate does not increase as expected and is not only inefficient, but also the organic residue remaining in the resulting polyolefin composition It is not preferable because the amount of the metal compound residue increases. Further, when the content of the electron donor (E1 + E2) is too large, the (co) polymerization reaction rate is remarkably reduced.

As the olefin main (co) polymerization catalyst, an organometallic compound (AL2) and an electron donor (E) which are additionally used as necessary in a preactivation catalyst for olefin (co) polymerization.
As for the type of 2), the same type as the above-mentioned organometallic compound (AL1) and electron donor (E1) can be used. Further, one kind may be used alone, or two or more kinds may be used in combination. Further, they may be the same or different from those used in the preactivation treatment for olefin (co) polymerization.

The olefin main (co) polymerization catalyst includes a solvent, an unreacted olefin, an organometallic compound (AL1), an electron donor (E1), and the like which are present in the olefin (co) polymerization preactivated catalyst. , Or a suspension obtained by adding a solvent to the granules, and an additional organometallic compound (AL2) and optionally an electron donor (E2). May be combined, and
The solvent and the unreacted olefin present are removed by distillation under reduced pressure or by evaporating with an inert gas stream or the like. AL2) and an electron donor (E2).

Next, in the process for producing a polyolefin composition of the present invention, the pre-activated catalyst for olefin (co) polymerization or the catalyst for olefin main (co) polymerization is used in the presence of the above-mentioned catalyst.
The olefin is (co) polymerized. The amount of the olefin (co) polymerization preactivation catalyst or olefin main (co) polymerization catalyst used is calculated as the transition metal atom in the olefin (co) polymerization preactivation catalyst per liter of polymerization volume. 0.0
01-1,000 mmol, preferably 0.005-50
Use 0 mmol. By setting the amount of the transition metal compound catalyst component in the above range, an efficient and controlled (co) polymerization reaction rate of the olefin can be maintained.

The olefin (co) polymerization of the olefin in the present invention can be carried out by a known olefin (co) polymerization process, specifically, propane, butane, pentane, hexane, heptane, octane, isooctane. , Decane, dodecane and other aliphatic hydrocarbons, cyclopentane, cyclohexane, methylcyclohexane and other alicyclic hydrocarbons, toluene, xylene, ethylbenzene and other aromatic hydrocarbons, as well as gasoline fractions and hydrogenated diesel oil fractions In an inert solvent such as, a slurry polymerization method of performing (co) polymerization of the olefin, a bulk polymerization method using the olefin itself as a solvent, a gas phase polymerization method of performing the (co) polymerization of the olefin in a gas phase, and Solution polymerization in which the polyolefin produced by (co) polymerization is liquid, or a combination of two or more of these processes A tailored polymerization process can be used.

When using any of the above polymerization processes, the polymerization conditions include a polymerization temperature of 20 to 120 ° C., preferably 30 to 100 ° C., particularly preferably 40 to 100 ° C.
℃, the polymerization pressure is 0.1 to 5 MPa, preferably 0.3.
In the range of 5 to 5 MPa, the polymerization time is continuously, semi-continuously, or batchwise, and the polymerization time is about 5 minutes to 24 hours. By employing the above polymerization conditions, a polyolefin can be produced with high efficiency and a controlled reaction rate.

In a more preferred embodiment of the method for producing a polyolefin composition of the present invention, the intrinsic viscosity [η] of the polyolefin produced in the present (co) polymerization and the finally obtained polyolefin composition are 0.2 to 10 dl /. g,
Preferably, it is in the range of 0.7 to 5 dl / g, and the olefin (co)
The polymerization conditions are selected so that the polyolefin (A) derived from the preactivation catalyst for polymerization falls in the range of 0.01 to 5% by weight. Further, similarly to the known olefin polymerization method, the molecular weight of the (co) polymer obtained by using hydrogen during the polymerization can be adjusted.

When the intrinsic viscosity [η] of the obtained polyolefin composition is less than 0.2 dl / g, the mechanical properties of the finally obtained polyolefin molded article deteriorate, and
If it exceeds dl / g, the moldability deteriorates.

On the other hand, if the content of the polyolefin (A) derived from the preactivated catalyst for olefin (co) polymerization is less than 0.01% by weight in the obtained polyolefin composition, the melting of the polyolefin composition may be prevented. The effect of improving the tension and the crystallization temperature is small, and if it exceeds 5% by weight, these effects are not only saturated, but also the homogeneity of the polyolefin composition may be impaired.

In the method for producing a polyolefin composition of the present invention, the olefin used for the main (co) polymerization is as follows:
An olefin having 2 to 12 carbon atoms is preferably used. Specifically, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 4-methyl-1-pentene, 3-methyl-1-pentene and the like, particularly preferably ethylene , Propylene, 1-butene, 4-methyl-
Examples thereof include 1-pentene, and these olefins can be used not only one kind but also two or more kinds.

The polyolefins obtained by the main (co) polymerization of these olefins include not only olefin homopolymers but also
An olefin / random copolymer or olefin / block copolymer containing 50% by weight or more of an olefin polymer unit as a main monomer, preferably an olefin homopolymer, and an olefin polymer unit content as a main monomer. Is 90
It is an olefin / random copolymer of at least 70% by weight or an olefin / block copolymer having an olefin polymerization unit content of at least 70% by weight.

After the completion of the main (co) polymerization of the olefin, if necessary, a post-treatment step such as a known catalyst deactivation treatment step, catalyst residue removal step, and drying step is carried out to obtain the desired high melt tension and high crystallinity. A polyolefin composition having a conversion temperature is finally obtained.

In the method for producing a polyolefin composition of the present invention, a method is employed in which a high-molecular-weight polyolefin (A) is produced in a preactivation step and is uniformly dispersed in the resulting polyolefin composition. While the required amount of the (co) polymerization pre-activation catalyst can be prepared collectively, in the present (co) polymerization, it is sufficient to carry out the usual olefin (co) polymerization using an existing process, The same productivity can be maintained as compared with ordinary polyolefin production.

As described above, the polyolefin composition obtained by employing the method for producing a polyolefin composition using the preactivated catalyst for olefin (co) polymerization of the present invention has a high melt tension. For example, when the polyolefin produced by the (co) polymerization is polypropylene, the melt tension (MS) at 230 ° C. of the finally obtained polypropylene composition and the intrinsic viscosity [η] measured in tetralin at 135 ° C. Is log (MS)> 4.24 × log [η] −
It has been found to have the relationship represented by 1.05.

However, the melt tension at 230 ° C. (MS)
Uses a melt tension tester type 2 (manufactured by Toyo Seiki Seisaku-sho, Ltd.) and converts polyolefin to 230 in the apparatus.
C., and the molten polyolefin was extruded from a 2.095 mm diameter nozzle at a rate of 20 mm / min into the atmosphere at 23.degree. C. to form strands.
It is a value (unit: cN) obtained by measuring the tension of the thread-like polyolefin when it is taken off at a speed of / min.

After completion of the (co) polymerization, if necessary, a post-treatment such as a known catalyst deactivation treatment step, catalyst residue removal step, and drying step is performed to obtain, for example, a polypropylene composition (PP).
Hereinafter, for convenience of explanation, the polypropylene composition (PP) will be described as an example.

In the present invention, the phenolic stabilizer is
The resulting polypropylene composition is added as a component that exhibits thermal stability during molding, high melt tension, and high crystallization temperature.

[0112] The amount of addition is as follows:
From the viewpoint of exhibiting the above-mentioned properties without deteriorating the inherent performance of (PP) and the cost of the stabilizer, 0.000 parts by weight based on 100 parts by weight of the polypropylene composition (PP) of the component A).
It is in the range of 1 to 2 parts by weight, preferably 0.005 to 1.5 parts by weight, particularly preferably 0.01 to 1 part by weight.

As the phenol-based stabilizer, a conventionally known phenol-based stabilizer having a phenol skeleton used in a polypropylene composition is used without any particular limitation. Specifically, the following compounds are used. Used.

2,6-di-tert-butyl-p-cresol, 2,
6-di-t-butyl-4-ethylphenol, 2,6-dicyclohexyl-p-cresol, 2,6-diisopropyl-4-
Ethylphenol, 2,6-di-t-amyl-p-cresol, 2,6-di-t-octyl-4-n-propylphenol, 2,6-dicyclohexyl-4-n-octylphenol, 2-isopropyl- 4-methyl-6-t-butylphenol, 2-t-butyl-4-ethyl-6-t-octylphenol, 2-isobutyl-4-ethyl-6-t-hexylphenol, 2-cyclohexyl-4-n-butyl -6-isopropylphenol, 2-t-butyl-6- (3'-t-butyl-5'-
Methyl-2'hydroxybenzyl) -4-methylphenyl acrylate, t-butylhydroquinone, 2,2'-methylenebis (4-methyl-6-t-butylphenol), 4,
4'-butylidenebis (3-methyl-6-t-butylphenol), 4,4'-thiobis (3-methyl-6-t-butylphenol), 2,2'-thiobis (4-methyl-6-t-butylphenol) ), 4,4'-methylenebis (2,6-di-t-
Butylphenol), 2,2'-methylenebis [6- (1-
Methylcyclohexyl) -p-cresol], 2,2'-ethylidenebis (4,6-di-t-butylphenol),
2'-butylidenebis (2-t-butyl-p-cresol), 1,1,3-tris (2-methyl-4-hydroxy-5-
t-butylphenyl) butane, triethylene glycol-
Bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-
Bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,2-thiodiethylenebis [3
-(3,5-di-t-butyl-4-hydroxyphenyl) propionate], n-octadecyl-3- (3 ', 5'-di-t
-Butyl-4'-hydroxyphenyl) propionate,
N, N'-hexamethylenebis (3,5-di-t-butyl-4-
Hydroxy-hydrocinnamide), 3,5-di-t-butyl-
4-hydroxybenzylphosphonate-diethyl ester, 1,3,5-tris (2,6-dimethyl-3-hydroxy-
4-t-butylbenzyl) isocyanurate, 1,3,5-
Tris [(3,5-di-t-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate,
2,4-bis (n-octylthio) -6- (4-hydroxy-
3,5-di-t-butylanilino) -1,3,5-triazine,
Tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane, bis (3,5-di-t-butyl-4-hydroxybenzylphosphonate ethyl) calcium, bis ( 3,5-di-t-butyl-4-
Ethyl hydroxybenzylphosphonate) nickel, N,
N'-bis [3,5-di-t-butyl-4-hydroxyphenyl) propionyl] hydrazine, 2,2'-methylenebis (4-methyl-6-t-butylphenol) terephthalate, 1,3,5-trimethyl -2,4,6-tris (3,5-di-
t-butyl-4-hydroxybenzyl) benzene, 3,9-
Bis [1,1-dimethyl-2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5,5 ] Undecane, 2,2-bis [4- {2- (3,5-di-t-butyl)
-4-hydroxyhydrocinnamoyloxy) {ethoxyphenyl] propane, β- (3,5-di-t-butyl-4-hydroxyphenyl) propionic acid alkyl ester, and the like.

Of these, 2,6-di-t-butyl-p-
Cresol, tetrakis [methylene-3- (3,5-di-t-
Butyl-4-hydroxyphenyl) propionate] methane, n-octadecyl-3- (3 ', 5'-di-t-butyl-
4'-hydroxyphenyl) propionate, 2-tert-butyl-6- (3'-tert-butyl-5'-methyl-2'-hydroxybenzyl) -4-methylphenylacrylate,
Particularly preferred is 2'-ethylidenebis (4,6-di-t-butylphenol), and these phenolic stabilizers can be used alone or in combination of two or more.

In the present invention, the phosphorus-based antioxidant comprises a high melt tension and a high crystallization temperature at the time of molding the desired polypropylene composition, a heat-resistant oxidative deterioration property of a molded product,
It is blended as a component that exhibits weather resistance and anti-coloring properties.

The amount is 0.001 to 2 parts by weight based on 100 parts by weight of the polypropylene composition (PP) of the component A) from the viewpoint of the performance development of the polypropylene composition of the present invention and the cost of the antioxidant. Parts by weight, preferably 0.005 to
1.5 parts by weight, particularly preferably 0.01 to 1 part by weight.

As the phosphorus-based antioxidant, a conventionally known phosphorus-based antioxidant used in a polypropylene composition can be used without particular limitation, and specific examples include the following compounds. These phosphorus-based antioxidants can be used alone, or two or more phosphorus-based antioxidants can be used in combination.

Tetrakis (2,4-di-t-butylphenyl) -4,4'-biphenylene-di-phosphonite, tetrakis (2,4-di-t-amylphenyl) -4,4'-biphenylene -Di-phosphonite, tetrakis (2,4-
Di-t-butyl-5-methylphenyl) -4,4'-biphenylene-diphosphonite, tetrakis (2,6-di-t-
Butyl-4-methylphenyl) -4,4'-biphenylene-di
-Phosphonite, tetrakis (2,6-di-t-butyl-
4-n-octadecyloxycarbonylethyl-phenyl) -4,4'-biphenylene-di-phosphonite, tetrakis [2,6-di-t-butyl-4- (2 ', 4'-di-t-
Butylphenoxycarbonyl) -phenyl] -4,4'-biphenylene-diphosphonite, tetrakis (2,6-
Di-t-butyl-4-n-hexadecyloxycarbonyl-phenyl) -4,4'-biphenylene-diphosphonite, bis [2,2'-methylene-bis (4-methyl-6-t-
Butylphenyl)]-4,4'-biphenylene-diphosphonite, bis [2,2'-methylene-bis (4,6-di-
t-butylphenyl)]-4,4'-biphenylene-di-phosphonite, bis [2,2'-ethylidene-bis (4-methyl-6-t-butylphenyl)]-4,4'-biphenylene
Biphenylene-di-phosphonite, such as bis- [2,2'-ethylidene-bis (4,6-di-t-butylphenyl)]-4,4'-biphenylene-di-phosphonite Phonite: catesil-2,6-di-t-butyl-4-methylphenylphosphite, catesil-2,4,6-tri
-t-butylphenylphosphite, α-naphthylcatesylphosphite, 2,2′-methylenebis (4-methyl-6-tert-butylphenyl) -2-naphthylphosphite, 4,4′-butylidene-bis ( 3-methyl-6-t-butylphenyl-di-tridecyl phosphite), 1,1,3
-Tris (2-methyl-4-di-tridecylphosphite-
5-t-butylphenyl) butane, trilauryl trithiophosphite, tricetyl trithiophosphite,
9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-1
0-oxide, triphenyl phosphite, tris (nonylphenyl) phosphite, tris (2,4-di
-Nonylphenyl) phosphite, tris (mono, dinonylphenyl) phosphite, tris (2,4-di-t-)
Butylphenyl) phosphite, tris (2,6-di-
t-butyl-4-methylphenyl) phosphite, etc .:
Distearyl-pentaerythritol-diphosphite, diphenyl-pentaerythritol-diphosphite, bis (nonylphenyl) -pentaerythritol-diphosphite, bis (2,4-di-t-butylphenyl)
Pentaerythritol diphosphite, bis (2,4
-Di-t-amylphenyl) pentaerythritol-diphosphite, bis (2,4-dicumylphenyl) pentaerythritol-diphosphite, bis (2,4-di-t
-Butyl-5-methylphenyl) -pentaerythritol-
Diphosphite, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol-diphosphite, bis (2,6-di-t-butyl-4-s-butylphenyl) pentaerythritol- Diphosphite, bis (2,4,6-tri-t-butylphenyl) pentaerythritol-diphosphite, bis (2,4,6-tri-t-amylphenyl) pentaerythritol-diphosphite, bis ( 2,6-di-t-butyl-4-n-octadecyloxycarbonylethyl-phenyl) pentaerythritol-diphosphite, bis [2,6-di-t-butyl-4-
(2 ', 4'-di-t-butylphenoxycarbonyl) -phenyl] pentaerythritol-diphosphite, bis (2,6-di-t-butyl-4-n-hexadecyloxycarbonyl-phenyl) pentaerythritol Pentaerythritol-diphosphite such as -diphosphite: tetrakis (2,4-di-t-butylphenyl) -3,9
-Bis (1,1-dimethyl-2-hydroxyethyl) -2,4,
8,10-tetraoxaspiro [5.5] undecane-diphosphite, tetrakis (2,4-di-t-amylphenyl) -3,9-bis (1,1-dimethyl-2-hydroxyethyl)- 2,4,8,10-tetraoxaspiro [5.5] undecane-diphosphite, tetrakis (2,6-di-t-
Butyl-4-methylphenyl) -3,9-bis (1,1-dimethyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane-diphosphite, tetrakis ( 2,4,6-tri-t-butylphenyl) -3,9-
Bis (1,1-dimethyl-2-hydroxyethyl) -2,4,
8,10-tetraoxaspiro [5.5] undecane-diphosphite, tetrakis (2,4,6-tri-t-amylphenyl) -3,9-bis (1,1-dimethyl-2-hydroxyethyl) ) -2,4,8,10-Tetraoxaspiro [5.
5] Undecane-diphosphite, tetrakis (2.6
-Di-t-butyl-4-n-octadecyloxycarbonylethyl-phenyl) -3,9-bis (1,1-dimethyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro [5 .5] undecane-diphosphite, tetrakis [2,6-di-t-butyl-4- (2 ', 4'-di-t-butylphenoxycarbonyl) -phenyl] -3,9-bis (1, 1-
Dimethyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane-diphosphite, tetrakis (2,6-di-t-butyl-4-n-hexadecyloxycarbonyl) -Phenyl) -3,9-bis (1,1-
Dimethyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane-diphosphite, bis [2,2'-methylene-bis (4-methyl-6-t-
Butylphenyl)]-3,9-bis (1,1-dimethyl-2-
(Hydroxyethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane-diphosphite, bis [2,
2'-methylene-bis (4,6-di-t-butylphenyl)]
-3,9-bis (1,1-dimethyl-2-hydroxyethyl)-
2,4,8,10-tetraoxaspiro [5.5] undecane-diphosphite, bis [2,2'-methylene-bis (4,6-di-t-amylphenyl)]-3,9- Screw (1,1
-Dimethyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane-diphosphite, bis [2,2'-ethylidene-bis (4-methyl-6-t
-Butylphenyl)]-3,9-bis (1,1-dimethyl-2-
(Hydroxyethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane-diphosphite, bis [2,
2'-ethylidene-bis (4,6-di-t-butylphenyl)]-3,9-bis (1,1-dimethyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro [ 5.5] Undecane-diphosphite, bis [2,2'-ethylidene-bis (4,6-di-t-amylphenyl)]-3,9-bis (1,1-dimethyl-2-hydroxyethyl) ) -2,4,8,1
Tetraoxaspiro [5.5] undecane-diphosphite such as 0-tetraoxaspiro [5.5] undecane-diphosphite: 2,2'-bis (4,6-di-t-butylphenyl) octyl Phosphite, 2,2'-bis (4,6-di-t-butylphenyl) nonyl phosphite, 2,2'-bis (4,6-di-t-butylphenyl) lauryl phosphite, 2,2 '-Bis (4,6-di-t-butylphenyl) tridecyl phosphite, 2,2'-bis (4,6-di-t-butylphenyl) myristyl phosphite, 2,2'-bis (4 , 6-Di-t-butylphenyl) stearyl phosphite, 2,2'-bis (4,6-di-t-
Butylphenyl) (2,4-di-t-butylphenyl) phosphite, 2,2'-bis (4,6-di-t-butylphenyl) (2,6-di-t-butyl-4-methyl) Phenyl) phosphite, 2,2'-bis (4,6-di-tert-butylphenyl) (2,4,6-tri-tert-butylphenyl) phosphite, 2,2'-bis (4.6) -Di-t-butylphenyl)
(2,6-di-t-butyl-4-n-octadecyloxycarbonylethyl-phenyl) phosphite, 2,2'-bis (4,6-di-t-butylphenyl) [2,6-di- t-butyl-4- (2 ', 4'-di-t-butylphenoxycarbonyl) -phenyl] phosphite, 2,2'-bis (4.6
-Di-t-butylphenyl) (2,6-di-t-butyl-4-n-
2,2'-bis (4,6-di-t-butylphenyl) phosphite such as hexadecyloxycarbonyl-phenyl) phosphite: 2,2'-methylene-bis (4-methyl-6-t-butyl) Phenyl) octylphosphite,
2,2'-methylene-bis (4-methyl-6-t-butylphenyl) nonyl phosphite, 2,2'-methylene-bis (4-methyl-6-t-butylphenyl) lauryl phosphite, 2'-methylene-bis (4-methyl-6-t-butylphenyl) tridecyl phosphite, 2,2'-methylene-bis (4-methyl-6-t-butylphenyl) myristyl phosphite, 2,2 '-Methylene-bis (4-methyl-6-t-butylphenyl) stearyl phosphite, 2,2'-methylene-bis (4-methyl-6-t-butylphenyl) (2,4-di-t- Butylphenyl) phosphite, 2,2'-methylene-bis (4-methyl-6-t-butylphenyl) (2,6-di-t-butyl-4-methylphenyl) phosphite, 2,2'- Methylene-bis (4-methyl-6-t-butylphenyl) (2,4,6-tri-t-butyl) Phenyl) phosphite, 2,2′-methylene-bis (4-methyl-6-tert-butylphenyl) (2,6-di-tert-butyl-4-n-octadecyloxycarbonylethyl-phenyl) phosphite, 2,2'-methylene-bis (4-methyl-6-t-butylphenyl) [2,6-di-t-butyl-4
-(2 ', 4'-Di-t-butylphenoxycarbonyl) -phenyl] phosphite, 2,2'-methylene-bis (4-
Methyl-6-t-butylphenyl) (2,6-di-t-butyl-
2,2'-methylene-bis (4-methyl-) such as 4-n-hexadecyloxycarbonyl-phenyl) phosphite
6-t-butylphenyl) phosphite: 2,2'-methylene-bis (4,6-di-t-butylphenyl) octylphosphite, 2,2'-methylene-bis (4,6-di-t -
Butylphenyl) nonyl phosphite, 2,2'-methylene-bis (4,6-di-t-butylphenyl) lauryl phosphite, 2,2'-methylene-bis (4,6-di-t-
Butylphenyl) tridecylphosphite, 2,2'-
Methylene-bis (4,6-di-t-butylphenyl) myristyl phosphite, 2,2'-methylene-bis (4,6-
Di-t-butylphenyl) stearyl phosphite,
2,2'-methylene-bis (4,6-di-t-butylphenyl) (2,4-di-t-butylphenyl) phosphite,
2,2'-methylene-bis (4,6-di-t-butylphenyl) (2,6-di-t-butyl-4-methylphenyl) phosphite, 2,2'-methylene-bis (4, 6-di-t-butylphenyl) (2,4,6-tri-t-butylphenyl) phosphite, 2,2'-methylene-bis (4,6-di-t-
Butylphenyl) (2,6-di-t-butyl-4-n-octadecyloxycarbonylethyl-phenyl) phosphite, 2,2'-methylene-bis (4,6-di-t-butylphenyl) [2 , 6-Di-t-butyl-4- (2 ', 4'-di-t-
Butylphenoxycarbonyl) -phenyl] phosphite, 2,2'-methylene-bis (4,6-di-t-butylphenyl) (2,6-di-t-butyl-4-n-hexadecyloxycarbonyl- 2, such as phenyl) phosphite
2'-methylene-bis (4,6-di-t-butylphenyl) phosphite: 2,2'-methylene-bis (4,6-di-t-
Amylphenyl) octyl phosphite, 2,2'-methylene-bis (4,6-di-t-amylphenyl) stearyl phosphite, 2,2'-methylene-bis (4,6-di-
t-amylphenyl) (2,4-di-t-butylphenyl)
Phosphite, 2,2'-methylene-bis (4,6-di-t
-Amylphenyl) (2,6-di-tert-butyl-4-methylphenyl) phosphite, 2,2'-methylene-bis (4,
6-di-t-amylphenyl) (2,4,6-tri-t-amylphenyl) phosphite, 2,2'-methylene-bis (4,6-di-t-amylphenyl) (2,6 -Di-t-butyl
-4-n-octadecyloxycarbonylethyl-phenyl) phosphite, 2,2'-methylene-bis (4,6-
Di-t-amylphenyl) [2,6-di-t-butyl-4-
(2 ′, 4′-Di-t-butylphenoxycarbonyl) -phenyl] phosphite, 2,2′-methylene-bis (4,
6-di-t-amylphenyl) (2,6-di-t-butyl-4-
2,2'-methylene-bis (4,6-di-t-amylphenyl) phosphite such as n-hexadecyloxycarbonyl-phenyl) phosphite: 2,2'-ethylidene-
Bis (4-methyl-6-t-butylphenyl) octyl phosphite, 2,2'-ethylidene-bis (4-methyl-6-
t-butylphenyl) nonyl phosphite, 2,2'-
Ethylidene-bis (4-methyl-6-t-butylphenyl)
Lauryl phosphite, 2,2'-ethylidene-bis (4-methyl-6-t-butylphenyl) tridecyl phosphite, 2,2'-ethylidene-bis (4-methyl-6-t
-Butylphenyl) myristyl phosphite, 2,2 '
-Ethylidene-bis (4-methyl-6-t-butylphenyl)
Stearyl phosphite, 2,2'-ethylidene-bis (4-methyl-6-t-butylphenyl) (2,4-di-t-butylphenyl) phosphite, 2,2'-ethylidene-
Bis (4-methyl-6-t-butylphenyl) (2,6-di-
t-butyl-4-methylphenyl) phosphite, 2,
2'-ethylidene-bis (4-methyl-6-t-butylphenyl) (2,4,6-tri-t-butylphenyl) phosphite, 2,2'-ethylidene-bis (4-methyl-6- t-butylphenyl) (2,6-di-t-butyl-4-n-octadecyloxycarbonylethyl-phenyl) phosphite, 2,2'-ethylidene-bis (4-methyl-6-t-butylphenyl) [2,6-di-t-butyl-4- (2 ', 4'-di
-t-butylphenoxycarbonyl) -phenyl] phosphite, 2,2'-ethylidene-bis (4-methyl-6-t
2,2'-ethylidene-bis (4-methyl-6-t-butylphenyl) such as -butylphenyl) (2,6-di-t-butyl-4-n-hexadecyloxycarbonyl-phenyl) phosphite Phosphite: 2,2'-ethylidene-bis (4,6-di-t-butylphenyl) octyl phosphite, 2,2'-ethylidene-bis (4,6-di-t-butylphenyl) nonyl phosphite 2,2'-ethylidene
-Bis (4,6-di-t-butylphenyl) lauryl phosphite, 2,2'-ethylidene-bis (4,6-di-t-butylphenyl) tridecyl phosphite, 2,2'-ethylidene- Bis (4,6-di-t-butylphenyl) myristyl phosphite, 2,2'-ethylidene-bis (4.6
-Di-t-butylphenyl) stearyl phosphite,
2,2'-ethylidene-bis (4,6-di-t-butylphenyl) (2,4-di-t-butylphenyl) phosphite,
2,2'-ethylidene-bis (4,6-di-t-butylphenyl) (2,6-di-t-butyl-4-methylphenyl) phosphite, 2,2'-ethylidene-bis (4, 6-di-t-butylphenyl) (2,4,6-tri-t-butylphenyl)
Phosphite, 2,2'-ethylidene-bis (4,6-di-
t-butylphenyl) (2,6-di-t-butyl-4-n-octadecyloxycarbonylethyl-phenyl) phosphite, 2,2'-ethylidene-bis (4,6-di-t-butylphenyl) [2,6-di-t-butyl-4- (2 ', 4'-di
-t-butylphenoxycarbonyl) -phenyl] phosphite, 2,2'-ethylidene-bis (4,6-di-t-butylphenyl) (2,6-di-t-butyl-4-n-hexadecyl 2,2'-ethylidene-bis (4,6-di-t-butylphenyl) phosphite such as oxycarbonyl-phenyl) phosphite: 2,2'-ethylidene-bis (4,
6-di-t-amylphenyl) octyl phosphite,
2,2'-ethylidene-bis (4,6-di-t-amylphenyl) stearyl phosphite, 2,2'-ethylidene-
Bis (4,6-di-t-amylphenyl) (2,4-di-t-amylphenyl) phosphite, 2,2'-ethylidene-
Bis (4,6-di-t-amylphenyl) (2,4,6-tri-
t-Amylphenyl) phosphite, 2,2'-ethylidene-bis (4,6-di-t-amylphenyl) (2,6-di-
t-butyl-4-n-octadecyloxycarbonylethyl
-Phenyl) phosphite, 2,2'-ethylidene-bis (4,6-di-t-amylphenyl) [2,6-di-t-butyl
-4- (2 ', 4'-Di-t-butylphenoxycarbonyl)
-Phenyl] phosphite, 2,2'-ethylidene-bis (4,6-di-t-amylphenyl) (2,6-di-t-butyl
2,2'-ethylidene-bis (4,6-di-) such as -4-n-hexadecyloxycarbonyl-phenyl) phosphite
t-Amylphenyl) phosphite: 2,2'-thio-bis (4-methyl-6-t-butylphenyl) octylphosphite, 2,2'-thio-bis (4-methyl-6-t-butyl) Phenyl) nonyl phosphite, 2,2'-thio-bis (4-methyl-6-t-butylphenyl) lauryl phosphite, 2,2'-thio-bis (4-methyl-6-t-butylphenyl) Tridecyl phosphite, 2,2'-thio
-Bis (4-methyl-6-t-butylphenyl) myristyl phosphite, 2,2'-thio-bis (4-methyl-6-t
-Butylphenyl) stearyl phosphite, 2,2 '
-Thio-bis (4-methyl-6-t-butylphenyl) (2,
4-di-t-butylphenyl) phosphite, 2,2'-
Thio-bis (4-methyl-6-t-butylphenyl) (2.6
-Di-t-butyl-4-methylphenyl) phosphite,
2,2'-thio-bis (4-methyl-6-t-butylphenyl) (2,4,6-tri-t-butylphenyl) phosphite, 2,2'-thio-bis (4-methyl- 6-t-butylphenyl) (2,6-di-t-butyl-4-n-octadecyloxycarbonylethyl-phenyl) phosphite,
2'-thio-bis (4-methyl-6-t-butylphenyl)
[2,6-di-tert-butyl-4- (2 ', 4'-di-tert-butylphenoxycarbonyl) -phenyl] phosphite,
2'-thio-bis (4-methyl-6-t-butylphenyl)
2,2'-thio- such as (2,6-di-t-butyl-4-n-hexadecyloxycarbonyl-phenyl) phosphite
Bis (4-methyl-6-t-butylphenyl) phosphite: 2,2'-bis (4,6-di-t-butylphenyl) fluorophosphite, 2,2'-bis (4-methyl-6 -t-
Butylphenyl) fluorophosphite, 2,2'-bis (4-t-amyl-6-methylphenyl) fluorophosphite, 2,2'-bis (4-s-eicosylphenyl)
Fluorophosphite, 2,2'-methylene-bis (4-
Methyl-6-t-butylphenyl) fluorophosphite, 2,2'-methylene-bis (4-ethyl-6-t-butylphenyl) fluorophosphite, 2,2'-methylene
-Bis (4-methyl-6-nonylphenyl) fluorophosphite, 2,2'-methylene-bis (4,6-dinonylphenyl) fluorophosphite, 2,2'-methylene-
Bis (4-methyl-6-cyclohexylphenyl) fluorophosphite, 2,2'-methylene-bis (4-methyl
-6- (1'-Methylcyclohexyl) phenyl) fluorophosphite, 2,2'-i-propylidene-bis (4
-Nonylphenyl) fluorophosphite, 2,2'-
Butylidene-bis (4,6-dimethylphenyl) fluorophosphite, 2,2'-methylene-bis (4,6-di-t
-Butylphenyl) fluorophosphite, 2,2'-
Methylene-bis (4,6-di-t-amylphenyl) fluorophosphite, 2,2'-ethylidene-bis (4-methyl-6-t-butylphenyl) fluorophosphite,
2,2'-ethylidene-bis (4-ethyl-6-t-butylphenyl) fluorophosphite, 2,2'-ethylidene
-Bis (4-s-butyl-6-t-butylphenyl) fluorophosphite, 2,2'-ethylidene-bis (4,6-di-
t-butylphenyl) fluorophosphite, 2,2 '
-Ethylidene-bis (4,6-di-t-amylphenyl) fluorophosphite, 2,2'-methylene-bis (4-methyl-6-t-octylphenyl) fluorophosphite, 2,2'-butylidene -Bis (4-methyl-6- (1'-
Methylcyclohexyl) phenyl) fluorophosphite, 2,2'-methylene-bis (4,6-dimethylphenyl) fluorophosphite, 2,2'-thio-bis (4-
t-octylphenyl) fluorophosphite, 2,
2'-thio-bis (4,6-di-s-amylphenyl) fluorophosphite, 2,2'-thio-bis (4,6-di-i-
Octylphenyl) fluorophosphite, 2,2'-
Thio-bis (5-t-butylphenyl) fluorophosphite, 2,2'-thio-bis (4-methyl-6-t-butylphenyl) fluorophosphite, 2,2'-thio-bis (4- Methyl-6-α-methylbenzylphenyl) fluorophosphite, 2,2′-thio-bis (3-methyl-4,
6-di-t-butylphenyl) fluorophosphite,
Fluorophosphites such as 2,2'-thio-bis (4-t-amylphenyl) fluorophosphite: bis [2,2'-methylene-bis (4,6-di-t-butylphenyl)]-ethylene Glycol-diphosphite, bis [2,2'-methylene-bis (4,6-di-t-butylphenyl)]-1,4-butanediol-diphosphite, bis [2,2'-methylene- Bis (4,6-di-t-butylphenyl)]-1,6-hexanediol-diphosphite, bis [2,2'-methylene-bis (4-methyl-6-t-butylphenyl)]- 3,9-bis (1,1-dimethyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro [5.
5] Undecane-diphosphite, bis [2,2'-methylene-bis (4,6-di-t-butylphenyl)]-3,9-
Bis (1,1-dimethyl-2-hydroxyethyl) -2,4,
8,10-tetraoxaspiro [5.5] undecane-diphosphite, bis [2,2'-methylene-bis (4,6-
Di-t-amylphenyl)]-3,9-bis (1,1-dimethyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane-diphosphite, bis [2,2'-ethylidene-bis (4-methyl-6-t-butylphenyl)]-3,9-bis (1,1-dimethyl-2-hydroxyethyl) -2,4,8,10-tetra Oxaspiro [5.
5] undecane-diphosphite, bis [2,2'-ethylidene-bis (4,6-di-t-butylphenyl)]-3,
9-bis (1,1-dimethyl-2-hydroxyethyl) -2,
4,8,10-tetraoxaspiro [5.5] undecane-
Diphosphite, bis [2,2'-ethylidene-bis (4,6-di-t-amylphenyl)]-3,9-bis (1,1
-Dimethyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane-diphosphite, bis [2,2'-methylene-bis (4,6-di-t- Butylphenyl)]-N, N'-bis (2-hydroxyethyl)
Diphosphites such as oxamide-diphosphite: tris [2,2'-methylene-bis (4,6-di-t-butylphenyl)]-glycerin-triphosphite, tris [2,2'-methylene- Bis (4,6-di-t-butylphenyl)]-trimethylolethane-triphosphite, tris [2,2'-methylene-bis (4,6-di-t-butylphenyl)]-trimethylolpropane -Triphosphite, tris [2,2'-bis (4,6-di-t-butylphenyl)]-triethanolamine-triphosphite, tris [2,2'-bis (4,6-di- t-amylphenyl)]-triethanolamine-triphosphite, tris [2,2'-methylene-bis (4,6-di-t-butylphenyl)]-triethanolamine-triphosphite, tris [2 , 2'-Methylene-bis (4,6-di-t- Mill phenyl)] - triethanolamine - triforine scan phosphite, tris [2,2'-ethylidene - bis (4,6-di -
t-butylphenyl)]-triethanolamine-triphosphite, tris [2,2'-ethylidene-bis (4,
6-di-t-amylphenyl)]-triethanolamine-
Triphosphite, tris [2,2'-methylene-bis (4,6-di-t-butylphenyl)]-N, N ', N "-tris (2-hydroxyethyl) isocyanurate-triphosphite Triphosphite: tetrakis [2,2'-methylene-bis (4,6-di-t-butylphenyl)]-erythritol-tetraphosphite, tetrakis [2,2'-methylene-bis (4,6- Di-t-butylphenyl)]-pentaerythritol-tetraphosphite, bis (2,4-di-t-butyl-6-methylphenyl) ethyl phosphite, bis (2,4-di-t-butyl-6) -Methylphenyl) 2-ethylhexyl phosphite, bis (2,4-di-t-butyl-6-methylphenyl) stearyl phosphite, 2,4,6-tri-t-butylphenyl-
2-ethyl-2-butyl-1,3-propanediol phosphite and the like.

An antioxidant other than the above-mentioned phosphorus-based antioxidants can be used in combination with the composition of the present invention as long as the object of the present invention is not impaired. Examples of such an antioxidant include the conventionally known phenolic antioxidants and thio-based antioxidants used in polypropylene compositions. As thio antioxidants, for example, dimyristyl thiodipropionate, distearyl thiodipropionate, lauryl stearyl thiodipropionate, dilauryl stearyl thiodipropionate, pentaerythritol-tetrakis (3-lauryl thiopropionate) , Dioctadecyl disulfide, distearyl thiodibutyrate and the like.

These phenol and thio antioxidants can be used alone or in combination of two or more. The amount of each of these antioxidants is 0.001 to 1.5 parts by weight, preferably 0.1 to 1.5 parts by weight, based on 100 parts by weight of the polypropylene composition.
005 to 1 part by weight, particularly preferably 0.01 to 0.5 part by weight.

Various stabilizers other than the above-mentioned stabilizers can be added to the composition of the present invention, if necessary, and used in combination, as long as the object of the present invention is not impaired. Examples of such a stabilizer include a halogen scavenger having an action of scavenging halogen that is a catalyst residue, which is present in the polypropylene used in the composition of the present invention. By using a halogen scavenger, the thermal stability of the composition of the present invention,
Odor, hue, corrosiveness, weather resistance and the like can be further improved.

Examples of the halogen scavenger include metal salts of fatty acids, metal salts of alkanoyl lactic acid, metal salts of aliphatic hydroxy acids, hydrotalcites, lithium aluminum composite hydroxide salts, metal oxides, metal hydroxides, metal carbonates, Metal salts of aliphatic phosphates, epoxy compounds, aliphatic amines, aliphatic amides, hindered amine compounds, aminotriazine compounds and the like can be used. Specific halogen scavengers are listed below.

Acetic acid, propionic acid, butyric acid, valeric acid, α-
Methyl butyric acid, hexanoic acid, sorbic acid, octanoic acid, 2
-Ethylhexanoic acid, nonanoic acid, decanoic acid, caproleic acid
Acid, undecanoic acid, undecylenic acid, lauric acid,
Ndelic acid, myristic acid, fiseteric acid, myristole
Inic acid, palmitic acid, palmitoleic acid, hiragoic acid,
Stearic acid, Petroselinic acid, Oleic acid, Elage
Acid, ascrepic acid, vaccenic acid, linoleic acid, α-
Eleostearic acid, β-eleostearic acid, punica
Acid, linolenic acid, γ-linolenic acid, moloctic acid, stear
Lidonic acid, stearolic acid, arachidic acid, gadrain
Acid, gondic acid, arachidonic acid, behenic acid, setley
Acid, erucic acid, brassic acid, succinic acid, lignoseri
Acid, seracoleic acid, nisinic acid, serotinic acid,
Fats such as acid, montanic, melicic, and rume citric acids
Metal salts of fatty acids: dodecanoyl lactic acid, tetradecanoyl milk
Acids and alkanoyl lactic acids such as octadecanoyl lactic acid
Metal salts, glycolic acid, lactic acid, hydroacrylic acid, α
-Oxybutyric acid, tartronic acid, glyceric acid, apple
Acid, tartaric acid, meso-tartaric acid, grape acid, citric acid, 2-H
Doxytetradecanoic acid, iprolic acid, 2-hydroxy
Cyhexadecanoic acid, yarapinolic acid, uniperic acid,
Mbretolic acid, alluritic acid, 2-hydroxy
Octadecanoic acid, 12-hydroxyoctadecanoic acid, 1
8-hydroxyoctadecanoic acid, 9,10-dihydroxy
Octadecanoic acid, ricinoleic acid, camlorenic acid, lican
Aliphatic hydroxy such as acid, ferronic acid, cerebronic acid
Acid metal salts: alicyclic carboxylic acids such as naphthenic acid metal salts
Metal salts: aromatics such as benzoic acid and pt-butyl benzoic acid
Carboxylic acid metal salt: metal hydroxynaphthenate
Metal salts of alicyclic hydroxy acids: salicylic acid, m-hydrido
Roxybenzoic acid, p-hydroxybenzoic acid, 3,5-di-t
Aromatic hydroxy such as -butyl-4-hydroxybenzoic acid
Metal salts of silicic acid: Various amino acid metal salts: Hydrotalsa
Sites: basic aluminum, lithium, hydroxy,
Carbonate hydrate and basic aluminum
・ Lithium hydroxy sulfate hydrate
Lithium aluminum composite hydroxide salts such as: Metal oxidation
Product: Metal hydroxide: Metal carbonate: Metal phosphate: (M
(No, dimixed) hexyl phosphate, (mono, dimic)
Sud) octyl phosphate, (mono, dimixed) 2-d
Tylhexyl phosphoric acid, (mono, dimixed) decyluri
Acid, (mono, dimixed) lauryl phosphoric acid,
(No, dimixed) myristyl phosphoric acid, (mono, dimixed)
Csudo) palmityl phosphate, (mono, dimixed) sulfur
Tearyl phosphoric acid, (mono, dimixed) oleyl phosphorus
Acid, (mono, dimixed) linoleic phosphoric acid, (mono,
Dimixed) linoleyl phosphate, (mono, dimixed)
Do) docosyl phosphate, (mono, dimixed) ercil
Phosphoric acid, (mono, dimixed) tetracosyl phosphoric acid,
(Mono, dimixed) hexacosyl phosphate, (mono, dimixed)
Aliphatic phosphorus such as dimixed) octacosyl phosphate
Acid metal salts: bis (pt-butylphenyl) phosphoric acid,
No (pt-butylphenyl) phosphoric acid, 2,2'-methylene
-Bis (4,6-di-t-butylphenyl) phosphoric acid, 2,2 '
-Methylene-bis (4,6-di-t-amylphenyl) phosphorus
Acid, 2,2'-ethylidene-bis (4,6-di-tert-butyl
Enyl) phosphoric acid, 2,2'-ethylidene-bis (4,6-di-
Metals of aromatic phosphoric acid such as t-amylphenyl) phosphoric acid
Salt: Tribasic lead sulfate: hydrazone: alkene: cyclic S
Ter: Organometallic compound: Benzhydrol: Epichlor
Condensation product of hydrin and bisphenol A
Condensation product of piclorhydrin and bisphenol A, tri
Glycidyl isocyanurate, epoxidized soybean oil, epo
Epoxidation of xylated linseed oil, epoxidized castor oil, etc.
Compound: hydroxylamine: octylamine, lauryl
Amine, myristylamine, palmitylamine, steer
Lilamine, oleylamine, cocoamine, tallowami
, Soiamine, N, N-dicocoamine, N, N-ditaro
Amine, N, N-disoiamine, N-lauryl-N, N-dimethyl
Tylamine, N-myristyl-N, N-dimethylamine, N
-Palmityl-N, N-dimethylamine, N-stearyl-
N, N-dimethylamine, N-coco-N, N-dimethylami
, N-tallow-N, N-dimethylamine, N-soy-N, N-
Dimethylamine, N-methyl-N, N-ditarowamine, N
-Methyl-N, N-dicocoamine, N-oleyl-1,3-dia
Minopropane, N-tallow-1,3-diaminopropane, f
Aliphatic amines such as xamethylenediamine: N-lauryl
-N, N, N-trimethylammonium chloride, N-PA
Lumityl-N, N, N-trimethylammonium chloride
, N-stearyl-N, N, N-trimethylammonium
Chloride, N-docosyl-N, N, N-trimethylammonium
Numium chloride, N-coco-N, N, N-trimethylan
Monium chloride, N-tallow-N, N, N-trimethyl
Ammonium chloride, N-soy-N, N, N-trimethyl
Luammonium chloride, N, N, N-triethyl-N-
Benzyl ammonium chloride, N-lauryl-N, N-
Dimethyl-N-benzylammonium chloride, N-mi
Listyl-N, N-dimethyl-N-benzylammonium
Chloride, N-stearyl-N, N-dimethyl-N-benzyl
Ammonium chloride, N-coco-N, N-dimethyl-N-
Benzyl ammonium chloride, N, N-dioleyl-
N, N-dimethylammonium chloride, N, N-dicoco
-N, N-dimethylammonium chloride, N, N-dita
Wax-N, N-dimethylammonium chloride, N, N-
Diiso-N, N-dimethylammonium chloride, N, N
-Bis (2-hydroxyethyl) -N-lauryl-N-methyl
Ammonium chloride, N, N-bis (2-hydroxy
Ethyl) -N-stearyl-N-methylammonium chloride
Id, N, N-bis (2-hydroxyethyl) -N-oley
Ru-N-methylammonium chloride, N, N-bis (2
-Hydroxyethyl) -N-coco-N-methylammonium
Chloride, N, N-bis (polyoxyethylene) -N-la
Uryl-N-methylammonium chloride, N, N-bis
(Polyoxyethylene) -N-stearyl-N-methylan
Monium chloride, N, N-bis (polyoxyethylene
) -N-oleyl-N-methylammonium chloride,
N, N-bis (polyoxyethylene) -N-coco-N-methyl
Ammonium chloride such as ammonium chloride
C: N, N-bis (2-hydroxyethyl) lauryl ami
Nobetaine, N, N-bis (2-hydroxyethyl) tri
Decylaminobetaine, N, N-bis (2-hydroxy
Chill) myristylaminobetaine, N, N-bis (2-H
Droxyethyl) pentadecylaminobetaine, N, N-
Bis (2-hydroxyethyl) palmitylaminobetai
N, N-bis (2-hydroxyethyl) stearyl urea
Minobetaine, N, N-bis (2-hydroxyethyl) o
Railaminobetaine, N, N-bis (2-hydroxy
Chill) docosylaminobetaine, N, N-bis (2-hydr
Roxyethyl) octacosylaminobetaine, N, N-bi
(2-hydroxyethyl) cocoaminobetaine, N, N
-Bis (2-hydroxyethyl) tallow amino betaine
Which Betaine: Hexamethylenetetramine: Trietano
Alcohol, triisopropanolamine, etc.
Nolamine: N- (2-hydroxyethyl) lauryl
Min, N- (2-hydroxyethyl) tridecylamine,
N- (2-hydroxyethyl) myristylamine, N-
(2-hydroxyethyl) pentadecylamine, N- (2
-Hydroxyethyl) palmitylamine, N- (2-hydrido)
Roxyethyl) stearylamine, N- (2-hydroxy
Ethyl) oleylamine, N- (2-hydroxyethyl)
Docosylamine, N- (2-hydroxyethyl) octaco
Silamine, N- (2-hydroxyethyl) cocoamine,
N- (2-hydroxyethyl) tallowamine, N-methyl-
N- (2-hydroxyethyl) laurylamine, N-methyl
-N- (2-hydroxyethyl) tridecylamine, N-
Methyl-N- (2-hydroxyethyl) myristyl ami
N-methyl-N- (2-hydroxyethyl) pentadec
Luamine, N-methyl-N- (2-hydroxyethyl) pal
Mytylamine, N-methyl-N- (2-hydroxyethyl)
Stearylamine, N-methyl-N- (2-hydroxyethyl
Le) oleylamine, N-methyl-N- (2-hydroxy
Tyl) docosylamine, N-methyl-N- (2-hydroxy
Ethyl) octacosylamine, N-methyl-N- (2-hydrido)
Roxyethyl) cocoamine, N-methyl-N- (2-hydro
N- (2-hydroxye) such as xyethyl) tallowamine
Tyl) amine: N, N-bis (2-hydroxyethyl) la
Urylamine, N, N-bis (2-hydroxyethyl) tol
Ridecylamine, N, N-bis (2-hydroxyethyl)
Myristylamine, N, N-bis (2-hydroxyethyl
Le) pentadecylamine, N, N-bis (2-hydroxy
Ethyl) palmitylamine, N, N-bis (2-hydroxy
Siethyl) stearylamine, N, N-bis (2-hydro
Xyethyl) oleylamine, N, N-bis (2-hydro
Xyethyl) docosylamine, N, N-bis (2-hydro
Xyethyl) octacosylamine, N, N-bis (2-H
Droxyethyl) cocoamine, N, N-bis (2-hydro
N, N-bis (2-hydr) such as (xylethyl) tallowamine
Roxyethyl) aliphatic amines: These N, N-bis (2
-Hydroxyethyl) aliphatic amine and lauric acid, millimeter
Stinic acid, palmitic acid, stearic acid, oleic acid,
Mono or die with fatty acids such as behenic acid and erucic acid
Stell: polyoxyethylene lauryl amino ether,
Polyoxyethylene stearyl amino ether, polio
Xylene ethylene oleyl amino ether, polyoxyethylene
Lencoco amino ether, polyoxyethylene tallower
Amino ethers such as minoethers: N, N, N ', N'-
Tetra (2-hydroxyethyl) -1,3-diaminopropa
, N, N, N ', N'-tetra (2-hydroxyethyl)-
1,6-diaminohexane, N-lauryl-N, N ', N'-
Tris (2-hydroxyethyl) -1,3-diaminopropa
, N-stearyl-N, N ', N'-tris (2-hydroxy
Ciethyl) -1,3-diaminopropane, N-coco-N,
N ', N'-tris (2-hydroxyethyl) -1,3-dia
Minopropane, N-tallow-N, N ', N'-tris (2-H
Droxyethyl) -1,3-diaminopropane, N, N-di
Coco-N ', N'-bis (2-hydroxyethyl) -1,3-
Diaminopropane, N, N-ditarow-N ', N'-bis
(2-hydroxyethyl) -1,3-diaminopropane, N
-Coco-N, N ', N'-tris (2-hydroxyethyl)-
1,6-diaminohexane, N-tallow-N, N ', N'-to
Squirrel (2-hydroxyethyl) -1,6-diaminohexa
, N, N-dicoco-N ', N'-bis (2-hydroxyethyl
Le) -1,6-diaminohexane, N, N-ditarow-N ',
N'-bis (2-hydroxyethyl) -1,6-diamino
Diaminoalkyls such as xane: oleic acid amide,
Tearamide, erucamide, behenamide,
Montanamide, N-stearylstearic acid amide
Dode, N-oleyl oleamide, N-stearyl oleate
Formic acid amide, N-oleyl stearamide, N-sulfur
Tearyl erucamide, N-oleyl palmitate
Amide, N, N'-methylene-bis-lauric amide, N,
N'-methylene-bis-myristic amide, N, N'-meth
Tylene-bis-palmitic acid amide, N, N'-methylene-
Bis-palmitoleic amide, N, N'-methylene-bis
-Stearamide, N, N'-methylene-bis-12-hydro
Xiestearic acid amide, N, N'-methylene-bis-ole
Amide, N, N'-methylene-bis-behenic acid amide
, N, N'-methylene-bis-erucamide, N, N'-
Methylene-bis-montanamide, N, N'-ethylene-
Bis-lauric amide, N, N'-ethylene-bis-milli
Stinamide, N, N'-ethylene-bis-palmitic acid
Amide, N, N'-ethylene-bis-palmitoleic acid amide
, N, N'-ethylene-bis-stearic acid amide, N,
N'-ethylene-bis-12-hydroxystearic acid ami
, N, N'-ethylene-bis-oleamide, N,
N'-ethylene-bis-behenamide, N, N'-ethyl
N-bis-erucamide, N, N'-ethylene-bis-monone
Tannic acid amide, N, N'-hexamethylene-bis-stearo
Amide, N, N'-hexamethylene-bis-oleate
, N, N'-hexamethylene-bis-behenamide,
N, N'-distearyl oxalate, N, N'-diole
Iroxalic acid amide, N, N'-distearyl succinic acid
Amide, N, N'-dioleylsuccinamide, N, N'-di
Stearyl adipamide, N, N'-dioleylazi
Pinic acid amide, N, N'-distearyl sebacic acid amide
And fatty acids such as N, N'-dioleyl sebacamide
Amide: N, N-bis (2-hydroxyethyl) lauryl
Amide, N, N-bis (2-hydroxyethyl) trideci
Luamide, N, N-bis (2-hydroxyethyl) myris
Cylamide, N, N-bis (2-hydroxyethyl) pen
Tadecylamide, N, N-bis (2-hydroxyethyl)
Palmitylamide, N, N-bis (2-hydroxyethyl
Le) stearylamide, N, N-bis (2-hydroxy
Tyl) oleylamide, N, N-bis (2-hydroxy
Tyl) docosylamide, N, N-bis (2-hydroxy
Tyl) octacosylamide, N, N-bis (2-hydroxy
Siethyl) cocoamide, N, N-bis (2-hydroxyd
Tyl) aliphatic amides such as tallowamide: polyoxye
Tylene lauryl amide ether, polyoxyethylenes
Tearylamide ether, polyoxyethylene oleyl
Amide ether, polyoxyethylene cocoamidate
Oils such as polyoxyethylene tallowamide ether
Polyoxyalkylene ether of aliphatic amide: 4-Hydro
Roxy-2,2,6,6-tetramethylpiperidine, 1-ant
4-Hydroxy-2,2,6,6-tetramethylpiperidi
1-benzyl-4-hydroxy-2,2,6,6-tetrame
Cylpiperidine, 1- (4-tert-butyl-2-butenyl) -4
-Hydroxy-2,2,6,6-tetramethylpiperidine, 4
-Stearoyloxy-2,2,6,6-tetramethylpiperi
Gin, 4-methacryloyloxy-1,2,2,6,6-pen
Tamethylpiperidine, 1-benzyl-2,2,6,6-tetra
Methyl-4-piperidylmalate, bis (2,2,6,6-te
Tramethyl-4-piperidyl) succinate, bis (1,1
2,2,6,6-pentamethyl-4-piperidyl) succine
To bis (2,2,6,6-tetramethyl-4-piperidyl)
Adipate, bis (2,2,6,6-tetramethyl-4-pipe
Lysyl) sebacate, bis (2,2,6,6-tetramethyl)
-4-Piperidyl) fumarate, bis (1,2,3,6-tet)
Lamethyl-2,6-diethyl-4-piperidyl)
To bis (1-allyl-2,2,6,6-tetramethyl-4-pi
Peridyl) phthalate, bis (1,2,2,6,6-penta)
Methyl-4-piperidyl) sebacate, 1,1 '-(1,2-
Ethanediyl) bis (3,3,5,5-tetramethylpipera
Dinone) 2-methyl-2- (2,2,6,6-tetramethyl-
4-piperidyl) imino-N- (2,2,6,6-tetramethyl)
Ru-4-piperidyl) propionamide, 2-methyl-2-
(1,2,2,6,6-pentamethyl-4-piperidyl) imi
No-N- (1,2,2,6,6-pentamethyl-4-piperidi
Le) propionamide, 1-propargyl-4-β-cyanoe
Tyloxy-2,2,6,6-tetramethylpiperidine, 1-
Acetyl-2,2,6,6-tetramethyl-4-piperidyl-a
Acetate, trimellitic acid-tris (2,2,6,6-tet)
Lamethyl-4-piperidyl) ester, 1-acryloyl-
4-benzyloxy-2,2,6,6-tetramethylpiperidi
, Bis (1,2,2,6,6-pentamethyl-4-piperidi
B) dibutyl malonate, bis (1,2,2,6,6-pen)
Tamethyl-4-piperidyl) dibenzyl-malonate,
(1,2,3,6-tetramethyl-2,6-diethyl-4-pi
Peridyl) dibenzyl-malonate, bis (1,2,2,
6,6-pentamethyl-4-piperidyl) -2- (3,5-di-
t-butyl-4-hydroxybenzyl) -2-n-butylmalo
Hindered amine compounds such as catenate: bis (2,2,
6,6-tetramethyl-4-piperidyl) -1,5-dioxa
Spiro [5.5] undecane-3,3-dicarboxylate
To bis (1,2,2,6,6-pentamethyl-4-piperidi
) -1,5-dioxaspiro [5.5] undecane-3,3
-Dicarboxylate, bis (1-acetyl-2,2,6,6
-Tetramethyl-4-piperidyl) -1,5-dioxaspiro
[5.5] Undecane-3,3-dicarboxylate, 1,
3-bis [2,2 '-[bis (2,2,6,6-tetramethyl-
4-piperidyl) -1,3-dioxacyclohexane-5,5
-Dicarboxylate]], bis (2,2,6,6-tetra
Methyl-4-piperidyl) -2- [1-methylethyl [1,3
-Dioxacyclohexane-5,5-dicarboxyle
G], 1,2-bis [2,2 '-[bis (2,2,6,6-
Tramethyl-4-piperidyl) -2-methyl-1,3-dioxy
Sacyclohexane-5,5-dicarboxylate]],
(2,2,6,6-tetramethyl-4-piperidyl) -2-
[2- (3,5-di-t-butyl-4-hydroxyphenyl)
L)] ethyl-2-methyl-1,3-dioxacyclohexa
5,5-dicarboxylate, bis (2,2,6,6-te
Tramethyl-4-piperidyl) -1,5-dioxaspiro
[5.11] heptadecane-3,3-dicarboxylate
Which hindered amine compound: Hexane-1 ', 6'-
Bis- (4-carbamoyloxy-1-n-butyl-2,2,
6,6-tetramethylpiperidine), toluene-2 ', 4'
-Bis (4-carbamoyloxy-1-n-butyl-2,2,
6,6-tetramethylpiperidine), dimethyl-bis (2,
2,6,6-tetramethylpiperidine-4-oxy) -sila
Phenyl-tris (2,2,6,6-tetramethylpipe
Lysine-4-oxy) -silane, tris (1-propyl-2,
2,6,6-tetramethyl-4-piperidyl) -phosphite
, Tris (1-propyl-2,2,6,6-tetramethyl-
4-piperidyl) -phosphate, phenyl- [bis
(1,2,2,6,6-pentamethyl-4-piperidyl)]-f
Phosphonate, tetrakis (2,2,6,6-tetramethyl
Ru-4-piperidyl) -1,2,3,4-butanetetracarbo
Xylate, tetrakis (1,2,2,6,6-pentamethyl
Ru-4-piperidyl) -1,2,3,4-butanetetracarbo
Xylate, tetrakis (2,2,6,6-tetramethyl-
4-piperidyl) -1,2,3,4-butanetetracarboxylic acid
Mid, tetrakis (1,2,2,6,6-pentamethyl-4-
Piperidyl) 1,2,3,4-butanetetracarbonamide
Hindered amine compounds such as: 2-dibutylamino-
4,6-bis (9-aza-3-ethyl-8,8,10,10-tet
Lamethyl-1,5-dioxaspiro [5.5] -3-unde
Silmethoxy) -s-triazine, 2-dibutylamino-
4,6-bis (9-aza-3-ethyl-8,8,9,10,10-
Pentamethyl-1,5-dioxaspiro [5.5] -3-un
Decylmethoxy) -s-triazine, tetrakis (9-a
The-3-ethyl-8,8,10,10-tetramethyl-1,5-di
Oxaspiro [5.5] -3-undecylmethyl) -1,2,
3,4-butanetetracarboxylate, tetrakis (9
-Aza-3-ethyl-8,8,9,10,10-pentamethyl-
1,5-dioxaspiro [5.5] -3-undecylmethi
Le) -1,2,3,4-butanetetracarboxylate,
Ridecyl Tris (2,2,6,6-tetramethyl-4-pipe
Lysyl) 1,2,3,4-butanetetracarboxylate,
Tridecyl tris (1,2,2,6,6-pentamethyl-4
-Piperidyl) 1,2,3,4-butanetetracarboxyle
, Di (tridecyl) bis (2,2,6,6-tetrame
Tyl-4-piperidyl) 1,2,3,4-butanetetracarbo
Xylate, di (tridecyl) bis (1,2,2,6,6)
-Pentamethyl-4-piperidyl) -1,2,3,4-butane
Tracarboxylate, 2,2,4,4-tetramethyl-7-
Oxa-3,20-diazadispiro [5.1.1.2] hen
Eicosan-21-one, 3,9-bis [1,1-dimethyl-
2- ｛tris (2,2,6,6-tetramethyl-4-piperidi
Ruoxycarbonyl) butylcarbonyloxydiethylene
-2,4,8,10-tetraoxaspiro [5.5] un
Decane, 3,9-bis [1,1-dimethyl-2-ditris
(1,2,2,6,6-pentamethyl-4-piperidyloxy
Carbonyl) butylcarbonyloxydiethyl] -2,
4,8,10-tetraoxaspiro [5.5] undecane
Which hindered amine compound: Poly (2,2,6,6-te)
Tramethyl-4-piperidyl acrylate), poly (1,
2,2,6,6-pentamethyl-4-piperidyl acrylate
G), poly (2,2,6,6-tetramethyl-4-piperidyl)
Methacrylate), poly (1,2,2,6,6-pentamethyl)
Ru-4-piperidyl methacrylate), poly [[bis
(2,2,6,6-tetramethyl-4-piperidyl) itacone
(Vinyl butyl ether)), poly ([bis
(1,2,2,6,6-pentamethyl-4-piperidyl) ita
Conate] [vinyl butyl ether]], poly [[bis
(2,2,6,6-tetramethyl-4-piperidyl) itacone
(Vinyl octyl ether)), poly ((bis
(1,2,2,6,6-pentamethyl-4-piperidyl) ita
Conate] [vinyl octyl ether]], dimethylsa
Succinate-2- (4-hydroxy-2,2,6,6-tetrame
Hindertors such as tilpiperidyl) ethanol condensate
Min-based compound: poly [hexamethylene [(2,2,6,6-
Tetramethyl-4-piperidyl) imino]], poly [ethyl
Ren [(2,2,6,6-tetramethyl-4-piperidyl) i
Mino] hexamethylene [(2,2,6,6-tetramethyl-
4-piperidyl) imino]], poly [[1,3,5-tria
Gin-2,4-diyl] [(2,2,6,6-tetramethyl-4
-Piperidyl) imino] hexamethylene [(2,2,6,6
-Tetramethyl-4-piperidyl) imino]], poly
[[6- (diethylimino) -1,3,5-triazine-2,
4-diyl] [(2,2,6,6-tetramethyl-4-piperi
Jyl) imino] hexamethylene [(2,2,6,6-tetra
Methyl-4-piperidyl) imino]], poly [[6-
[(2-ethylhexyl) imino] -1,3,5-triazi
2,4-diyl] [(2,2,6,6-tetramethyl-4-
Piperidyl) imino] hexamethylene [(2,2,6,6-
Tetramethyl-4-piperidyl) imino]], poly [[6
-[(1,1,3,3-tetramethylbutyl) imino] -1,
3,5-triazine-2,4-diyl] [(2,2,6,6-te
Tramethyl-4-piperidyl) imino] hexamethylene
[(2,2,6,6-tetramethyl-4-piperidyl) imi
No]], poly [[6- (cyclohexylimino) -1,3,
5-triazine-2,4-diyl] [(2,2,6,6-tetra
Methyl-4-piperidyl) imino] hexamethylene
[(2,2,6,6-tetramethyl-4-piperidyl) imi
No]], poly [[6-morpholino-1,3,5-triadiene]
2,4-diyl] [(2,2,6,6-tetramethyl-4-
Piperidyl) imino] hexamethylene [(2,2,6,6-
Tetramethyl-4-piperidyl) imino]], poly [[6
-(Butoxyimino) -1,3,5-triazine-2,4-dii
L] ((2,2,6,6-tetramethyl-4-piperidyl) i
Mino] hexamethylene [(2,2,6,6-tetramethyl-
4-piperidyl) imino]], poly [[6-[(1,1,
3,3-tetramethylbutyl) oxy] -1,3,5-tria
Gin-2,4-diyl] [(2,2,6,6-tetramethyl-4
-Piperidyl) imino] hexamethylene [(2,2,6,6
-Tetramethyl-4-piperidyl) imino]]
Dartamine compounds: poly [oxy [6-[(1-pipe
Lysyl) -1,3,5-triazine-2,4-diyloxy-
1,2-ethanediyl] [(2,2,6,6-tetramethyl-
3-oxo-1,4-piperidyl) -1,2-ethanediyl]
[(3,3,5,5-tetramethyl-2-oxo-1,4-pipe
Lysyl) -1,2-ethanediyl]], poly [oxy [6-
[(1,1,3,3-tetramethylbutyl) imino] -1,
3,5-triazine-2,4-diyloxy-1,2-ethanedi
Yl] [(2,2,6,6-tetramethyl-3-oxo-1,4
-Piperidyl) -1,2-ethanediyl] [(3,3,5,5-
Tetramethyl-2-oxo-1,4-piperidyl) -1,2-d
Tandiyl]], poly [[6-[(ethylacetyl) I
Mino] -1,3,5-triazine-2,4-diyl] [(2,
2,6,6-tetramethyl-4-piperidyl) imino] hex
Samethylene [(2,2,6,6-tetramethyl-4-piperidi
Le) imino]], poly [[6-[(2,2,6,6-tetra
Methyl-4-piperidyl) butylimino] -1,3,5-tri
Azin-2,4-diyl] [(2,2,6,6-tetramethyl-
4-piperidyl) imino] hexamethylene [(2,2,6,
6-tetramethyl-4-piperidyl) imino]]
Dartamine compound: 1,6,11-tris [$ 4.6
-Bis (N-butyl-N- (2,2,6,6-tetramethyl-4-
Piperidyl) amino) -1,3,5-triazin-2-yl
Amino] undecane, 1,6,11-tris [$ 4,6-bi
(N-butyl-N- (1,2,2,6,6-pentamethyl-4-
Piperidyl) amino) -1,3,5-triazin-2-yl
Amino] undecane, 1,6,11-tris [$ 4,6-bi
(N-octyl-N- (2,2,6,6-tetramethyl-4-
Piperidyl) amino) -1,3,5-triazin-2-yl
Amino] undecane, 1,6,11-tris [$ 4,6-bi
(N-octyl-N- (1,2,2,6,6-pentamethyl-
4-piperidyl) amino) -1,3,5-triazine-2-i
[Ruamino] undecane, 1,5,8,12-tetrakis
[4,6-bis (N- (2,2,6,6-tetramethyl-4-pi
Peridyl) -butylamino) -1,3,5-triazine-2-
Yl] -1,5,8,12-tetraazadodecane, 1,5,8,
12-tetrakis [4,6-bis (N- (1,2,2,6,6-
Pentamethyl-4-piperidyl) -butylamino) -1,3,
5-Triazin-2-yl] -1,5,8,12-tetraazad
Hindered amine compounds such as decane: 2,4,6-to
Riamino-1,3,5-triazine, 2,4-diamino-6-me
Cyl-1,3,5-triazine, 2,4-diamino-6-phenyl
1,3,5-triazine, 1,4-bis (3,5-diamino
-2,4,6-triazinyl) butane, 3,9-bis [2-
(3,5-diamino-2,4,6-triazaphenyl) ethyl
L] -2,4,8,10-Tetraoxaspiro [5.5] u
Aminotriazine-based compounds such as ndecane;
Lithium, sodium, potassium
, Magnesium, calcium, strontium, burr
, Zinc or aluminum, etc.
As a metal salt, not only the normal salt but also various basic
And salts. Especially fatty acid metal salts, alkanoyl lactate gold
Genus salt, aliphatic hydroxy acid metal salt, hydrotalcite
, Lithium aluminum composite hydroxide salt, metal oxidation
Substances, metal hydroxides, metal carbonates, aliphatic metal phosphates,
Epoxy compounds, aliphatic amines, aliphatic amides, hinder
Amine compounds, aminotriazine compounds and
A mixture of two or more of these is preferred. These halogens
In addition to using the scavenger alone, two or more types of halogen
A trapping agent may be used in combination.

The amount of the halogen scavenger added is 0.0001 per 100 parts by weight of the polypropylene composition (PP) of the component A).
To 2 parts by weight, preferably 0.005 to 1.5 parts by weight, particularly preferably 0.01 to 1 part by weight.

The composition of the present invention may contain, in addition to the above-mentioned halogen scavengers, various additives usually added to polypropylene, such as light stabilizers, heavy metal deactivators, clarifiers,
Nucleating agents, lubricants, antistatic agents, antifogging agents, antiblocking agents, drip-free agents, radical generators such as peroxides, flame retardants, flame retardant aids, pigments, organic and inorganic antibacterial agents, Talc, mica, clay, wollastonite, zeolite,
Kaolin, bentonite, perlite, diatomaceous earth, asbestos, silicon dioxide, titanium dioxide, zinc sulfide, barium sulfate, magnesium sulfate, calcium silicate, aluminum silicate, glass fiber, potassium titanate, carbon fiber, carbon black, graphite and metal Inorganic filler such as fiber, silane-based, titanate-based, boron-based, aluminate-based, zircoaluminate-based coupling agent and the like, and the above-mentioned inorganic filler or wood powder surface-treated with a surface-treating agent such as a coupling agent And organic fillers such as pulp, waste paper, synthetic fibers and natural fibers can be used in combination as long as the object of the present invention is not impaired.

Olefin (co) obtained as described above
The polymer composition is heated and melted, if necessary, after blending an antioxidant, an ultraviolet absorber, an antistatic agent, a nucleating agent, a lubricant, a difficult agent, an antiblocking agent, and various synthetic resins. It can be used for the production of various molded products in the form of pellets that are mixed and further cut into granules.

The olefin (co) polymer composition itself is
Compared with olefin (co) polymer resin obtained by a generally known method, hollow molding, foam molding, suitable for extrusion molding, and,
It has a high melt tension and a high crystallization temperature capable of exhibiting high-speed productivity in other various molding methods.

In the present invention, by irradiating the olefin (co) polymer composition with ionizing radiation, a modified olefin (co) polymer composition having more excellent moldability can be obtained.
A molded article of a modified olefin (co) polymer composition having excellent physical properties such as rigidity and heat resistance can be obtained.

The modified olefin (co) polymer composition and the molded article of the modified olefin (co) polymer composition of the present invention are more excellent than the above-mentioned olefin (co) polymer composition and the molded article of the composition. In order to improve the moldability or physical properties of the molded product, the strength and crystallization temperature of the modified olefin (co) polymer composition at the time of melting, the rigidity of the modified olefin (co) polymer composition, and the heat resistance It is an essential requirement that the physical properties such as properties be improved over those of the olefin (co) polymer composition and the molded article of the composition described above.

The melt strength of the modified olefin (co) polymer composition, specifically, the melt tension at 230 ° C. (MS) at 230 ° C. for the modified propylene polymer composition as follows:
And the intrinsic viscosity [η] measured in tetralin at 135 ° C. It is preferable to satisfy the relationship expressed by log (MS)> 4.24 × log [η] −0.950.

Further, 4.24 × log [η _T ] +0.40> log (MS)>
It is preferable to have a relationship represented by 4.24xlog [η _T ] −0.950. However, strictly speaking, since the preferred strength at the time of melting differs depending on the application, the melt tension as in the above formula,
In some cases, the strength at the time of melting cannot be evaluated. For example, in the case of foam molding, when a large amount of gel is generated by adjusting the irradiation conditions such as the irradiation dose of ionizing radiation, and when the strength at the time of melting is extremely changed, the moldability is improved. There is also.

As described above, when the amount of the generated gel component is large, the melt tension cannot be measured, and the improvement of the strength during melting cannot be expressed by the above-mentioned relational expression between the melt tension and the intrinsic viscosity. In this case, as long as the moldability has been improved, it does not fall outside the scope of the present invention.

The improvement of the heat resistance and rigidity of a molded product is usually carried out by
It is preferable that a gel component is generated by appropriately adjusting conditions such as an irradiation dose of ionizing radiation, and that a crosslinked structure is introduced into a molded article. However, since the preferred rigidity and heat resistance of the molded article differ depending on the application, modification below the detection limit of the gel component may be sufficient in some cases. Also in this case, the present invention is within the scope of the present invention if the physical properties such as heat resistance and rigidity of the molded article are appropriately improved according to the use.

As the ionizing radiation used in the present invention,
Examples include α-rays, β-rays, γ-rays, X-rays, and electron beams. Preferred are γ-rays and electron beams, and most preferred in practice is electron beams. Although the irradiation dose rate of these ionizing radiations is not particularly defined, in the case of γ-rays, the irradiation dose rate is about 2.6 × 10 ⁻² C · kg ⁻¹ / h. Irradiation at an irradiation dose rate of 500 times or more of the line becomes possible. An electron beam that can be irradiated at a high dose rate is economically preferable because a large amount of the modified olefin (co) polymer composition can be obtained in a short time.

The dose of the ionizing radiation to be absorbed by the olefin (co) polymer composition is not particularly limited. However, from the viewpoint of improving the strength at the time of melting and economical efficiency, it is preferably from 0.1 to 1000.
The range of KGy is appropriate, and more preferably 0.5 kg.
~ 800 kGy, most preferably 1-600 kG
y. The physical properties such as the required strength at the time of melting, the required rigidity, and the heat resistance vary depending on the application, and accordingly, the dose of the ionizing radiation to be absorbed must be adjusted accordingly.

Here, (Gy) is generally defined as the amount of ionizing radiation that causes absorption of 1 J of energy per 1 kg of irradiated object, regardless of the radiation source. In the present invention, the absorbed dose is not directly measured, but means that the dose is absorbed by a known ordinary dosimeter placed on the surface of the irradiation object and is equivalent to the measured and displayed dose.

The temperature at which the olefin (co) polymer composition is irradiated with ionizing radiation is -10 to 80 ° C, preferably -5.
It is appropriate that the temperature is in the range of -60 ° C, particularly preferably 0-50 ° C. The irradiation can be carried out in air, but the resulting modified olefin
From the viewpoint of controllability of the intrinsic viscosity of the (co) polymer composition and improvement of physical properties such as melt strength, rigidity and heat resistance, it is preferable to carry out the reaction under an inert gas atmosphere, for example, a nitrogen atmosphere.

In some applications, the moldability of the olefin (co) polymer composition is satisfactory, and it is desired to improve only the physical properties such as rigidity and heat resistance of the molded article of the composition.
In such a case, first, the powdered olefin (co)
In the polymer composition, if necessary, a phenolic stabilizer, a phosphorus-based antioxidant, a thio-based antioxidant as described above,
Halogen supplements are added as described above, and if necessary, other antioxidants, ultraviolet absorbers, antistatic agents, nucleating agents, lubricants, difficult agents, antiblocking agents After blending various additives such as a coloring agent, an inorganic or organic filler, and various synthetic resins as required, the mixture is subjected to a usual heating kneader to form granular pellets. Next, this pelletized olefin
After molding the (co) polymer composition according to various applications, the olefin (co) polymer composition molded article is irradiated with ionizing radiation, whereby the physical properties such as rigidity and heat resistance are improved. Obtaining the modified olefin (co) polymer composition molded article is also one method of the present invention. In this case, the irradiation dose, the irradiation temperature, the irradiation atmosphere, and other conditions can be the same as those used for irradiation of the olefin (co) polymer composition.

In the method of the present invention, the object to be irradiated after the above-mentioned ionizing radiation irradiation is subsequently subjected to a heat treatment at a temperature of 60 to 350 ° C., preferably 80 to 300 ° C.
The heat treatment is performed for the purpose of eliminating residual radicals in the irradiation object. One embodiment of the heat treatment is performed using a melt kneader at 190 to 350 ° C, more preferably 190 to 350 ° C.
Heat melting and kneading at 0 ° C, most preferably 200 to 280 ° C. The melt-kneading time varies depending on the melt-kneader and is not specified, but usually about 20 seconds to 30 minutes is sufficient. Usually, after melt-kneading, it is subsequently cut into granules and pelletized. As the melt kneader, a known ordinary melt kneader is used. For example, a single-screw extruder, a twin-screw extruder, an extruder combining these with a gear pump, a Brabender, a Banbury mixer, and the like. In addition, at the time of melt-kneading, if necessary, before heating and melting, the above-described antioxidant, ultraviolet absorber, antistatic agent, nucleating agent, lubricant, flame retardant, anti-blocking agent, coloring agent, inorganic material Alternatively, various additives such as an organic filler can be blended.

As another mode of the heat treatment, 80 to 150
There is a method of performing heat treatment at a temperature of 100 ° C, more preferably 100 to 150 ° C. This embodiment is a preferred embodiment when the resulting modified olefin (co) polymer composition is used in the form of a powder for the production of a molded article. 80-150 ° C
Is a further preferred embodiment of the present invention.

The above-mentioned heat treatment can be carried out even in the air. However, the controllability of the intrinsic viscosity of the resulting modified olefin (co) polymer composition and the improvement of the strength at the time of melting can be obtained. From the viewpoint of improving physical properties such as rigidity and heat resistance of the molded article of the modified olefin (co) polymer composition, it is more preferable to carry out the reaction under an inert gas atmosphere, for example, a nitrogen atmosphere.

If the heat treatment is not carried out, the resulting modified olefin (co) polymer composition becomes unstable with large deterioration over time. The modified olefin (co) polymer composition obtained by the above method, the modified olefin (co) polymer composition molded article must have the above-mentioned essential requirements in order to achieve the object of the present invention. Must.

The modified olefin of the present invention thus obtained
The (co) polymer composition has improved melt strength such as melt tension and crystallization temperature, and is excellent in moldability, and also the modified olefin (co) polymer composition of the present invention thus obtained. Molded products have excellent physical properties such as rigidity and heat resistance, so they can be used for hollow molding, foam molding, extrusion molding, thermoforming, injection molding, and T-molding.
It can be used for various industrial parts, various containers such as hollow containers, and various molded products such as films, sheets, pipes, and fibers by die molding and the like.

[0145]

The present invention will be described below in more detail with reference to Examples and Comparative Examples. However, the present invention is not limited to the following examples.

The definitions of the terms used in the examples and comparative examples and the measuring method are as follows. In the following Examples and Comparative Examples, polypropylene may be abbreviated as PP and polyethylene may be abbreviated as PE. (1) Intrinsic viscosity [η]: The intrinsic viscosity in tetralin at 135 ° C was measured using an Ostwald viscometer (Mitsui Toatsu Chemical Co., Ltd.)
(Unit: dl / g). (2) Melt tension (MS): Melt tension tester type 2
A value (unit: cN) measured by (manufactured by Toyo Seiki Seisaku-sho, Ltd.). (3) Crystallization temperature (Tc): DSC type 7 differential scanning calorimeter
The temperature of the polypropylene composition was raised from room temperature to 230 ° C. under a temperature rising condition of 30 ° C./min by using (Perkin-Elmer Co.), and maintained at the same temperature for 10 minutes, followed by −20 ° C./min.
After the temperature was lowered to 0 ° C and kept at the same temperature for 10 minutes,
The temperature was raised to 230 ° C. under a temperature rising condition of ° C./min, kept at the same temperature for 10 minutes, then lowered to −150 ° C. at −80 ° C./min. Measured temperature that shows the maximum peak of the heat of absorption during crystallization while decreasing the temperature
(Unit: ° C). (4) Gel fraction: Pellet or test piece resin was finely cut and placed in a 500 mesh wire mesh.
Extraction was performed with boiling xylene for 24 hours, the extraction residue was calculated, and this was evaluated as a gel fraction (%) and used as an index of the degree of crosslinking. (5) Heating behavior of the sheet: A sheet having a thickness of 0.4 mm is used as a sample sheet. This sample sheet is opened at 300 × 30
The sample sheet is fixed to a frame having a size of 0 mm, and the fixed sample sheet is held horizontally in a heating furnace maintained at 180 ° C. for a certain time.

When the above-mentioned evaluation is performed on a sheet using a polyolefin resin and its composition, the following phenomena generally occur. First, the central portion of the sheet hangs down when heated first. Next, a part of the sag returns, and the returned state continues for a certain period of time. Finally, the sagging occurs again and does not return again.

The amount of the initial sag was defined as the "amount of sag" (mm). The “holding time” (seconds) is the time during which the part of the sagging has returned.
And The “return rate” (%) was determined from the following equation. [{Amount of part of sagging caused return (mm)} /
{Amount initially sagged (mm)}] × 100 These “sag amount”, “return rate”, and “holding time” were used as indices for evaluating the formability of the sheet.

[0149]

Example 1 (1) Adjustment of transition metal compound catalyst component Decane 0. 1 in a stainless steel reactor equipped with a stirrer.
3 liters, 48 g of anhydrous magnesium chloride, 170 g of n-butyl orthotitanate and 195 g of 2-ethyl-1-hexanol were mixed, and the mixture was heated to 130 ° C. while stirring.
The mixture was heated for a period of time to dissolve to form a uniform solution. This homogeneous solution was heated to 70 ° C., 18 g of di-i-butyl phthalate was added with stirring, and after 1 hour, 520 g of silicon tetrachloride was added over 2.5 hours to precipitate a solid.
For 1 hour. The solid was separated from the solution and washed with hexane to give a solid product.

The total amount of the solid product was mixed with 1.5 liter of titanium tetrachloride dissolved in 1.5 liter of 1,2-dichloroethane, and 36 g of di-i-butyl phthalate was added. After the reaction, the liquid phase was removed by decantation at the same temperature, and 1.5 l of 1,2-dichloroethane and 1.5 l of titanium tetrachloride were added again. 2.8% by weight of titanium
, A titanium-containing supported catalyst component (transition metal compound catalyst component).

(2) Preparation of preactivated catalyst After replacing a stainless steel reactor having an internal volume of 5 liters with inclined blades with nitrogen gas, 2.8 liters of n-hexane was added.
Triethyl aluminum (organic metal compound (AL1))
9.0 g of 4 mmol and the titanium-containing supported catalyst component prepared in the preceding paragraph (5.26 mmol in terms of titanium atoms)
After the addition, 20 g of propylene was supplied, and prepolymerization was performed at −2 ° C. for 10 minutes.

Separately, when the polymer produced by the prepolymerization performed under the same conditions was analyzed, 2 g of propylene was converted to polypropylene (B) per 1 g of the titanium-containing supported catalyst component, and the polypropylene (B) was dissolved in tetralin at 135 ° C. The intrinsic viscosity [η _B ] measured at 2.8 dl / g
Met.

After the completion of the reaction time, unreacted propylene was discharged to the outside of the reactor, and the gas phase of the reactor was replaced with nitrogen once. Ethylene was continuously supplied to the reactor for 2 hours so that the internal pressure was maintained at 0.59 MPa to perform preactivation.

Separately, as a result of analyzing the polymer formed by the preactivation polymerization performed under the same conditions, 24 g of the polymer was present per 1 g of the titanium-containing supported catalyst component, and the polymer was measured in tetralin at 135 ° C. The intrinsic viscosity [η _T2 ] was 31.4 dl / g.

The amount (W ₂ ) of polyethylene (A) per 1 g of the titanium-containing supported catalyst component produced by the preactivation polymerization with ethylene is the amount of the polymer produced per 1 g of the titanium-containing supported catalyst component after the preactivation treatment. The difference between (W _T2 ) and the amount of polypropylene (B) produced per gram of the titanium-containing supported catalyst component after prepolymerization (W1) is determined by the following equation.

[0156] W ₂ = W _T2 -W ₁ The intrinsic viscosity of the polyethylene produced in the preliminary activating polymerization with ethylene _(A) [η A] has an intrinsic viscosity [eta _B of the polypropylene produced in the preliminary polymerization (B) ] And the intrinsic viscosity [ηT ₂ ] of the polymer formed by the pre-activation treatment are determined by the following equation.

[Η _A ] = ([η _T2 ] × W _T2 − [η _B ] × W ₁ ) /
(W _T2 −W ₁ ) = [η _E ] According to the above equation, the amount of polyethylene (A) produced by preactivated polymerization with ethylene is 22 g per 1 g of the titanium-containing supported catalyst component, and the intrinsic viscosity [η _A ] is 34. 0 dl / g
Met.

After completion of the reaction time, unreacted ethylene was discharged to the outside of the reactor, and the gas phase of the reactor was replaced with nitrogen once, and then diisopropyldimethoxysilane (electron donor (E1)) was introduced into the reactor. After adding 1.6 mmol, 20 g of propylene was supplied, and the mixture was kept at 1 ° C. for 10 minutes to perform addition polymerization after the preactivation treatment.

Separately, the results of analysis of the polymer formed by addition polymerization performed under the same conditions show that the intrinsic viscosity of 26 g of the polymer per 1 g of the titanium-containing supported catalyst component was measured in tetralin at 135 ° C. [η _T3 ] is 2
9.2 dl / g, the amount of polypropylene produced by addition polymerization calculated in the same manner as above (W ₃ )
Was 2 g per 1 g of the titanium-containing supported catalyst component, and the intrinsic viscosity [η _C ] was 2.8 dl / g.

After the completion of the reaction time, unreacted propylene was discharged outside the reactor, and the gas phase of the reactor was replaced with nitrogen once.
A preactivated catalyst slurry for the main (co) polymerization was obtained. (3) Production of polypropylene composition (propylene book
(Co-polymerization) After replacing the stainless steel polymerization vessel with a stirrer having an inner volume of 500 l with nitrogen, n-hexane 24 at 20 ° C.
0 liter, 780 mmol of triethylaluminum (organic metal compound (AL2)), 78 mmol of diisopropyldimethoxysilane (electron donor (E2)) and 1/2 of the pre-activated catalyst slurry obtained above were introduced into the polymerization vessel. did. Subsequently, 15 liters of hydrogen was introduced into the polymerization vessel, and the temperature was raised to 70 ° C. Then, propylene was continuously fed under a polymerization temperature of 70 ° C while maintaining the gas phase pressure in the polymerization vessel at 0.79 MPa. For 2 hours to carry out main polymerization of propylene.

After the elapse of the polymerization time, 1 liter of methanol was introduced into the polymerization vessel, and the catalyst deactivation reaction was carried out at 70 ° C. for 15 minutes. Subsequently, after unreacted gas was discharged, the solvent was separated and the polymer was dried. And the intrinsic viscosity [η _T ] is 2.73 dl / g
40.1 Kg of a polymer were obtained. The obtained polymer is a polypropylene composition having a polyethylene (A) content of 0.25% by weight corresponding to the preactivated polymerization corresponding to the component (a), and the intrinsic viscosity [η _p ] of the polypropylene as the component (b).
Was 2.65 dl / g.

Similarly, 2,6-di-t-butyl-butyl was added to 100 parts by weight of the separately prepared polypropylene composition.
0.1 parts by weight of p-cresol and 0.1 parts by weight of calcium stearate are mixed, and the mixture is mixed with a screw having a screw diameter of 4 parts.
It granulated at 230 degreeC using the 0-mm extrusion granulator, and was set as the pellet. When various physical properties of the pellets were evaluated and measured, the MFR was 0.50 g / 10 min, the crystallization temperature was 116.8 ° C., and the melt tension (MS) was 9.0 cN. Other detailed physical properties are shown in Table 1.

(4) Electron Beam Irradiation of Powder of Polypropylene Composition 200 g of the obtained powder of the propylene polymer composition was put in a bag made of polyethylene terephthalate with a cock. Next, the operation of evacuating the inside of the bag and then supplying nitrogen gas to the atmospheric pressure is repeated 10 times to make the inside of the bag a nitrogen gas atmosphere,
The bag was fixed on the electron beam irradiation conveyor so that the thickness of the polypropylene composition became 1 cm.

For electron beam irradiation, a Cockcroft-Walton type electron beam accelerator was used, and the acceleration voltage was 2 MV and the current value was 1.
Under a condition of 0 mA, a portion 20 cm below the irradiation window was passed through the conveyor so that the absorbed dose of the propylene polymer composition contained in the polyethylene terephthalate bag on the conveyor was 10.0 kGy (conveyor speed: 0.97 m / min). The temperature during irradiation at this time was 25 ° C.

Subsequently, the polypropylene composition after the electron beam irradiation was carried into an oven in a state of nitrogen atmosphere in a polyethylene terephthalate bag, and heat-treated in the oven at 135 ° C. for 30 minutes. As a result, a powder of the modified polypropylene composition was obtained.

(5) Granulation of powder of modified polypropylene composition To 100 parts by weight of the polypropylene composition obtained in the same manner up to the irradiation step, tetrakis [methylene-3-
(3'-5'-di-t-butyl-4'-hydroxyphenyl)
[Propionate] 0.1 part by weight of methane and 0.1 part by weight of calcium stearate are mixed, and the mixture is melt-kneaded at 230 ° C. using an extrusion granulator having a screw diameter of 40 mm, granulated, and pelletized to form a modified polypropylene composition. I got something.

The pellets were evaluated for various physical properties. The MFR was 0.80 g / 10 minutes, the crystallization temperature was 133.4 ° C., and the melt tension (MS) was 13.0 cN. Other detailed physical properties are shown in Table 1.

By irradiating the electron beam, the melt tension,
It was confirmed that the crystallization temperature was significantly improved.

[0169]

Example 2 A pellet-like polypropylene composition obtained in the same manner as in Example 1 was obtained, and a JIS type test piece was prepared from the pellets using an injection molding machine at a molten resin temperature of 230 ° C and a mold temperature of 50 ° C. . The test piece was put in a bag made of polyethylene terephthalate with a cock. Then, the operation of evacuating the inside of the bag and then supplying nitrogen gas to atmospheric pressure was repeated 10 times to make the inside of the bag a nitrogen gas atmosphere, and the bag was fixed on a conveyor for electron beam irradiation.

For electron beam irradiation, a Cockcroft-Walton type electron beam accelerator was used, and the acceleration voltage was 2 MV and the current value was 1.
Under the condition of 0 mA, the absorbed dose of the propylene polymer composition in a polyethylene terephthalate film bag on the conveyor 20 cm below the irradiation window was 200 kGy.
(Conveyor speed: 0.97 m / min). The temperature during irradiation at this time was 25 ° C.

Subsequently, the test piece of the polypropylene composition after the electron beam irradiation was carried into an oven under a nitrogen atmosphere in a bag made of a polyethylene terephthalate film, and was placed in the oven under a temperature condition of 135 ° C.
A heat treatment for 30 minutes gave a test piece of the modified polypropylene composition.

The test piece was evaluated for various physical properties and found to have an MFR of 1.50 g / 10 minutes, a crystallization temperature of 131.0 ° C., and a gel fraction of 35.0%.
Other detailed physical properties are shown in Table 1.

The irradiation with an electron beam greatly increased the crystallization temperature and the gel fraction as high as 35.0%. Therefore, a crosslinked structure was introduced, which contributed to the improvement in rigidity. Was confirmed.

[0174]

Comparative Example 1 In Example 1 (2), 220 g of propylene was replaced by 80 g at the start of the preactivation polymerization, and 80 g 30 minutes after the start, instead of the preactivation polymerization by ethylene.
A powdery polypropylene composition was prepared in the same manner as in Example 1 except that 60 g after the start, 60 g of the mixture was fed into the reactor in three portions, and the electron beam irradiation step (4) was omitted. , And then a pelletized polypropylene composition was obtained.

The pellets were evaluated for various physical properties and found to have an MFR of 0.50 g / 10 minutes, a crystallization temperature of 114.5 ° C., and a melt tension of 4.1 cN. Other detailed physical properties are shown in Table 1.

The crystallization temperature and the melt tension are significantly lower than those of the polypropylene composition before irradiation obtained in the step (3) of Example 1 and the modified polypropylene composition finally obtained in Example 1. You can see that.

[0177]

Comparative Example 2 An electron beam irradiation step similar to that of Example 1 was performed, except that a sample obtained in the same manner as the powdery polypropylene composition obtained in Comparative Example 1 was used. A pellet-shaped polypropylene composition was obtained.

Various physical properties of the pellets were evaluated and measured. The MFR was 1.30 g / 10 minutes, the crystallization temperature was 120.5 ° C., and the melt tension was 2.8 cN. Other detailed physical properties are shown in Table 1.

It can be seen that the crystallization temperature and the melt tension are significantly lower than those of Example 1.

[0180]

Comparative Example 3 A polypropylene composition pellet obtained in the same manner as in Comparative Example 1 was melted at a molten resin temperature of 23 using an injection molding machine.
A JIS test piece was prepared at 0 ° C. and a mold temperature of 50 ° C. The test piece was put in a bag made of polyethylene terephthalate with a cock. Then, the operation of evacuating the inside of the bag and then supplying nitrogen gas to atmospheric pressure was repeated 10 times to make the inside of the bag a nitrogen gas atmosphere, and the bag was fixed on a conveyor for electron beam irradiation.

For electron beam irradiation, a Cockcroft-Walton type electron beam accelerator was used, at an acceleration voltage of 2 MV and a current value of 1.
Under a condition of 0 mA, a portion 20 cm below the irradiation window was passed through the conveyor so that the absorbed dose of the propylene polymer composition contained in the polyethylene terephthalate bag on the conveyor was 200 kGy (conveyor speed:
0.97 m / min). The temperature during irradiation at this time was 25 ° C.

Subsequently, the test piece of the polypropylene composition after the electron beam irradiation was carried into an oven under a nitrogen atmosphere in a bag made of polyethylene terephthalate, and was placed in the oven at a temperature of 135 ° C. for 30 minutes. A heat treatment was performed for a minute to obtain a test piece of the irradiated polypropylene composition.

Various physical properties of the test piece were evaluated and measured. The MFR was 1.70 g / 10 minutes, the crystallization temperature was 130.2 ° C., and the gel fraction was 10.2%. Other detailed physical properties are shown in Table 1. It can be seen that the gel fraction was low and the electron beam irradiation efficiency was inferior to Example 2.

[0184]

Comparative Example 4 In Example 1 (2), except that the preactivated polymerization with ethylene was not performed, and the electron beam irradiation step of (4) was omitted, the same procedure as in Example 1 was carried out. To obtain a powdery polypropylene composition,
A pelletized polypropylene composition was obtained.

The pellets were evaluated for various physical properties. The MFR was 0.50 g / 10 minutes, the crystallization temperature was 114.5 ° C., and the melt tension was 4.1 cN. Other detailed physical properties are shown in Table 1.

The crystallization temperature and the melt tension are significantly lower than those of the polypropylene composition before irradiation obtained in the step (3) of Example 1 and the modified polypropylene composition finally obtained in Example 1. You can see that.

[0187]

[Table 1]

[0188]

Comparative Example 5 The same procedure as in Example 1 was repeated except that the powdery polypropylene composition obtained in Comparative Example 4 was used as a sample, and the pellets were obtained through the following steps. A polypropylene composition was obtained.

The pellets were evaluated for various physical properties and found to have an MFR of 1.30 g / 10 min, a crystallization temperature of 120.5 ° C., and a melt tension of 2.8 cN. Other detailed physical properties are shown in Table 2. It can be seen that the crystallization temperature and the melt tension are significantly lower than those of Example 1.

[0190]

COMPARATIVE EXAMPLE 6 Except that a powdery polypropylene composition obtained in Comparative Example 4 was used in the same manner as in Example 2, the same procedure as in Example 2 and Comparative Example 3 was carried out. A test piece of the polypropylene composition was obtained.

Various physical properties of the test piece were evaluated and measured. The MFR was 1.70 g / 10 minutes, the crystallization temperature was 130.0 ° C., and the gel fraction was 10.0%. Other detailed physical properties are shown in Table 2. It can be seen that the gel fraction was significantly lower than in Example 2, and the electron beam irradiation efficiency was inferior to Example 2.

[0192]

Comparative Example 7 In Example 1 (2), the prepolymerization and addition polymerization with propylene were omitted, and only the preactivation polymerization with ethylene was performed. One liter of methanol was added to the obtained preactivated catalyst slurry, and the catalyst was deactivated at 70 ° C. for 1 hour. After completion of the reaction, polyethylene was separated from the slurry by filtration and dried under reduced pressure,
Polyethylene 20 having an intrinsic viscosity [η _A ] of 34.0 dl / g
0 g was obtained.

In Example 1, 20 kg of polypropylene obtained by main polymerization of propylene and 50 g of the above-prepared polyethylene were mixed, omitting the pre-activation polymerization using ethylene and the addition polymerization using propylene in (2). The same irradiation step as in Example 1 was performed.
After adding 20 g of -di-t-butyl-p-cresol and 20 g of calcium stearate and mixing for 3 minutes using a Henschel mixer having an internal volume of 100 liters, the mixture was subjected to 230 g using an extrusion granulator having a screw diameter of 40 mm.
Pellets were obtained by granulation at ℃.

When various physical properties of the pellets were evaluated and measured, the MFR was 0.51 g / 10 min, and the melt tension (M
S) was 4.1 cN, and the crystallization temperature was 115.0 ° C. Other detailed physical properties are shown in Table 2.

The crystallization temperature and melt tension are significantly lower than the polypropylene composition before irradiation obtained in step (3) of Example 1 and the modified polypropylene composition finally obtained in Example 1. You can see that.

[0196]

Comparative Example 8 Except that a powdery polypropylene composition obtained in Comparative Example 7 was used in the same manner as in Example 1, except that a powdery polypropylene composition was used as a sample, pellets were obtained through the following steps of electron beam irradiation. A polypropylene composition was obtained.

Various physical properties of the pellets were evaluated and measured. As a result, the MFR was 1.30 g / 10 minutes, the crystallization temperature was 121.0 ° C., and the melt tension was 2.8 cN. Other detailed physical properties are shown in Table 2. It can be seen that the crystallization temperature and the melt tension are significantly lower than those of Example 1.

[0198]

COMPARATIVE EXAMPLE 9 Except that a powdery polypropylene composition obtained in Comparative Example 7 was used as a sample, the same procedure as in Example 2 and Comparative Example 3 was carried out. A test piece of the polypropylene composition was obtained.

Various physical properties of the test piece were evaluated and measured. As a result, the MFR was 1.70 g / 10 minutes, the crystallization temperature was 130.2 ° C., and the gel fraction was 12.2%. Other detailed physical properties are shown in Table 2. It can be seen that the gel fraction was significantly lower than in Example 2, and the electron beam irradiation efficiency was inferior to Example 2.

[0200]

[Table 2]

[0201]

Example 3 A pellet-shaped modified polypropylene composition obtained in the same manner as in Example 1 was used.
With a 5 mm T-die sheet molding machine, the resin temperature is 230 ° C,
A sheet was prepared at a cooling temperature of 60 ° C. so as to have a sheet thickness of 0.4 mm. Table 3 collectively shows heating behavior data indicating the formability of the sheet at this time.

The amount of droop was small, the reversion rate was 100%, and the holding time was as long as 150 seconds. Thus, the sheet exhibited excellent sheet formability, particularly suitable for thermoforming large sheets.

[0203]

Comparative Example 10 A sheet thickness of 0.4 mm was obtained in the same manner as in Example 3, except that a pellet obtained in the same manner as the polypropylene composition pellet before irradiation obtained in the step (3) of Example 1 was used. A sheet was created so that Table 3 shows the heating behavior data indicating the sheet formability at this time.
Are shown together. It shows good moldability, but is slightly inferior to Example 3.

[0204]

Comparative Example 11 A sheet was prepared to have a sheet thickness of 0.4 mm in the same manner as in Example 3 except that a pellet obtained in the same manner as the polypropylene composition pellet obtained in Comparative Example 1 was used. . Table 3 collectively shows heating behavior data indicating the formability of the sheet at this time. It can be seen that the moldability was considerably inferior to that of Example 3.

[0205]

Comparative Example 12 A sheet having a sheet thickness of 0.4 m was obtained in the same manner as in Example 3 except that a pellet obtained in the same manner as the polypropylene composition pellet finally obtained in Comparative Example 2 was used.
m was prepared. Table 3 collectively shows heating behavior data indicating the formability of the sheet at this time. It can be seen that the moldability is considerably inferior to that of Example 3.

[0206]

Comparative Example 13 A sheet was prepared in the same manner as in Example 3 except that a pellet obtained in the same manner as the polypropylene composition pellet obtained in Comparative Example 4 was used so that the sheet thickness was 0.4 mm. Table 3 collectively shows heating behavior data indicating the formability of the sheet at this time. Example 3
It can be seen that the moldability was considerably inferior to that of.

[0207]

Comparative Example 14 A sheet having a sheet thickness of 0.4 m was obtained in the same manner as in Example 3 except that a pellet obtained in the same manner as the polypropylene composition pellet finally obtained in Comparative Example 5 was used.
m was prepared. Table 3 collectively shows heating behavior data indicating the formability of the sheet at this time. It can be seen that the moldability is considerably inferior to that of Example 3.

[0208]

Comparative Example 15 A sheet was prepared in the same manner as in Example 3 except that a pellet obtained in the same manner as the polypropylene composition pellet obtained in Comparative Example 7 was used so that the sheet thickness was 0.4 mm. Table 3 collectively shows heating behavior data indicating the formability of the sheet at this time. It can be seen that the moldability is considerably inferior to that of Example 3.

[0209]

Comparative Example 16 A sheet having a sheet thickness of 0.4 m was prepared in the same manner as in Example 3 except that a pellet obtained in the same manner as the polypropylene composition pellet finally obtained in Comparative Example 8 was used.
m was prepared. Table 3 collectively shows heating behavior data indicating the formability of the sheet at this time. It can be seen that the moldability was considerably inferior to that of Example 3.

[0210]

[Table 3]

[0211]

As described above, according to the present invention, a high-molecular-weight polyethylene is formed by preliminary polymerization, and this is added during the main polymerization of an olefin such as polypropylene, and the high-molecular-weight polyethylene is converted to a polyolefin such as polypropylene. The olefin (co) polymer composition, which is finely dispersed as fine particles, is irradiated with ionizing radiation, and subsequently heat-treated to modify the composition. Further improve the crystallization temperature,
Modified olefin (co) polymer composition excellent in moldability such as high-speed productivity, and heat-resistant, modified olefin (co) polymer composition molded articles excellent in physical properties such as rigidity and methods for producing them Can be provided.

Claims (31)

[Claims] 1. A modified olefin (co) polymer composition, comprising (a) an ethylene homopolymer or an ethylene polymerized unit comprising 50
A high-molecular-weight polyethylene having an intrinsic viscosity [η _E ] of at least 135 ° C. in the range of 15 to 100 dl / g.
0.01 to 5.0 parts by weight, and (b) 100 parts by weight of an olefin other than the high molecular weight polyethylene (co) polymer, (c) and the high molecular weight polyethylene has a number average particle diameter of 1 to 5000 nm.
The modified olefin (co) polymer composition obtained by irradiating ionizing radiation to the olefin (co) polymer composition finely dispersed as fine particles in the range of 1) and subsequently subjecting the composition to heat treatment. 2. The ionizing radiation is at least one selected from a γ-ray and an electron beam, and the dose of the ionizing radiation is
The modified olefin (co) polymer composition according to claim 1, wherein the composition is in the range of 0.1 to 1000 KGy. 3. The modified olefin (co) polymer composition according to claim 1, wherein the number average particle diameter of the high molecular weight polyethylene is in the range of 10 to 500 nm. 4. The modified olefin according to claim 1, wherein an intrinsic viscosity [η] of the olefin (co) polymer composition measured with tetralin at 135 ° C. is in a range of 0.2 to 10 dl / g.
(Co) polymer compositions. 5. An olefin other than high molecular weight polyethylene
The modified olefin according to claim 1 or 2, wherein the (co) polymer is at least one selected from a propylene homopolymer or a propylene-olefin copolymer containing at least 50% by weight of propylene polymerized units. (Co) polymer compositions. 6. The modified olefin according to claim 1, wherein the high-molecular-weight polyethylene fine particles are added before or during olefin (co) polymerization.
(Co) polymer compositions. 7. The modified olefin (co) polymer, wherein the olefin (co) polymer is at least one polymer selected from a propylene homopolymer and a propylene-olefin copolymer containing at least 50% by weight of propylene polymer units. 3. The polymer composition according to claim 1, having a relationship represented by the following formula (1) between the melt tension (MS) at 230 ° C. and the intrinsic viscosity [η _T ] measured at 135 ° C. 3. Modified olefins
(Co) polymer compositions. Embedded image log (MS)> 4.24 × log [η _T ] −0.950 8. The modified olefin (co) polymer composition, wherein the olefin (co) polymer is a propylene homopolymer or a propylene-olefin copolymer containing 50% by weight or more of propylene polymer units. Melt tension at ℃ (M
The modified olefin (co) polymer composition according to claim 1 or 2, having a relationship represented by the following formula (Chemical Formula 2) between S) and the intrinsic viscosity [η _T ] measured at 135 ° C. . Embedded image 4.24xlog [η _T ] +0.40> log (MS)> 4.24xlog
[η _T ] -0.950 9. The modified olefin (co) according to claim 1 or 2, wherein the olefin (co) polymer is an ethylene homopolymer or an ethylene-olefin copolymer containing 50% by weight or more of ethylene polymerized units. Polymer composition. 10. A modified olefin (co) polymer composition 100.
At least one stabilizer selected from phenol-based antioxidants and phosphorus-based antioxidants is added to parts by weight.
3. The modified olefin (co) polymer composition according to claim 1, wherein 0.001 to 2 parts by weight are added. 11. An olefin (co) polymer other than a high-molecular-weight polyethylene is a propylene homopolymer or a propylene-olefin copolymer containing 50% by weight or more of propylene polymerized units, wherein a transition metal compound catalyst component, a transition metal atom Periodic table of 0.01 to 1,000 moles per mole (1991 version) No. 1
Group, a group 2 metal, an organometallic compound of a metal selected from the group consisting of metals belonging to group 12 and group 13 (AL1) and 0 to 500 moles of an electron donor (E1) per mole of a transition metal atom In the presence of a polyolefin production catalyst consisting of a combination of, and a pre-activated catalyst containing polyethylene supported on this catalyst, propylene alone or propylene and other olefins having 2 to 12 carbon atoms, the present (co) The modified olefin (co) polymer composition according to claim 1, which is produced by polymerization. 12. The periodic table (1991 version) is used for the preactivated catalyst.
Organometallic compound (AL1) of a metal contained in the preactivation catalyst comprising an organometallic compound of a metal selected from the group consisting of metals belonging to Group 1, Group 2, Group 12 and Group 13 (AL2) Per mole of transition metal atoms in the preactivated catalyst
0.05 to 5,000 mol, and further contains 0 to 3,000 mol per mol of transition metal atom in the preactivated catalyst in total of the electron donor (E2) and the electron donor (E1) contained in the preactivated catalyst. In the presence of the olefin main (co) polymerization catalyst
Propylene alone or propylene and other carbon number 2-1
The modified olefin (co) polymer composition according to claim 11, wherein the olefin (2) is subjected to main (co) polymerization. 13. The preactivated catalyst may be a polyethylene having an intrinsic viscosity [η _A ] of 15 to 100 dl / g in tetralin at 135 ° C. per 1 g of the transition metal compound catalyst component.
13. The modified olefin (co) polymer composition according to claim 1, which carries 000 g. 14. The preactivated catalyst comprises 50% by weight of a propylene homopolymer or a propylene polymerized unit having an intrinsic viscosity [η _B ] of less than 15 dl / g measured in tetralin at 135 ° C. per 1 g of the transition metal compound catalyst component. % Or more of propylene-olefin copolymer (B) 0.01
100100 g and intrinsic viscosity measured in tetralin at 135 ° C
[η _A ] 0.01 to 5,000 g of polyethylene with a range of 15 to 100 dl / g
The modified olefin (co) polymer composition according to claim 11 or 12, which carries a polymer. 15. A propylene homopolymer other than a high-molecular-weight polyethylene or a propylene-olefin copolymer containing 50% by weight or more of propylene polymerized units has a (co) polymerization volume of propylene or propylene and other olefins of 1 or more.
0.01 to liters of transition metal atoms in the catalyst per liter
The modified olefin (co) polymer composition according to claim 11 or 12, which is produced with a catalyst amount of 1,000 mmol. 16. An olefin (co) polymer other than high molecular weight polyethylene, comprising: a) a propylene homopolymer or 50
A propylene-olefin copolymer containing at least 0.01% by weight of a transition metal compound catalyst component, and from 0.01 to 1,000 mol per mol of transition metal atom of the Periodic Table (1991 edition), Groups 1 and 2.
Consisting of a combination of an organometallic compound of a metal selected from the group consisting of metals belonging to Group 12, Group 12 and Group 13 (AL1) and 0 to 500 moles of an electron donor (E1) per mole of transition metal atom In the presence of a polyolefin production catalyst, and a preactivation catalyst containing polyethylene supported on this catalyst, propylene alone or propylene
(Co) polymers produced by subjecting (co) polymerizing other olefins to (b) to (b), and b) a propylene homopolymer or propylene
3. The modified olefin according to claim 1, which is a mixture of a propylene-olefin copolymer containing at least about 10 wt%.
(Co) polymer compositions. 17. The modified olefin (co) polymer composition according to claim 1, wherein the heating temperature is in the range of 60 to 350 ° C. 18. The transition metal compound catalyst component, in the periodic table (1991 version) No. 1 of 0.01 to 1,000 mol per mol of transition metal atom.
Group, a group 2 metal, an organometallic compound of a metal selected from the group consisting of metals belonging to group 12 and group 13 (AL1) and 0 to 500 moles of an electron donor (E1) per mole of a transition metal atom And a catalyst for polyolefin production comprising a combination of the above, and 0.1 g / g of the titanium-containing solid catalyst component supported on the catalyst.
Intrinsic viscosity measured in tetralin between 135g and 01g-5,000g
In the presence of a preactivated catalyst containing polyethylene consisting of an ethylene homopolymer or an ethylene-olefin copolymer containing 50% by weight or more of ethylene polymerized units, where [η] is 15 to 100 dl / g, Co) polymerizing to produce an olefin (co) polymer composition, further irradiating the composition with ionizing radiation, and then subjecting the composition to a heat treatment. Production method. 19. The olefin to be (co) polymerized is propylene alone or an olefin having 2 to 12 carbon atoms, and the olefin (co) polymer contains at least 50% by weight of a propylene homopolymer or a propylene polymer unit. And carbon number
The method for producing a modified olefin (co) polymer composition according to claim 18, which is a copolymer with an olefin of 2 to 12. 20. The preactivated catalyst, further comprising: a) an organoaluminum compound (AL1) contained in the preactivated catalyst per 1 mol of transition metal atoms in the preactivated catalyst
0.05 to 5,000 mol of organoaluminum compound in total
(AL2), and b) a total of 0 to 1 mol of the transition metal atom in the preactivated catalyst and the electron donor (E1) contained in the preactivated catalyst.
19. The method for producing a modified olefin (co) polymer composition according to claim 18, wherein 3,000 mol of the electron donor (E2) is added. 21. The catalyst having an olefin (co) polymerization volume of 1
0.01 to 1, converted to titanium atoms in the catalyst per liter
19. The modified olefin of claim 18, wherein the amount is 000 mmol.
A method for producing a (co) polymer composition. 22. A transition metal compound catalyst component, wherein the preactivated catalyst is supported on the catalyst in addition to polyethylene.
Per gram, the intrinsic viscosity [η
_B] is 15 dl / g smaller than propylene homopolymer or propylene containing propylene polymerization unit at least 50 wt% - modified olefin according to claim 18 comprising a polypropylene (B) 0.01 to 100 g of olefin copolymer ( (Co) A method for producing a polymer composition. 23. The amount of the catalyst is 0.01 0.01 in terms of transition metal atoms in the catalyst per liter of the (co) polymerization volume of the olefin.
23. The method for producing a modified olefin (co) polymer composition according to claim 22, wherein the amount of the modified olefin (co) polymer composition is from 1,000 to 1,000 mmol. 24. a) transition metal compound catalyst component, from 0.01 to 1,000 mol per 1 mol of transition metal atom, from metals belonging to Groups 1, 2, 12 and 13 of the Periodic Table (1991 edition); Organometallic compounds of metals selected from the group consisting of (AL1) and 0 to 500 moles of electron donor per mole of transition metal atom
The olefin is (co) polymerized in the presence of a polyolefin production catalyst comprising the combination of (E1), and the polyolefin (B) having an intrinsic viscosity [η] of less than 15 dl / g measured in tetralin at 135 ° C. is transitioned. 0.0 per g of metal compound catalyst component
Preliminary (co) polymerization step to produce 1 g to 100 gg, b) polyolefin (A) having the intrinsic viscosity [η] of 15 to 100 dl / g measured in tetralin at 135 ° C. by subsequent (co) polymerization of the olefin. Including the pre-activation (co) polymerization step of producing 0.01 g to 5,000 g per 1 g of the transition metal compound catalyst component. C) The polyolefin (B) and the polyolefin (A) are supported by the transition metal compound catalyst component. In the presence of a preactivated catalyst for olefin (co) polymerization,
19. The method for producing a modified olefin (co) polymer composition according to claim 18, wherein the olefin of 2 to 12 is subjected to main (co) polymerization. 25) a) a metal belonging to Group 1, Group 2, Group 12, or Group 13 of the periodic table (1991 edition) in an amount of 0.01 to 1,000 mol per 1 mol of the transition metal atom as the transition metal compound catalyst component; Organometallic compounds of metals selected from the group consisting of (AL1) and 0 to 500 moles of electron donor per mole of transition metal atom
The olefin is (co) polymerized in the presence of a catalyst for producing a polyolefin comprising the combination of (E1), and the polyolefin (B) having an intrinsic viscosity [η] of less than 15 dl / g measured in tetralin at 135 ° C. is transitioned. 0.1 g / g of metal compound catalyst component.
Preliminary (co) polymerization step for producing 01 g to 100 g, followed by (co) polymerization of the olefin to transition polyolefin (A) having an intrinsic viscosity [η] of 15 to 100 dl / g measured in tetralin at 135 ° C. 0.01 g to 5,000 per 1 g of metal compound catalyst component
g. an olefin obtained by a method including a pre-activated (co) polymerization step for producing a polyolefin (B) and a polyolefin (A) supported on a transition metal compound catalyst component.
(Co) pre-activation catalyst for polymerization, b) total of 1 mol of transition metal atom in pre-activation catalyst and organometallic compound (AL1) of metal contained in pre-activation catalyst for olefin (co) polymerization Periodic table of 0.05-5,000 mol
(1991 edition) Organometallic compounds of metals selected from the group consisting of metals belonging to Group 1, Group 2, Group 12 and Group 13 (A
L2), and c) a total of 0 to 3,000 moles of electron donation with respect to 1 mole of transition metal atoms in the preactivation catalyst and the electron donor (E1) contained in the preactivation catalyst for olefin (co) polymerization. The modified olefin according to claim 18, wherein the olefin is subjected to the (co) polymerization in the presence of an olefin (co) polymerization catalyst comprising the isomer (E2).
A method for producing a (co) polymer composition. 26. After (co) polymerizing the olefin, it is irradiated with ionizing radiation, and then, after subjecting it to a heat treatment,
19. The method for producing a modified olefin (co) polymer composition according to claim 18, further comprising 0.01 to 2 parts by weight of at least one stabilizer selected from a phenolic antioxidant and a phosphorus antioxidant. 27. The method for producing a modified olefin (co) polymer composition according to claim 18, wherein the heating temperature is in the range of 60 to 350 ° C. 28. An olefin (co) polymer obtained by a known method is further added to 100 parts by weight of the modified olefin (co) polymer composition obtained by the production method according to claim 18. A process for producing a modified olefin (co) polymer composition mixed in the range of up to 10,000 parts by weight. 29. A modified olefin (co) polymer composition which is a mixture of the modified olefin (co) polymer composition according to claim 1 and an olefin (co) polymer. 30. A molded article of a modified olefin (co) polymer composition obtained from the modified olefin (co) polymer composition according to any one of claims 1 to 28. 31. A molded article of a modified olefin (co) polymer composition, wherein (a) an ethylene homopolymer or an ethylene-olefin copolymer containing 50% by weight or more of ethylene polymerized units, at least Intrinsic viscosity [η _E ] measured with tetralin at 135 ° C. is 0.01 to 5.0 parts by weight of a high molecular weight polyethylene having a range of 15 to 100 dl / g, and (b) an olefin (co) polymer other than the high molecular weight polyethylene is 100 Including parts by weight,
(c) And the high molecular weight polyethylene has a number average particle diameter of 1
A molded article obtained from an olefin (co) polymer composition that is present as finely dispersed as fine particles in the range of
A modified olefin (co) polymer composition molded article obtained by irradiating with ionizing radiation.