JP2002275325A - Propylene polymer composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a propylene polymer composition excellent in moldability, resistances to impact and heat, external appearance, stiffness, and elongation at break. SOLUTION: This composition comprises a propylene polymer (A2) and a propylene polymer (A1) which is selected from propylene polymers (A). Propylene polymer A is prepared by using a metallocene catalyst and contains different kinds of bonds based on 2,1-insertion and 1,3-insertion of propylene, the ratio (obtained from a<13> C-NMR spectrum) of each kind of bonds being 0.2% or lower of the total propylenederived structural units. The composition may comprise propylene polymer A or a propylene block copolymer (B) of which the ratio of each of different kinds of bonds based on 2,1-insertion and 1,3-insertion of propylene is 0.2% or lower of the total propylene-derived structural units, an elastomer (C), an olefin polymer (D), and an olefin polymer modified by grafting a polar monomer (E).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a propylene polymer composition, and more particularly, to a propylene polymer composition having excellent moldability and appearance, excellent impact resistance, heat resistance, rigidity and tensile elongation at break. About things.

[0002]

BACKGROUND OF THE INVENTION Propylene-based polymers are molded by various molding methods and are used in a variety of products such as daily goods, kitchenware, packaging films, fibers and non-woven fabrics, home appliances, machine parts, electric parts, and automobile parts. It is used for various purposes. Propylene polymers also require different properties depending on the molding method and application, but generally require physical properties such as moldability, appearance, impact resistance, heat resistance, mechanical strength, and high tensile elongation. Is done.

[0003] Such a propylene-based polymer includes a catalyst comprising a transition metal compound and an organoaluminum compound;
It is generally manufactured using a so-called Ziegler-type catalyst. Among Ziegler type catalysts, a propylene-based polymer obtained using a so-called titanium-based catalyst containing a halogen-containing titanium catalyst component is excellent in moldability and rigidity, but has a problem of inferior tensile elongation at break. For this reason, blending of two types of propylene-based polymers having different molecular weights obtained with a titanium-based catalyst has been conventionally performed, but the propylene-based polymer composition obtained by such a blend has poor moldability. Although improved, there is a problem that the tensile elongation at break is greatly reduced.

Therefore, it has been practiced to blend a propylene-based polymer obtained with a titanium-based catalyst with a soft polymer such as an elastomer to improve tensile elongation at break and impact resistance. However, even in such a composition, the balance of moldability, rigidity, tensile elongation at break, impact resistance and the like cannot be said to be sufficient, and further improvement is required.

On the other hand, a propylene-based polymer obtained using an organometallic complex catalyst containing a cyclopentadienyl group, a so-called metallocene catalyst, has a higher tensile elongation at break than a propylene-based polymer obtained using a titanium-based catalyst. In addition, problems such as poor moldability and rigidity have been pointed out.
The reason for this is that propylene-based polymers produced with ordinary metallocene catalysts have propylene units of ordinary 1,2-
A binding mode derived from 2,1-insertion or 1,3-insertion, which is not insertion, that is, about 0.4 to 1% of a so-called hetero bond is contained, which is said to have an adverse effect on physical properties.

Therefore, if a propylene-based polymer composition having excellent moldability and excellent impact resistance, heat resistance, appearance, rigidity and tensile elongation at break can be produced, its industrial value will be extremely large. The emergence of a novel propylene-based polymer composition has been eagerly desired. The present inventors have conducted intensive studies in view of the above situation, and as a result, a propylene polymer composition containing a specific propylene polymer, moldability,
The present inventors have found that this is a desirable composition excellent in impact resistance, heat resistance, appearance, rigidity, tensile elongation at break, and the like, and have completed the present invention.

[0007]

SUMMARY OF THE INVENTION That is, the present invention provides moldability, impact resistance,
Excellent heat resistance, appearance, rigidity and tensile elongation at break,
It is intended to provide a propylene-based polymer composition.

[0008]

SUMMARY OF THE INVENTION The propylene polymer composition according to the present invention is a propylene polymer (A1) selected from propylene polymers (A) produced using a metallocene catalyst.
And (1) the propylene-based polymer (A1) and the propylene-based polymer (A2) have a propylene homopolymer or an α-olefin content of 10 mol% or less. It is a propylene / α-olefin random copolymer, (2) 230 ° C, load 2.
The melt flow rate (MFR) measured at 16 kg is in the range of 0.01 to 1000 g / 10 min, and (3) ¹³ C
-Determined from the NMR spectrum, the proportion of the heterogeneous bond based on the 2,1-insertion and the proportion of the heterogeneous bond based on the 1,3-insertion of the propylene monomer in all the propylene structural units are all 0.2% or less, (4) The ratio of the MFR (MFR _A1 ) of the propylene-based polymer (A1) to the MFR (MFR _A2 ) of the propylene-based polymer (A2) (MFR _A1 / MFR)
_A2 ) is 10 or more.

A propylene polymer composition according to another embodiment of the present invention comprises a propylene polymer (A) produced using a metallocene catalyst, an elastomer (C), ethylene, butene and 4-methyl-1. -1 to be selected from Penten
At least one polymer selected from the group consisting of an olefin polymer (D) containing 90 mol% or more of structural units derived from various kinds of monomers and a modified olefin polymer (E) graft-modified with a polar monomer; Including
The propylene-based polymer (A) is (1) a propylene homopolymer or a propylene / α-olefin random copolymer having an α-olefin content of 10 mol% or less, (2) 230 ° C., load 2. The melt flow rate (MFR) measured at 16 kg is 0.01 to 1000 g /
(3) The ratio of the hetero bond based on the 2,1-insertion and the hetero bond based on the 1,3-insertion of the propylene monomer in all the propylene constitutional units as determined from the ( ¹³ ) ¹³ C-NMR spectrum. Each of them is characterized in that the ratio is 0.2% or less.

A propylene-based polymer composition according to another aspect of the present invention is a propylene-based block copolymer (B) produced using a metallocene catalyst, wherein (1) a propylene homopolymer part or α-olefin content is 1
It consists of a propylene / α-olefin random copolymer portion of 0 mol% or less and an amorphous olefin polymer portion produced using a metallocene catalyst, and is measured at (2) 230 ° C. under a load of 2.16 kg. Melt flow rate (MF
R) is in the range of 0.01 to 1000 g / 10 minutes,
(3) Both the ratio of the hetero bond based on the 2,1-insertion and the ratio of the hetero bond based on the 1,3-insertion of the propylene monomer in all the propylene structural units in the total propylene constitutional unit, which are determined from the ¹³ C-NMR spectrum, are both 0.2. % Or less.

Further, a propylene-based polymer composition according to another embodiment of the present invention comprises a propylene-based block copolymer (B) produced using a metallocene catalyst, an elastomer (C), ethylene, butene and Polymer (D) containing a structural unit derived from one type of monomer selected from 1-methyl-1-pentene in a proportion of 90 mol% or more, and a modified olefin polymer (E) graft-modified with a polar monomer Wherein the propylene-based block copolymer (B) comprises (1) a propylene homopolymer part or a propylene / α-olefin having an α-olefin content of 10 mol% or less. Consisting of a random copolymer part and an amorphous olefin polymer part produced using a metallocene catalyst,
(2) The melt flow rate (MFR) measured at 230 ° C. under a load of 2.16 kg is in the range of 0.01 to 1000 g / 10 min, and (3) all propylene constituent units determined from ¹³ C-NMR spectrum The ratio of the heterogeneous bond based on the 2,1-insertion and the ratio of the heterogeneous bond based on the 1,3-insertion of the propylene monomer therein are both 0.2% or less.

[0012]

DETAILED DESCRIPTION OF THE INVENTION The propylene polymer composition according to the present invention will be specifically described below. The propylene polymer composition according to the present invention includes a propylene polymer (A1) selected from propylene polymers (A) produced using a metallocene catalyst, and a propylene polymer (A2). I have.

A propylene polymer composition according to another embodiment of the present invention comprises a propylene polymer (A) produced using a metallocene catalyst, an elastomer (C), ethylene, butene and 4-methyl-1. -1 to be selected from Penten
At least one polymer selected from the group consisting of an olefin polymer (D) containing 90 mol% or more of structural units derived from various kinds of monomers and a modified olefin polymer (E) graft-modified with a polar monomer; Contains.

A propylene polymer composition according to another embodiment of the present invention comprises a propylene block copolymer (B) produced using a metallocene catalyst and, if necessary, an elastomer (C), ethylene, Butene and 4-methyl-1
At least one selected from an olefin polymer (D) containing a constituent unit derived from one kind of monomer selected from -pentene in a proportion of 90 mol% or more and a modified olefin polymer (E) graft-modified with a polar monomer. 1
Species of polymer.

First, each component forming the propylene polymer composition according to the present invention will be described. Propylene Polymer (A) The propylene polymer (A) forming the propylene polymer composition according to the present invention is propylene homopolymer obtained by homopolymerizing propylene using an olefin polymerization catalyst containing a metallocene catalyst. A polymer or a propylene / α-olefin random copolymer having an α-olefin content of 10 mol% or less obtained by random copolymerizing propylene with another α-olefin other than propylene.

Other α-olefins other than propylene include ethylene, 1-butene, 1-pentene, 1-hexene,
4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, norbornene, tetracyclododecene, butadiene, pentadiene, isoprene, hexadiene Olefins having 2 to 20 carbon atoms, such as polyenes having 4 to 20 carbon atoms.

This propylene-based polymer (A) has an AST
230 ° C, load 2.16 kg according to MD 1238
Melt flow rate (MFR) measured at 0.01
To 1000 g / 10 min, preferably 0.05 to 500 g /
The molecular weight distribution (Mw / Mn) determined by gel permeation chromatography (GPC) is desirably 1 to 4, preferably 1.5 to 10 minutes.
It is desirable to be in the range of 3.5.

The propylene polymer (A) has the following ^properties:
The ratio of the hetero bond based on the 2,1-insertion and the ratio of the hetero bond based on the 1,3-insertion of the propylene monomer in all the propylene structural units obtained from the C-NMR spectrum are all 0.2% or less, preferably Is desirably 0.15% or less, and the isotactic pentad fraction (mmmm) determined from the ¹³ C-NMR spectrum is
85% or more, preferably 90% or more, more preferably 9%
It is desirable that it be 5% or more.

Isotactic pentad fraction (mm
mm) indicates the abundance ratio of isotactic chains in pentad units in the molecular chain measured using ¹³ C-NMR, and indicates the center of the chain in which five propylene monomer units are consecutively meso-bonded. Is the fraction of propylene monomer units in Specifically, it is a value calculated as a fraction of the mmmm peak in the total absorption peak in the methyl carbon region observed in the ¹³ C-NMR spectrum.

Such a propylene-based polymer (A) is
(A) a metallocene compound, (b-1) an organometallic compound,
(B-2) at least one compound selected from an organoaluminum oxy compound and (b-3) a compound which forms an ion pair by reacting with the metallocene compound (a), and if necessary, (c) fine particles It can be produced by polymerizing or copolymerizing propylene in the presence of an olefin polymerization catalyst composed of a linear carrier.

(A) Metallocene Compound (a) The metallocene compound is not particularly limited as long as it can produce a propylene-based polymer (A) satisfying the above physical properties. A metallocene compound having a structure of the formula (1) or (2) is given.

[0022]

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(In the formulas (1) and (2), R ³ is selected from a hydrocarbon group and a silicon-containing hydrocarbon group, and R ¹ , R ² , R
^{4, R 5, R 6,} R 7, R 8, R 9, R 10, R 11, R 12, R 13
And R ¹⁴ are selected from hydrogen, a hydrocarbon group and a silicon-containing hydrocarbon group, each of which may be the same or different;
Adjacent substituents from ¹ to R ¹² may combine with each other to form a ring, and in general formula (1), R ¹ , R ⁴ , R
⁵ and the substituents selected from R ^12, bonded R ^{1 3} or R ¹⁴ with each other may form a ring, in the general formula (2) A is an unsaturated bond and / or an aromatic ring A divalent hydrocarbon group having 2 to 20 carbon atoms, and A may have two or more ring structures including a ring formed with Y, and Y is carbon or silicon; , M
Is a metal selected from Group 4 of the periodic table, and Q may be selected from the same or different combinations of halogen, a hydrocarbon group, an anionic ligand or a neutral ligand capable of coordinating with a lone pair, and j Is an integer of 1 to 4. Hereinafter, the metallocene compounds represented by the general formulas (1) and (2) will be described more specifically.

In the above general formulas (1) and (2), R ³ is selected from a hydrocarbon group and a silicon-containing hydrocarbon group. Preferred examples of the hydrocarbon group include an alkyl group having 1 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an alkylaryl group having 7 to 20 carbon atoms. , May contain one or more ring structures.

Specific examples thereof include methyl, ethyl, n-
Propyl, isopropyl, 2-methylpropyl, 1,1-dimethylpropyl, 2,2-dimethylpropyl, 1,1-diethylpropyl, 1-ethyl-1-methylpropyl, 1,1,2,2-tetramethylpropyl , Sec-butyl, tert-butyl, 1,1-dimethylbutyl, 1,1,3-trimethylbutyl, neopentyl,
Cyclohexylmethyl, cyclohexyl, 1-methyl-1-
Cyclohexyl, 1-adamantyl, 2-adamantyl, 2-
Methyl-2-adamantyl, menthyl, norbornyl, benzyl, 2-phenylethyl, 1-tetrahydronaphthyl,
Examples include 1-methyl-1-tetrahydronaphthyl, phenyl, naphthyl, tolyl and the like.

The silicon-containing hydrocarbon group is preferably an alkylsilyl group or an arylsilyl group having 1 to 4 silicon atoms and 3 to 20 carbon atoms, and specific examples thereof include trimethylsilyl, tert-butyldimethylsilyl and trisilyl. Phenylsilyl and the like. Note that R ³
Is preferably a sterically bulky substituent, more preferably a substituent having 4 or more carbon atoms.

In the above general formulas (1) and (2), R ¹ ,
R ² , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R
¹² , R ¹³ and R ¹⁴ are selected from hydrogen, a hydrocarbon group and a silicon-containing hydrocarbon group, and may be the same or different. Specific examples of preferable hydrocarbon groups and silicon-containing hydrocarbon groups include the same as described above. Adjacent substituents R ¹ to R ⁴ on the cyclopentadienyl ring may combine with each other to form a ring. Such substituted cyclopentadienyl groups include indenyl, 2-
Methylindenyl, tetrahydroindenyl, 2-methyltetrahydroindenyl, 2,4,4-trimethyltetrahydroindenyl and the like can be mentioned.

Adjacent substituents from R ⁵ to R ¹² on the fluorene ring may be bonded to each other to form a ring. Such substituted fluorenyl groups include benzofluorenyl, dibenzofluorenyl, octahydrodibenzofluorenyl, octamethyloctahydrodibenzofluorenyl, and the like. Further, the substituents of R ⁵ to R ¹² on the fluorene ring are symmetrical in terms of ease of synthesis, that is, R ⁵ = R ¹² , R ⁶ = R ¹¹ , R ⁷ = R ¹⁰ , and R ⁸ =
R ⁹ is preferable, and unsubstituted fluorene, 3,6-disubstituted fluorene, 2,7-disubstituted fluorene or 2,3,6,7-
More preferably, it is a tetrasubstituted fluorene. Here, the 3-, 6-, 2-, and 7-positions on the fluorene ring correspond to R ⁷ , R ¹⁰ , R ⁶ , and R ¹¹ , respectively.

Y is carbon or silicon. In the general formula (1), R ¹³ and R ¹⁴ are bonded to Y to form a substituted methylene group or a substituted silylene group as a crosslinking portion.
Preferred specific examples include, for example, methylene, dimethylmethylene, diisopropylmethylene, methyl tert-butylmethylene, dicyclohexylmethylene, methylcyclohexylmethylene, methylphenylmethylene, diphenylmethylene, methylnaphthylmethylene, dinaphthylmethylene or dimethylsilylene, diisopropylsilylene,
Examples thereof include methyl tert-butylsilylene, dicyclohexylsilylene, methylcyclohexylsilylene, methylphenylsilylene, diphenylsilylene, methylnaphthylsilylene, and dinaphthylsilylene.

In the general formula (1), R ¹ , R ⁴ ,
A substituent selected from R ⁵ and R ¹² and R ¹³ or R ¹⁴ of the crosslinked portion may be bonded to each other to form a ring. As an example of such a structure, the case where R ¹ and R ¹⁴ are bonded to each other to form a ring is illustrated below. However, the crosslinked portion and the cyclopentadienyl group are integrated, and the general formula (3) Such a tetrahydropentalene skeleton or a tetrahydroindenyl skeleton as represented by the general formula (4) may be formed. Similarly, the crosslinked portion and the fluorenyl group may be bonded to each other to form a ring.

[0031]

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In the general formula (2), Y is bonded to a divalent hydrocarbon group A having 2 to 20 carbon atoms which may contain an unsaturated bond and / or an aromatic ring, and forms a cycloalkylidene group; Constructs a cyclomethylenesilylene group or the like.
A may have two or more ring structures including a ring formed with Y. Preferred specific examples include, for example, cyclopropylidene, cyclobutylidene, cyclopentylidene, cyclohexylidene, cycloheptylidene, bicyclo [3.3.1] nonylidene, norbornylidene,
Adamantylidene, tetrahydronaphthylidene, dihydroindanilidene, cyclodimethylenesilylene, cyclotrimethylenesilylene, cyclotetramethylenesilylene, cyclopentamethylenesilylene, cyclohexamethylenesilylene, cycloheptamethylenesilylene and the like can be mentioned.

M in the general formulas (1) and (2) is a metal selected from Group 4 of the periodic table. Examples of M include titanium, zirconium and hafnium. Q is selected from the same or different combinations of halogen, a hydrocarbon group having 1 to 20 carbon atoms, an anionic ligand or a neutral ligand capable of coordinating with a lone pair of electrons. Specific examples of the halogen include fluorine, chlorine, bromine, and iodine, and specific examples of the hydrocarbon group include the same as those described above.
Specific examples of the anion ligand, methoxy, tert-butoxy, alkoxy groups such as phenoxy, acetate,
Carboxylate groups such as benzoate; mesylate;
And a sulfonate group such as tosylate. Specific examples of the neutral ligand capable of coordinating with a lone electron pair include organic phosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine, and diphenylmethylphosphine; tetrahydrofuran, diethyl ether, dioxane, 1,2-dimethoxy Ethers such as ethane; Of these, Q may be the same or different combinations, but at least one is preferably a halogen or an alkyl group.

Next, a method for producing the metallocene compound represented by the general formula (1) or (2) will be described. First, the precursor compound (5) of the metallocene compound represented by the general formula (1) can be produced by a method as shown in the general formula (A) or (B).

[0035]

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[0036]

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(Wherein, R ^{1 to} R ¹⁴ and Y have the same meanings as in the general formula (1), and L is an alkali metal. Z ¹ and Z ² are halogen or an anion ligand, and these are the same.) But
Alternatively, different combinations may be used. [7], [1]
[0] and [5] can be considered to be the isomers that differ only in the position of the double bond in the cyclopentadienyl ring, and only one of them is exemplified. It may be another isomer that differs only in the position of the heavy bond, or may be a mixture thereof. In addition, the precursor compound [6] of the general formula [2] can be produced by a method like the general formula [C] or [D].

[0038]

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[0039]

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[0040] ^{(wherein, R 1 ~R 14, Y,} A is the same as the general formula (2), .Z ¹ L is an alkali metal,
Z ² is a halogen or an anionic ligand, which may be the same or a different combination. Also,
In [18] and [6], it is possible to consider the existence of isomers that differ only in the position of the double bond in the cyclopentadienyl ring, and only one of them is exemplified. May be other isomers that differ only in the position of the double bond in or may be a mixture thereof. Further, [7], which is a common precursor of the metallocene compound represented by the general formula (1) or (2), can be produced by a method such as the general formulas [E] and [F].

[0041]

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(Wherein R ¹ , R ² , R ³ and R ⁴ have the same meanings as in formula (1) or (2), and M ¹ is an alkali metal or an alkaline earth metal. Z ³ is The same as R ³ , or a halogen or an anionic ligand, and e is a valency of M ^1. )

[0043]

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(Wherein R ¹ , R ² , R ³ and R ⁴ have the same meanings as in formula (1) or (2), L is an alkali metal, and Z ¹ is a halogen or an anionic ligand. .) Further, when R ³ is a substituent represented by CR ¹⁵ R ¹⁶ R ¹⁷ , [7] can be produced also by a method such as the general formula [G].

[0045]

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Wherein R ¹ , R ² and R ⁴ are the same as those in the general formula (1) or (2), and R ¹⁵ , R ¹⁶ and R
¹⁷ is selected from hydrogen, a hydrocarbon group and a silicon-containing hydrocarbon group, which may be the same or different, and L is an alkali metal. In the above methods [E] to [G], the method of introducing the substituent R ³ is exemplified, but R ¹ , R ² and R ⁴ are also
It can be introduced in a similar manner.

The alkali metals used in the reactions of the above general formulas [A] to [G] include lithium, sodium and potassium, and the alkaline earth metals include magnesium and calcium. Examples of the halogen include fluorine, chlorine, bromine, and iodine. Specific examples of the anion ligand include an alkoxy group such as methoxy, tert-butoxy and phenoxy, a carboxylate group such as acetate and benzoate, and a sulfonate group such as mesylate and tosylate.

Next, an example of producing a metallocene compound from the precursor compound of the general formula [5] or [6] will be described below. Formulas [A] and [B] or Formulas [C] and [D]
The precursor compound of the general formula [5] or [6] obtained by the reaction of the above is reacted with an alkali metal, an alkali metal hydride or an organic alkali metal in an organic solvent at a reaction temperature of -80 ° C to 2 ° C.
By contacting in the range of 00 ° C., a dialkali metal salt is obtained.

The organic solvent used in the above reaction includes
Aliphatic hydrocarbons such as pentane, hexane, heptane, cyclohexane, decalin, or benzene, toluene,
Examples thereof include aromatic hydrocarbons such as xylene, ethers such as THF, diethyl ether, dioxane, and 1,2-dimethoxyethane, and halogenated hydrocarbons such as dichloromethane and chloroform.

The alkali metal used in the above reaction includes lithium, sodium, potassium and the like. The alkali metal hydride includes sodium hydride,
Examples include potassium hydride and the like, and examples of the organic alkali metal include methyl lithium, butyl lithium, and phenyl lithium. Next, the dialkali metal salt described above is
General formula [30] MZ _k [30] (wherein, M is a transition metal selected from Group 4 of the periodic table, and Z is a halogen, an anion ligand or a neutral coordination capable of coordinating with a lone pair of electrons. And k is an integer of 3 to 6), and a compound represented by the general formula (1):
Alternatively, the metallocene compound represented by (2) can be synthesized.

Preferred specific examples of the compound represented by the general formula [30] include trivalent or tetravalent titanium fluoride, chloride, bromide and iodide, tetravalent zirconium fluoride, chloride, bromide and iodine. And tetravalent hafnium fluoride, chloride, bromide and iodide, or complexes thereof with ethers such as THF, diethyl ether, dioxane or 1,2-dimethoxyethane.

As the organic solvent to be used, the same organic solvents as described above can be used. The reaction between the dialkali metal salt and the compound represented by the general formula [30] is preferably performed by an equimolar reaction, and can be performed in the above-mentioned organic solvent at a reaction temperature in the range of -80 ° C to 200 ° C. it can. The metallocene compound obtained by the reaction can be isolated and purified by a method such as extraction, recrystallization, or sublimation.

Preferred specific examples of the metallocene compound represented by formula (1) or (2) are shown below. First, the ligand structure of the metallocene compound excluding MQ _j (metal portion) is represented by Cp (cyclopentadienyl ring portion),
Bridge (bridge), Flu (fluorenyl ring) 3
Specific examples of the respective partial structures, and specific examples of the ligand structure by their combination are shown below.

[0054]

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[0055]

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[0056]

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Specific examples of the ligand structure are shown in the following table.

[0058]

[Table 1]

[0059]

[Table 2]

[0060]

[Table 3]

[0061]

[Table 4]

[0062]

[Table 5]

[0063]

[Table 6]

[0064]

[Table 7]

[0065]

[Table 8]

[0066]

[Table 9]

[0067]

[Table 10]

[0068]

[Table 11]

[0069]

[Table 12]

[0070]

[Table 13]

[0071]

[Table 14]

[0072]

[Table 15]

[0073]

[Table 16]

[0074]

[Table 17]

[0075]

[Table 18]

[0076]

[Table 19]

[0077]

[Table 20]

[0078]

[Table 21]

[0079]

[Table 22]

[0080]

[Table 23]

[0081]

[Table 24]

[0082]

[Table 25]

[0083]

[Table 26]

[0084]

[Table 27]

[0085]

[Table 28]

[0086]

[Table 29]

[0087]

[Table 30]

[0088]

[Table 31]

[0089]

[Table 32]

[0090]

[Table 33]

[0091]

[Table 34]

[0092]

[Table 35]

[0093]

[Table 36]

[0094]

[Table 37]

[0095]

[Table 38]

[0096]

[Table 39]

[0097]

[Table 40]

[0098]

[Table 41]

[0099]

[Table 42]

[0100]

[Table 43]

[0101]

[Table 44]

[0102]

[Table 45]

[0103]

[Table 46]

[0104]

[Table 47]

[0105]

[Table 48]

[0106]

[Table 49]

[0107]

[Table 50]

[0108]

[Table 51]

[0109]

[Table 52]

[0110]

[Table 53]

[0111]

[Table 54]

[0112]

[Table 55]

[0113]

[Table 56]

According to the above table, the ligand structure of No. 752 means a combination of a2-b1-c3, and when MQj of the metal part is ZrCl ₂ , the following metallocene compounds are exemplified.

[0115]

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[0116] Specific examples of MQ _j, ZrC
l ₂ , ZrBr ₂ , ZrMe ₂ , Zr (OTs) ₂ , Zr (O
Ms) ₂ , Zr (OTf) ₂ , TiCl ₂ , TiBr ₂ , Ti
Me ₂ , Ti (OTs) ₂ , Ti (OMs) ₂ , Ti (OT
_{f) 2, HfCl 2, HfBr} 2, HfMe 2, Hf (OT
s) ₂ , Hf (OMs) ₂ , Hf (OTf) _{2 and the} like. Further, examples of the metallocene compound in which the substituent of the Cp ring and the substituent of the crosslinked portion are bonded to each other to form a ring include the following compounds.

[0117]

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Next, the components (b) and (c) forming the olefin polymerization catalyst will be described. (b-1) Organometallic compound As the (b-1) organometallic compound, specifically, the following organometallic compounds of Groups 1, 2 and 12 and 13 of the periodic table are used.

[0119] (b-1a) In the formula _{^{R a m Al (OR b)}} n H p X q ( wherein, R ^a and R ^b may be the same or different from each other, the number of carbon atoms from 1 to 15 , Preferably 1 to 4 hydrocarbon groups, X represents a halogen atom, and m represents 0 <m
≦ 3, n is 0 ≦ n <3, p is 0 ≦ p <3, q is 0 ≦ q <
The number is 3, and m + n + p + q = 3. The organoaluminum compound represented by).

[0120] (b-1b) In the general formula M ² AlR ^a ₄ (wherein, M ² represents a Li, Na or K, R ^a is the number of carbon atoms 1 to 15, preferably 1 to 4 hydrocarbon groups A complex alkylated product of a Group 1 metal and aluminum represented by the formula: (b-1c) a general formula R ^a R ^b M ³ (where R ^a and R ^b may be the same or different and each have 1 to 15, preferably 1 to 4 hydrocarbon groups) And M ³ represents Mg, Zn or Cd.) A dialkyl compound of a Group 2 or 12 metal.

As the organoaluminum compound belonging to (b-1a), the following compounds can be exemplified. In the general formula _{^{R a m Al (OR b)}} 3-m ( wherein, R ^a and R ^b may be the same or different, 1 to 15, preferably 1 to 4 hydrocarbon group having carbon atoms are shown, m is preferably a number 1.5 ≦ m ≦ 3.) an organoaluminum compound represented by the general formula R ^a _m AlX _3-m (wherein, R ^a is 1 to carbon atoms 15, preferably 1
4 represents a hydrocarbon group, X represents a halogen atom, and m is preferably 0 <m <3. An organic aluminum compound represented by the formula: R ^a _m AlH _3-m (where R ^a has 1 to 15 carbon atoms, preferably 1 to
4 represents a hydrocarbon group, and m is preferably 2 ≦ m <3. An organoaluminum compound represented by), the general formula _{^{R a m Al (OR b)}} n X q ( wherein, R ^a and R ^b may be the same or different from each other, the number of carbon atoms 1 to 15, It preferably represents 1 to 4 hydrocarbon groups, X represents a halogen atom, and m represents 0 <m
≦ 3, n is a number of 0 ≦ n <3, q is a number of 0 ≦ q <3, and m + n + q = 3. The organoaluminum compound represented by).

More specifically, the aluminum compound belonging to (b-1a) includes trimethylaluminum, triethylaluminum, trin-butylaluminum, tripropylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum. Tri-n-alkyl aluminums such as;
Triisopropylaluminum, triisobutylaluminum, trisec-butylaluminum, tritert-butylaluminum, tri2-methylbutylaluminum, tri3-methylbutylaluminum, tri2-methylpentylaluminum, tri3-methylpentylaluminum, tri4 -Methylpentyl aluminum, tri-2-methylhexyl aluminum, tri-3-methylhexyl aluminum,
Tri-branched alkyl aluminum such as tri-2-ethylhexyl aluminum; tricycloalkyl aluminum such as tricyclohexyl aluminum and tricyclooctyl aluminum; triaryl aluminum such as triphenyl aluminum and tritolyl aluminum; diisopropyl aluminum hydride and diisobutyl aluminum hydride dialkylaluminum _{hydride; (i-C 4 H 9} ) x Al y (C 5 H 10) z ( wherein, x, y, z
Is a positive number and z ≧ 2x. Alkenyl aluminum such as isoprenyl aluminum represented by the following formulas); alkyl aluminum alkoxides such as isobutyl aluminum methoxide, isobutyl aluminum ethoxide and isobutyl aluminum isopropoxide;
Represented by like ^{_{R a 2.5 Al (OR b)}} 0.5; alkyl sesquichloride alkoxides such as ethyl aluminum sesqui ethoxide, butyl aluminum sesqui butoxide; dimethyl aluminum methoxide, diethyl aluminum ethoxide, dialkylaluminum alkoxides such as dibutyl aluminum butoxide Partially alkoxylated alkylaluminum having an average composition; diethylaluminum phenoxide, diethylaluminum (2,6-di-t-butyl-4-methylphenoxide),
Ethyl aluminum bis (2,6-di-t-butyl-4-methylphenoxide), diisobutyl aluminum (2,6-di-t-
Alkyl aluminum aryloxides such as butyl-4-methylphenoxide) and isobutylaluminum bis (2,6-di-t-butyl-4-methylphenoxide); dimethylaluminum chloride, diethylaluminum chloride,
Dialkylaluminum halides such as dibutylaluminum chloride, diethylaluminum bromide and diisobutylaluminum chloride; alkylaluminum sesquichlorides such as ethylaluminum sesquichloride, butylaluminum sesquichloride and ethylaluminum sesquibromide; ethylaluminum dichloride, propylaluminum dichloride and butylaluminum dibromide Partially halogenated alkylaluminums such as alkylaluminum dihalides; dialkylaluminum hydrides such as diethylaluminum hydride, dibutylaluminum hydride;
Other partially hydrogenated alkyl aluminums such as alkyl aluminum dihydrides such as ethyl aluminum dihydride, propyl aluminum dihydride;
Partially alkoxylated and halogenated alkylaluminums such as ethylaluminum ethoxycyclolide, butylaluminum butoxycyclolide, ethylaluminum ethoxybromide and the like can be mentioned.

Further, a compound similar to (b-1a) can also be used, and examples thereof include an organic aluminum compound in which two or more aluminum compounds are bonded via a nitrogen atom. Specifically, as such a compound,
(C ₂ H ₅ ) ₂ AlN (C ₂ H ₅ ) Al (C ₂ H ₅ ) _{2 and the} like. Examples of the compound belonging to (b-1b) include LiAl (C ₂ H ₅ ) ₄ LiAl (C ₇ H ₁₅ ) _{4 and the} like.

Further, (b-1) the organometallic compounds include methyllithium, ethyllithium, propyllithium, butyllithium, methylmagnesium bromide, methylmagnesium chloride, ethylmagnesium bromide, ethylmagnesium chloride, and propylmagnesium bromide. , Propyl magnesium chloride, butyl magnesium bromide, butyl magnesium chloride, dimethyl magnesium, diethyl magnesium, dibutyl magnesium, butyl ethyl magnesium and the like can also be used.

Further, a compound that forms the above-mentioned organoaluminum compound in the polymerization system, for example, a combination of an aluminum halide and an alkyl lithium, or a combination of an aluminum halide and an alkyl magnesium can also be used. Of these, organoaluminum compounds are preferred.

The (b-1) organometallic compound as described above has 1
These are used alone or in combination of two or more. (b-2) Organoaluminum oxy compound (b-2) The organoaluminum oxy compound used in the present invention may be a conventionally known aluminoxane, or as exemplified in JP-A-2-78687. It may be a benzene-insoluble organic aluminum oxy compound.

The conventionally known aluminoxane can be produced, for example, by the following method, and is usually obtained as a solution of a hydrocarbon solvent. (1) Compounds containing adsorbed water or salts containing water of crystallization, for example, magnesium chloride hydrate, copper sulfate hydrate,
An organic aluminum compound such as trialkylaluminum is added to a hydrocarbon medium suspension such as aluminum sulfate hydrate, nickel sulfate hydrate or cerous chloride hydrate, and adsorbed water or water of crystallization is added to the organic aluminum. A method of reacting with a compound. (2) A method in which water, ice or steam is allowed to directly act on an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether or tetrahydrofuran. (3) A method of reacting an organoaluminum compound such as trialkylaluminum with an organotin oxide such as dimethyltin oxide or dibutyltin oxide in a medium such as decane, benzene or toluene.

The aluminoxane may contain a small amount of an organic metal component. The solvent or unreacted organoaluminum compound may be removed from the recovered solution of the aluminoxane by distillation, and then redissolved in a solvent or suspended in a poor solvent for the aluminoxane. Specific examples of the organoaluminum compound used in preparing the aluminoxane include the same organoaluminum compounds as those exemplified as the organoaluminum compound belonging to (B-1a).

Of these, trialkylaluminum and tricycloalkylaluminum are preferred, and trimethylaluminum is particularly preferred. The above-mentioned organoaluminum compounds are used alone or in combination of two or more. The aluminoxane prepared from trimethylaluminum is called methylaluminoxane or MAO, and is a particularly frequently used compound.

Solvents used for the preparation of aluminoxanes include aromatic hydrocarbons such as benzene, toluene, xylene, cumene and cymene; and aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane and octadecane. Alicyclic hydrocarbons such as cyclopentane, cyclohexane, cyclooctane and methylcyclopentane; petroleum fractions such as gasoline, kerosene and light oil or halides of the above aromatic hydrocarbons, aliphatic hydrocarbons and alicyclic hydrocarbons Among them, hydrocarbon solvents such as chlorinated products and brominated products are exemplified. Further, ethers such as ethyl ether and tetrahydrofuran can also be used. Among these solvents, aromatic hydrocarbons and aliphatic hydrocarbons are particularly preferred.

In the benzene-insoluble organic aluminum oxy compound, the Al component soluble in benzene at 60 ° C. is usually 10% or less, preferably 5% or less in terms of Al atom.
It is particularly preferably at most 2%, and is insoluble or hardly soluble in benzene. Examples of the organic aluminum oxy compound include an organic aluminum oxy compound containing boron represented by the following general formula (i).

R ^d ₂ AlOB (R ^c ) OAlR ^d ₂ (i) (wherein R ^c represents a hydrocarbon group having 1 to 10 carbon atoms. R ^d may be the same or different. Often, it represents a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 10 carbon atoms.) The organic aluminum oxy compound containing boron represented by the general formula (i) is represented by the following general formula (ii) An alkylboronic acid represented by the formula and an organoaluminum compound are reacted in an inert solvent under an inert gas atmosphere
It can be produced by reacting at a temperature of 80 ° C. to room temperature for 1 minute to 24 hours.

R ^c B (OH) ₂ ... (Ii) (wherein, R ^c is the same group as described above). Methylboronic acid, ethylboronic acid, isopropylboronic acid, n-propylboronic acid, n-butylboronic acid, isobutylboronic acid, n-hexylboronic acid, cyclohexylboronic acid, phenylboronic acid, 3,5-difluorophenylboronic acid, pentafluoro Examples include phenylboronic acid and 3,5-bis (trifluoromethyl) phenylboronic acid. Among these, methylboronic acid,
Preferred are n-butylboronic acid, isobutylboronic acid, 3,5-difluorophenylboronic acid, and pentafluorophenylboronic acid. These are used alone or in combination of two or more.

Specific examples of such an organoaluminum compound to be reacted with an alkylboronic acid are described above (B
The same organoaluminum compounds as those exemplified as the organoaluminum compounds belonging to -1) can be mentioned. Of these, trialkylaluminum and tricycloalkylaluminum are preferable, and trimethylaluminum, triethylaluminum and triisobutylaluminum are particularly preferable. These are used alone or in combination of two or more.

The above-mentioned (a-2) organoaluminum oxy compounds are used alone or in combination of two or more. (b-3) reacting with the metallocene compound (a) to form an ion pair
The compound (b-3) (hereinafter referred to as "ionized ionic compound") which forms an ion pair by reacting with the formed metallocene compound (a) is described in JP-A-1-501950 and JP-A-1-501950. Japanese Patent Application Laid-Open No. 502036, Japanese Patent Application Laid-Open No. 3-179005, Japanese Patent Application Laid-Open No. 3-179006, Japanese Patent Application Laid-open No. 3-20
7703, JP-A-3-207704, US
Examples thereof include Lewis acids, ionic compounds, borane compounds and carborane compounds described in P-5321106 and the like.

Specifically, examples of the Lewis acid include BR
₃ (R is a phenyl group which may have a substituent such as fluorine, a methyl group, and a trifluoromethyl group or fluorine.), For example, trifluoroboron, Tris (4-fluorophenyl) boron, tris (3,5-difluorophenyl) boron, tris (4-fluoromethylphenyl) boron, tris (pentafluorophenyl) boron, tris (p-tolyl) boron, tris (o- Tolyl) boron, tris (3,5-dimethylphenyl) boron and the like.

Examples of the ionized ionic compound include compounds represented by the following general formula (iii).

[0138]

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In the formula, R ^e includes H ⁺ , carbenium cation, oxonium cation, ammonium cation, phosphonium cation, cycloheptyltrienyl cation, ferrocenium cation having a transition metal, and the like. R ^{f to} R ⁱ may be the same or different and are an organic group, preferably an aryl group or a substituted aryl group.

Specific examples of the carbenium cation include trisubstituted carbenium cations such as triphenylcarbenium cation, tris (methylphenyl) carbenium cation, and tris (dimethylphenyl) carbenium cation. Specific examples of the ammonium cation include trialkylammonium cations such as trimethylammonium cation, triethylammonium cation, tri (n-propyl) ammonium cation, triisopropylammonium cation, tri (n-butyl) ammonium cation, and triisobutylammonium cation. , N, N-dimethylanilinium cation, N, N-diethylanilinium cation, N, N-
Examples thereof include N, N-dialkylanilinium cations such as 2,4,6-pentamethylanilinium cation, dialkylammonium cations such as diisopropylammonium cation and dicyclohexylammonium cation.

Specific examples of the phosphonium cation include triarylphosphonium cations such as triphenylphosphonium cation, tris (methylphenyl) phosphonium cation, and tris (dimethylphenyl) phosphonium cation. Of the above, R
^e is preferably a carbenium cation, an ammonium cation, or the like, and particularly preferably a triphenylcarbenium cation, an N, N-dimethylanilinium cation, or an N, N-diethylanilinium cation.

Specific examples of the carbenium salt include triphenylcarbenium tetraphenylborate, triphenylcarbenium tetrakis (pentafluorophenyl) borate, triphenylcarbenium tetrakis (3,5-ditrifluoromethylphenyl) borate, tris ( 4-methylphenyl) carbenium tetrakis (pentafluorophenyl) borate; tris (3,5-dimethylphenyl) carbenium tetrakis (pentafluorophenyl) borate;

Examples of the ammonium salt include trialkyl-substituted ammonium salts, N, N-dialkylanilinium salts, dialkylammonium salts and the like. Specific examples of the trialkyl-substituted ammonium salt include, for example, triethylammonium tetraphenyl borate, tripropyl ammonium tetraphenyl borate, tri (n-butyl) ammonium tetraphenyl borate, trimethyl ammonium tetrakis (p-tolyl) borate, trimethyl ammonium tetrakis ( o-tolyl) borate, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, triethylammonium tetrakis (pentafluorophenyl) borate, tripropylammonium tetrakis (pentafluorophenyl)
Borate, tripropylammonium tetrakis (2,4-
Dimethylphenyl) borate, tri (n-butyl) ammonium tetrakis (3,5-dimethylphenyl) borate,
Tri (n-butyl) ammonium tetrakis (4-trifluoromethylphenyl) borate, tri (n-butyl) ammonium tetrakis (3,5-ditrifluoromethylphenyl) borate, tri (n-butyl) ammonium tetrakis (o-tolyl) ) Borate and the like.

Specific examples of the N, N-dialkylanilinium salt include N, N-dimethylanilinium tetraphenyl borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium N, N-diethylanilinium tetrakis (pentafluorophenyl) borate, N, N-diethylanilinium tetrakis (pentafluorophenyl) borate, N, N-diethylanilinium tetrakis (3,5-ditrifluoromethylphenyl) borate , 5-Ditrifluoromethylphenyl) borate, N, N-2,4,6-pentamethylanilinium tetraphenylborate, N, N-2,4,6-pentamethylanilinium tetrakis (pentafluorophenyl) borate, etc. Is mentioned.

Specific examples of the dialkylammonium salt include di (1-propyl) ammonium tetrakis (pentafluorophenyl) borate and dicyclohexylammonium tetraphenylborate. Further, ferrocenium tetrakis (pentafluorophenyl) borate, triphenylcarbenium pentaphenylcyclopentadienyl complex, N, N-diethylanilinium pentaphenylcyclopentadienyl complex,
Alternatively, borate compounds represented by the following formula (iv) or (v) can also be mentioned.

[0146]

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(In the formula, Et represents an ethyl group.)

[0148]

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Specific examples of the borane compound include decaborane (14), bis [tri (n-butyl) ammonium] nonaborate, bis [tri (n-butyl) ammonium] decaborate, and bis [tri (n-butyl) ammonium Anions such as undecaborate, bis [tri (n-butyl) ammonium] dodecaborate, bis [tri (n-butyl) ammonium] decachlorodecaborate, bis [tri (n-butyl) ammonium] dodecachlorododecaborate And metal such as tri (n-butyl) ammonium bis (dodecahydride dodecaborate) cobaltate (III), bis [tri (n-butyl) ammonium] bis (dodecahydride dodecaborate) nickelate (III) And borane anion salts.

Specific examples of the carborane compound include, for example, 4-carbanonaborane (14), 1,3-dicarbanonaborane (13), 6,9-dicarbadecaborane (14), dodecahydride-1-phenyl- 1,3-dicarbanonaborane, dodeca hydride-1-methyl-1,3-dicarbanonaborane,
Undecahydride-1,3-dimethyl-1,3-dicarbanonaborane, 7,8-dicarboundecaborane (13), 2,7-dicarboundecaborane (13), undecahydride
-7,8-dimethyl-7,8-dicarboundecaborane, dodecahydride-11-methyl-2,7-dicarboundecaborane,
Tri (n-butyl) ammonium 1-carbadecaborate,
Tri (n-butyl) ammonium 1-carboundecaborate, tri (n-butyl) ammonium 1-carbadodecaborate, tri (n-butyl) ammonium 1-trimethylsilyl-1-carbadecaborate, tri (n-butyl) Ammonium bromo-1-carbadodecaborate, tri (n-butyl) ammonium 6-carbadecaborate (14), tri (n-butyl) ammonium 6-carbadecaborate (1
2), tri (n-butyl) ammonium 7-carboundecaborate (13), tri (n-butyl) ammonium 7,8-
Dicarboundecaborate (12), tri (n-butyl)
Ammonium 2,9-dicarboundecaborate (12),
Tri (n-butyl) ammonium dodecahydride-8-
Methyl-7,9-dicarboundecaborate, tri (n-butyl) ammonium undecahydride-8-ethyl-7,9-
Dicarbaune decaborate, tri (n-butyl) ammonium undecahydride-8-butyl-7,9-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-8-allyl-7,9-dicarbaune Decaborate, tri (n-butyl) ammonium undecahydride-9-trimethylsilyl-7,8-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-4,6-dibromo-7-carboundecaborate Salts of anions such as tri (n-butyl) ammonium bis (nonahydride-1,3-dicarbanonaborate) cobaltate (III), tri (n-butyl) ammonium bis (undecahydride-7,8 -Dicarboundecaborate) ferrate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarboundecaborate) co Belt salt (III), tri (n- butyl) ammonium bis (undecapeptide 7,8-dicarbaundecaborate deca borate)
Nickelate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarboundecaborate) cuprate (III), tri (n-butyl) ammonium bis (undecahydride-7) , 8-Dicarboundecaborate) aurate (III), tri (n-butyl) ammonium bis (nonahydride-7,8-dimethyl-7,8-dicarboundecaborate) ferrate (III) (N-butyl) ammonium bis (nonahydride-7,8-dimethyl-7,8-dicarboundecaborate) chromate (III), tri (n-butyl) ammonium bis (tribromooctahydride-7,8 -Dicarboundecaborate) cobaltate (II
I), tris [tri (n-butyl) ammonium] bis (undecahydride-7-carboundecaborate) chromate (III), bis [tri (n-butyl) ammonium]
Bis (undecahydride-7-carboundecaborate) manganate (IV), bis [tri (n-butyl) ammonium] bis (undecahydride-7-carboundecaborate) cobaltate (III), Bis [tri (n-butyl) ammonium] bis (undecahydride-7-
Metal carborane anions such as (carboundecaborate) nickelate (IV).

The above (b-3) ionized ionic compounds are used alone or in combination of two or more. (C) Particulate carrier If necessary, (c) the particulate carrier is an inorganic or organic compound, and is a granular or particulate solid having a particle size of 5 to 300 µm, preferably 10 to 200 µm. used. Of these, porous oxides and chlorides are preferable as the inorganic compound, specifically, SiO ₂ ,
Al ₂ O ₃ , MgCl ₂ , MgO, ZrO, TiO ₂ , B ₂
O ₃ , CaO, ZnO, BaO, ThO _{2 and the} like, or a mixture containing them, for example, SiO ₂ —MgO, SiO ₂ —A
l ₂ O ₃ , SiO ₂ -TiO ₂ , SiO ₂ -V ₂ O ₅ , SiO _2-
Cr ₂ O ₃ , SiO ₂ -MgCl ₂ , MgO-MgCl ₂ , S
iO ₂ -TiO ₂ -MgO, etc. can be exemplified. Among them, those containing at least one component selected from the group consisting of SiO ₂ and Al ₂ O ₃ as a main component are preferable.

The inorganic oxide contains a small amount of Na ₂ C
O ₃ , K ₂ CO ₃ , CaCO ₃ , MgCO ₃ , Na ₂ SO ₄ ,
Al ₂ (SO ₄ ) ₃ , BaSO ₄ , KNO ₃ , Mg (NO ₃ ) ₂ ,
Carbonate, sulfate, nitrate and oxide components such as Al (NO ₃ ) ₃ , Na ₂ O, K ₂ O and Li ₂ O may be contained. Further, an ion-exchange layered silicate can be used as the particulate carrier. When an ion-exchange layered silicate is used, the use of an organic aluminum oxy compound such as an alkylaluminoxane can be reduced by utilizing its ion-exchange property and layer structure in addition to the function as a carrier. Is also possible. The ion-exchanged layered silicate is mainly produced naturally as a main component of a clay mineral, but is not particularly limited to a naturally-occurring one and may be an artificial synthetic product. Specific examples of the ion-exchange layered silicate include kaolinite, montmorillonite, hectorite, bentonite, smectite, vermiculite, synthetic mica, synthetic hectorite, and the like.

The properties of the fine particle carrier (c) vary depending on the kind and the production method, but have a specific surface area of 50 to 50%.
1000 m ² / g, preferably in the range of 100~800m ² / g, it is desirable that the pore volume is in the range of 0.3~3.0cm ³ / g. The carrier may optionally be 80
It is used by firing at a temperature of from 1000 to 1000C, preferably from 100 to 800C.

Further, examples of the particulate carrier (c) that can be used in the present invention include a granular or particulate solid of an organic compound having a particle size in the range of 5 to 300 μm. Examples of these organic compounds include ethylene, propylene, 1-butene, a polymer or copolymer formed mainly of an α-olefin having 2 to 14 carbon atoms such as 4-methyl-1-pentene, or vinyl. Cyclohexane, a polymer or copolymer formed mainly of styrene, or a polar functional group obtained by copolymerizing or graft-polymerizing a polar monomer such as acrylic acid, acrylic acid ester, or maleic anhydride with these polymers. Can be exemplified.

In the polymerization, the method of use and the order of addition of each catalyst component are arbitrarily selected, and the following methods are exemplified. (1) Component (a) and at least one component (b) selected from the group consisting of (b-1) an organometallic compound, (b-2) an organoaluminum oxy compound and (b-3) an ionized ionic compound Simply referred to as “component (b)”) in any order. (2) A method in which the catalyst in which the component (a) and the component (b) are brought into contact in advance is added to the polymerization reactor. (3) A method in which the catalyst component in which the component (a) and the component (b) are brought into contact in advance and the component (b) are added to the polymerization reactor in an arbitrary order. In this case, each component (b) may be the same or different. (4) A method in which the catalyst component in which the component (a) is supported on the particulate carrier (c) and the component (b) are added to the polymerization reactor in any order. (5) Component (a) and component (b) are combined with a particulate carrier (c).
A method in which a catalyst supported on a polymer is added to a polymerization reactor. (6) Component (a) and component (b) are combined with a particulate carrier (c).
A method in which the catalyst component supported on the polymer and the component (b) are added to the polymerization reactor in any order. In this case, each component (b)
They may be the same or different. (7) A method in which the catalyst component in which the component (b) is supported on the particulate carrier (c) and the component (a) are added to the polymerization reactor in an arbitrary order. (8) A method in which the catalyst component in which the component (b) is supported on the fine-particle carrier (c), the component (a), and the component (b) are added to the polymerization reactor in an arbitrary order. In this case, each component (b) may be the same or different. (9) The component (a) and the component (b) are mixed with the fine particle carrier (c).
A method in which a catalyst component, which has been brought into contact with a component (b) in advance with a catalyst supported on a catalyst, is added to a polymerization reactor. In this case, each component (b) may be the same or different. (10) The component (a) and the component (b) are combined with the fine particle carrier (c).
A method in which the catalyst supported on the catalyst is brought into contact with the component (b) in advance and the catalyst component and the component (b) are added to the polymerization reactor in any order. In this case, each component (b) may be the same or different.

In the solid catalyst component in which the component (a) and the component (b) are supported on the fine particle carrier (c), an olefin may be preliminarily polymerized. This pre-polymerized solid catalyst component usually contains 0.1 to 1000 g, preferably 0.3 to 500 g, of polyolefin per 1 g of the solid catalyst component.
g, particularly preferably from 1 to 200 g.

For the purpose of promoting the polymerization smoothly, an antistatic agent or an antifouling agent may be used in combination or may be carried on a carrier. In the present invention, the polymerization can be carried out by either a liquid phase polymerization method such as solution polymerization or suspension polymerization or a gas phase polymerization method. Specific examples of the inert hydrocarbon solvent used in the liquid phase polymerization include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; cyclopentane, cyclohexane, and methylcyclopentane Alicyclic hydrocarbons such as benzene, toluene, xylene, etc .; halogenated hydrocarbons such as ethylene chloride, chlorobenzene, dichloromethane and the like, and mixtures thereof, and α-olefins used for polymerization. It may itself be used as a solvent.

In carrying out the polymerization, the component (a) is used in an amount of usually 10 ^-8 to 10 ^-2 mol, preferably 10 ^-7 to 10 ^-3 mol, per liter of reaction volume.
Component (b-1) has a molar ratio [(b-1) / M] of component (b-1) to transition metal atom (M) in component (a) of usually 0.01 to
It is used in an amount of 5,000, preferably 0.05 to 2,000. The component (b-2) has a molar ratio [(b-2) / M] of the aluminum atom in the component (b-2) to the transition metal atom (M) in the component (a) of usually 10 to 10. It is used in an amount of 5000, preferably 20-2000. component
(b-3) has a molar ratio [(b-3) / M] of component (b-3) to transition metal atom (M) in component (a) of usually 1 to 10, preferably 1 to 10. Used in an amount such that

The polymerization temperature of olefin using such an olefin polymerization catalyst is usually -50 to 200 ° C.
Preferably it is in the range of 0 to 170 ° C. The polymerization pressure is usually from normal pressure to 10 MPa gauge pressure, preferably from normal pressure to 5 MPa.
Under the condition of a gauge pressure, the polymerization reaction can be carried out by any of a batch system, a semi-continuous system, and a continuous system. Further, the polymerization can be performed in two or more stages having different reaction conditions.

In the polymerization, hydrogen can be added for the purpose of controlling the molecular weight and polymerization activity of the produced polymer, and the amount thereof is suitably about 0.001 to 100 NL per kg of olefin. Propylene block copolymer (B) The propylene block copolymer (B) used in the present invention is a propylene homopolymer part or a propylene / α-olefin copolymer part having an α-olefin content of 10 mol% or less. And an amorphous olefin polymer part.

The propylene homopolymer portion and the propylene / α-olefin copolymer portion constitute n-decane-insoluble components at room temperature, and the amorphous olefin polymer portion comprises n-decane at room temperature.
Make up the decane solubles. As the other α-olefin forming the propylene / α-olefin copolymer part, specifically, ethylene and 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 3-methyl-1 -Pentene, 4-
Α-olefins having 4 to 20 carbon atoms, such as methyl-1-pentene.

The propylene homopolymer part and the propylene / α-olefin copolymer part of the propylene block copolymer (B) used in the present invention have the following properties. (I) Melt flow rate (ASTM D 1238,2
30 ° C., 2.16 kg load) is 0.01 to 1000 g
/ 10 minutes, preferably 0.05 to 500 g / 10 minutes, particularly preferably 0.1 to 100 g / 10 minutes, (ii)
2,1-insertion or 1,3-insertion of propylene monomer in all propylene structural units determined from ¹³ C-NMR spectrum
0.2% for all irregular units based on insertion
(Iii) a molecular weight distribution (Mw / Mn) determined by gel permeation chromatography (GPC) of 1 to 3, preferably 1 to 2.5, more preferably 1 to
It is in the range of 2.3.

The propylene homopolymer portion and the propylene / α-olefin copolymer portion further include the following (i)
It preferably has the characteristics of v), (v) and (vi). (Iv) n-decane soluble content (propylene homopolymer
After being treated with n-decane at 150 ° C. for 2 hours, the temperature is returned to room temperature,
(% by weight dissolved in n-decane) is 2% by weight or less, preferably 1% by weight or less, and (v) the isotactic pentad fraction determined from ¹³ C-NMR spectrum measurement is 90% or more, preferably 95% or more. (Vi) The temperature (Tm) at the maximum peak position of the endothermic curve measured by a differential scanning calorimeter (DSC) is usually 153 to 165.
° C, preferably 155-163 ° C, more preferably 15 ° C.
It is desirable to be in the range of 7 to 161 ° C.

The amorphous olefin polymer part is a (co) polymer of an α-olefin having 2 to 20 carbon atoms,
MFR measured at 0 ° C. under a load of 2.16 kg is 0.01
-100 g / 10 min, preferably 0.05-50 g / 10 min. This amorphous olefin polymer part has a crystallinity of 3 measured by an X-ray diffraction method.
It is desirably less than 0% and amorphous.

Examples of the α-olefin having 2 to 20 carbon atoms include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene and And mixtures thereof. Among them, α-olefins having 2 to 10 carbon atoms are particularly preferred. The amorphous olefin polymer part is preferably a copolymer of ethylene and an α-olefin other than ethylene, and the α-olefin has, for example, 3 carbon atoms.
To 20 α-olefins, and preferably 3 to 8 carbon atoms. Further, the amorphous olefin polymer portion is also preferably a copolymer of propylene and an α-olefin other than propylene.
It is an olefin, preferably ethylene and an α-olefin having 4 to 8 carbon atoms, particularly preferably ethylene.

Particularly preferred copolymers as the amorphous olefin polymer portion include ethylene / propylene copolymer, ethylene / butene copolymer, ethylene / hexene copolymer and ethylene / octene copolymer. it can. The amorphous olefin polymer portion may contain a component unit other than a component unit derived from an α-olefin, such as a component unit derived from a diene compound, as long as its properties are not impaired.

Examples of the component units that can be contained in the amorphous olefin polymer portion include 1,4-hexadiene, 1,6-octadiene, 2-methyl-1,5-hexadiene,
Linear non-conjugated dienes such as -methyl-1,5-heptadiene and 7-methyl-1,6-octadiene; cyclohexadiene, dicyclopentadiene, methyltetrahydroindene, 5-vinylnorbornene, 5-ethylidene-2-norbornene, Five-
Cyclic non-conjugated dienes such as methylene-2-norbornene, 5-isopropylidene-2-norbornene, 6-chloromethyl-5-isopropylenyl-2-norbornene; 2,3-diisopropylidene-5-norbornene, 2- Component units derived from diene compounds such as ethylidene-3-isopropylidene-5-norbornene and 2-propenyl-2,2-norbornadiene can be mentioned.

Such diene components can be used alone or in combination. The content of the diene component is usually 10 mol% or less, preferably 0 to 5 mol%. As the amorphous olefin polymer part, a component unit derived from propylene is 0 to 95 mol%, preferably 5 to 92 mol%, more preferably 10 to 90 mol%, and ethylene or a C 4 to C 20 carbon atom. The component unit derived from the α-olefin is 1 to 100 mol%, preferably 4 to 100 mol%.
To 95 mol%, more preferably 10 to 90 mol%, and a copolymer having a component unit derived from a diene component of 0 to 10 mol, preferably 0 to 5 mol%, more preferably 0 to 3 mol%. Can be mentioned.

The propylene-based block copolymer (B) is
60-99% by weight, preferably 70-99% by weight of the propylene homopolymer part and the propylene / α-olefin copolymer part
It is contained in an amount of 97% by weight, and it is desirable that the amorphous olefin polymer part is contained in an amount of 1 to 40% by weight, preferably 3 to 30% by weight. This propylene-based block copolymer (B) has a particle size of 23 according to ASTM D1238.
It is desirable that the melt flow rate (MFR) measured at 0 ° C. under a load of 2.16 kg is in the range of 0.1 to 1000 g / 10 min, preferably 0.05 to 500 g / 10 min, and gel permeation chromatography Graphy (GP
The molecular weight distribution (Mw / Mn) determined by C) is 1 to
6, preferably in the range of 1.5 to 5.5.

The propylene-based block copolymer (B) was obtained from the ¹³ C-NMR spectrum to determine the proportion of the heterogeneous bond based on the 2,1-insertion of the propylene monomer in all the propylene constituent units and the 1,3-insertion. Is 0.2% or less, preferably 0.15% or less.
% Desirably less is, ¹³ C-NMR isotactic pentad fraction determined from the spectrum (m
mmm) is 85% or more, preferably 90% or more, and more preferably 95% or more.

The propylene-based block copolymer (B) is
(A) a metallocene compound, (b-1) an organometallic compound,
(B-2) at least one compound selected from the group consisting of an organoaluminum oxy compound and (b-3) a compound which reacts with the metallocene compound (a) to form an ion pair, and if necessary, (c) fine particles In the presence of an olefin polymerization catalyst composed of a fibrous carrier, polymerization is carried out in two or more stages having different reaction conditions, and at least one stage comprises a propylene homopolymer portion or a propylene / α-olefin copolymer portion. Or by preparing an amorphous olefin polymer part in another step, or using a plurality of polymerization vessels, and using one of the polymerization vessels to produce a propylene homopolymer part or a propylene α-olefin. It can be produced by preparing a copolymer part and preparing an amorphous olefin polymer part in the other polymerization vessel.

Specific examples of the olefin polymerization catalyst used for producing the propylene-based block copolymer (B) include:
The same olefin polymerization catalyst as used in producing the propylene-based polymer (A) can be used. The polymerization conditions are the same as those for the propylene-based polymer (A). Elastomer (C) The elastomer (C) is a polymer of one kind of monomer selected from the group consisting of olefins having 2 to 20 carbon atoms and polyenes having 5 to 20 carbon atoms, or a polymer having 2 carbon atoms.
A random copolymer or a block copolymer of two or more monomers selected from the group consisting of olefins having from 20 to 20 and polyene having from 5 to 20 carbon atoms. The elastomer (C) has a content of a structural unit derived from ethylene, propylene, butene or 4-methyl-1-pentene of 9%.
It is less than 0 mol%, preferably 85 mol% or less, and the glass transition temperature (Tg) is 10 ° C or less, preferably -100 to 0 ° C, more preferably -100 to -10 ° C.

Examples of the olefin having 2 to 20 carbon atoms include ethylene, propylene, 1-butene, 1-pentene, 2-methyl-1-butene, 3-methyl-1-butene, 1-hexene and 3-methyl-1 -Pentene, 4-methyl-1-pentene, 3,3-dimethyl-1
-Butene, 1-heptene, methyl-1-hexene, dimethyl-1
-Pentene, trimethyl-1-butene, ethyl-1-pentene, 1-octene, methyl-1-pentene, dimethyl-1-hexene, trimethyl-1-pentene, ethyl-1-hexene, methylethyl-1-pentene, Diethyl-1-butene, propyl
1-pentene, 1-decene, methyl-1-nonene, dimethyl-1
-Octene, trimethyl-1-heptene, ethyl-1-octene, methylethyl-1-heptene, diethyl-1-hexene,
1-dodecene, hexadodecene, styrene and the like.

The polyene having 5 to 20 carbon atoms includes
Polyenes having two or more conjugated or non-conjugated olefinic double bonds include, for example, 1,3-pentadiene, 1,4-pentadiene, 1,3-hexadiene, 1,4-hexadiene, , 5-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 6-methyl-1,6-octadiene, 7-methyl-1,6-octadiene, 6-ethyl-1 , 6-octadiene, 6-propyl-1,6-octadiene, 6-butyl-
1,6-octadiene, 6-methyl-1,6-nonadiene, 7-methyl-1,6-nonadiene, 6-ethyl-1,6-nonadiene, 7-ethyl-1,6-nonadiene, 6-methyl- 1,6-decadiene, 7-methyl-1,6-decadiene, 6-methyl-1,6-undecadiene, 1,
Chain polyene compounds such as 7-octadiene, 1,9-decadiene, 2,4,6-octatriene, 1,3,7-octatriene, 1,5,9-decatriene and divinylbenzene; Pentadiene, 1,3-cyclohexadiene, 5-ethyl-1,3-
Cyclohexadiene, 1,3-cycloheptadiene, dicyclopentadiene, dicyclohexadiene, 5-ethylidene
2-norbornene, 5-vinyl-2-norbornene, 5-isopropylidene-2-norbornene, methylhydroindene,
2,3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, 2-ethylidene
-3-isopropylidene-5-norbornene, 2-propenyl-
And cyclic polyene compounds such as 2,5-norbornadiene.

The elastomer (C) has a density of 0.85 to 0.92 g / cm ³ , preferably 0.85 to 0.92 g / cm ³ .
The intrinsic viscosity [η] measured in decalin at 135 ° C. is 0.1 to 20 dl / cm ^3.
g, preferably 0.5 to 10 dl / g, more preferably 1 to 5 dl / g. Also, X
It is desirable that the degree of crystallinity measured by a line diffraction method is less than 30% or amorphous.

As the elastomer (C), for example, a copolymer of two or more monomers selected from olefins having 2 to 20 carbon atoms, one monomer selected from olefins having 2 to 20 carbon atoms, A copolymer with one type of monomer selected from polyenes having 5 to 20 atoms,
Copolymers of two or more monomers selected from olefins having 2 to 20 carbon atoms and one monomer selected from polyenes having 5 to 20 carbon atoms can be used.

More specifically, 50 to 90 mol% of a constituent unit derived from ethylene, a constituent unit derived from a monomer selected from an olefin having 3 to 20 carbon atoms and a polyene having 5 to 20 carbon atoms. Containing from 10 to 50 mol% of a monomer, a composition derived from a monomer selected from an olefin having 3 to 6 carbon atoms and a polyene having 5 and 6 carbon atoms, from 60 to 90 mol% of a constituent unit derived from ethylene. An elastomer containing 10 to 40 mol% of units, an elastomer containing 65 to 90 mol% of constituent units derived from ethylene, and an elastomer containing 10 to 35 mol% of constituent units derived from a monomer selected from propylene and butene; 50 to 90 mol% of the derived structural unit, ethylene, and 4 to 4 carbon atoms
Structural units derived from monomers selected from olefins of 20 and polyenes having 5 to 20 carbon atoms
50 to 85 mol% of an elastomer containing 50 mol% of a structural unit derived from propylene, and a structural unit derived from a monomer selected from ethylene, an olefin having 4 to 6 carbon atoms and a polyene having 5 or 6 carbon atoms. 1
Elastomer containing 5 to 50 mol%, 50 to 80 mol% of a constituent unit derived from propylene, and an elastomer containing 20 to 50 mol% of a constituent unit derived from a monomer selected from ethylene and butene, styrene.
Examples include butadiene rubber (SBR) and a styrene-based block copolymer (SEBS) having poly (ethylene-butene) in a rubber intermediate block.

The elastomer (C) has 2 to 2 carbon atoms.
It is obtained by polymerizing or copolymerizing at least one monomer selected from the group consisting of 0 olefins and a polyene having 5 to 20 carbon atoms by a conventionally known method. This polymerization reaction can be carried out in a gas phase (gas phase method) or in a liquid phase (liquid phase method). The elastomer (C) can be used in combination of two or more.

Olefin Polymer (D) The olefin polymer (D) is composed of ethylene, butene and 4-
An olefin polymer containing at least 90 mol% of a structural unit derived from one monomer selected from the group consisting of methyl-1-pentene, An ethylene (co) polymer containing at least 95 mol%, preferably at least 95 mol%, of at least 90 mol% of structural units derived from butene;
90 mol% or more, preferably 95 mol% of a butene (co) polymer containing 95 mol% or more of a structural unit derived from 4-methyl-1-pentene
It is a 4-methyl-1-pentene (co) polymer contained in the above ratio.

The ethylene copolymer has a carbon number of 3 to 3.
It may contain a constituent unit derived from a monomer selected from the group consisting of 20 olefins and a polyene having 5 to 20 carbon atoms in a proportion of less than 10 mol%. The above-mentioned butene copolymer has a constitutional unit derived from a monomer selected from the group consisting of olefins having 2 to 20 carbon atoms other than butene and polyenes having 5 to 20 carbon atoms.
It may be contained at a ratio of less than 0 mol%.

The 4-methyl-1-pentene copolymer is
Even if it contains a structural unit derived from a monomer selected from the group consisting of an olefin having 2 to 20 carbon atoms other than methyl-1-pentene and a polyene having 5 to 20 carbon atoms in a proportion of less than 10 mol% Good. 2 to 2 carbon atoms
Examples of the olefin of 0 include the same olefins as those exemplified in the section of the elastomer (C).

Examples of the polyene having 5 to 20 carbon atoms include:
The same polyenes as those exemplified in the section of the elastomer (C) can be given. Such olefin polymer (D) has a density of 0.80~0.98g / cm ^3, preferably in the range of 0.85~0.96g / cm ^3,
The intrinsic viscosity [η] measured in decalin at 135 ° C. is
0.1 to 20 dl / g, preferably 0.5 to 10 dl / g
g, more preferably in the range of 1 to 5 dl / g.

The olefin polymer (D) is preferably an ethylene homopolymer or an ethylene copolymer.
Particularly preferred is an ethylene homopolymer. Olefin polymer (D) is composed of ethylene, butene and 4-methyl
One monomer selected from the group consisting of -1-pentene is polymerized by a conventionally known method, or one monomer selected from the group consisting of ethylene, butene and 4-methyl-1-pentene; and 2 to 2 carbon atoms other than monomer
It is obtained by copolymerizing at least one monomer selected from the group consisting of 20 olefins and a polyene having 5 to 20 carbon atoms by a conventionally known method. This polymerization reaction can be carried out in a gas phase (gas phase method) or in a liquid phase (liquid phase method).

The olefin polymer (D) can be used in combination of two or more. Modified olefin polymer (E) The modified olefin polymer (E) is an olefin polymer such as an olefin homopolymer or an olefin copolymer (hereinafter also referred to as a “raw polymer”) and a polar monomer.
It is obtained by heating and graft-modifying in the presence of a radical initiator.

As the raw material polymer, for example, the above-mentioned propylene-based polymer (A), propylene-based block copolymer (B), elastomer (C), olefin polymer (D)
Specific examples thereof include a propylene homopolymer, a propylene / ethylene block copolymer, a crystalline propylene / ethylene random copolymer, an ethylene / propylene copolymer rubber, and ethylene / 1-
Butene copolymer rubber, ethylene / propylene / 1-butene copolymer rubber, ethylene / propylene / non-conjugated diene copolymer rubber, ethylene / 1-butene / non-conjugated diene copolymer rubber, ethylene / propylene / 1- Butene / non-conjugated diene copolymer rubber. Further, high-density polyethylene, high-pressure low-density polyethylene, linear low-density polyethylene, poly 1-butene, poly 4-methyl 1-pentene and the like can also be used.

Among them, a propylene homopolymer and a crystalline propylene / ethylene random copolymer containing a unit derived from ethylene in an amount of 10 mol% or less are preferably used. Examples of the polar monomer include a compound having a polar group such as a carboxyl group and an acid anhydride group, and an aromatic vinyl compound.

Specific examples of the polar monomer include acrylic acid, methacrylic acid, α-ethylacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, maleic anhydride, and itaconic anhydride. Anhydrides of unsaturated carboxylic acids such as α, β-unsaturated carboxylic anhydrides such as acid, citraconic anhydride and tetrahydrophthalic acid, and bicyclo [2.2.1] hept-2-ene-5,6-dicarboxylic anhydride Things. Among these, acrylic acid, maleic acid, itaconic acid, maleic anhydride and itaconic anhydride are preferred.

As the aromatic vinyl compound, styrene,
α-methylstyrene, o-methylstyrene, p-methylstyrene, m-methylstyrene, p-chlorostyrene, m-chlorostyrene and p-chloromethylstyrene, 4-vinylpyridine, 2-vinylpyridine, 5-ethyl- 2-vinylpyridine, 2-methyl-5-vinylpyridine, 2-isopropenylpyridine, 2-vinylquinoline, 3-vinylisoquinoline, N-
Vinyl carbazole, N-vinyl pyrrolidone and the like.

These polar monomers can be used in combination of two or more. When producing a modified olefin polymer, an organic peroxide, an azo compound, or the like can be used as a radical initiator. Specific examples of the organic peroxide include 1,1-bis (t-butylperoxy)
-3,5,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 2,2-bis (t-butylperoxy) octane, n-butyl-4,4-bis (t- Peroxyketals such as butylperoxy) bararate and 2,2-bis (t-butylperoxy) butane; di-t-butyl peroxide, dicumyl peroxide, t-butylcumyl peroxide, α, α ′ -Bis (t-butylperoxy-m-isopropyl) benzene, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, 2,5-dimethyl-2,5-
Dialkyl peroxides such as bis (t-butylperoxy) hexine-3; acetyl peroxide, isobutyryl peroxide, octanoyl peroxide,
Diacyl peroxides such as decanoyl peroxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, and m-trioyl peroxide; t- Butyl peroxyacetate,
t-butylperoxyisobutyrate, t-butylperoxy-2-ethylhexanoate, t-butylperoxylaurate, t-butylperoxybenzoate, di-t-butylperoxyisophthalate, 2,5 Peroxyesters such as -dimethyl-2,5-di (benzoylperoxy) hexane, t-butylperoxymaleic acid, t-butylperoxyisopropyl carbonate, cumylperoxyoctate; t-butyl hydroperoxide , Cumene hydroperoxide, diisopropylbenzene hydroperoxide, 2,5-dimethylhexane
Hydroperoxides such as -2,5-dihydroperoxide and 1,1,3,3-tetramethylbutyl hydroperoxide;

Among these, 1,1-bis (t-butylperoxy) -3,5,5-trimethylcyclohexane, di-t-butyl peroxide, dicumyl peroxide, 2,5-dimethyl-2 2,5-bis (t-butylperoxy) hexane, 2,5
-Dimethyl-2,5-bis (t-butylperoxy) hexyne-
3, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, m-trioyl peroxide, t-butylperoxy-2-ethylhexanoate and the like are preferably used.

Examples of the azo compound include azobisisobutyronitrile. Such a radical initiator can be used in combination of two or more kinds.
In graft-modifying the raw material polymer, the polar monomer as described above is used for 100 parts by weight of the raw material polymer.
Usually, it is used in an amount of 0.01 to 50 parts by weight, preferably 0.1 to 40 parts by weight.

The radical initiator is the same as the starting polymer 100
It is used in an amount of usually 0.01 to 10 parts by weight, preferably 0.05 to 8 parts by weight, based on parts by weight. The graft modification can be performed by a known method. Specifically, for example, the following method is used. (I) A method of melt-kneading a raw material polymer and a polar monomer in the presence of a radical initiator. (Ii) A method in which a polar monomer and a radical initiator are added to an organic solvent solution of a raw material polymer and heated. (Iii) A method in which a polar monomer and a radical initiator are added to an aqueous dispersion of a raw material polymer and heated. (Iv) A method in which the starting polymer and the polar monomer are heated at a temperature equal to or lower than the melting point of the olefin polymer in the presence of a radical initiator.

The temperature below the melting point of the raw material polymer is specifically 165 ° C. or less for a propylene polymer and 140 ° C. or less for an ethylene polymer. The intrinsic viscosity [η] of such a modified olefin polymer in decalin is such that the modified olefin polymer is a propylene homopolymer, a crystalline propylene / ethylene random copolymer, a crystalline propylene / ethylene block copolymer. And the like, it is usually 0.1 to 1 dl / g, preferably 0.1 to 1 dl / g.
5 to 0.8 dl / g, more preferably 0.2 to 0.6
dl / g.

The modified olefin-based polymer may be a high-density polyethylene, a medium-density polyethylene, a high-pressure low-density polyethylene, a linear low-density polyethylene, an ethylene / propylene random copolymer, an ethylene / 1-butene random copolymer, In the case of a modified olefin polymer obtained by modifying an ethylene copolymer such as an ethylene / polar group-containing unsaturated compound copolymer, usually 0.05 to 1 dl /
g, preferably 0.08 to 0.6 dl / g, and more preferably 0.1 to 0.5 dl / g.

Propylene Polymer Composition Next, each embodiment of the propylene polymer composition according to the present invention will be described in detail. (First propylene-based polymer composition)
Is composed of a propylene polymer (A1) and a propylene polymer (A2) selected from the propylene polymer (A), and the propylene polymer (A1) is 1 to 99% by weight. %, Preferably 10-9
0% by weight of a propylene-based polymer (A2)
In an amount of 1 to 99% by weight, preferably 10 to 90% by weight.

The MFR of the propylene polymer (A1)
MFR of (MFR _A1 ) and propylene polymer (A2)
(MFR _A2) the ratio between (MFR _A1 / MFR _A2) is 10 or more, preferably 30 or more. The first propylene polymer composition according to the present invention has a temperature of 230 ° C. and a load of 2.16 k.
The melt flow rate (MFR) measured in grams is 0.0
1 to 1000 g / 10 min, preferably 0.5 to 200 g /
Mw / Mn of the entire propylene component constituting the propylene polymer composition is 1.5 to 5.5.
Is desirably within the range.

The density is 0.88 to 0.92 g / cm ³ ,
Preferably, it is in the range of 0.90 to 0.92 g / cm ³ . Heat distortion temperature (HDT) is 95 ℃ or more,
Preferably, it is in the range of 100 to 150 ° C. Flexural modulus (FM) is 1000-3000MP
a, preferably in the range of 1500 to 2500 MPa.

The Izod impact value (IZ) at 23 ° C. is desirably in the range of 10 to 90 J / m, preferably 15 to 70 J / m. The ratio of the heterogeneous bond based on the 2,1-insertion and the ratio of the heterogeneous bond based on the 1,3-insertion of the propylene monomer in all the propylene constitutional units, which is determined from the ¹³ C-NMR spectrum, is 0.2% or less. Desirably.

The first propylene polymer composition according to the present invention may contain another polymer different from the propylene polymer (A1) and the propylene polymer (A2). In addition, the first propylene polymer composition according to the present invention includes a weather resistance stabilizer, a heat resistance stabilizer, an antistatic agent, an anti-slip agent, an anti-blocking agent, and an anti-fogging agent as long as the object of the invention is not impaired. If necessary, additives such as a lubricant, a pigment, a dye, a nucleating agent, a plasticizer, an antioxidant, a hydrochloric acid absorbent, and an antioxidant may be incorporated.

[0200] Such a first propylene polymer composition can be produced by using a known method, for example, the following method. (1) A method of mechanically blending a propylene polymer (A1), a propylene polymer (A2), and other components to be added as desired using an extruder, a kneader, or the like. (2) A propylene polymer (A1), a propylene polymer (A2), and other components to be added as required are mixed with a suitable good solvent (for example, hexane, heptane, decane, cyclohexane, benzene, toluene, xylene, etc.). (Hydrocarbon solvent) and then removing the solvent. (3) Propylene polymer (A1), propylene polymer (A2), and other components to be added as required are separately dissolved in a suitable good solvent, and then mixed. How to remove. (4) A method in which the above methods (1) to (3) are combined. (5) The polymerization is performed in two or more stages having different reaction conditions,
It is prepared by producing a propylene polymer (A1) in at least one step and producing a propylene polymer (A2) in another step, or using a plurality of polymerization vessels,
A method in which a propylene polymer (A1) is produced in one polymerization vessel and a propylene polymer (A2) is produced in the other polymerization vessel.

Such a first propylene polymer composition is excellent in heat resistance, rigidity and tensile elongation at break, and also excellent in moldability. Furthermore, since the catalyst residue in the polymer composition is small, the molded article is not colored and the sanitary property is good. (Second propylene-based polymer composition)
Is composed of the propylene polymer (A) and the elastomer (C), and the propylene polymer (A) is 5 to 99% by weight, preferably 3
0 to 95% by weight, more preferably 50 to 90% by weight, and the elastomer (C) in a ratio of 1 to 95% by weight, preferably 5 to 70% by weight, more preferably 10 to 50% by weight. It is desirable to contain.

The second propylene polymer composition according to the present invention has a melt flow rate (MFR) measured at 230 ° C. under a load of 2.16 kg of 0.01 to 1000 g / 10
Min, preferably in the range of 0.5 to 200 g / 10 min,
The Mw / Mn of the entire propylene component constituting the propylene-based polymer composition is desirably in the range of 1.5 to 5.5.

The density is 0.88 to 0.92 g / cm ³ ,
Preferably, it is in the range of 0.90 to 0.92 g / cm ³ . Heat distortion temperature (HDT) is 95 ℃ or more,
Preferably, it is in the range of 100 to 150 ° C. Flexural modulus (FM) is 800 to 2500 MPa,
Preferably, it is in the range of 1000-2200 MPa.

The Izod impact value (IZ) at 23 ° C. is 50 to 700 J / m, preferably 70 to 600 J / m.
m is desirable. The second propylene-based polymer composition according to the present invention may include another polymer different from the propylene-based polymer (A) and the elastomer (C). In addition, the second propylene polymer composition according to the present invention requires the additives exemplified as the additives that may be blended with the first propylene polymer composition as long as the object of the present invention is not impaired. It may be blended accordingly.

Such a second propylene polymer composition can be produced by using a known method, for example, the following method. (1) Propylene polymer (A) and elastomer (C)
And a method of mechanically blending, with an optional component, an extruder or a kneader. (2) Propylene polymer (A) and elastomer (C)
And other components to be added as required are dissolved in a suitable good solvent (for example, a hydrocarbon solvent such as hexane, heptane, decane, cyclohexane, benzene, toluene and xylene), and then the solvent is removed. (3) Propylene polymer (A) and elastomer (C)
A method in which a solution is prepared by separately dissolving and optionally other components in an appropriate good solvent, and then mixed, and then the solvent is removed. (4) A method in which the above methods (1) to (3) are combined.

Such a second propylene polymer composition is excellent in heat resistance, rigidity and tensile elongation at break, and also excellent in moldability. Furthermore, since the catalyst residue in the polymer composition is small, the molded article is not colored and the sanitary property is good. (Third propylene-based polymer composition)
Is composed of the propylene polymer (A) and the olefin polymer (D),
5 to 99% by weight, preferably 30 to 97% by weight, more preferably 50 to 95% by weight of the propylene polymer (A)
And the olefin polymer (D) in an amount of 1 to 95% by weight, preferably 30 to 70% by weight, more preferably 5 to 95% by weight.
It is desirable to contain it in a proportion of about 50% by weight.

The third propylene polymer composition according to the present invention has a melt flow rate (MFR) measured at 230 ° C. under a load of 2.16 kg of 0.01 to 1000 g / 10.
Min, preferably in the range of 0.5 to 200 g / 10 min,
The Mw / Mn of the entire propylene component constituting the propylene-based polymer composition is desirably in the range of 1.5 to 5.5.

The density is 0.88 to 0.92 g / cm ³ ,
Preferably, it is in the range of 0.90 to 0.92 g / cm ³ . Heat distortion temperature (HDT) is 95 ℃ or more,
Preferably, it is in the range of 100 to 150 ° C. Flexural modulus (FM) is 800 to 2500 MPa,
Preferably, it is in the range of 1000-2200 MPa.

The Izod impact value (IZ) at 23 ° C. is 50 to 700 J / m, preferably 70 to 600 J / m.
m is desirable. The third propylene-based polymer composition according to the present invention may contain another polymer different from the propylene-based polymer (A) and the olefin polymer (D). In addition, the third propylene polymer composition according to the present invention requires the additives exemplified as the additives that may be blended in the first propylene polymer composition, as long as the object of the present invention is not impaired. It may be blended accordingly.

Such a third propylene polymer composition can be produced by using a known method. For example, a propylene polymer (A) and an olefin polymer (D)
It can be produced in the same manner as in the second propylene polymer composition, using other components optionally added. Such a third propylene polymer composition is excellent in heat resistance, rigidity and tensile elongation at break, and also excellent in moldability. Furthermore, since the catalyst residue in the polymer composition is small, the molded article is not colored and the sanitary property is good.

(Fourth propylene polymer composition) The fourth propylene polymer composition according to the present invention comprises the propylene polymer (A) and the modified olefin polymer (E). , The propylene-based polymer (A) is 5 to 9
It contains 9% by weight, preferably 30 to 97% by weight, more preferably 50 to 95% by weight, and contains the modified olefin polymer (E) at 1 to 95% by weight, preferably 3 to 70% by weight, more preferably Is desirably contained at a ratio of 5 to 50% by weight.

The fourth propylene polymer composition according to the present invention has a melt flow rate (MFR) measured at 230 ° C. under a load of 2.16 kg of 0.01 to 1000 g / 10.
Min, preferably in the range of 0.5 to 200 g / 10 min,
The Mw / Mn of the entire propylene component constituting the propylene-based polymer composition is desirably in the range of 1.5 to 5.5.

The density is 0.88 to 0.92 g / cm ³ ,
Preferably, it is in the range of 0.90 to 0.92 g / cm ³ . Heat distortion temperature (HDT) is 95 ℃ or more,
Preferably, it is in the range of 100 to 150 ° C. Flexural modulus (FM) is 800 to 2500 MPa,
Preferably, it is in the range of 1000-2200 MPa.

The Izod impact value (IZ) at 23 ° C. is 50 to 700 J / m, preferably 70 to 600 J / m.
m is desirable. The fourth propylene polymer composition according to the present invention may contain another polymer different from the propylene polymer (A) and the modified olefin polymer (E). In addition, the fourth propylene polymer composition according to the present invention requires the additives exemplified as the additives that may be blended with the first propylene polymer composition, as long as the object of the present invention is not impaired. It may be blended accordingly.

Such a fourth propylene polymer composition can be produced by a known method. For example, a propylene polymer (A), a modified olefin polymer (E), and Second using other components
Can be produced in the same manner as the propylene polymer composition. Such a fourth propylene polymer composition comprises:
Excellent heat resistance, rigidity and tensile elongation at break,
Excellent moldability. Furthermore, since the catalyst residue in the polymer composition is small, the molded article is not colored and the sanitary property is good.

(Fifth propylene polymer composition) The fifth propylene polymer composition according to the present invention comprises the propylene polymer (A), the elastomer (C),
The olefin polymer (D) comprises 4 to 98% by weight, preferably 27 to 97% by weight of the propylene polymer (A).
% By weight, more preferably 45 to 90% by weight, and contains the elastomer (C) at a rate of 1 to 95% by weight, preferably 3 to 70% by weight, more preferably 5 to 50% by weight, 1 to 95% by weight of the olefin polymer (D),
Preferably, it is contained in an amount of preferably 3 to 70% by weight, more preferably 5 to 50% by weight.

The fifth propylene polymer composition according to the present invention has a melt flow rate (MFR) measured at 230 ° C. under a load of 2.16 kg of 0.01 to 1000 g / 10ｇ.
Min, preferably in the range of 0.5 to 200 g / 10 min,
The Mw / Mn of the entire propylene component constituting the propylene-based polymer composition is desirably in the range of 1.5 to 5.5.

The density is 0.88 to 0.92 g / cm ³ ,
Preferably, it is in the range of 0.90 to 0.92 g / cm ³ . Heat distortion temperature (HDT) is 95 ℃ or more,
Preferably, it is in the range of 100 to 150 ° C. Flexural modulus (FM) is 800 to 2500 MPa,
Preferably, it is in the range of 1000-2200 MPa.

The Izod impact value (IZ) at 23 ° C. is 50 to 700 J / m, preferably 70 to 600 J / m.
m is desirable. The fifth propylene polymer composition according to the present invention comprises a propylene polymer (A), an elastomer (C), and an olefin polymer (D).
May be included.

[0220] The fifth propylene polymer composition according to the present invention may further comprise the additives exemplified as additives which may be blended with the first propylene polymer composition within a range not to impair the object of the present invention. May be blended as needed. Such a fifth propylene polymer composition can be produced by using a known method. For example, a propylene polymer (A), an elastomer (C), an olefin polymer (D), It can be manufactured in the same manner as the second propylene polymer composition using other components added by the above.

Such a fifth propylene polymer composition is excellent in heat resistance, rigidity and tensile elongation at break, and also excellent in moldability. Furthermore, since the catalyst residue in the polymer composition is small, the molded article is not colored and the sanitary property is good. (Sixth propylene-based polymer composition)
Is composed of the above-mentioned propylene-based polymer (A), the above-mentioned elastomer (C), and the above-mentioned modified olefin polymer (E). %, Preferably 27 to 94% by weight, more preferably 45 to 90% by weight,
1 to 95% by weight, preferably 3 to 95% by weight of the elastomer (C)
70% by weight, more preferably 5 to 50% by weight, the modified olefin polymer (E) is 1 to 95% by weight,
Preferably, it is contained in an amount of preferably 3 to 70% by weight, more preferably 5 to 50% by weight.

The sixth propylene polymer composition according to the present invention has a melt flow rate (MFR) measured at 230 ° C. under a load of 2.16 kg of 0.01 to 1000 g / 10.
Min, preferably in the range of 0.5 to 200 g / 10 min,
The Mw / Mn of the entire propylene component constituting the propylene-based polymer composition is desirably in the range of 1.5 to 5.5.

The density is 0.88 to 0.92 g / cm ³ ,
Preferably, it is in the range of 0.90 to 0.92 g / cm ³ . Heat distortion temperature (HDT) is 95 ℃ or more,
Preferably, it is in the range of 100 to 150 ° C. Flexural modulus (FM) is 800 to 2500 MPa,
Preferably, it is in the range of 1000-2200 MPa.

The Izod impact value (IZ) at 23 ° C. is 50 to 700 J / m, preferably 70 to 600 J / m.
m is desirable. The sixth propylene-based polymer composition according to the present invention may contain another polymer different from the propylene-based polymer (A), the elastomer (C), and the modified olefin polymer (E).

[0225] The sixth propylene polymer composition according to the present invention may contain the additives exemplified as the additives which may be blended with the first propylene polymer composition within a range not to impair the object of the present invention. May be blended as needed. Such a sixth propylene polymer composition can be produced by using a known method. For example, a propylene polymer (A), an elastomer (C), a modified olefin polymer (E), It can be produced in the same manner as the second propylene polymer composition by using other components added as desired.

Such a sixth propylene polymer composition is excellent in heat resistance, rigidity and tensile elongation at break, and also excellent in moldability. Furthermore, since the catalyst residue in the polymer composition is small, the molded article is not colored and the sanitary property is good. (Seventh propylene-based polymer composition)
Is composed of the propylene polymer (A), the olefin polymer (D), and the modified olefin polymer (E), and the propylene polymer (A) is 4 to 98% by weight, preferably 27 to 94% by weight, more preferably 45 to 90% by weight,
The olefin polymer (D) is contained at a ratio of 1 to 95% by weight, preferably 3 to 70% by weight, more preferably 5 to 50% by weight, and the modified olefin polymer (E) is 1 to 95% by weight, preferably Is 3 to 70% by weight, more preferably 5 to 5% by weight.
Desirably, the content is 0% by weight.

The seventh propylene polymer composition according to the present invention has a melt flow rate (MFR) measured at 230 ° C. under a load of 2.16 kg of 0.01 to 1000 g / 10 ／.
Min, preferably in the range of 0.5 to 200 g / 10 min,
The Mw / Mn of the entire propylene component constituting the propylene-based polymer composition is desirably in the range of 1.5 to 5.5.

The density is 0.88 to 0.92 g / cm ³ ,
Preferably, it is in the range of 0.90 to 0.92 g / cm ³ . Heat distortion temperature (HDT) is 95 ℃ or more,
Preferably, it is in the range of 100 to 150 ° C. Flexural modulus (FM) is 800 to 2500 MPa,
Preferably, it is in the range of 1000-2200 MPa.

The Izod impact value (IZ) at 23 ° C. is 50 to 700 J / m, preferably 70 to 600 J / m.
m is desirable. The seventh propylene-based polymer composition according to the present invention may include another polymer different from the propylene-based polymer (A), the olefin polymer (D), and the modified olefin polymer (E). .

[0230] The seventh propylene polymer composition according to the present invention may contain the additives exemplified as additives which may be blended with the first propylene polymer composition within a range not to impair the object of the present invention. May be blended as needed. Such a seventh propylene polymer composition can be produced using a known method, for example, a propylene polymer (A), an olefin polymer (D), and a modified olefin polymer (E). It can be produced in the same manner as the second propylene polymer composition, using other components optionally added.

The seventh propylene polymer composition is excellent in heat resistance, rigidity and tensile elongation at break, and also excellent in moldability. Furthermore, since the catalyst residue in the polymer composition is small, the molded article is not colored and the sanitary property is good. (Eighth propylene-based polymer composition)
Is composed of the propylene polymer (A), the elastomer (C), the olefin polymer (D), and the modified olefin polymer (E). The combined amount (A) is 3 to 97% by weight, preferably 24 to 91% by weight, more preferably 40% by weight.
To 85% by weight, and 1% of elastomer (C).
The olefin polymer (D) is contained in an amount of 1 to 95% by weight, preferably 3 to 70% by weight, more preferably 3 to 70% by weight, more preferably 5 to 50% by weight. Preferably, it is contained at a ratio of 5 to 50% by weight, and the modified olefin polymer (E) is contained at a ratio of 1 to 95% by weight, preferably 3 to 70% by weight, more preferably 5 to 50% by weight. desirable.

The eighth propylene polymer composition according to the present invention has a melt flow rate (MFR) measured at 230 ° C. under a load of 2.16 kg of 0.01 to 1000 g / 10ｇ.
Min, preferably in the range of 0.5 to 200 g / 10 min,
The Mw / Mn of the entire propylene component constituting the propylene-based polymer composition is desirably in the range of 1.5 to 5.5.

The density is 0.88 to 0.92 g / cm ³ ,
Preferably, it is in the range of 0.90 to 0.92 g / cm ³ . Heat distortion temperature (HDT) is 95 ℃ or more,
Preferably, it is in the range of 100 to 150 ° C. Flexural modulus (FM) is 800 to 2500 MPa,
Preferably, it is in the range of 1000-2200 MPa.

The Izod impact value (IZ) at 23 ° C. is 50 to 700 J / m, preferably 70 to 600 J / m.
m is desirable. The eighth propylene polymer composition according to the present invention comprises another polymer different from the propylene polymer (A), the elastomer (C), the olefin polymer (D), and the modified olefin polymer (E). May be included.

[0235] The eighth propylene polymer composition according to the present invention may contain the additives exemplified as the additives which may be blended with the first propylene polymer composition within a range not to impair the object of the present invention. May be blended as needed. Such an eighth propylene polymer composition can be produced by using a known method. For example, a propylene polymer (A), an elastomer (C), an olefin polymer (D), a modified It can be produced in the same manner as in the second propylene polymer composition using the olefin polymer (E) and other components added as required.

Such an eighth propylene polymer composition is excellent in heat resistance, rigidity and tensile elongation at break, and also excellent in moldability. Furthermore, since the catalyst residue in the polymer composition is small, the molded article is not colored and the sanitary property is good. (Ninth propylene-based polymer composition)
Is the above-mentioned propylene-based block copolymer (B).

It is desirable that the ninth propylene polymer composition according to the present invention has a heat distortion temperature (HDT) of 95 ° C. or higher, preferably in the range of 100 to 150 ° C. The flexural modulus (FM) is desirably in the range of 800 to 2500 MPa, preferably 1000 to 2200 MPa. The Izod impact value (IZ) at 23 ° C. is 50
７００700 J / m, preferably 70-600 J / m.

The ninth propylene polymer composition according to the present invention may contain another polymer different from the propylene block copolymer (B). In addition, the ninth propylene polymer composition according to the present invention may have the above-mentioned additive exemplified as an additive that may be blended with the first propylene polymer composition within a range not to impair the object of the present invention. Agents may be added as needed.

Such a ninth propylene polymer composition can be produced by the following method. (1) A propylene homopolymer forming a propylene homopolymer part or a propylene / α-olefin copolymer forming a propylene / α-olefin copolymer part, and an amorphous forming a non-crystalline olefin polymer part A method of mechanically blending a water-soluble olefin polymer and other components to be added as required with an extruder, a kneader or the like. (2) A propylene homopolymer forming a propylene homopolymer portion or a propylene / α-olefin copolymer forming a propylene / α-olefin copolymer portion and an amorphous forming an amorphous olefin polymer portion The soluble olefin polymer and other optional components are dissolved in a suitable good solvent (for example, a hydrocarbon solvent such as hexane, heptane, decane, cyclohexane, benzene, toluene and xylene), and then the solvent is removed. Method. (3) A propylene homopolymer forming a propylene homopolymer part or a propylene / α-olefin copolymer forming a propylene / α-olefin copolymer part, and an amorphous forming a non-crystalline olefin polymer part The water-soluble olefin polymer and other components to be added as needed are mixed separately after preparing solutions separately dissolved in a suitable good solvent,
Then, a method of removing the solvent. (4) A method in which the above methods (1) to (3) are combined. (5) As described above, in the presence of an olefin polymerization catalyst, polymerization is carried out in two or more stages having different reaction conditions, and at least one stage comprises a propylene homopolymer portion or a propylene / α-olefin copolymer portion. A propylene polymer is prepared, and is produced by preparing an amorphous olefin polymer part at another stage, or using a plurality of polymerization vessels, and using one of the polymerization vessels, a propylene homopolymer part or propylene-α. -A method of preparing an olefin copolymer portion and preparing an amorphous olefin polymer portion in the other polymerization vessel.

Such a ninth propylene polymer composition is excellent in heat resistance, rigidity and tensile elongation at break, and also excellent in moldability. Furthermore, since the catalyst residue in the polymer composition is small, the molded article is not colored and the sanitary property is good. (Tenth propylene-based polymer composition) A tenth propylene-based polymer composition according to the present invention comprises the propylene-based block copolymer (B) and the elastomer (C), and comprises a propylene-based block. When the copolymer (B) is
99% by weight, preferably 30 to 97% by weight, more preferably 50 to 95% by weight, and the elastomer (C) is 1 to 95% by weight, preferably 3 to 70% by weight,
More preferably, the content is preferably 5 to 50% by weight.

The tenth propylene polymer composition according to the present invention has a melt flow rate (MFR) measured at 230 ° C. under a load of 2.16 kg of 0.01 to 1000 g / m.
10 minutes, preferably in the range of 0.5 to 200 g / 10 minutes, and the Mw / Mn of the entire propylene component constituting the propylene-based polymer composition is desirably in the range of 1.5 to 5.5. .

The density is 0.88 to 0.92 g / cm ³ ,
Preferably, it is in the range of 0.90 to 0.92 g / cm ³ . Heat distortion temperature (HDT) is 95 ℃ or more,
Preferably, it is in the range of 100 to 150 ° C. Flexural modulus (FM) is 800 to 2500 MPa,
Preferably, it is in the range of 1000-2200 MPa.

The Izod impact value (IZ) at 23 ° C. is 50 to 700 J / m, preferably 70 to 600 J / m.
m is desirable. The tenth propylene polymer composition according to the present invention may contain another polymer different from the propylene block copolymer (B) and the elastomer (C). In addition, the tenth propylene polymer composition according to the present invention requires the additives exemplified as the additives that may be blended with the first propylene polymer composition within a range not to impair the object of the present invention. It may be blended accordingly.

The tenth propylene polymer composition can be produced by a known method. For example, a propylene-based block copolymer (B), an elastomer (C), and an It can be produced in the same manner as the second propylene polymer composition using other components to be produced. Such a tenth propylene polymer composition is excellent in heat resistance, rigidity and tensile elongation at break, and also excellent in moldability. Furthermore, since the catalyst residue in the polymer composition is small, the molded article is not colored and the sanitary property is good.

(Eleventh propylene-based polymer composition) The eleventh propylene-based polymer composition according to the present invention comprises the propylene-based block copolymer (B) and the olefin polymer (D). The propylene-based block copolymer (B) in an amount of 5 to 99% by weight, preferably 30 to 97% by weight, more preferably 50 to 95% by weight, and the olefin polymer (D) in an amount of 1 to 95% by weight. %, Preferably 3 to 70% by weight, more preferably 5 to 50% by weight.

The eleventh propylene polymer composition according to the present invention has a melt flow rate (MFR) measured at 230 ° C. under a load of 2.16 kg of 0.01 to 1000 g / m.
10 minutes, preferably in the range of 0.5 to 200 g / 10 minutes, and the Mw / Mn of the entire propylene component constituting the propylene-based polymer composition is desirably in the range of 1.5 to 5.5. .

The density is 0.88 to 0.92 g / cm ³ ,
Preferably, it is in the range of 0.90 to 0.92 g / cm ³ . Heat distortion temperature (HDT) is 95 ℃ or more,
Preferably, it is in the range of 100 to 150 ° C. Flexural modulus (FM) is 800 to 2500 MPa,
Preferably, it is in the range of 1000-2200 MPa.

The Izod impact value (IZ) at 23 ° C. is 50 to 700 J / m, preferably 70 to 600 J / m.
m is desirable. The eleventh propylene-based polymer composition according to the present invention may contain another polymer different from the propylene-based block copolymer (B) and the olefin polymer (D).

The eleventh propylene polymer composition according to the present invention contains the first propylene polymer composition as long as the object of the present invention is not impaired.
The additives exemplified as the additives which may be blended in the propylene polymer composition of the present invention may be blended as necessary. Such an eleventh propylene polymer composition can be produced using a known method. For example, a propylene-based block copolymer (B), an olefin polymer (D), Second using other components
Can be produced in the same manner as the propylene polymer composition.

The eleventh propylene polymer composition is excellent in heat resistance, rigidity and tensile elongation at break, and also excellent in moldability. Furthermore, since the catalyst residue in the polymer composition is small, the molded body is not colored,
Moreover, the hygiene is good. (Twelfth propylene-based polymer composition) A twelfth propylene-based polymer composition according to the present invention comprises the propylene-based block copolymer (B) and the modified olefin polymer (E), 5 to 99% by weight, preferably 30 to 97% by weight, more preferably 50 to 95% by weight of the propylene-based block copolymer (B),
It is desirable that the modified olefin polymer (E) is contained at a ratio of 1 to 95% by weight, preferably 3 to 70% by weight, more preferably 5 to 50% by weight.

The twelfth propylene polymer composition according to the present invention has a melt flow rate (MFR) measured at 230 ° C. under a load of 2.16 kg of 0.01 to 1000 g / m.
10 minutes, preferably in the range of 0.5 to 200 g / 10 minutes, and the Mw / Mn of the entire propylene component constituting the propylene-based polymer composition is desirably in the range of 1.5 to 5.5. .

The density is 0.88 to 0.92 g / cm ³ ,
Preferably, it is in the range of 0.90 to 0.92 g / cm ³ . Heat distortion temperature (HDT) is 95 ℃ or more,
Preferably, it is in the range of 100 to 150 ° C. Flexural modulus (FM) is 800 to 2500 MPa,
Preferably, it is in the range of 1000-2200 MPa.

The Izod impact value (IZ) at 23 ° C. is 50 to 700 J / m, preferably 70 to 600 J / m.
m is desirable. The twelfth propylene-based polymer composition according to the present invention may contain another polymer different from the propylene-based block copolymer (B) and the modified olefin polymer (E).

Further, the twelfth propylene polymer composition according to the present invention may contain the above additives as necessary, as long as the object of the present invention is not impaired.
Such a twelfth propylene polymer composition can be produced by using a known method. For example, a propylene-based block copolymer (B), a modified olefin polymer (E), and Second using other components
Can be produced in the same manner as the propylene polymer composition.

Such a twelfth propylene polymer composition is excellent in heat resistance, rigidity and tensile elongation at break, and also excellent in moldability. Furthermore, since the catalyst residue in the polymer composition is small, the molded body is not colored,
Moreover, the hygiene is good. (Thirteenth propylene-based polymer composition) The thirteenth propylene-based polymer composition according to the present invention comprises the propylene-based block copolymer (B) and the elastomer (C).
And the olefin polymer (D), and contains the propylene-based block copolymer (B) in a proportion of 4 to 98% by weight, preferably 27 to 94% by weight, more preferably 45 to 90% by weight. 1 to 95% by weight of the elastomer (C), preferably 3 to 70% by weight, more preferably 5 to 5% by weight.
0% by weight, and contains 1 olefin polymer (D).
The content is desirably in the range of about 95% by weight, preferably 3% to 70% by weight, and more preferably 5% to 50% by weight.

The thirteenth propylene polymer composition according to the present invention has a melt flow rate (MFR) measured at 230 ° C. under a load of 2.16 kg of 0.01 to 1000 g / m.
10 minutes, preferably in the range of 0.5 to 200 g / 10 minutes, and the Mw / Mn of the entire propylene component constituting the propylene-based polymer composition is desirably in the range of 1.5 to 5.5. .

The density is 0.88 to 0.92 g / cm ³ ,
Preferably, it is in the range of 0.90 to 0.92 g / cm ³ . Heat distortion temperature (HDT) is 95 ℃ or more,
Preferably, it is in the range of 100 to 150 ° C. Flexural modulus (FM) is 800 to 2500 MPa,
Preferably, it is in the range of 1000-2200 MPa.

The Izod impact value (IZ) at 23 ° C. is 50 to 700 J / m, preferably 70 to 600 J / m.
m is desirable. The thirteenth propylene-based polymer composition according to the present invention may contain another polymer different from the propylene-based block copolymer (B), the elastomer (C), and the olefin polymer (D).

The thirteenth propylene polymer composition according to the present invention contains the first propylene polymer as long as the object of the present invention is not impaired.
The additives exemplified as the additives which may be blended in the propylene polymer composition of the present invention may be blended as necessary. Such a thirteenth propylene polymer composition can be produced by using a known method, for example, a propylene-based block copolymer (B), an elastomer (C), and an olefin polymer (D). It can be produced in the same manner as the second propylene polymer composition using other components which are added as desired.

The thirteenth propylene polymer composition has excellent heat resistance, rigidity and tensile elongation at break, as well as excellent moldability. Furthermore, since the catalyst residue in the polymer composition is small, the molded body is not colored,
Moreover, the hygiene is good. (14th propylene-based polymer composition) The 14th propylene-based polymer composition according to the present invention comprises the propylene-based block copolymer (B) and the elastomer (C).
And the modified olefin polymer (E), and the propylene-based block copolymer (B) is contained in an amount of 4 to 98% by weight, preferably 27 to 94% by weight, and more preferably 45 to 90% by weight.
% By weight, and the elastomer (C) is contained in an amount of 1 to 95.
%, Preferably 3 to 70% by weight, more preferably 5% by weight.
1 to 95% by weight, preferably 3 to 70% by weight of the modified olefin polymer (E).
More preferably, the content is preferably 5 to 50% by weight.

The fourteenth propylene polymer composition according to the present invention has a melt flow rate (MFR) measured at 230 ° C. under a load of 2.16 kg of 0.01 to 1000 g / m.
10 minutes, preferably in the range of 0.5 to 200 g / 10 minutes, and the Mw / Mn of the entire propylene component constituting the propylene-based polymer composition is desirably in the range of 1.5 to 5.5. .

The density is 0.88 to 0.92 g / cm ³ ,
Preferably, it is in the range of 0.90 to 0.92 g / cm ³ . Heat distortion temperature (HDT) is 95 ℃ or more,
Preferably, it is in the range of 100 to 150 ° C. Flexural modulus (FM) is 800 to 2500 MPa,
Preferably, it is in the range of 1000-2200 MPa.

The Izod impact value (IZ) at 23 ° C. is 50 to 700 J / m, preferably 70 to 600 J / m.
m is desirable. The fourteenth propylene-based polymer composition according to the present invention may contain another polymer different from the propylene-based block copolymer (B), the elastomer (C), and the modified olefin polymer (E). .

The fourteenth propylene polymer composition according to the present invention contains the first propylene polymer as long as the object of the present invention is not impaired.
The additives exemplified as the additives which may be blended in the propylene polymer composition of the present invention may be blended as necessary. Such a fourteenth propylene polymer composition can be produced using a known method. For example, a propylene-based block copolymer (B) and an elastomer (C)
And the modified olefin polymer (E), and other components added as desired, in the same manner as in the second propylene polymer composition.

The fourteenth propylene polymer composition has excellent heat resistance, rigidity and tensile elongation at break, as well as excellent moldability. Furthermore, since the catalyst residue in the polymer composition is small, the molded body is not colored,
Moreover, the hygiene is good. (Fifteenth propylene-based polymer composition) The fifteenth propylene-based polymer composition according to the present invention comprises the propylene-based block copolymer (B), the olefin polymer (D), and the modified olefin. The propylene block copolymer (B) is composed of the polymer (E) in an amount of 4 to 98% by weight, preferably 27 to 94% by weight, more preferably 4 to 98% by weight.
The olefin polymer (D) is contained in an amount of 5 to 90% by weight, and preferably 1 to 95% by weight,
More preferably, it is contained at a ratio of 5 to 50% by weight, and the modified olefin polymer (E) is contained at 1 to 95% by weight, preferably 3% by weight.
It is desirable to contain it at a ratio of 70 to 70% by weight, more preferably 5 to 50% by weight.

The fifteenth propylene polymer composition according to the present invention has a melt flow rate (MFR) measured at 230 ° C. under a load of 2.16 kg of 0.01 to 1000 g / m.
10 minutes, preferably in the range of 0.5 to 200 g / 10 minutes, and the Mw / Mn of the entire propylene component constituting the propylene-based polymer composition is desirably in the range of 1.5 to 5.5. .

The density is 0.88 to 0.92 g / cm ³ ,
Preferably, it is in the range of 0.90 to 0.92 g / cm ³ . Heat distortion temperature (HDT) is 95 ℃ or more,
Preferably, it is in the range of 100 to 150 ° C. Flexural modulus (FM) is 800 to 2500 MPa,
Preferably, it is in the range of 1000-2200 MPa.

The Izod impact value (IZ) at 23 ° C. is 50 to 700 J / m, preferably 70 to 600 J / m.
m is desirable. The fifteenth propylene-based polymer composition according to the present invention contains another polymer different from the propylene-based block copolymer (B), the olefin polymer (D), and the modified olefin polymer (E). Is also good.

The fifteenth propylene polymer composition according to the present invention contains the first propylene polymer within the range not impairing the object of the present invention.
The above-mentioned additives exemplified as the additives which may be blended in the propylene polymer composition of the present invention may be blended as necessary. Such a fifteenth propylene polymer composition can be produced using a known method,
For example, a propylene-based block copolymer (B), an olefin polymer (D), a modified olefin polymer (E),
It can be produced in the same manner as the second propylene polymer composition by using other components added as required.

Such a fifteenth propylene polymer composition is excellent in heat resistance, rigidity and tensile elongation at break, and also excellent in moldability. Furthermore, since the catalyst residue in the polymer composition is small, the molded body is not colored,
Moreover, the hygiene is good. (Sixteenth propylene-based polymer composition) A sixteenth propylene-based polymer composition according to the present invention comprises the propylene-based block copolymer (B) and the elastomer (C).
And the olefin polymer (D) and the modified olefin polymer (E), and the propylene-based block copolymer (B) is contained in an amount of 3 to 97% by weight, preferably 24 to 91% by weight, more preferably The olefin polymer (D) contains 40 to 85% by weight, and contains the elastomer (C) at 1 to 95% by weight, preferably 3 to 70% by weight, more preferably 5 to 50% by weight. From 1 to 95% by weight, preferably from 3 to 70% by weight, more preferably from 5 to 5% by weight.
0% by weight, modified olefin polymer (E)
In an amount of 1 to 95% by weight, preferably 5 to 70% by weight, more preferably 5 to 50% by weight.

The sixteenth propylene polymer composition according to the present invention has a melt flow rate (MFR) measured at 230 ° C. under a load of 2.16 kg of 0.01 to 1000 g / m.
10 minutes, preferably in the range of 0.5 to 200 g / 10 minutes, and the Mw / Mn of the entire propylene component constituting the propylene-based polymer composition is desirably in the range of 1.5 to 5.5. .

The density is 0.88 to 0.92 g / cm ³ ,
Preferably, it is in the range of 0.90 to 0.92 g / cm ³ . Heat distortion temperature (HDT) is 95 ℃ or more,
Preferably, it is in the range of 100 to 150 ° C. Flexural modulus (FM) is 800 to 2500 MPa,
Preferably, it is in the range of 1000-2200 MPa.

The Izod impact value (IZ) at 23 ° C. is 50 to 700 J / m, preferably 70 to 600 J / m.
m is desirable. The sixteenth propylene-based polymer composition according to the present invention comprises another polymer different from the propylene-based block copolymer (B), the elastomer (C), the olefin polymer (D), and the modified olefin polymer (E). It may include coalescence.

The sixteenth propylene polymer composition according to the present invention contains the first propylene polymer as long as the object of the present invention is not impaired.
The additives exemplified as the additives which may be blended in the propylene polymer composition of the present invention may be blended as necessary. Such a sixteenth propylene polymer composition can be produced by using a known method. For example, a propylene-based block copolymer (B) and an elastomer (C)
, A olefin polymer (D), a modified olefin polymer (E), and other components added as desired.
Can be produced in the same manner as the propylene polymer composition.

The sixteenth propylene polymer composition is excellent in heat resistance, rigidity and tensile elongation at break, and also excellent in moldability. Furthermore, since the catalyst residue in the polymer composition is small, the molded body is not colored,
Moreover, the hygiene is good.

[0276]

EXAMPLES Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples. In the present invention, the melting point (Tm) of the polymer
Is determined by differential scanning calorimetry (DSC) from the crystal melting peak of a polymer sample held at 240 ° C. for 10 minutes, cooled to 30 ° C., held for 5 minutes, and then heated at 10 ° C./min. Calculated.

The molecular weight (Mw, Mn) was measured by GPC (gel permeation chromatography).
Stereoregularity of polymer (mmmm, 2,1-insertion, 1,3-insertion)
Was calculated from ¹³ C-NMR spectrum measurement. The melt flow rate (MFR) was measured at 230 ° C. under a load of 2.16 kg according to ASTM D1238.

The mechanical properties of the polymer were measured as follows. [Flexural modulus (FM)] Measured in accordance with ASTM D790. Test piece: 12.7 (width) x 6.4 (thickness) x 127 (length), span: 100 mm, bending speed: 2 mm / min [Izod impact value (IZ)] Measured in accordance with ASTM D256 did.

Temperature: 23 ° C. Test piece: 12.7 (width) × 6.4 (thickness) × 64 (length), notch machined [Heat deformation temperature (HDT)] Measured in accordance with ASTM D648 did. Test piece: 12.7 (width) x 6.4 (thickness) x 127 (length)

[0280]

[Production Example] [Synthesis of Metallocene Compound] Dimethylmethylene (3-tert-butyl-5-methylcyclopen
Tadienyl) (3,6-di-tert-butylfluorenyl) zirco
Synthesis of ammonium dichloride (1) Synthesis of 4,4'-Di-t-butyldiphenylmethane
38.4 g (289 mmol) of l ₃ were added, and CH ₃ NO ₂
Eighty milliliters were added to dissolve, and this was used as a solution. A 500-ml three-necked flask equipped with a dropping funnel and a magnetic stirrer was sufficiently purged with nitrogen.
6g (152mmol) and 2,6-di-t-butyl-4-methylphe
nol 43.8 g (199 mmol) was added, and CH ₃ NO ₂
80 ml was added and dissolved. It was cooled in an ice bath with stirring. Was added dropwise over 35 minutes, and the reaction solution was
Stirred at 2 ° C. for 1 h. The reaction solution was poured into 500 ml of ice water and extracted with 800 ml of hexane. 5% aq of organic layer
Washed with 600 ml of NaOH, followed by drying over MgSO ₄ . After filtering off the MgSO ₄ , the oil obtained by evaporating the solvent was cooled to −78 ° C. to precipitate a solid, which was collected by filtration and washed with 300 ml of EtOH. Drying under reduced pressure gave 4,4'-Di-t-butyldiphenylmethane. Yield: 18.9 g (2) Synthesis of 2,2'-Diiodo-4,4'-Di-t-butyldiphenylmethane 4,4'-Di-t-butyl-in a 200 ml flask equipped with a magnetic stirrer
1.95 g (6.96 mmol) of butyldiphenylmethane
And HIO ₄ 0.78 g (3.48 mmol), I ₂
1.55 g (6.12 mmol), concH ₂ SO ₄ 0.1.
48 ml were charged. 17.5 ml of acetic acid and 3.7 parts of water
5 ml was added, and the mixture was heated to 90 ° C. with stirring to react for 5 hours. The reaction mixture was poured into ice water 50 ml, and extracted with Et ₂ O. The organic layer was washed with saturated aqNaHSO ₄ 100ml, followed by Na a ₂ CO ₃ was added, filtered off after stirring Na ₂ CO _3. Further, the organic layer was washed with 800 ml of water, and then Mg ₂ SO ₄
And dried. After filtration with Mg ₂ SO ₄ , the solvent was distilled off to obtain a yellow oil. Purification by column chromatography gave 2,2'-Diiodo-4,4'-Di-t-butyldiphenylmethane. Yield 3.21 g (3) Synthesis of 3,6-di-t-Butylfluorene 2,2′-Diiodo-4,4′-Di-t-buty
3.21 g (6.03 mmol) of ldiphenylmethane,
2.89 g (47.0 mmol) of copper powder was added, and the temperature was 230 ° C.
, And reacted for 5 hours with stirring. After extraction with acetone and evaporation of the solvent, a reddish-brown oil was obtained. Column chromatography provided a pale yellow oil. The fraction containing the unreacted raw material was again applied to the column to collect only the target substance. Recrystallization from methanol gave a white solid. Yield 1.08 g (4) Synthesis of 1-tert-butyl-3-methylcyclopentadiene Under a nitrogen atmosphere, a 2.0 mol / l tert-butylmagnesium chloride / diethyl ether solution (45
0 ml, 0.90 mol) with dehydrated diethyl ether (3
50 ml) was added to the solution while maintaining the temperature at 0 ° C. under ice cooling with 3-methylcyclopentenone (43.7 g, 0.45 m).
mol.) of anhydrous diethyl ether (150 ml) was added dropwise, and the mixture was further stirred at room temperature for 15 hours. A solution of ammonium chloride (80.0 g, 1.50 mol) in water (350 ml) was added dropwise to the reaction solution while maintaining 0 ° C. under ice cooling. After water (2500 ml) was added to this solution and stirred, the organic layer was separated and washed with water. A 10% hydrochloric acid aqueous solution (82 ml) was added to the organic layer while maintaining the temperature at 0 ° C under ice cooling.
Was added and stirred at room temperature for 6 hours. The organic layer of this reaction solution was separated, and water, a saturated aqueous solution of sodium hydrogen carbonate, water,
After washing with saturated saline, it was dried over anhydrous magnesium sulfate. The drying agent was filtered, and the solvent was distilled off from the filtrate to obtain a liquid. This liquid was distilled under reduced pressure (45-47 ° C./10 mmH
g) to obtain 14.6 g of a pale yellow liquid.
The analytical values are shown below. ¹ H-NMR (270 MHz, in CDCl ₃ , TMS standard) δ 6.31 + 6.13 + 5.94 + 5.87 (s +
s + t + d, 2H), 3.04 + 2.95 (s + s, 2
H), 2.17 + 2.09 (s + s, 3H), 1.27
(D, 9H) (5) Synthesis of 3-tert-butyl-5,6,6-trimethylfulvene Dehydration of 1-tert-butyl-3-methylcyclopentadiene (13.0 g, 95.6 mmol) under a nitrogen atmosphere Dehydrated acetone (55.2 g, 950.4 mmol) was added dropwise to a methanol (130 ml) solution while maintaining the temperature at 0 ° C under ice cooling, and pyrrolidine (68.0 g, 956.1 mmol) was further added.
After l) was added dropwise, the mixture was stirred at room temperature for 4 days. The reaction solution was diluted with diethyl ether (400 ml), and then diluted with water (400 ml).
l) was added. The organic layer was separated, washed with a 0.5N aqueous hydrochloric acid solution (150 ml × 4), water (200 ml × 3) and saturated saline (150 ml), and dried over anhydrous magnesium sulfate. The drying agent was filtered, and the solvent was distilled off from the filtrate to obtain a liquid. This liquid was distilled under reduced pressure (70-80 ° C / 0.1
mmHg) to obtain 10.5 g of a yellow liquid. The analytical values are shown below. ¹ H-NMR (270 MHz, in CDCl ₃ , TMS standard) δ 6.23 (s, 1H), 6.05 (d, 1H),
2.23 (s, 3H), 2.17 (d, 6H), 1.1
7 (s, 9H) (6) Synthesis of 2- (3-tert-butyl-5-methylcyclopentadienyl) -2- (3,6-di-tert-butylfluorenyl) propane Di-tert-butylfluorene (0.9 g, 3.4 mm
ol) in a THF (30 ml) solution under ice cooling with n-butyllithium in hexane (2.1 ml, 3.4 mmol).
1) was added dropwise under a nitrogen atmosphere, and the mixture was further stirred at room temperature for 6 hours. Furthermore, 3-tert-butyl- was added to this red solution under ice cooling.
5,6,6-trimethylfulvene (0.6 g, 3.5 mmol
A solution of l) in THF (15 ml) was added dropwise under a nitrogen atmosphere. After stirring at room temperature for 12 hours, water (30 ml) was added. The organic phase extracted and separated with diethyl ether was dried over magnesium sulfate, filtered, and the solvent was removed from the filtrate under reduced pressure to obtain a solid. This solid was recrystallized from hot methanol to give 1.2 g of a pale yellow solid. The analytical values are shown below. ¹ H-NMR (270 MHz, in CDCl ₃ , TMS standard) δ 7.72 (d, 2H), 7.18-7.05
(M, 4H), 6.18-5.99 (s + s, 1H),
4.32-4.18 (s + s, 1H), 3.00-2.
90 (s + s, 2H), 2.13-1.98 (t + s,
3H), 1.38 (s, 18H), 1.19 (s, 9
H), 1.10 (d, 6H) (7) Synthesis of dimethylmethylene (3-tert-butyl-5-methylcyclopentadienyl) (3,6-di-tert-butylfluorenyl) zirconium dichloride Ice 2- (3-tert-butyl-5-methylcyclopentadienyl) -2- (3,6-di-tert-butylfluorenyl) propane (1.3 g, 2.8 mmol) diethyl ether under cooling A hexane solution of n-butyllithium (3.6 ml, 5.8 mmol) was added dropwise to the (40 ml) solution under a nitrogen atmosphere, and the mixture was further stirred at room temperature for 16 hours. The solvent was removed from the reaction mixture under reduced pressure to give a red-orange solid. Dichloromethane (150 ml) was added to the solid at −78 ° C., and the mixture was stirred and dissolved.
(2.7 mmol) in dichloromethane (10 ml), stirred at -78 ° C for 6 hours, and stirred at room temperature for 24 hours. The solvent was removed from this reaction solution under reduced pressure to obtain an orange solid. Further, the solid was extracted with toluene, filtered through celite, the solvent was removed from the filtrate under reduced pressure, and then recrystallized from diethyl ether to obtain 0.18 g of an orange solid. The analytical values are shown below. ¹ H-NMR (270 MHz, in CDCl ₃ , TMS standard) δ 7.98 (dd, 2H), 7.90 (d, 1
H), 7.69 (d, 1H), 7.32-7.25
(M, 2H), 6.01 (d, 1H), 5.66 (d,
1H), 2.54 (s, 3H), 2.36 (s, 3
H), 2.28 (s, 1H), 1.43 (d, 18
H), 1.08 (s, 9H) dimethylsilylenebis (2-methyl-4- phenylindenyl)
B) Synthesis of zirconium dichloride The compound was synthesized according to the method described in Organometallics, 13, 954 (1994).

[Preparation of Silica-Supported Methylaluminoxane] 20 g of silica (H-121, manufactured by Asahi Glass Co., Ltd., 150 ° C. under nitrogen) was placed in a 500 ml reactor sufficiently purged with nitrogen.
After drying for 60 hours) and 200 ml of toluene, 60 ml of methylaluminoxane (10 wt% toluene solution, manufactured by Albemarle Co., Ltd.) was added dropwise with stirring under a nitrogen atmosphere. Next, the mixture was reacted at 110 ° C. for 4 hours, and then the reaction system was allowed to cool to precipitate a solid component, and the supernatant solution was removed by decantation. Subsequently, the solid component was washed three times with toluene and three times with hexane,
A silica-supported methylaluminoxane was obtained.

[Production of propylene polymer (PP-1)] In a 100 ml two-necked flask sufficiently purged with nitrogen, methylaluminoxane supported on silica was added in an amount of 2.
0 mmol was added and suspended in 50 ml of heptane. To the suspension, 5.4 mg (8.8 μm) of dimethylmethylene (3-tert-butyl-5-methylcyclopentadienyl) (3,6-di-tert-butylfluorenyl) zirconium dichloride was added.
ol) as a toluene solution, and then triisobutylaluminum (8 mmol) was added, followed by stirring for 30 minutes to form a catalyst suspension. The above catalyst suspension was added to a 17-liter autoclave sufficiently purged with nitrogen, and 4 k
g of liquefied propylene and 1 NL of hydrogen,
Polymerization was performed at 70 ° C. for 30 minutes under a pressure of 3.0 to 3.5 MPa. After the completion of the first-stage polymerization, an additional 10 NL of hydrogen is added,
The second stage polymerization was performed at 70 ° C. for 30 minutes. After completion of the polymerization, methanol was added to stop the polymerization, and propylene was purged to obtain homo-PP. Dry at 80 ° C. under vacuum for 6 hours. The weight of the polymer (PP-1) after drying was 2.5 kg. This polymer has a Tm = 158 ° C., MFR = 50 g / 10 min, Mw /
Mn = 3.3. The stereoregularity of the polymer is
mmmm = 95.8%, neither 2,1-insertion nor 1,3-insertion was detected.

By separately and independently performing the polymerization corresponding to the first and second stages of the above polymerization, MFR = 6 in the first stage
g / 10 min, yield 1.0 kg, MFR = 200 in the second stage
It was found that g / 10 minutes and a yield of 1.5 kg of homo PP were obtained. [Production of Propylene Polymer (PP-2)] In a 100 ml two-necked flask sufficiently purged with nitrogen, 2.0 mmol of methylaluminoxane supported on silica was converted into aluminum and suspended in 50 ml of heptane. To the suspension, 5.4 mg (8.8 μmol) of dimethylmethylene (3-tert-butyl-5-methylcyclopentadienyl) (3,6-di-tert-butylfluorenyl) zirconium dichloride in a toluene solution Then, triisobutylaluminum (8 mmol) was added, and the mixture was stirred for 30 minutes to form a catalyst suspension. The above catalyst suspension was added to a 17-liter autoclave sufficiently purged with nitrogen, charged with 4 kg of liquefied propylene and 3 NL of hydrogen, and 3.0 to 3.5.
Polymerization was performed at 70 ° C. for 60 minutes under a pressure of MPa. After completion of the polymerization, methanol was added to stop the polymerization, and propylene was purged to obtain homo-PP. Dry at 80 ° C. under vacuum for 6 hours.
The weight of the polymer (PP-2) after drying was 1.7 kg. This polymer has Tm = 158 ° C., MFR = 60 g / 10 min, M
w / Mn = 2.1. The stereoregularity of the polymer was mmmm = 95.8%, and neither 2,1-insertion nor 1,3-insertion was detected.

[Production of Propylene Polymer (PP-3)] In a 100 ml two-necked flask sufficiently purged with nitrogen, methylaluminoxane supported on silica was added in an amount of 2.
0 mmol was added and suspended in 50 ml of heptane. 5.4 mg (8.8 μm) of dimethylmethylene (3-tert-butyl-5-methylcyclopentadienyl) (3,6-di-tert-butylfluorenyl) zirconium dichloride was added to the suspension.
mol) was added as a toluene solution, and then triisobutylaluminum (8 mmol) was added, followed by stirring for 30 minutes to form a catalyst suspension. The above catalyst suspension was added to a 17-liter autoclave sufficiently purged with nitrogen,
kg of liquefied propylene, 2.4 NL of ethylene, and 3 NL of hydrogen were charged and polymerized at 60 ° C. for 60 minutes under a pressure of 3.0 to 3.5 MPa. After completion of the polymerization, methanol was added to stop the polymerization, and propylene was purged to obtain a random PP. Dry at 80 ° C. under vacuum for 6 hours. The polymer (PP-3) after drying was 2.1 kg. This polymer had Tm = 149 ° C., MFR = 50 g / 10 min, Mw / Mn
= 2.1, ethylene content = 1.3 mol%. The stereoregularity of the polymer was mmmm = 95.0%, 2,1-
Insertion = 0.02%, 1,3-insertion = 0.09%.

[Production of propylene polymer (PP-4)] In a 100 ml two-necked flask sufficiently purged with nitrogen, silica-supported methylaluminoxane was added in an amount of 2.
0 mmol was added and suspended in 50 ml of heptane. To the suspension was added 5.4 mg (8.8 μm) of dimethylmethylene (3-tert-butyl-5-methylcyclopentadienyl) (3,6-di-tert-butylfluorenyl) zirconium dichloride.
mol) was added as a toluene solution, and then triisobutylaluminum (8 mmol) was added, followed by stirring for 30 minutes to form a catalyst suspension. The above catalyst suspension was added to a 17-liter autoclave sufficiently purged with nitrogen,
3.2 kg of liquefied propylene and 2 NL of hydrogen were charged, and bulk homopolymerization was performed at 70 ° C for 30 minutes under a pressure of 3.0 to 3.5 MPa.

After the completion of the homopolymerization, the vent valve was opened, and unreacted propylene and hydrogen were depressurized until the pressure in the polymerization reactor became normal pressure. After the depressurization was completed, copolymerization of ethylene and propylene was subsequently performed. That is, an ethylene / propylene mixed gas (ethylene 25 mol%, propylene 75
Mol%) was continuously supplied while adjusting the vent opening of the polymerization reactor so that the pressure in the polymerization reactor was 1 MPa.
Polymerization was performed at 60 ° C for 60 minutes. After completion of the polymerization, the polymerization was stopped by adding methanol, and propylene was purged to block P.
P was obtained. Dry at 80 ° C. under vacuum for 6 hours. The weight of the polymer (PP-4) after drying was 1.4 kg. This polymer had a Tm of 158 ° C., an MFR of 58 g / 10 min, and a decane-soluble component amount of 15% by weight. Decane soluble component is MFR
= 2 g / 10 min, the ethylene content was 40 mol%.
Further, the propylene homopolymer part has T = 158 ° C., MF
R = 80 g / 10 min, Mw / M = 2.1. Further, the stereoregularity of the propylene homopolymer portion was mmmm = 9.
At 5.8%, neither the 2,1-insertion nor the 1,3-insertion was detected.

Here, identification of the amount, composition, molecular weight, stereoregularity, etc. of the polymer obtained in each stage was performed as follows. First, the above block PP (PP-4) is n-
The mixture was heat-treated with decane for 2 hours, cooled to room temperature, and the precipitated solid component was filtered. The solid component obtained at this time is
The propylene homopolymer obtained in the step was used. A component obtained by concentrating and drying the filtrate under reduced pressure was used as a decane-soluble component. Various analyzes were performed on each component according to a conventional method.

[Production of Propylene Polymer (PP-5)] In a 100 ml two-necked flask sufficiently purged with nitrogen, silica-supported methylaluminoxane was converted to aluminum in an amount of 2.
0 mmol was added and suspended in 50 ml of heptane. 4.8 mg of dimethylsilylenebis (2-methyl-4-phenylindenyl) zirconium dichloride was added to the suspension.
(7.6 μmol) was added as a toluene solution, then triisobutylaluminum (7 mmol) was added, and the mixture was stirred for 30 minutes to form a catalyst suspension. The above catalyst suspension was added to a 17-liter autoclave sufficiently purged with nitrogen, 4 kg of liquefied propylene and 10 NL of hydrogen were charged, and 70 ° C. under a pressure of 3.0 to 3.5 MPa.
For 60 minutes. After completion of the polymerization, methanol was added to stop the polymerization, and propylene was purged to obtain homo-PP. Dry at 80 ° C. under vacuum for 6 hours. Dried polymer (PP-
5) was 3.1 kg. This polymer has a Tm = 15
At 0 ° C., MFR = 42 g / 10 min, Mw / Mn = 2.2. The stereoregularity of the polymer is mmmm = 95.
7%, 2,1-insertion = 0.80%, 1,3-insertion = 0.05%.

[Production of Propylene Polymer (PP-6)] In a 100 ml two-necked flask sufficiently purged with nitrogen, methylaluminoxane supported on silica was added in an amount of 2.
0 mmol was added and suspended in 50 ml of heptane. 4.8 mg of dimethylsilylenebis (2-methyl-4-phenylindenyl) zirconium dichloride was added to the suspension.
(7.6 μmol) was added as a toluene solution, then triisobutylaluminum (7 mmol) was added, and the mixture was stirred for 30 minutes to form a catalyst suspension. The above catalyst suspension was added to a 17-liter autoclave sufficiently purged with nitrogen, charged with 4 kg of liquefied propylene, 2.3 NL of ethylene, and 10 NL of hydrogen, and 3.0 to 3.5.
Polymerization was performed at 60 ° C. for 60 minutes under a pressure of MPa. After completion of the polymerization, methanol was added to stop the polymerization, and propylene was purged to obtain a random PP. Dry at 80 ° C. under vacuum for 6 hours. The weight of the polymer (PP-6) after drying was 2.3 kg.
This polymer has Tm = 138 ° C., MFR = 36 g / 10
Min, Mw / Mn = 2.3, ethylene content = 1.5 mol%
Met. The stereoregularity of the polymer is mmmm = 9.
4.8%, 2,1-insertion = 0.91%, 1,3-insertion = 0.11
%Met.

[Production of propylene polymer (PP-7)] The polymer was produced by a conventional homo PP polymerization method using a titanium catalyst. This polymer has Tm = 161 ° C., MFR = 40 g /
Mw / Mn = 5.1 for 10 minutes. The stereoregularity of the polymer was mmmm = 95.0%, and neither 2,1-insertion nor 1,3-insertion was detected.

[Production of Propylene Polymer (PP-8)] A block polymer PP was produced by a conventional polymerization method using a titanium catalyst. This polymer has a Tm of 161 ° C. and an MFR of 45.
g / 10 minutes, the amount of the decane-soluble component was 15% by weight. The decane-soluble component is an ethylene / propylene copolymer, MFR = 2 g / 10 min, ethylene content is 40 mol%
Met.

[Production of Ethylene / Propylene Copolymer (Elastomer-1)] An ethylene / propylene copolymer was produced by a conventional ethylene / propylene copolymerization method using a titanium-based catalyst. This polymer had an MFR of 2 g / 10 min and an ethylene content of 42 mol%. [Production of ethylene-butene copolymer (elastomer-2)] The copolymer was produced by a common ethylene-butene copolymerization method using a vanadium catalyst. This polymer had an MFR of 7 g / 10 min and an ethylene content of 89 mol%.
Met.

[Production of ethylene polymer (PE-1)] The polymer was produced by a conventional homo PE polymerization method using a titanium catalyst. This polymer has MFR = 5 g / 10 min, Mw / Mn
= 4.6.

[0294]

Example 1 PP-1 polymerized in the above production example: 40 parts by weight,
PP-2: A mixture consisting of 60 parts by weight was mechanically blended, melt-kneaded and pelletized. Using the propylene polymer composition thus obtained, a resin temperature of 200
AST with an injection molding machine under the condition of 40 ° C and mold temperature 40 ° C
M test pieces were molded and each physical property was measured. Table 1 shows the results.

[0295]

Example 2 PP-4 polymerized in the above production example was melt-kneaded and pelletized. Using the propylene polymer composition thus obtained, the AST was obtained in the same manner as in Example 1.
M test pieces were molded and each physical property was measured. Table 1 shows the results.

[0296]

Comparative Example 1 PP-8 polymerized in the above Production Example was melt-kneaded and pelletized. Using the propylene polymer composition thus obtained, the AST was obtained in the same manner as in Example 1.
M test pieces were molded and each physical property was measured. Table 1 shows the results.

[0297]

Example 3 PP-2 polymerized in the above production example: 70 parts by weight,
A mixture consisting of Elastomer-1: 20 parts by weight and talc: 10 parts by weight was mechanically blended, melt-kneaded and pelletized. Using the propylene polymer composition thus obtained, an ASTM test piece was molded in the same manner as in Example 1, and each physical property was measured. Table 1 shows the results.

[0298]

Example 4 PP-2 polymerized in the above production example: 70 parts by weight,
A mixture consisting of Elastomer-1: 5 parts by weight, Elastomer-2: 15 parts by weight, and talc: 10 parts by weight was mechanically blended, melt-kneaded and pelletized. Example 1 was prepared using the propylene polymer composition thus obtained.
In the same manner as in the above, an ASTM test piece was molded and each physical property was measured. Table 1 shows the results.

[0299]

Comparative Example 2 PP-5 polymerized in the above Production Example: 70 parts by weight,
A mixture consisting of Elastomer-1: 20 parts by weight and talc: 10 parts by weight was mechanically blended, melt-kneaded and pelletized. Using the propylene polymer composition thus obtained, an ASTM test piece was molded in the same manner as in Example 1, and each physical property was measured. Table 1 shows the results.

[0300]

Comparative Example 3 PP-7 polymerized in the above Production Example: 70 parts by weight,
A mixture consisting of Elastomer-1: 20 parts by weight and talc: 10 parts by weight was mechanically blended, melt-kneaded and pelletized. Using the propylene polymer composition thus obtained, an ASTM test piece was molded in the same manner as in Example 1, and each physical property was measured. Table 1 shows the results.

[0301]

Example 5 PP-3 polymerized in the above Production Example: 85 parts by weight,
Elastomer-2: A mixture consisting of 15 parts by weight was mechanically blended, melt-kneaded and pelletized. Using the propylene polymer composition thus obtained, an ASTM test piece was molded in the same manner as in Example 1, and each physical property was measured. Table 1 shows the results.

[0302]

Comparative Example 4 PP-6 polymerized in the above Production Example: 85 parts by weight,
Elastomer-2: A mixture consisting of 15 parts by weight was mechanically blended, melt-kneaded and pelletized. Using the propylene polymer composition thus obtained, an ASTM test piece was molded in the same manner as in Example 1, and each physical property was measured. Table 1 shows the results.

[0303]

Example 6 PP-2 polymerized in the above production example: 70 parts by weight,
A mixture consisting of 15 parts by weight of elastomer-1, 5 parts by weight of PE-1, and 10 parts by weight of talc was mechanically blended, melt-kneaded and pelletized. Using the propylene polymer composition thus obtained, an ASTM test piece was molded in the same manner as in Example 1, and each physical property was measured.
Table 1 shows the results.

[0304]

Example 7: PP-4 polymerized in the above production example: 65 parts by weight,
A mixture consisting of Elastomer-2: 20 parts by weight and talc: 15 parts by weight was mechanically blended, melt-kneaded and pelletized. Using the propylene polymer composition thus obtained, an ASTM test piece was molded in the same manner as in Example 1, and each physical property was measured. Table 1 shows the results.

[0305]

Example 8 PP-4 polymerized in the above production example: 65 parts by weight,
A mixture consisting of elastomer-2: 15 parts by weight, PE-1: 5 parts by weight, and talc: 15 parts by weight was mechanically blended, melt-kneaded and pelletized. Using the propylene polymer composition thus obtained, an ASTM test piece was molded in the same manner as in Example 1, and each physical property was measured.
Table 1 shows the results.

[0306]

[Table 57]

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 101/00 C08L 101/00 (72) Inventor Nobuo Kawahara 580-32 Nagaura Sodegaura-shi, Chiba Mitsui Chemicals (72) Inventor Yasushi Dohi 580-32 Nagaura, Sodegaura City, Chiba Prefecture Mitsui Chemicals Corporation (72) Inventor Hiroshi Kaneyoshi 580-32 Nagaura, Sodegaura City, Chiba Prefecture Mitsui Chemicals Corporation (72) 72) Inventor Ryoji Mori 580-32 Nagaura, Sodegaura-shi, Chiba F-term in Mitsui Chemicals, Inc. 4J002 BB033 BB053 BB12W BB14X BB153 BB173 BN033

Claims (4)

[Claims] 1. A propylene polymer (A1) selected from a propylene polymer (A) produced using a metallocene catalyst, and a propylene polymer (A2),
(1) The propylene-based polymer (A1) and the propylene-based polymer (A2) are propylene homopolymer or α
-Propylene α-having an olefin content of 10 mol% or less
An olefin random copolymer, (2) 230 ° C,
Melt flow rate measured at a load of 2.16 kg (M
FR) is in the range of 0.01 to 1000 g / 10 minutes,
(3) Both the ratio of the hetero bond based on the 2,1-insertion and the ratio of the hetero bond based on the 1,3-insertion of the propylene monomer in all the propylene structural units in the total propylene constitutional unit, which are determined from the ¹³ C-NMR spectrum, are both 0.2. % Or less, and (4) the ratio of the MFR (MFR _A1 ) of the propylene-based polymer (A1) to the MFR (MFR _A2 ) of the propylene-based polymer (A2) (MFR _A1 /
(MFR _A2 ) is 10 or more. 2. A propylene-based polymer (A) produced using a metallocene catalyst, an elastomer (C), ethylene, butene and 4-methyl
Selected from olefin polymers (D) containing at least 90 mol% of structural units derived from one type of monomer selected from 1-pentene and modified olefin polymers (E) graft-modified with polar monomers. The propylene-based polymer (A) is (1) a propylene homopolymer or a propylene / α-olefin random copolymer having an α-olefin content of 10 mol% or less. (2) The melt flow rate (MFR) measured at 230 ° C. under a load of 2.16 kg is 0.01 to 1000 g /
(3) The ratio of the hetero bond based on the 2,1-insertion and the hetero bond based on the 1,3-insertion of the propylene monomer in all the propylene constitutional units as determined from the ( ¹³ ) ¹³ C-NMR spectrum. A propylene-based polymer composition having a ratio of 0.2% or less in each case. 3. A propylene-based block copolymer (B) produced using a metallocene catalyst, wherein (1) a propylene homopolymer part or a propylene / α-olefin having an α-olefin content of 10 mol% or less. It consists of an olefin random copolymer part and an amorphous olefin polymer part produced using a metallocene catalyst, and (2) 230 ° C., load 2.
The melt flow rate (MFR) measured at 16 kg is in the range of 0.01 to 1000 g / 10 min, and (3) ¹³ C
-The ratio of the heterogeneous bond based on the 2,1-insertion and the ratio of the heterogeneous bond based on the 1,3-insertion of the propylene monomer in all the propylene constituent units, which are determined from NMR spectra, are both 0.2% or less. A propylene polymer composition characterized by the following. 4. A propylene block copolymer (B) produced using a metallocene catalyst, an elastomer (C), ethylene, butene and 4-methyl
Selected from olefin polymers (D) containing at least 90 mol% of structural units derived from one type of monomer selected from 1-pentene and modified olefin polymers (E) graft-modified with polar monomers. Wherein the propylene-based block copolymer (B) has (1) a propylene homopolymer portion or an α-olefin content of 1
It consists of a propylene / α-olefin random copolymer portion of 0 mol% or less and an amorphous olefin polymer portion produced using a metallocene catalyst, and is measured at (2) 230 ° C. under a load of 2.16 kg. Melt flow rate (MF
R) is in the range of 0.01 to 1000 g / 10 minutes,
(3) Both the ratio of the hetero bond based on the 2,1-insertion and the ratio of the hetero bond based on the 1,3-insertion of the propylene monomer in all the propylene structural units in the total propylene constitutional unit, which are determined from the ¹³ C-NMR spectrum, are both 0.2. % Of the propylene polymer composition.