JP3506537B2 - Graft-modified propylene polymer - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel graft-modified propylene-based polymer, and more specifically, in hot-melt adhesion with a metal or a polar resin, it has a low-temperature adhesive property and an adhesive force retention property in a high-temperature atmosphere. The present invention relates to a graft-modified propylene polymer having an excellent balance.

[0002]

TECHNICAL BACKGROUND OF THE INVENTION Propylene polymer, propylene
Propylene-based polymers such as α-olefin copolymers are
It is molded by various molding methods and is used for various purposes. Further, among the propylene / α-olefin copolymers, those having a low propylene content, that is, those in the so-called elastomer region are also used as impact resistance improving materials for thermoplastic resins. Such a propylene-based polymer may be used for lamination with other resins, metal foils, etc., or blending with other resins. However, since the propylene-based polymer is a so-called non-polar resin having no polar group in the molecule, it has a poor affinity with various polar substances such as metals, and it has been difficult to use for such applications. For this reason, when used for applications such as adhesion with a metal or blending with a polar resin, by graft-copolymerizing a polar monomer with a propylene-based polymer,
It was necessary to improve the affinity with polar substances.

By the way, in recent years, improvement of productivity and energy saving have been required in many manufacturing fields, and in the case of adhering a graft-modified propylene-based polymer and a metal or the like, from the viewpoint of high speed molding and energy saving, a lower temperature is used. There is a need for a graft-modified propylene-based polymer that can be bonded with (low energy). However, conventionally known graft-modified propylene-based polymers, when using a lower melting point in order to improve low-temperature adhesion,
The adhesive strength in a high temperature atmosphere may be extremely reduced.
Therefore, if a graft-modified propylene-based polymer that has good low-temperature adhesiveness to metals and the like and has little decrease in adhesive strength in a high-temperature atmosphere appears, its industrial value will be extremely great.

The inventors of the present invention have conducted intensive studies in view of the above-mentioned prior art, and as a result, the triad tacticity is high, and the ratio of 2,1-insertion-based positional irregular units is within a specific range. A graft-modified propylene-based polymer in which a polar monomer is graft-copolymerized with a propylene polymer having a small proportion of regio-irregular units based on 3-insertion and an intrinsic viscosity [η] within a specific range. 5-
The content of 5 mol% is high, the triad tacticity is high, the proportion of regio irregular units based on 2,1-insertion is within a specific range, and the proportion of regio irregular units based on 1,3-insertion. And a graft-modified propylene polymer in which a polar monomer is graft-copolymerized with a propylene copolymer having an intrinsic viscosity [η] within a specific range, and an ethylene unit in an amount of 5 to 50 mol%. High tacticity, ratio of 2,1-insertion-based regio-irregular units in a specific range, low ratio of 1,3-insertion-based regio-irregular units, and specific range of intrinsic viscosity [η] The graft-modified propylene-based polymer, in which a polar monomer is graft-copolymerized with the propylene / ethylene random copolymer, is a low-temperature adhesive property and a contact in a high-temperature atmosphere for adhesion with a metal or a polar resin. This has led to the completion of the present invention have found that the excellent balance of the force.

[0005]

It is an object of the present invention to provide a graft-modified propylene-based polymer having an excellent balance between low-temperature adhesiveness and adhesiveness retention in a high-temperature atmosphere in adhesion to a metal or polar resin. There is.

[0006]

SUMMARY OF THE INVENTION The first graft-modified propylene-based polymer according to the present invention has (i) a triad tacticity of a propylene unit chain portion composed of a head-to-tail bond of 90.0 as determined by ¹³ C-NMR. % Or more, (ii) ¹³
The proportion of regio-irregular units based on 2,1-insertion of propylene monomer in the total propylene insertion determined by C-NMR is 0.7% or more, and 1,3-of propylene monomer is 1,3-
The proportion of regio-irregular units based on insertion is 0.05% or less, and (iii) a polar monomer is added to a propylene polymer having an intrinsic viscosity measured in decalin in the range of 0.1 to 12 dl / g. It is characterized by being graft-copolymerized.

In the present invention, it is desirable that the polar monomer is at least one kind of monomer selected from a hydroxyl group-containing ethylenically unsaturated compound, an aromatic vinyl compound, an unsaturated carboxylic acid and a derivative thereof, which is derived from the polar monomer. It is desirable that the graft amount of the graft group is 0.1 to 50% by weight.

The second graft-modified propylene-based polymer according to the present invention comprises (i) a propylene unit of 95 to 99.5.
Mol%, comprising 0.5 to 5 mol% of ethylene units,
(Ii) determined by ¹³ C-NMR, head - triad tacticity of the propylene unit chain consisting of tail bonds is not less 90.0% or more, (iii) ¹³ obtained by C-NMR, all propylene insertions in The proportion of regio-irregular units based on 2,1-insertion of propylene monomer is 0.5% or more, and the proportion of regio-irregular unit based on 1,3-insertion of propylene monomer is 0.05% or less. , (Iv) 13
Intrinsic viscosity of 0.1-12d measured in decalin at 5 ° C
A polar monomer is graft-copolymerized with a propylene copolymer in the range of 1 / g.

In the present invention, the polar monomer is preferably at least one monomer selected from a hydroxyl group-containing ethylenically unsaturated compound, an aromatic vinyl compound, an unsaturated carboxylic acid and a derivative thereof, which is derived from the polar monomer. It is desirable that the graft amount of the graft group is 0.1 to 50% by weight.

The third graft-modified propylene-based polymer according to the present invention comprises (i) 50 to 95 mol% of propylene units and 5 to 50 mol% of ethylene units, and (ii)
The triad tacticity of the chain portion of the propylene unit consisting of the head-to-tail bond was 9 determined by ¹³ C-NMR.
0.03% or more, (iii) 2,3 of the propylene monomer in the total propylene insertion determined by ¹³ C-NMR
1-Ratio of positional irregular unit based on insertion is 0.5% or more,
And the proportion of regio-irregular units based on 1,3-insertion of propylene monomer is 0.05% or less, (iv) 135
The intrinsic viscosity measured in decalin at ℃ is 0.1-12dl
It is characterized in that a polar monomer is graft-copolymerized with a propylene / ethylene random copolymer in the range of / g.

In the present invention, the polar monomer is preferably at least one monomer selected from a hydroxyl group-containing ethylenically unsaturated compound, an aromatic vinyl compound, an unsaturated carboxylic acid and a derivative thereof, which is derived from the polar monomer. It is desirable that the graft amount of the graft group is 0.1 to 50% by weight.

[0012]

DETAILED DESCRIPTION OF THE INVENTION The graft-modified propylene polymer according to the present invention will be specifically described below.

The graft-modified propylene polymer according to the present invention comprises a propylene polymer and an ethylene unit of 0.5 to 5
A polar monomer is graft-copolymerized with a propylene-based polymer such as a propylene copolymer containing ethylene at a ratio of 5 to 50 mol% and a propylene-based polymer containing ethylene units at a ratio of 5 to 50 mol%.

First, the propylene polymer, propylene copolymer and propylene / ethylene random copolymer used in the present invention will be explained. [Propylene polymer] A propylene polymer is a polymer composed of propylene units, but the constituent units derived from olefins other than propylene are less than 0.5 mol%, preferably less than 0.3 mol%, and more preferably 0. .1 mol%
You may contain in the ratio of less than.

The propylene polymer of the present invention has a triad tacticity of a chain portion of a propylene unit consisting of a head-to-tail bond (of any three propylene unit chains in the polymer chain, the direction of the methyl branch in the propylene unit is the same). And the proportion of three propylene units in which each propylene unit is bonded head-to-tail (hereinafter sometimes referred to as "mm fraction") is 90% or more, preferably 93% or more, more preferably 95% or more. It is desirable that the ratio of the regio-irregular units based on the 2,1-insertion of the propylene monomer in the total propylene insertion is 0.7% or more, preferably 0.7 to 2.
It is desirable to be in the range of 0%, and the ratio of regio-irregular units based on 1,3-insertion of propylene monomer is 0.05.
% Or less, preferably 0.04% or less, more preferably 0.03% or less, and the intrinsic viscosity [η] measured in decalin at 135 ° C. is 0.1 to 12 dl /
g, preferably 0.5 to 12 dl / g, and more preferably 1 to 12 dl / g.

The triad tacticity, the proportion of regio disordered units due to 2,1-insertion and the proportion of regioregular units due to 1,3-insertion are, as described later, ¹³ C-NMR spectrum of propylene polymer. Required from.

Such a propylene polymer can be produced, for example, by polymerizing propylene in the presence of an olefin polymerization catalyst described later. Polymerization can be carried out by any of liquid phase polymerization methods such as suspension polymerization and solution polymerization, or gas phase polymerization methods.

In the liquid phase polymerization method, an inert hydrocarbon may be used as a solvent, or propylene itself may be used as a solvent. Specifically as the inert hydrocarbon solvent used in the liquid phase polymerization method, butane, isobutane, pentane, hexane, octane, decane, dodecane, hexadecane,
Aliphatic hydrocarbons such as octadecane; alicyclic hydrocarbons such as cyclopentane, methylcyclopentane, cyclohexane, cyclooctane; benzene, toluene,
Aromatic hydrocarbons such as xylene; petroleum fractions such as gasoline, kerosene, and light oil. Of these inert hydrocarbon media, aliphatic hydrocarbons, alicyclic hydrocarbons,
Petroleum fraction and the like are preferable.

The polymerization temperature of propylene is usually -50 to 100 ° C, preferably 0 to 0 when carrying out the suspension polymerization method.
It is preferably in the range of 90 ° C, and when carrying out the solution polymerization method, it is usually 0 to 250 ° C, preferably 20 to 20
It is preferably in the range of 0 ° C. Further, when carrying out the gas phase polymerization method, the polymerization temperature is usually 0 to 120 ° C., preferably 20 to 100 ° C. The polymerization pressure is usually atmospheric pressure to 100 kg / cm ² , preferably atmospheric pressure to 50 kg / cm ² , and the polymerization reaction is
It can be carried out by any of batch method, semi-continuous method and continuous method. It is also possible to carry out the polymerization in two or more stages under different reaction conditions.

The molecular weight of the obtained propylene polymer can be adjusted by allowing hydrogen to be present in the polymerization system or by changing the polymerization temperature and the polymerization pressure. [Propylene Copolymer] The propylene copolymer has a propylene unit content of 95 to 99.5 mol%, preferably 95 to 9
Propylene-ethylene random copolymer comprising 9 mol%, more preferably 95 to 98 mol%, and 0.5 to 5 mol% of ethylene units, preferably 1 to 5 mol%, more preferably 2 to 5 mol%. Is.

Such a propylene copolymer may contain a constitutional unit derived from an olefin other than propylene and ethylene in a proportion of, for example, 5 mol% or less. The propylene copolymer has a triad tacticity of a propylene unit chain portion composed of a head-to-tail bond of 90%.
Or more, preferably 93% or more, more preferably 96% or more, the proportion of regio-irregular units based on the 2,1-insertion of propylene monomer in the total propylene insertion is 0.5% or more, preferably It is desirable that the content is 0.5 to 1.5%, and the proportion of regio-irregular units based on 1,3-insertion of propylene monomer is 0.05% or less, preferably 0.04% or less, and more preferably 0. It is preferably 03% or less, and the intrinsic viscosity [η] measured in decalin at 135 ° C. is 0.1 to 12 dl / g, preferably 0.5.
It is desirable to be in the range of -12 dl / g, more preferably 1-12 dl / g.

Triad tacticity, based on 2,1-insertion
Position based on the ratio of irregular units and 1,3-insertion
The proportion of irregular units is determined by propylene copolymerization as described below.
of a body ¹³It can be determined from a C-NMR spectrum.

Such a propylene copolymer can be produced, for example, by copolymerizing propylene and ethylene in the presence of an olefin polymerization catalyst as described below. The copolymerization can be carried out by any of liquid phase polymerization methods such as suspension polymerization and solution polymerization or gas phase polymerization methods.

In the liquid phase polymerization method, the same inert hydrocarbon solvent used in the above-mentioned catalyst preparation can be used, and propylene and / or ethylene can also be used as a solvent.

The copolymerization temperature of propylene and ethylene is
When carrying out the suspension polymerization method, usually -50 to 100 ° C,
It is preferably in the range of 0 to 90 ° C., and when carrying out the solution polymerization method, it is usually in the range of 0 to 250 ° C., preferably 20 to 200 ° C. When carrying out the gas phase polymerization method, the copolymerization temperature is usually 0.
It is desirable to be in the range of 120 to 120 ° C, preferably 20 to 100 ° C. The copolymerization pressure is usually from normal pressure to 100 kg.
/ Cm ² , preferably under atmospheric pressure to 50 kg / cm ² , and the copolymerization reaction can be carried out by any of batch method, semi-continuous method and continuous method. It is also possible to carry out the copolymerization in two or more stages under different reaction conditions.

The molecular weight of the propylene copolymer obtained is
The presence of hydrogen in the copolymerization system, or the copolymerization temperature,
It can be adjusted by changing the copolymerization pressure.

[Propylene / Ethylene Random Copolymer] The propylene / ethylene random copolymer has a propylene unit content of 50 to 95 mol%, preferably 60 to 93 mol%, more preferably 70 to 90 mol%. It is a propylene-ethylene random copolymer (elastomer) containing 5 to 50 mol%, preferably 7 to 40 mol%, and more preferably 10 to 30 mol%.

Such a propylene / ethylene random copolymer may contain a structural unit derived from an olefin other than propylene and ethylene in an amount of, for example, 10 mol% or less.

The propylene / ethylene random copolymer has a triad tacticity of 90.0% or more, preferably 9 at the chain portion of the propylene unit consisting of head-to-tail bonds.
It is desirable to be 2.0% or more, more preferably 95.0% or more, and the proportion of regio-irregular units based on the 2,1-insertion of propylene monomer in the total propylene insertion is 0.5%
Or more, preferably 0.5 to 2.0%, and more preferably 0.5 to 1.5%, and the position irregular unit based on the 1,3-insertion of the propylene monomer is 0.0.
It is desirable to be 5% or less, preferably 0.03% or less, and the intrinsic viscosity [η] measured in decalin at 135 ° C.
Is 0.1 to 12 dl / g, preferably 0.5 to 12 dl
/ G, and more preferably in the range of 1 to 12 dl / g.

The triad tacticity, the proportion of regio-irregular units based on 2,1-insertion and the proportion of regio-irregular units based on 1,3-insertion are, as described later, ¹³ % of that of propylene / ethylene random copolymer. It can be determined from a C-NMR spectrum.

Such a propylene / ethylene random copolymer can be produced, for example, by copolymerizing propylene and ethylene in the presence of an olefin polymerization catalyst as described below. Copolymerization is suspension polymerization,
It can be carried out by either a liquid phase polymerization method such as solution polymerization or a gas phase polymerization method.

In the liquid phase polymerization method, the same inert hydrocarbon solvent used in the above catalyst preparation can be used, and propylene and / or ethylene can also be used as a solvent.

The copolymerization temperature of propylene and ethylene is
When carrying out the suspension polymerization method, usually -50 to 100 ° C,
It is preferably in the range of 0 to 90 ° C., and when carrying out the solution polymerization method, it is usually in the range of 0 to 250 ° C., preferably 20 to 200 ° C. When carrying out the gas phase polymerization method, the copolymerization temperature is usually 0.
It is desirable to be in the range of 120 to 120 ° C, preferably 20 to 100 ° C. The copolymerization pressure is usually from normal pressure to 100 kg.
/ Cm ² , preferably under atmospheric pressure to 50 kg / cm ² , and the copolymerization reaction can be carried out by any of batch method, semi-continuous method and continuous method. It is also possible to carry out the copolymerization in two or more stages under different reaction conditions.

The molecular weight of the resulting propylene / ethylene random copolymer can be adjusted by allowing hydrogen to be present in the copolymerization system or by changing the copolymerization temperature and the copolymerization pressure.

[Olefin Polymerization Catalyst] Next, the propylene polymer, propylene copolymer and propylene.
The olefin polymerization catalyst used for producing the ethylene random copolymer will be described.

The olefin polymerization catalyst used in the production of the propylene polymer, the propylene copolymer and the propylene / ethylene random copolymer is (A) a transition metal compound represented by the following general formula (I): B) (B-1) organoaluminum oxy compound, and (B-
2) A compound that reacts with the transition metal compound (A) to form an ion pair, and optionally (C) an organoaluminum compound.

The transition metal compound is a transition metal compound represented by the following general formula (I) (hereinafter sometimes referred to as "component (A)").

[0038]

[Chemical 1]

In the formula, M represents a transition metal of Groups IV to VIb of the Periodic Table, and specifically, titanium, zirconium,
Hafnium, vanadium, niobium, tantalum, chromium,
It is molybdenum or tungsten, preferably titanium, zirconium or hafnium, particularly preferably zirconium.

R ¹ and R ^{2, which} may be the same or different, are each a hydrogen atom, a halogen atom or a carbon atom of 1
To a hydrocarbon group having 20 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group or a phosphorus-containing group, and specifically,
Halogen atoms such as fluorine, chlorine, bromine and iodine; alkyl groups such as methyl, ethyl, propyl, butyl, hexyl, cyclohexyl, octyl, nonyl, dodecyl, aicosyl, norbornyl and adamantyl; alkenyl groups such as vinyl, propenyl and cyclohexenyl. Arylalkyl groups such as benzyl, phenylethyl, phenylpropyl; phenyl, tolyl, dimethylphenyl,
A hydrocarbon group having 1 to 20 carbon atoms such as an aryl group such as trimethylphenyl, ethylphenyl, propylphenyl, biphenyl, naphthyl, methylnaphthyl, anthracenyl, phenanthryl; a halogenated hydrocarbon in which a halogen atom is substituted for the hydrocarbon group. Group; methylsilyl,
Monohydrocarbon-substituted silyl such as phenylsilyl; Dihydrocarbon-substituted silyl such as dimethylsilyl and diphenylsilyl; Trimethylsilyl, triethylsilyl, tripropylsilyl, tricyclohexylsilyl, triphenylsilyl, dimethylphenylsilyl, methyldiphenylsilyl, tritolyl Trihydrocarbon-substituted silyl such as silyl and trinaphthylsilyl, hydrocarbon-substituted silyl silyl ether such as trimethylsilyl ether; silicon-substituted alkyl groups such as trimethylsilylmethyl; silicon-substituted aryl groups such as trimethylphenyl; silicon-containing groups such as hydroxy; Group; alkoxy group such as methoxy, ethoxy, propoxy, butoxy; allyoxy group such as phenoxy, methylphenoxy, dimethylphenoxy, naphthoxy; phenyl The oxygen-sulfur-containing group oxygen is replaced with sulfur-containing group; an amino group; butoxy, oxygen-containing groups such as arylalkoxy group such as phenyl ethoxymethyl amino, dimethylamino, diethylamino,
Alkylamino groups such as dipropylamino, dibutylamino, dicyclohexylamino; nitrogen-containing groups such as arylamino groups such as phenylamino, diphenylamino, ditolylamino, dinaphthylamino, methylphenylamino or alkylarylamino groups; dimethylphosphino, A phosphorus-containing group such as a phosphino group such as diphenylphosphino.

Of these, R ¹ is preferably a hydrocarbon group, and particularly preferably one group selected from a hydrocarbon group having 1 to 3 carbon atoms such as methyl, ethyl and propyl. R ² is preferably a hydrogen atom or a hydrocarbon group, particularly a hydrogen atom, or
It is preferably one group selected from a hydrocarbon group having 1 to 3 carbon atoms such as methyl, ethyl and propyl.

R ³ represents one kind of group selected from an alkyl group having 2 to 20 carbon atoms, and R ⁴ represents 1 to 20 carbon atoms.
1 group selected from the alkyl groups of R ³ is preferably a secondary or tertiary alkyl group. Also, R
^The alkyl group represented by ³ and R ⁴ may be substituted with a halogen atom or a silicon-containing group, and examples of the halogen atom and the silicon-containing group include the substituents exemplified for R ¹ and R ² .

Examples of the alkyl group having 2 to 20 carbon atoms include ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, tert-butyl, pentyl, hexyl, cyclohexyl, heptyl and octyl. , Chain alkyl and cyclic alkyl groups such as nonyl, dodecyl, eicosyl, norbornyl and adamantyl; and arylalkyl groups such as benzyl, phenylethyl, phenylpropyl and tolylmethyl.

These groups may be substituted with a group containing a double bond or a triple bond. Examples of the alkyl group having 1 to 20 carbon atoms include methyl and the same alkyl groups having 2 to 20 carbon atoms as described above.

X¹And X²Are the same or different from each other
Optionally, hydrogen atom, halogen atom, carbon atom 1
To hydrocarbon groups, halogenated with 1 to 20 carbon atoms
Represents a hydrocarbon group, an oxygen-containing group or a sulfur-containing group,
Physically, the R¹And R ²A halogen atom similar to
Hydrocarbon group having 1 to 20 carbon atoms, 1 to 20 carbon atoms
The halogenated hydrocarbon group and the oxygen-containing group can be exemplified.

Examples of the sulfur-containing group include the same groups as R ¹ and R ² described above, methyl sulfonate, trifluoromethane sulfonate, phenyl sulfonate, benzyl sulfonate, p-toluene sulfonate and trimethylbenzene sulfonate. Sulfonate groups such as phonate, triisobutylbenzene sulfonate, p-chlorobenzene sulfonate, pentafluorobenzene sulfonate, methylsulfinate, phenylsulfinate, benzenesulfinate, p-toluenesulfinate Examples thereof include sulfinate groups such as trimethylbenzenesulfinate and pentafluorobenzenesulfinate.

Y is a divalent hydrocarbon group having 1 to 20 carbon atoms, a divalent halogenated hydrocarbon group having 1 to 20 carbon atoms, a divalent silicon-containing group, a divalent germanium-containing group,
Divalent tin-containing group, -O-, -CO-, -S-, -SO
_{-, - SO 2 -, -} NR 5 -, - P (R 5) -, - P
^{(O) (R 5) -} , - BR 5 - or -AlR ⁵ - [however, R ⁵ is a hydrogen atom, a halogen atom, 1 to carbon atoms
20 hydrocarbon groups, halogenated hydrocarbon groups having 1 to 20 carbon atoms], specifically, methylene, dimethylmethylene, 1,2-ethylene, dimethyl-1,2-ethylene, 1,3-
1 to 20 carbon atoms such as alkylene groups such as trimethylene, 1,4-tetramethylene, 1,2-cyclohexylene and 1,4-cyclohexylene, aryl alkylene groups such as diphenylmethylene and diphenyl-1,2-ethylene A divalent hydrocarbon group having 1 to 2 carbon atoms such as chloromethylene
Halogenated hydrocarbon group obtained by halogenating a divalent hydrocarbon group of 0; methylsilylene, dimethylsilylene, diethylsilylene, di (n-propyl) silylene, di (i-propyl) silylene, di (cyclohexyl) silylene, methyl Alkylsilylene such as phenylsilylene, diphenylsilylene, di (p-tolyl) silylene, di (p-chlorophenyl) silylene, alkylarylsilylene, arylsilylene group, tetramethyl-1,2-disilyl, tetraphenyl-1,2- Divalent silicon-containing groups such as alkyldisilyl such as disilyl, alkylaryldisilyl, and arylsilyl groups; Divalent germanium-containing groups obtained by substituting germanium for silicon in the above divalent silicon-containing groups; and the like divalent tin-containing group substituents of the silicon-containing groups is replaced with tin, R ⁵ is Wherein R ^1, R ² the same halogen atom, hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms.

Of these, a divalent silicon-containing group, a divalent germanium-containing group and a divalent tin-containing group are preferable, and a divalent silicon-containing group is more preferable,
Of these, alkylsilylene, alkylarylsilylene, and arylsilylene are particularly preferable.

Specific examples of the transition metal compound represented by the above general formula (I) are shown below. rac-Dimethylsilyl-bis {1- (2,7-dimethyl-4-ethylindenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- (2,7
-Dimethyl-4-n-propylindenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- (2,7-dimethyl-4-i-propylindenyl)} zirconium dichloride, rac-dimethylsilyl-bis { 1- (2,7-dimethyl-4-n-
Butylindenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- (2,7-dimethyl-4-sec-butylindenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- (2,7- Dimethyl-4-t-butylindenyl)} zirconium dichloride, rac-dimethylsilyl-
Bis {1- (2,7-dimethyl-4-n-pentylindenyl)}
Zirconium dichloride, rac-dimethylsilyl-bis {1
-(2,7-Dimethyl-4-n-hexylindenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- (2,7-
Dimethyl-4-cyclohexylindenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- (2,7-dimethyl-4-methylcyclohexylindenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- (2 , 7
-Dimethyl-4-phenylethylindenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- (2,7-dimethyl-4-phenyldichloromethylindenyl)} zirconium dichloride, rac-dimethylsilyl-bis { 1-
(2,7-Dimethyl-4-chloromethylindenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- (2,7
-Dimethyl-4-trimethylsilylmethylindenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1-
(2,7-Dimethyl-4-trimethylsiloxymethylindenyl)} zirconium dichloride, rac-diethylsilyl-
Bis {1- (2,7-dimethyl-4-i-propylindenyl)}
Zirconium dichloride, rac-di (i-propyl) silyl
-Bis {1- (2,7-dimethyl-4-i-propylindenyl)}
Zirconium dichloride, rac-di (n-butyl) silyl-
Bis {1- (2,7-dimethyl-4-i-propylindenyl)}
Zirconium dichloride, rac-di (cyclohexyl) silyl-bis {1- (2,7-dimethyl-4-i-propylindenyl)} zirconium dichloride, rac-methylphenylsilyl-bis {1- (2,7-dimethyl) -4-i-Propylindenyl)} zirconium dichloride, rac-methylphenylsilyl-bis {1- (2,7-dimethyl-4-t-butylindenyl)} zirconium dichloride, rac-diphenylsilyl
-Bis {1- (2,7-dimethyl-4-t-butylindenyl)} zirconium dichloride, rac-diphenylsilyl-bis {1
-(2,7-Dimethyl-4-i-propylindenyl)} zirconium dichloride, rac-diphenylsilyl-bis {1- (2,7
-Dimethyl-4-ethylindenyl)} zirconium dichloride, rac-di (p-tolyl) silyl-bis {1- (2,7-dimethyl-4-i-propylindenyl)} zirconium dichloride, rac-di ( p-chlorophenyl) silyl-bis {1-
(2,7-Dimethyl-4-i-propylindenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- (2-methyl-4-i-propyl-7-ethylindenyl)} zirconium dibromide, rac-dimethylsilyl-bis {1- (2,3,7-
Trimethyl-4-ethylindenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- (2,3,7-trimethyl-4-n-propylindenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1 -(2,3,7-Trimethyl-4-i-propylindenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- (2,3,7-trimethyl-
4-n-butylindenyl)} zirconium dichloride, ra
c-Dimethylsilyl-bis {1- (2,3,7-trimethyl-4-sec-
Butylindenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- (2,3,7-trimethyl-4-t-butylindenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- (2, 3,7-Trimethyl-4-n-pentylindenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- (2,3,7-trimethyl-4-n-hexylindenyl)} zirconium dichloride, rac- Dimethylsilyl-
Bis {1- (2,3,7-trimethyl-4-cyclohexylindenyl)} zirconium dichloride, rac-dimethylsilyl
-Bis {1- (2,3,7-trimethyl-4-methylcyclohexylindenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- (2,3,7-trimethyl-4-trimethylsilylmethylindenyl) } Zirconium dichloride, rac-
Dimethylsilyl-bis {1- (2,3,7-trimethyl-4-trimethylsiloxymethylindenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- (2,3,7-trimethyl-4-phenylethyl) Indenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- (2,3,7-trimethyl-4-phenyldichloromethylindenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- (2,
3,7-Trimethyl-4-chloromethylindenyl)} zirconium dichloride, rac-diethylsilyl-bis {1- (2,
3,7-Trimethyl-4-i-propylindenyl)} zirconium dichloride, rac-di (i-propyl) silyl-bis {1
-(2,3,7-Trimethyl-4-i-propylindenyl)} zirconium dichloride, rac-di (n-butyl) silyl-bis {1- (2,3,7-trimethyl-4-i-propyl) Indenyl)}
Zirconium dichloride, rac-di (cyclohexyl) silyl-bis {1- (2,3,7-trimethyl-4-i-propylindenyl)} zirconium dichloride, rac-methylphenylsilyl-bis {1- (2,3 , 7-Trimethyl-4-i-propylindenyl)} zirconium dichloride, rac-methylphenylsilyl-bis {1- (2,3,7-trimethyl-4-t-butylindenyl)} zirconium dichloride, rac- Diphenylsilyl-bis {1- (2,3,7-trimethyl-4-t-butylindenyl)} zirconium dichloride, rac-diphenylsilyl
-Bis {1- (2,3,7-trimethyl-4-i-propylindenyl)} zirconium dichloride, rac-diphenylsilyl
-Bis {1- (2,3,7-trimethyl-4-ethylindenyl)}
Zirconium dichloride, rac-di (p-tolyl) silyl-
Bis {1- (2,3,7-trimethyl-4-i-propylindenyl)} zirconium dichloride, rac-di (p-chlorophenyl) silyl-bis {1- (2,3,7-trimethyl-4- i-Propylindenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- (2-methyl-4-i-propyl-7-methylindenyl)} zirconium dimethyl, rac-dimethylsilyl-bis {1- ( 2-Methyl-4-i-propyl-7-methylindenyl)} zirconium methyl chloride, rac-dimethylsilyl-bis {1- (2-methyl-4-i-propyl-7-methylindenyl)} zirconium- Bis (methanesulfonato), rac-dimethylsilyl-bis {1- (2-methyl-4-i-propyl-7-methylindenyl)} zirconium-bis (p-
Phenylsulfinato), rac-dimethylsilyl-bis {1
-(2-Methyl-3-methyl-4-i-propyl-7-methylindenyl)} zirconium dichloride, rac-dimethylsilyl-
Bis {1- (2-ethyl-4-i-propyl-7-methylindenyl)} zirconium dichloride, rac-dimethylsilyl-
Bis {1- (2-phenyl-4-i-propyl-7-methylindenyl)} zirconium dichloride, rac-dimethylsilyl-
Bis {1- (2-methyl-4-i-propyl-7-methylindenyl)} titanium dichloride, rac-dimethylsilyl-bis {1- (2-methyl-4-i-propyl-7-methylindenyl) )} Hafnium dichloride, etc.

Among these, those having a branched alkyl group such as i-propyl, sec-butyl and tert-butyl at the 4-position are particularly preferable. In the present invention, zirconium metal in the above compounds, titanium metal, hafnium metal, vanadium metal, niobium metal, tantalum metal,
It is also possible to use a transition metal compound in which chromium metal, molybdenum metal, or tungsten metal is replaced.

The above transition metal compound is usually used as a racemate as a catalyst component for olefin polymerization, but R type or S type can also be used. Such a transition metal compound can be synthesized from these indene derivatives by a known method, for example, the method described in JP-A-4-268307.

The (B-1) organoaluminum oxy compound (hereinafter sometimes referred to as "component (B-1)") may be a conventionally known aluminoxane, and JP-A-2-7.
It may be a benzene-insoluble organoaluminum oxy compound as exemplified in 8687.

The conventionally known aluminoxane can be produced, for example, by the following method. (1) Compounds containing adsorbed water or salts containing water of crystallization, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, ceric chloride hydrate, etc. The method of adding an organoaluminum compound such as trialkylaluminum to the suspension of a hydrocarbon medium, and reacting adsorbed water or crystal water with the organoaluminum compound. (2) A method in which water, ice or water vapor 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 organometallic component. Further, the solvent or the unreacted organoaluminum compound may be removed by distillation from the recovered solution of the aluminoxane and then redissolved in the solvent.

Specific examples of the organoaluminum compound used for preparing the aluminoxane include trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, trisec-butyl. Aluminum, trialkyl aluminum such as tri-tert-butyl aluminum, tripentyl aluminum, trihexyl aluminum, trioctyl aluminum, and tridecyl aluminum; tricycloalkyl aluminum such as tricyclohexyl aluminum and tricyclooctyl aluminum; dimethyl aluminum chloride, diethyl aluminum Chloride, diethyl aluminum bromide, diisobutyl aluminum chloride, etc. Alkylaluminum halides; diethylaluminum hydride, dialkylaluminum hydride such as diisobutylaluminum hydride; dimethyl aluminum methoxide, dialkylaluminum alkoxides such as diethylaluminum ethoxide; and dialkylaluminum Ally Loki Sid such as diethyl aluminum phenoxide and the like.

Of these, trialkylaluminum and tricycloalkylaluminum are particularly preferable.
Further, as the organoaluminum compound used when preparing the aluminoxane, isoprenylaluminum represented by the following general formula (II) can also be used.

(I-C ₄ H ₉ ) _x Al _y (C ₅ H ₁₀ ) _z (II) (In the formula, x, y, and z are positive numbers, and z ≧ 2x.) Such organoaluminum compounds may be used alone or in combination.

As the solvent used for the preparation of aluminoxane, aromatic hydrocarbons such as benzene, toluene, xylene, cumene and cymene, and aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane and octadecane. , Cyclopentane, cyclohexane, cyclooctane, methylcyclopentane, and other alicyclic hydrocarbons, petroleum fractions such as gasoline, kerosene, and light oil, or the above aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbon halides Among these, hydrocarbon solvents such as chlorinated compounds and brominated compounds are mentioned. In addition, ethers such as ethyl ether and tetrahydrofuran can also be used. Of these solvents, aromatic hydrocarbons are particularly preferable.

(B-2) As a compound which reacts with the above transition metal compound (A) to form an ion pair (hereinafter sometimes referred to as "component (B-2)"), it is described in Japanese Patent Publication No. -50195
No. 0, Japanese Patent Publication No. 1-502036, Japanese Patent Laid-Open No.
179005, JP-A-3-179006,
JP-A-3-207703, JP-A-3-20770
Examples thereof include Lewis acids, ionic compounds, borane compounds, and carborane compounds described in JP-A No. 4 and US-547718.

As the Lewis acid, a Lewis acid containing a magnesium atom, a Lewis acid containing an aluminum atom,
Examples thereof include a Lewis acid containing a boron atom, and among these, a Lewis acid containing a boron atom is preferable.

Specific examples of the Lewis acid containing a boron atom include compounds represented by the following general formula. BR ^a R ^b R ^c (In the formula, R ^a R ^b and R ^c may be the same or different from each other, and may be a phenyl group which may have a substituent such as a fluorine atom, a methyl group and a trifluoromethyl group. Or a fluorine atom.) Specific examples of the compound represented by the above general formula include trifluoroboron, triphenylboron, 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.
Of these, tris (pentafluorophenyl) boron is particularly preferable.

The ionic compound is a salt composed of a cationic compound and an anionic compound. The anion has a function of cationizing the transition metal compound (A) by reacting with the transition metal compound (A) and stabilizing the transition metal cation species by forming an ion pair.

Examples of such anions include an organic boron compound anion, an organic arsenic compound anion, and an organic aluminum compound anion, and those which are relatively bulky and stabilize the transition metal cation species are preferable.

Examples of the cation include a metal cation, an organometallic cation, a carbonium cation, a tripium cation, an oxonium cation, a sulfonium cation, a phosphonium cation and an ammonium cation. More specifically, it includes a triphenylcarbenium cation, a tributylammonium cation, an N, N-dimethylammonium cation, and a ferrocenium cation.

The ionic compound is preferably a boron atom-containing ionic compound in which the anionic compound is a boron compound, and specific examples thereof include triethylammonium tetra (phenyl) boron and tripropylammonium tetra (phenyl) boron. Tri (n-butyl) ammonium tetra (phenyl) boron, trimethylammonium tetra (p-tolyl) boron, trimethylammonium tetra (o-tolyl) boron, tributylammonium tetra (pentafluorophenyl) boron, tripropylammonium tetra (o, p-Dimethylphenyl) boron, tributylammonium tetra (m, m-dimethylphenyl) boron, tributylammonium tetra (p-trifluoromethylphenyl) boron, tri (n-butyl) ammonium tetra (o-tri) ) Boron, trialkyl-substituted ammonium salts such as tri (n-butyl) ammonium tetra (4-fluorophenyl) boron; N, N-dimethylanilinium tetra (phenyl) boron, N, N-diethylanilinium tetra (phenyl) N, N-dialkylanilinium salts such as boron, N, N-2,4,6-pentamethylanilinium tetra (phenyl) boron; di (n-propyl) ammonium tetra (pentafluorophenyl) boron,
Dialkylammonium salts such as dicyclohexylammonium tetra (phenyl) boron; triphenylphosphonium tetra (phenyl) boron, tri (methylphenyl) phosphonium tetra (phenyl) boron, tri (dimethylphenyl) phosphonium tetra (phenyl) Examples include triarylphosphonium salts such as boron.

Further, as an ionic compound containing a boron atom, triphenylcarbenium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, ferrocenium tetra (pentafluorophenyl) borate Borate can also be mentioned.

Further, the following compounds can be exemplified as the ionic compound containing a boron atom. (Note that in the ionic compounds listed below, the counter ion is, but not limited to, tri (n-butyl) ammonium.) Anion salts, such as bis {tri (n-butyl) ammonium} nonaborate, bis {tri (N-Butyl) ammonium} decaborate, bis {tri (n-butyl) ammonium} undecaborate, bis {tri (n-butyl) ammonium} dodecaborate, bis {tri (n-butyl) ammonium} decachlorodecaborate , Bis {tri (n-
Butyl) ammonium} dodecachloro dodecaborate,
Tri (n-butyl) ammonium-1-carbadecaborate, tri (n-butyl) ammonium-1-carbaundecaborate, tri (n-butyl) ammonium-1-carbadodecaborate, tri (n-butyl) ammonium -1-Trimethylsilyl-1-carbadecaborate, tri (n-butyl) ammonium bromo-1-carbadodecaborate, etc.

As the borane compound and carborane compound, the following compounds can be mentioned. These compounds are used as Lewis acids or ionic compounds.

Decaborane (14), 7,8-Dicarbaundecaborane (13), 2,7-Dicarbaundecaborane (1
3), undecahydride-7,8-dimethyl-7,8-dicarbaundecaborane, dodecahydride-11-methyl-2,7
-Dicarbaundecaborane, tri (n-butyl) ammonium 6-carbadecaborate (14), tri (n-butyl)
Ammonium 6-carbadecaborate (12), tri (n-
Butyl) ammonium 7-carbaundecaborate (1
3), tri (n-butyl) ammonium 7,8-dicarbaundecaborate (12), tri (n-butyl) ammonium
2,9-Dicarbaundecaborate (12), tri (n-butyl) ammonium dodecahydride-8-methyl-7,9-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-8-ethyl-7, 9-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-8-butyl-7,9-dicarbaundecaborate,
Tri (n-butyl) ammonium undeca hydride-8
-Allyl-7,9-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-9-trimethylsilyl-7,8-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-4,6 -Dibromo-
Boranes such as 7-carbaundecaborate, carborane complex compounds or salts of carborane anions; 4-carbanonaborane (14), 1,3-dicarbanonaborane (13), 6,9-
Dicarba decaborane (14), Dodeca hydride-1-
Carboranes or carboranes such as phenyl-1,3-dicarbanonaborane, dodecahydride-1-methyl-1,3-dicarbanonaborane, undecahydride-1,3-dimethyl-1,3-dicarbanonaborane Salt.

Further, as the borane compound and carborane compound, the following salts of metal carborane and metal borane anion can be exemplified. (Note that the counter ion in the ionic compounds listed below is tri (n-butyl))
It is, but not limited to, ammonium. ) Tri (n-butyl) ammonium bis (nonahydride
-1,3-Dicarbanonaborate) cobaltate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbaundecaborate) ferrate (ferrate) (III), tri (n) -Butyl) ammonium bis (undecahydride-7,8-dicarbaundecaborate)
Cobaltate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbaundecaborate) nickelate (III), tri (n-butyl) ammonium bis (undecahydride-7,8- Dicarbaundecaborate) cubrate (cuprate) (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbaundecaborate) aurate (metal salt) (III), tri (n-) Butyl) ammonium bis (nonahydride-7,8-dimethyl-7,8-dicarbaundecaborate) ferrate (III), tri (n-butyl) ammonium bis (nonahydride-7,8-dimethyl-7,8- Dicarbaundecaborate) Chromate (Chromate) (II
I), tri (n-butyl) ammonium bis (tribromooctahydride-7,8-dicarbaundecaborate)
Cobaltate (III), tri (n-butyl) ammonium bis (dodecahydride dicarbadodecaborate) cobaltate (III), bis {tri (n-butyl) ammonium} bis (dodecahydride dodecaborate) nickelate (III), tris {Tri (n-butyl) ammonium} bis (undecahydride-7-carbaundecaborate) chromate (III), bis {tri (n-butyl) ammonium} bis (undecahydride-7-carbaundecaborate) Manganate (IV), bis {tri (n-butyl) ammonium} bis (undecahydride-7-carbaundecaborate) cobaltate (II
I), bis {tri (n-butyl) ammonium} bis (undecahydride-7-carbaundecaborate) nickelate (IV), etc.

The compound (B-2) which reacts with the above transition metal compound (A) to form an ion pair can be used as a mixture of two or more kinds. (C) Organoaluminum compound (hereinafter sometimes referred to as "component (C)")
For example, an organoaluminum compound represented by the following general formula (III) can be exemplified.

R ^d _n AlX _3-n (III) (In the formula, R ^d represents a hydrocarbon group having 1 to 12 carbon atoms, X represents a halogen atom or a hydrogen atom, and n represents 1 to 1).
It is 3. ) In the general formula (III), R ^d has 1 to 1 carbon atoms.
2 hydrocarbon groups such as an alkyl group, a cycloalkyl group or an aryl group, specifically, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an isobutyl group,
Examples include a pentyl group, a hexyl group, an octyl group, a cyclopentyl group, a cyclohexyl group, a phenyl group and a tolyl group.

Such an organoaluminum compound (C)
Specifically, the following compounds may be mentioned. Trialkyl aluminum such as trimethyl aluminum, triethyl aluminum, triisopropyl aluminum, triisobutyl aluminum, trioctyl aluminum, tri (2-ethylhexyl) aluminum; alkenyl aluminum such as isoprenyl aluminum; dimethyl aluminum chloride, diethyl aluminum chloride, diisopropyl aluminum chloride. , Dialkyl aluminum halides such as diisobutyl aluminum chloride and dimethyl aluminum bromide; alkyl aluminum sesquihalides such as methyl aluminum sesquichloride, ethyl aluminum sesquichloride, isopropyl aluminum sesquichloride, butyl aluminum sesquichloride and ethyl aluminum sesquibromide; Chill aluminum dichloride, ethyl aluminum dichloride, alkyl aluminum dihalides such as isopropyl aluminum dichloride, ethyl aluminum dibromide; diethylaluminum hydride, and alkyl aluminum hydride such as diisobutyl aluminum hydride.

Further, as the organoaluminum compound (C), a compound represented by the following general formula (IV) can be used. During ^{_{R d n AlL 3-n ...}} (IV) ( wherein, R ^d represents a similar hydrocarbon group in the above formula (III), L is -OR ^e group, -OSiR ^f ₃ group, -OAlR ^g
₂ groups, -NR ^h ₂ group, -SiR ⁱ ₃ group or -N
(R ^j ) AlR ^k ₂ group, n is 1 to 2,
R ^e , R ^f , R ^g and R ^k are a methyl group, an ethyl group, an isopropyl group, an isobutyl group, a cyclohexyl group, a phenyl group and the like, and R ^h is a hydrogen atom, a methyl group, an ethyl group, an isopropyl group, a phenyl group. , Trimethylsilyl group and the like, and R ⁱ and R ^j are methyl group, ethyl group and the like. ) As such an organoaluminum compound, the following compounds are specifically used. (1) A compound represented by R ^d _n Al (OR ^e ) _3-n , such as dimethyl aluminum methoxide, diethyl aluminum ethoxide, diisobutyl aluminum methoxide, etc. (2) R ^d _n Al (OSiR ^f ₃ ) ₃ a compound represented by _-n ,
For example, Et ₂ Al (OSiMe ₃ ), (iso-Bu) ₂ Al
_{(OSiMe 3), (iso-} Bu) 2 Al (OSiEt 3)
(3) a compound represented by R ^d _n Al (OAlR ^g ₂ ) _3-n ,
For example, Et ₂ AlOAlEt ₂ , (iso-Bu) ₂ AlOA
l (iso-Bu) _{2 and the} like; (4) a compound represented by R ^d _n Al (NR ^h ₂ ) _3-n , for example, Me ₂ AlNEt ₂ , Et ₂ AlNHMe, Me ₂ Al
_{NHEt, Et 2 AlN (SiMe 3} ) 2, (iso-Bu) 2
AlN (SiMe ₃ ) _{2 and the} like; (5) R ^d _n Al (SiR ⁱ ₃ ) _3-n represented by compounds such as (iso-Bu) ₂ AlSiMe _{3 and the} like; (6) R ^d _n Al [N ( R ^j ) AlR ^k ₂ ] _3-n , for example, Et ₂ AlN (Me) AlEt ₂ , (iso
-Bu) ₂ AlN (Et) Al (iso-Bu) _{2 and the} like.

Among the organoaluminum compounds represented by the above general formulas (III) and (IV), the general formula R ^d ₃ Al,
_{^{R d n Al (OR e)}} 3-n, R d n Al (OAlR g 2)
A compound represented by _3-n is preferable, and a compound in which R ^d is an isoalkyl group and n = 2 is particularly preferable.

The olefin polymerization catalyst is a solid in which at least one of the above-mentioned component (A), component (B-1), component (B-2) and component (C) is supported on a fine particle carrier. It may be a catalyst.

The olefin polymerization catalyst is a fine particle carrier, the component (A), the component (B-1) (or the component (B-2)) and an olefin polymer produced by prepolymerization, and if necessary, It may be a prepolymerization catalyst composed of the component (C).

The fine particle carrier used for the solid catalyst and the prepolymerization catalyst is an inorganic or organic compound and has a particle size of 10 to 300 μm, preferably 20 to 200.
It is a solid in the form of granules or fine particles of μm.

Among these, porous oxide is used as the inorganic carrier.
Preferably, specifically, SiO₂, Al₂O₃, MgO, Z
rO₂, TiO₂, B₂O₃, CaO, ZnO, BaO, T
hO ₂Or a mixture thereof, such as SiO₂-M
gO, SiO₂-Al₂O₃, SiO₂-TiO₂, SiO₂-
V₂O_Five, SiO₂-Cr₂O₃, SiO₂-TiO₂-MgO
What can be illustrated. Among these SiO₂And
And Al₂O₃At least one selected from the group consisting of
Those containing minutes as the main component are preferable.

The above 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 )
_It does not matter if it contains a carbonate, a sulfate, a nitrate or an oxide component such as ₂ , Al (NO ₃ ) ₃ , Na ₂ O, K ₂ O and Li ₂ O.

The properties of such a fine particle carrier differ depending on the type and production method, but the specific surface area is 50 to 1000.
m ² / g, preferably 100~700m ² / g, it is desirable that the pore volume is 0.3~2.5cm ³ / g. The particulate carrier may be 100 to 1000, if necessary.
It is used after firing at a temperature of 150 ° C, preferably 150 to 700 ° C.

Further, the fine particle carrier has a particle size of 1
A granular or fine particle solid of an organic compound having a particle size of 0 to 300 μm can be mentioned. As these organic compounds, ethylene, propylene, 1-butene, 4-methyl-1-
Examples thereof include a (co) polymer produced mainly from an α-olefin having 2 to 14 carbon atoms such as pentene, or a polymer produced from vinylcyclohexane or styrene as a main component.

When an α-olefin having 3 or more carbon atoms is polymerized with the above-mentioned olefin polymerization catalyst, many different bonds are present in the molecule of the olefin polymer obtained. Α- with 3 or more carbon atoms using a chiral metallocene catalyst
In the insertion form of α-olefin when olefin is polymerized, in addition to the usual 1,2-insertion, 2,1-insertion and 1,3-insertion occur, resulting in head-to-head in the olefin polymer molecule. It is known that heterologous bonds such as bonds are formed (for example, K. Soga, T. Shiono, S. Takemura and W. Kamin
sky, Makromol.Chem, .Rapid Commun., 8,305 (1987)). It is also known that the melting point of an olefin polymer is low relative to its stereoregularity when heterogeneous bonds are present in the olefin polymer molecule (T.Tsutsui, N. Ishimura, AM).
izuno, A.Toyota and N.Kashiwa, Polymer, 30,1350 (198
9)).

Further, since many different bonds are present in the olefin polymer molecule obtained by polymerizing an α-olefin having 3 or more carbon atoms with the above olefin polymerization catalyst, a conventional catalyst is used. It is considered that the melting point is lower than that of the obtained olefin polymer having the same molecular weight.

[Graft-modified propylene-based polymer] The graft-modified propylene-based polymer of the present invention is obtained by reacting the above-mentioned propylene-based polymer with a polar monomer as described below in the presence of a radical initiator. Can be obtained by

Examples of polar monomers include hydroxyl group-containing ethylenically unsaturated compounds, amino group-containing ethylenically unsaturated compounds, epoxy group-containing ethylenically unsaturated compounds, aromatic vinyl compounds, unsaturated carboxylic acids and their derivatives, vinyl ester compounds. , Vinyl chloride and the like.

Specific examples of the hydroxyl group-containing ethylenically unsaturated compound include hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate and 2-hydroxy.
-3-phenoxy-propyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, glycerin mono (meth) acrylate, pentaerythritol mono (meth) acrylate, trimethylolpropane mono (meth) acrylate, tetramethylol (Meth) acrylic acid ester such as ethane mono (meth) acrylate, butanediol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, 2- (6-hydroxyhexanoyloxy) ethyl acrylate; 10-undecene-1- All, 1-octen-3-ol, 2-methanol norbornene, hydroxystyrene,
Hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, N-methylol acrylamide, 2- (meth) acryloyloxyethyl acid phosphate,
Examples thereof include glycerin monoallyl ether, allyl alcohol, allyloxyethanol, 2-butene-1,4-diol, and glycerin monoalcohol.

The amino group-containing ethylenically unsaturated compound is
A compound having an ethylenic double bond and an amino group,
Examples of such a compound include a vinyl-based monomer having at least one amino group and a substituted amino group represented by the following formula.

[0089]

[Chemical 2]

In the formula, R ⁶ represents a hydrogen atom, a methyl group or an ethyl group, and R ⁷ represents a hydrogen atom or a carbon atom number of 1 to 1.
2, preferably an alkyl group having 1 to 8 or a cycloalkyl group having 6 to 12, preferably 6 to 8 carbon atoms. The above-mentioned alkyl group and cycloalkyl group may further have a substituent.

Specific examples of the amino group-containing ethylenically unsaturated compound include aminoethyl (meth) acrylate, propylaminoethyl (meth) acrylate,
Alkyl ester derivatives of acrylic acid or methacrylic acid such as dimethylaminoethyl methacrylate, aminopropyl (meth) acrylate, phenylaminoethyl methacrylate and cyclohexylaminoethyl methacrylate; N-vinyldiethylamine and N-acetylvinylamine Vinylamine derivatives of allylamine, methacrylamine, N-methylacrylamine, N, N-
Allylamine derivatives such as dimethylacrylamide and N, N-dimethylaminopropylacrylamide; Acrylamide derivatives such as acrylamide and N-methylacrylamide; Aminostyrenes such as p-aminostyrene; 6-Aminohexylsuccinimide, 2- Aminoethyl succinimide or the like is used.

The epoxy group-containing ethylenically unsaturated compound is a monomer having at least one polymerizable unsaturated bond and one or more epoxy groups in one molecule. As such an epoxy group-containing ethylenically unsaturated compound, Specifically, glycidyl acrylate, glycidyl methacrylate, mono and diglycidyl esters of maleic acid, mono and diglycidyl esters of fumaric acid, mono and diglycidyl esters of crotonic acid, mono and diglycidyl esters of tetrahydrophthalic acid, itaconic acid Mono and glycidyl esters, butene tricarboxylic acid mono and diglycidyl esters, citraconic acid mono and diglycidyl esters, endo-cis-bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylic acid (nadic acid mono and ^TM) Glycidyl esters, end - cis - bicyclo [2.2.1] hept-5-ene-2-methyl-2,
3-Dicarboxylic acid (methyl nadic acid ^TM ) mono and diglycidyl ester, allyl succinic acid mono and glycidyl ester and other dicarboxylic acid mono and alkyl glycidyl esters (in the case of monoglycidyl ester, the alkyl group has 1 to 12 carbon atoms) , Alkyl glycidyl ester of p-styrenecarboxylic acid, allyl glycidyl ether, 2-methylallyl glycidyl ether, styrene-p-glycidyl ether, 3,4-epoxy-1-butene, 3,
4-epoxy-3-methyl-1-butene, 3,4-epoxy-1-pentene, 3,4-epoxy-3-methyl-1-pentene, 5,6-epoxy-1-hexene, vinylcyclohexene monoxide And the like.

Examples of aromatic vinyl compounds include compounds represented by the following formula.

[0094]

[Chemical 3]

In the above formula, R ⁸ and R ^{9, which} may be the same or different, each represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, specifically, a methyl group, an ethyl group, Mention may be made of propyl and isopropyl groups. R ¹⁰ represents a hydrocarbon group having 1 to 3 carbon atoms or a halogen atom, and specific examples thereof include a methyl group, an ethyl group, a propyl group and an isopropyl group, a chlorine atom, a bromine atom and an iodine atom. be able to. Further, n is usually 0 to 5, preferably 1 to
Represents an integer of 5.

Specific examples of such an aromatic vinyl compound include 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-isopropenyl pyridine, 2-vinyl quinoline, 3-vinyl isoquinoline, N-vinyl carbazole, N-vinyl pyrrolidone etc. can be mentioned.

As the unsaturated carboxylic acid, acrylic acid,
Methacrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, norbornene dicarboxylic acid, bicyclo [2,
Unsaturated carboxylic acids such as 2,1] hept-2-ene-5,6-dicarboxylic acid, or their acid anhydrides or their derivatives (for example, acid halides, amides, imides, esters, etc.) can be mentioned. Specific examples of the compound include maleenyl chloride, maleenyl imide, maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, bicyclo [2,2,1] hept-2-ene-5,6-dicarboxylic acid. Acid anhydride, dimethyl maleate, monomethyl maleate, diethyl maleate, diethyl fumarate, dimethyl itaconate, diethyl citracone, dimethyl tetrahydrophthalate, bicyclo [2,2,1] hept-2-ene-5,6 -
Dimethyl dicarboxylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate,
Examples thereof include glycidyl (meth) acrylate, aminoethyl methacrylate and aminopropyl methacrylate. Among these, (meth) acrylic acid,
Maleic anhydride, hydroxyethyl (meth) acrylate, glycidyl methacrylate and aminopropyl methacrylate are preferred.

Examples of vinyl ester compounds are vinyl acetate, vinyl propionate, vinyl n-butyrate, vinyl isobutyrate, vinyl pivalate, vinyl caproate, vinyl versatate, vinyl laurate, vinyl stearate, benzoic acid. Examples thereof include vinyl, vinyl pt-butylbenzoate, vinyl salicylate and vinyl cyclohexanecarboxylate.

The polar monomer is used in an amount of usually 1 to 100 parts by weight, preferably 5 to 80 parts by weight, based on 100 parts by weight of the propylene polymer. Examples of the radical initiator include organic peroxides and azo compounds.

Specific examples of the organic peroxide include dicumyl peroxide, di-t-butyl peroxide, and 2,5.
-Dimethyl-2,5-bis (t-butylperoxy) hexane, 2,
5-Dimethyl-2,5-bis (t-butylperoxy) hexine-
3,1,3-bis (t-butylperoxyisopropyl) benzene, 1,1-bis (t-butylperoxy) valerate, benzoyl peroxide, t-butylperoxybenzoate, acetyl peroxide, isobutyryl peroxide , Octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide and 2,4-dichlorobenzoyl peroxide, and m-toluyl peroxide. Examples of the azo compound include azoisobutyronitrile and dimethylazoisobutyronitrile.

Such a radical initiator is generally used in an amount of 0.0 to 100 parts by weight of the propylene polymer.
It is preferably used in an amount of 01 to 10 parts by weight. The radical initiator can be used as it is by mixing it with the propylene polymer and the polar monomer, or can be used by dissolving the radical initiator in a small amount of an organic solvent. The organic solvent used here is not particularly limited as long as it is an organic solvent capable of dissolving the radical initiator. Such organic solvents include aromatic hydrocarbon solvents such as benzene, toluene and xylene; aliphatic hydrocarbon solvents such as pentane, hexane, heptane, octane, nonane and decane;
Alicyclic hydrocarbon solvents such as cyclohexane, methylcyclohexane and decahydronaphthalene; chlorinated hydrocarbons such as chlorobenzene, dichlorobenzene, trichlorobenzene, methylene chloride, chloroform, carbon tetrachloride and tetrachloroethylene; methanol, Alcohol solvents such as ethanol, n-propynol, iso-propanol, n-butanol, sec-butanol and tert-butanol; ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; ester solvents such as ethyl acetate and dimethyl phthalate. Examples thereof include ether solvents such as dimethyl ether, diethyl ether, di-n-amyl ether, tetrahydrofuran and dioxyanisole.

In the present invention, a reducing substance may be used when graft-modifying the propylene polymer. The reducing substance has a function of improving the graft amount in the obtained graft-modified propylene-based polymer.

Examples of the reducing substance include iron (II) ion, chromium ion, cobalt ion, nickel ion, palladium ion, sulfite, hydroxylamine and hydrazine, as well as —SH, SO ₃ H, —NHNH ₂ , CO
Examples include compounds containing groups such as CH (OH)-.

Specific examples of such reducing substances include ferrous chloride, potassium dichromate, cobalt chloride,
Cobalt naphthenate, palladium chloride, ethanolamine, diethanolamine, N, N-dimethylaniline, hydrazine, ethyl mercaptan, benzenesulfonic acid, p-
Examples include toluene sulfonic acid.

The reducing substance is usually added in an amount of 0.001 to 5 with respect to 100 parts by weight of the propylene polymer.
It is used in an amount of parts by weight, preferably 0.1 to 3 parts by weight. The graft modification of the propylene-based polymer can be carried out by a conventionally known method, for example, by dissolving the propylene-based polymer in an organic solvent and then adding a polar monomer and a radical initiator to the solution, and preferably at 70 to 200 ° C. Is 8
The reaction is carried out at a temperature of 0 to 190 ° C. for 0.5 to 15 hours, preferably 1 to 10 hours.

The organic solvent used for graft-modifying the propylene-based polymer can be used without particular limitation as long as it is an organic solvent capable of dissolving the propylene-based polymer.

As such an organic solvent, benzene,
Examples thereof include aromatic hydrocarbon solvents such as toluene and xylene, and aliphatic hydrocarbon solvents such as pentane, hexane and heptane.

Further, a graft-modified propylene-based polymer can be produced by kneading and reacting the propylene-based polymer and the polar monomer in the absence of solvent using an extruder or the like. The reaction temperature is usually the melting point of the propylene-based polymer or higher, specifically in the range of 120 to 250 ° C. The reaction time under such temperature conditions is usually 0.5 to 10
It's a minute.

The graft amount of the graft group derived from the polar monomer in the graft-modified propylene-based polymer thus prepared is usually 0.1 to 50% by weight, preferably 0.2 to 30% by weight. Is within the range of.

The graft-modified propylene-based polymer of the present invention contains a weather resistance stabilizer, a heat resistance stabilizer, an antistatic agent, an antislip agent, an antiblocking agent, an antifogging agent, within the range not impairing the object of the present invention. Additives such as a lubricant, a pigment, a dye, a nucleating agent, a plasticizer, an antiaging agent, a hydrochloric acid absorbent, and an antioxidant may be added if necessary. Further, a small amount of another polymer compound can be blended without departing from the spirit of the present invention.

[0111]

The graft-modified propylene-based polymer of the present invention has an excellent balance between low-temperature adhesiveness and adhesive force in a high-temperature atmosphere in adhering to a metal or polar resin.

Next, the method for measuring the physical properties used in the present invention will be described. (1) Measurement of triad tacticity (mm fraction), proportion of regio irregular units based on 2,1-insertion of propylene monomer and proportion of regio irregular units based on 1,3-insertion of propylene monomer Propylene weight The combined ¹³ C-NMR spectrum shows NM of 50 to 60 mg of the sample.
Completely in an R sample tube (5 mmφ) in a solvent containing about 0.05 ml of hexachlorobutadiene, o-dichlorobenzene or 1,2,4-trichlorobenzene and about 0.05 ml of deuterated benzene as a lock solvent. After dissolving
It was measured at 120 ° C. by the complete proton decoupling method.
The measurement conditions are a flip angle of 45 ° and a pulse interval of 3.
4T ₁ or more (T ₁ is the longest value of the spin lattice relaxation time of the methyl group) is selected. Since T ₁ of methylene group and methine group is shorter than that of methyl group, the recovery of magnetization of all carbons is 99% or more under the measurement conditions.

The chemical shift is set to 21.593 ppm as the third methyl group of the propylene unit 5 chain having head-to-tail bonds and the same methyl branch direction, and the chemical shifts of other carbon peaks are set to this. It was used as a standard. According to this standard, the peak based on the methyl group of the second unit in the propylene unit 3 chain represented by PPP (mm) is 21.1 to
In the range of 21.8 ppm, the peak based on the methyl group of the second unit of the propylene unit 3 chain represented by PPP (mr) is in the range of 20.2 to 21.1 ppm, and PPP (rr)
The peak based on the methyl group at the second unit of the propylene unit 3 chain shown by appears in the range of 19.4 to 20.2 ppm.

Here, PPP (mm), PPP (mr) and P
PP (rr) is respectively

[0115]

[Chemical 4]

Shown are three propylene units linked by head-to-tail represented by: The propylene polymer has a regular structure represented by the above-mentioned PPP (mm), PPP (mr), and PPP (rr), as well as partial structures (i) and 1 including a position irregular unit based on 2,1-insertion. It has a small amount of substructure (ii) containing positional irregular units based on the 1,3-insertion.

[0117]

[Chemical 5]

Of the carbons labeled A to D, A,
Propylene units with carbons B, C and D do not meet the definition of mm fraction above. Carbons A and B are 1
Carbon C is 20.8 p in the range of 6.5 to 17.5 ppm
Near pm (mr region), carbon D is 20.7p
Resonation occurs near pm (mr region) (however, confirmation of structure (i) and structure (ii) must be performed together with confirmation of peaks of not only these methyl groups but also adjacent methylene groups and methine groups. is there).

Further, in the partial structure (ii), as a result of hydrogen transfer polymerization, — (CH ₂ ) ₄ — units are produced and one methyl group equivalent is lost. Therefore, the mm fraction in the total polymer chain can be expressed by the following equation.

[0120]

[Equation 1]

(In the formula, ΣIMe represents the total peak area derived from the methyl group.) Iαδ and Iβγ are αδ peak (3
Area of resonance around 7.1 ppm), βγ peak (27.
Resonance near 3 ppm). The methylene peaks are named by the method of Carman et al. (Rubber Chem. T
echnol., 44 (1971), 781).

During the polymerization of the propylene polymer, the propylene monomer is 1,2-inserted (the methylene side is bonded to the catalyst), but rarely may be 2,1-inserted or 1,3-inserted.
The monomer formed by the 2,1-insertion forms the position disordered unit represented by the partial structure (i) in the polymer chain. The ratio of 2,1-propylene monomer insertion to total propylene insertion was calculated by the following formula.

[0123]

[Equation 2]

Similarly, the frequency of 1,3-propylene monomer insertion represented by the partial structure (ii) with respect to the total propylene insertion was calculated by the following formula.

[0125]

[Equation 3]

[0126] triad tacticity of the propylene copolymer propylene copolymer (mm
The fraction) is calculated from the ¹³ C-NMR spectrum of the propylene copolymer by the following formula.

[0127]

[Equation 4]

(Wherein PPP (mm), PPP (mr) and P
PP (rr) is the same as above. The peak area derived from the methyl group of the 2nd unit of the propylene unit 3 chain | strand connected by the head-tail represented by () is shown. ) ¹³ C-NMR spectrum is measured in the same manner as in the case of the propylene polymer. Methyl carbon region (16-23
ppm), the peak region is the first region (21.1 to 21.9 ppm) and the second region (20.3 to
21.0 ppm), third region (19.5 to 20.3 pp)
m), and the fourth region (16.5 to 17.5 ppm). Each peak in the spectrum was assigned with reference to the literature (Polymer, 30 (1989) 1350).

In the first region, the methyl group at the second unit in the propylene unit 3 chain represented by PPP (mm) resonates. In the second region, the methyl group of the second unit of the propylene unit 3 chain represented by PPP (mr) and the methyl group of the propylene unit (PPE-methyl group) in which the adjacent units are a propylene unit and an ethylene unit are resonant. (20.7
(around ppm).

In the third region, the methyl group of the second unit of the propylene unit 3 chain represented by PPP (rr) and the methyl group of the propylene unit (EPE-methyl group) whose adjacent units are all ethylene units. Is a resonance (19.8pp
(near m).

Further, the propylene copolymer has the following structures (i) and (iii) as a partial structure containing a position disorder unit.

[0132]

[Chemical 6]

Of the carbons labeled A to G, carbon C
The peak and carbon C'peak appear in the second region, and the carbon G peak appears in the third region. Further, the carbon A peak and the carbon B peak appear in the fourth region.

Among the peaks appearing in the first to fourth regions, the peaks not based on the head-to-tail bonded propylene unit 3 chain are PPE-methyl group, EPE-methyl group, carbon C, carbon C ', and carbon. It is a peak based on G, carbon A, and carbon B.

The peak area based on the PPE-methyl group is
The peak area of the PPE-methine group (resonance near 30.6 ppm) can be evaluated, and the peak area based on the EPE-methyl group can be evaluated from the peak area of the EPE-methine group (resonance near 32.9 ppm). The peak area based on carbon C is the carbon F of the position disordered partial structure (structure (i)).
And carbon E (around 35.6 ppm and 35.4 pp
It can be evaluated from 1/2 of the sum of the peak areas of (resonance near m), and the peak area based on carbon C ′ is αβ methylene carbon (34.3 pp) of the position disordered partial structure (structure (iii)).
It can be evaluated from 1/2 of the sum of the peak areas of resonance near m and around 34.5 ppm. The peak area based on carbon G can be evaluated by the peak areas of adjacent methine carbons (resonance near 33.7 ppm).

Therefore, when these peak areas were subtracted from the peak areas of the second and third regions, head-to-tail linked propylene unit 3 chains (PPP (mr) and PP (mr)
The peak area based on P (rr)) can be obtained.

The positions of the carbon A peak and the carbon B peak do not need to be considered because they do not participate in the peak of the propylene unit 3 chain (PPP) at all. From the above, PP
Since the peak areas of P (mm), PPP (mr) and PPP (rr) can be evaluated, the triad tacticity of the propylene unit chain part composed of head-to-tail bonds can be determined according to the above formula.

During the polymerization, the propylene monomer makes 1,2-insertion (the methylene side bonds with the catalyst), but rarely makes 2,1-insertion. The 2,1-inserted monomer forms regioregular units in the polymer.

The ratio of the 2,1-insertions in the total propylene insertions of the propylene copolymer was measured by using ¹³ C-NMR to measure the polymer.
It was calculated from the following formula with reference to r, 30 (1989) 1350.

[0140]

[Equation 5]

Here, the peaks were named according to the method of Carman et al. (Rubber Chem. Technol., 44 (1971), 781). In addition, Iαβ and the like indicate peak areas such as αβ peaks. The amount of three chains based on 1,2-, 1,3-, 1,2-insertion of propylene is 1/2 of the area of βγ peak (resonance around 27.4 ppm), which is 1 of total methyl group peak and βγ peak. The ratio was calculated in% by dividing by the sum of / 2 and multiplying by 100.

[0142] Propylene-ethylene random copolymer of propylene-ethylene random copolymer triad tacticity of (mm fraction) is obtained by the following equation from the ¹³ C-NMR spectrum of the propylene-ethylene random copolymer.

[0143]

[Equation 6]

(Wherein PPP (mm), PPP (mr) and P
PP (rr) is the same as above. ) ¹³ C-NMR spectrum is measured in the same manner as in the case of the propylene polymer. Methyl carbon region (19-23
ppm), the peak region is the first region (21.2 to 21.9 ppm) and the second region (20.3 to
21.0 ppm) and the third region (19.5 to 20.3)
ppm). Each peak in the spectrum was assigned with reference to the literature (Polymer, 30 (1989) 1350).

In the first region, the methyl group at the second unit in the propylene unit 3 chain represented by PPP (mm) resonates. In the second region, the methyl group of the second unit of the propylene unit 3 chain represented by PPP (mr) and the methyl group of the propylene unit (PPE-methyl group) in which the adjacent units are a propylene unit and an ethylene unit are resonant. (20.7
(around ppm).

In the third region, the methyl group of the second unit of the propylene unit 3 chain represented by PPP (rr) and the methyl group of the propylene unit (EPE-methyl group) whose adjacent units are all ethylene units. Is a resonance (19.8pp
(near m).

Further, the propylene / ethylene random copolymer has the following structures (iii) and (iv) as a partial structure containing a position disorder unit.

[0148]

[Chemical 7]

Among the carbons labeled C and G, the carbon C'peak and the carbon C '' peak appear in the second region, and the carbon G peak and the carbon G'peak appear in the third region. Of the peaks appearing in the first to third regions, the peaks not based on the head-to-tail bonded propylene unit 3 chain are PPE-methyl group, EPE-methyl group, carbon C ′, carbon C ″, carbon G.
And a peak based on carbon G ′.

The peak area based on the PPE-methyl group is
The peak area of the PPE-methine group (resonance near 30.6 ppm) can be evaluated, and the peak area based on the EPE-methyl group can be evaluated from the peak area of the EPE-methine group (resonance near 32.9 ppm). The peak area based on carbon C ′ can be evaluated from twice the peak area of methine carbon (resonance around 33.6 ppm) to which the methyl group of carbon G is directly bound, and the peak area based on carbon C ″ is '
It can be evaluated by the peak area of the methine carbon adjacent to the methyl group (resonance near 33.2 ppm). The peak area based on carbon G can be evaluated by the peak area of the adjacent methine carbon (resonance near 33.6 ppm), and the peak area based on carbon G ′ is also similar to the adjacent methine carbon (33.2 ppm).
It can be evaluated by the peak area of (resonance near ppm).

Therefore, when these peak areas were subtracted from the peak areas of the second and third regions, head-to-tail linked propylene unit 3 chains (PPP (mr) and PP (mr)
The peak area based on P (rr)) can be obtained.

As described above, the peak areas of PPP (mm), PPP (mr) and PPP (rr) can be evaluated.
According to the above formula, the triad tacticity of the propylene unit chain portion composed of the head-to-tail bond can be determined.

The proportion of 2,1-insertions in the total propylene insertion of the propylene / ethylene random copolymer was determined by ¹³ C-NMR.
Was calculated with reference to Polymer, 30 (1989) 1350.

[0154]

[Equation 7]

Here, the peaks were named according to the method of Carman et al. (Rubber Chem. Technol., 44 (1971), 781). In addition, Iαβ and the like indicate peak areas such as αβ peaks. When it is difficult to directly obtain the area such as Iαβ from the spectrum due to overlapping peaks, a carbon peak having a corresponding area can be used as a substitute.

The amount of three chains based on 1,2-, 1,3-, and 1,2-insertion of propylene was determined so that 1/2 of the area of the βγ peak (resonance near 27.4 ppm) was determined as the total methyl group peak and βγ. The ratio was calculated in% by dividing by the sum of 1/2 of the peak and multiplying by 100.

In the present invention, the intrinsic viscosity [η], molecular weight distribution (Mw / Mn), stereoregularity (mmmm), heterogeneous bond and melting point (Tm) are measured as follows. (2) Measurement of intrinsic viscosity [η] It was measured in decalin at 135 ° C and shown in dl / g.

(3) Measurement of molecular weight distribution (Mw / Mn) The molecular weight distribution (Mw / Mn) is GPC-1 manufactured by Millipore.
It measured using 50C as follows.

The separation column was TSK GNH HT, the column size was 72 mm in diameter and 600 mm in length, the column temperature was 140 ° C., the mobile phase was o-dichlorobenzene (Wako Pure Chemical Industries) and an antioxidant. As BH
Using 0.025% by weight of T (Takeda Yakuhin), 1.0 ml /
The sample concentration was 0.1% by weight, the sample injection amount was 500 microliters, and a differential refractometer was used as a detector. Standard polystyrene has a molecular weight of Mw <1
000 and Mw> 4 × 10 ⁶ manufactured by Tosoh Corporation, and 1000 <Mw <4 × 10 ⁶ manufactured by Pressure Chemical.

(4) Melting point (Tm) measurement Approximately 5 mg of a sample was packed in an aluminum pan and heated at 200 ° C. at 10 ° C./min.
The temperature was raised to 200 ° C. for 5 minutes, the temperature was lowered to room temperature at 20 ° C./min, and then the temperature was raised at 10 ° C./min. The measurement is DS made by Perkin Elmer
A C-7 type device was used.

[0161]

The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited to these examples.

[0162]

[Production Example 1] 500 g of propylene was charged into a 2 liter autoclave that had been sufficiently replaced with nitrogen, and the temperature was raised to 40 ° C. to obtain 0.2 mmol of triisobutylaluminum, 0.2 mmol of methylaluminoxane, and rac-dimethylsilyl.
-Bis {1- (2,7-dimethyl-4-isopropyl-1-indenyl)} zirconium dichloride was added in an amount of 0.001 mmol in terms of Zr atom, and polymerization was carried out at 50 ° C for 1 hour. After polymerization, degas to remove propylene and remove polymer
It dried at 10 degreeC. The propylene polymer obtained is
It was 158 g. The physical properties of the resulting propylene polymer are shown in Table 1.

[0163]

[Production Example 2] 750 ml of hexane was charged into a 2 liter autoclave which had been sufficiently replaced with nitrogen, and propylene /
The mixture was placed in an ethylene mixed gas (ethylene: 2.9 mol%) atmosphere and stirred at 25 ° C. for 20 minutes. In the reaction system, triisobutylaluminum 0.25 mmol, methylaluminoxane 0.5 mmol, rac-diphenylsilyl-bis {1
-(2,7-Dimethyl-4-isopropylindenyl)} zirconium dichloride was added in an amount of 0.0015 mmol in terms of Zr atom, and the temperature was raised to 50 ° C and the total pressure was kept at ² kg / cm ² -G for 1 hour. Polymerization was carried out. After the polymerization, the mixture was degassed, the polymer was recovered in a large amount of methanol, and dried under reduced pressure at 80 ° C. for 10 hours. The propylene copolymer obtained was 26.9.
It was g. Table 1 shows the physical properties of the obtained propylene copolymer.
Shown in.

[0164]

[Production Example 3] Propylene was homopolymerized using a conventionally known MgCl ₂ -supporting Ti-based catalyst. The physical properties of the resulting propylene polymer are shown in Table 1.

[0165]

Example 1 Toluene was used as a reaction solvent, and 825 g of the propylene polymer obtained in Production Example 1 was dissolved at 160 ° C. per 5.7 liters of toluene. Then, a toluene solution of maleic anhydride (4.
13g / 250ml) and dicumyl peroxide (D
A solution of PC) in toluene (0.33 g / 50 ml) was fed slowly via separate conduit over 4 hours.

After the feed yield, the reaction was further continued at 160 ° C. for 30 minutes and then cooled to room temperature to precipitate a polymer. The precipitated polymer was filtered, washed repeatedly with acetone, and dried under reduced pressure at 80 ° C. for 24 hours to obtain a target modified propylene polymer.

The modified propylene polymer was subjected to elemental analysis and the grafted amount of maleic anhydride was measured. As a result, it was found that 2.0 g of maleic anhydride was graft-polymerized per 100 g of the modified propylene polymer. . Table 1 shows the physical properties of the modified polymer.

A film was prepared from the thus obtained modified polymer as follows, and the heat-sealing start temperature and 10 were obtained.
The 0 ° C peel strength was measured as follows. The results are shown in Table 1.
Shown in.

[Production of Film] On the press plate, the thickness of 0.
A 1 mm aluminum sheet, a polyethylene terephthalate (PET) sheet, and a 100 μm thick aluminum sheet obtained by cutting the center into 15 cm × 15 cm squares were laid in this order, and 3.3 g of a sample (modified) was placed in the center (cut portion). Polymer). Next, a PET sheet,
An aluminum sheet and a press plate were further stacked in this order.

The sample sandwiched between the above-mentioned press plates was put in a hot press at 200 ° C., preheated for about 7 minutes, and then,
Pressurized (50 kg / cm ^2- to remove bubbles in the sample
G) The depressurization operation was repeated several times. Then 100 kg /
The pressure was raised to cm ² -G, and pressure heating was performed for 2 minutes. After depressurizing, it was taken out from the press machine of the press plate, transferred to another press machine whose pressure-bonded part was kept at 0 ° C., pressure-cooled at 100 kg / cm ² -G for 4 minutes, and then depressurized to make the sample. I took it out. The obtained film (modified polymer film) has a uniform thickness of about 150 to
The portion having a thickness of 170 μm was used for measuring the heat sealing start temperature and the 100 ° C. peel strength.

[Measurement of heat-sealing start temperature] The modified polymer film was cut into 25 mm wide strips, and this was cut into 25
It was sandwiched between two aluminum foils each having a thickness of 50 mm and a thickness of 50 μm, and heat-sealed. The heat sealing was performed by keeping the lower temperature of the heat sealer constant at 70 ° C. and changing only the temperature of the upper portion of the hot plate in steps of 5 ° C. Pressure during heat sealing is 1
The heat sealing time was 1 second in kg / cm ² . The obtained laminate was cut into 15 mm wide strips and left overnight in a thermostatic chamber at 25 ° C., after which the heat seal strength was measured.

The heat-sealing strength was determined by performing a tensile test on the peel strength of the modified polymer film heat-sealed at each of the above heat-sealing temperatures under the condition of 200 mm / min.

The peel strength at each heat-sealing temperature in steps of 5 ° C. was obtained by the method described above, and a plot of the heat-sealing temperature vs. the peel strength was connected by a curve. 500g / based on this curve
The heat-sealing temperature at which the peel strength was 15 mm was obtained and used as the heat-sealing start temperature. The lower the heat seal initiation temperature, the better the low temperature adhesion.

[Measurement of Peel Strength at 100 ° C.] The modified polymer film was sandwiched between two 15 cm × 15 cm square aluminum sheets (thickness: 200 μm), and the aluminum sheet was pressed under the same pressing conditions as in the above-mentioned “Production of film”. And the modified polymer film were stuck together. The obtained laminate was cut into 15 mm wide strips, attached to a chamber installed in a thermostat kept at 100 ° C., and allowed to stand for 10 minutes, after which the adhesive interface between the aluminum sheet and the modified polymer film was oriented at 180 °. Then, the peel strength was measured. 100
The higher the peel strength, the better the adhesive strength in a high temperature atmosphere.

[0175]

Example 2 A modified polymer was obtained in the same manner as in Example 1 except that the modifying monomer in Example 1 was changed to the one described in Table 1. A film was prepared from this modified polymer in the same manner as in Example 1, and the heat-sealing start temperature and 100 ° C. peel strength were measured. The results are shown in Table 1.

[0176]

Example 3 A modified polymer was obtained in the same manner as in Example 1 except that the propylene polymer produced in Production Example 2 was replaced with the propylene copolymer produced in Production Example 2. A film was prepared from this modified polymer in the same manner as in Example 1, and the heat-sealing start temperature and 100 ° C. peel strength were measured. The results are shown in Table 1.

[0177]

Comparative Example 1 A modified polymer was obtained in the same manner as in Example 1 except that the propylene polymer produced in Production Example 3 was replaced with the propylene polymer produced in Production Example 3. Table 1 shows the physical properties of the modified polymer thus obtained.

A film was prepared from this modified polymer in the same manner as in Example 1, and the heat-sealing start temperature and 100 were applied.
C peel strength was measured. The results are shown in Table 1.

[0179]

[Table 1]

─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP-A-6-206947 (JP, A) JP-A-6-206946 (JP, A) JP-A-6-128323 (JP, A) JP-A-1- 236259 (JP, A) JP 7-70227 (JP, A) JP 7-149832 (JP, A) JP 7-138326 (JP, A) JP 7-145212 (JP, A) (58) Fields surveyed (Int.Cl. ⁷ , DB name) C08F 255/02

Claims (9)

(57) [Claims] (I) The triad tacticity of the propylene unit chain portion comprising a head-to-tail bond is 90.0% or more, determined by ¹³ C-NMR, and (ii) ¹³ C-N.
The ratio of the regio-irregular units based on the 2,1-insertion of propylene monomer in the total propylene insertion determined by MR is 0.7% or more, and the regio-irregular unit based on the 1,3-insertion of propylene monomer is The ratio is 0.05% or less,
(Iii) A graft-modified propylene-based polymer characterized in that a polar monomer is graft-copolymerized with a propylene polymer having an intrinsic viscosity in the range of 0.1 to 12 dl / g measured at 135 ° C. in decalin. 2. The graft-modified propylene-based polymer according to claim 1, wherein the polar monomer is at least one monomer selected from hydroxyl group-containing ethylenically unsaturated compounds, aromatic vinyl compounds, unsaturated carboxylic acids and their derivatives. Coalescing. 3. The graft-modified propylene-based polymer according to claim 1, wherein the graft amount of the graft group derived from the polar monomer is in the range of 0.1 to 50% by weight. 4. (i) It comprises 95-99.5 mol% of propylene units and 0.5-5 mol% of ethylene units,
(Ii) determined by ¹³ C-NMR, head - triad tacticity of the propylene unit chain consisting of tail bonds is not less 90.0% or more, (iii) ¹³ obtained by C-NMR, all propylene insertions in The proportion of regio-irregular units based on 2,1-insertion of propylene monomer is 0.5% or more, and the proportion of regio-irregular unit based on 1,3-insertion of propylene monomer is 0.05% or less. , (Iv) 13
Intrinsic viscosity of 0.1-12d measured in decalin at 5 ° C
A graft-modified propylene-based polymer, wherein a polar monomer is graft-copolymerized with a propylene copolymer in the range of 1 / g. 5. The graft-modified propylene-based polymer according to claim 4, wherein the polar monomer is at least one monomer selected from a hydroxyl group-containing ethylenically unsaturated compound, an aromatic vinyl compound, an unsaturated carboxylic acid and its derivative. Coalescing. 6. The graft-modified propylene-based polymer according to claim 4, wherein the graft amount of the graft group derived from the polar monomer is in the range of 0.1 to 50% by weight. 7. (i) It comprises 50 to 95 mol% of propylene units and 5 to 50 mol% of ethylene units, and (ii)
The triad tacticity of the chain portion of the propylene unit consisting of the head-to-tail bond was 9 determined by ¹³ C-NMR.
0.03% or more, (iii) 2,3 of the propylene monomer in the total propylene insertion determined by ¹³ C-NMR
1-Ratio of positional irregular unit based on insertion is 0.5% or more,
And the proportion of regio-irregular units based on 1,3-insertion of propylene monomer is 0.05% or less, (iv) 135
The intrinsic viscosity measured in decalin at ℃ is 0.1-12dl
A graft-modified propylene-based polymer characterized in that a polar monomer is graft-copolymerized with a propylene-ethylene random copolymer in the range of 1 / g. 8. The graft-modified propylene-based polymer according to claim 7, wherein the polar monomer is at least one monomer selected from a hydroxyl group-containing ethylenically unsaturated compound, an aromatic vinyl compound, an unsaturated carboxylic acid and its derivative. Coalescing. 9. The graft-modified propylene-based polymer according to claim 7, wherein the graft amount of the graft group derived from the polar monomer is in the range of 0.1 to 50% by weight.