JP2002348316A - Propylene polymer, its composition and molded article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a molded article excellent in rigidity, a propylene polymer which exhibits a high rigidity suitable for the production of the molded article and has a low melting point and good processability, and its composition. SOLUTION: The propylene polymer has a head-to-tail bonded propylene unit chain part with a triad tacticity [mm] of 95.0 mol% or higher, a proportion P of the positional irregular units of propylene due to the 2,1-insertion of 0.40-2.00 mol%, a ratio of the weight-average molecular weight to the number- average molecular weight, i.e., Mw/Mn, of 2.0 or greater, an intrinsic viscosity [η]measured in decalin at 135 deg.C of 0.1-4.50 dl/g, a content Xs of xylene-solubles at 25 deg.C of 2.0 wt.% or less, and a content F of an α-olefin other than propylene of 1.0 mol% or less, of which the triad tacticity [mm] (mol%) and the melting point Tm ( deg.C) measured with a differential scanning calorimeter satisfies the relation of the formula: 140.0<=Tm<=[mm]+60.0. Its composition and molded article are provided.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a propylene polymer, a composition thereof and a molded article. The present invention particularly relates to a molded article of a propylene polymer having excellent rigidity, a propylene polymer composition suitable for the production thereof, and a propylene polymer.

[0002]

2. Description of the Related Art Propylene polymers are used for various applications by utilizing their excellent rigidity. In general, the rigidity and processability of a propylene polymer have an opposite relationship. That is, when the rigidity is improved by improving the stereoregularity, the melting point is increased, and as a result, the workability is reduced. On the other hand, if the stereoregularity is lowered or the processability is improved by copolymerizing ethylene or the like, the rigidity is lowered.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a molded article having excellent rigidity, a propylene polymer having a high rigidity, a low melting point and a good processability, which is suitable for the production thereof and a composition thereof. To provide things.

[0004]

Means for Solving the Problems As a result of intensive studies in view of the above situation, the present inventors have found that a propylene polymer having a specific molecular structure is effective for solving the above problems, and have completed the present invention. It has been reached. That is,
The present invention relates to (1) (A) (a) a triad tacticity [mm] of a head-to-tail bonded propylene unit chain portion of 95.0 mol% or more, and (b) a 2,1-insertion of propylene. The ratio P of the position irregularity unit is 0.40 to 2.00 mol%
And (c) a ratio Mw between the weight average molecular weight and the number average molecular weight.
/ Mn is 2.0 or more, and (d) the intrinsic viscosity [η] measured in decalin at 135 ° C. is 0.1 to 4.50 dl /.
(e) the xylene-soluble content Xs at 25 ° C. is 2.0% by weight or less, and (f) α-
The olefin content F is 1.0 mol% or less;
(G) The triad tacticity [mm] (mol%) of the head-to-tail bonded propylene unit chain and the melting point Tm (° C.) measured by a differential scanning calorimeter are as follows: (1) 140.0 ≦ Tm ≦ [Mm] +60.0 (1) 2) 100 parts by weight of the propylene polymer (A) of the above 1) and (B) any one of the heat-resistant stabilizer and the weather-resistant stabilizer
3) A propylene polymer composition comprising 0.001 to 5 parts by weight of the above additive; 3) 99 to 20 parts by weight of the propylene polymer (A) and 1 to 80 parts by weight of the olefin elastomer (C). 4) A propylene polymer composition comprising 99 to 70 parts by weight of the propylene polymer (A) of the above 1) and 1 to 30 parts by weight of an inorganic or organic filler, 5) the above 2) A) a molded article obtained by molding the propylene polymer composition of 6), a molded article obtained by molding the propylene polymer composition of 3), and 7) a molded article obtained by molding the propylene polymer composition of 4). Molded articles.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, a preferred embodiment of the present invention will be described in detail. The propylene polymer of the present invention has (a) a triad tacticity [mm] of a head-to-tail bonded propylene unit chain portion of 95.0 mol% or more, preferably 96.0 mol% or more, more preferably 97.0 mol% or more, more preferably 97.5 mol% or more, still more preferably 98.0 mol% or more, particularly preferably 98.5 mol% or more, and most preferably 9
It is more than 9.0 mol%. The triad tacticity [mm] of the head-to-tail bonded propylene unit chain is 95.0.
If the amount is less than mol%, the workability is improved, but the rigidity is reduced.

In the present invention, the triad tacticity [mm] of the propylene unit chain portion indicates the ratio of those having meso-meso regularity in the structure of all propylene unit triple chains. That is, it is calculated by calculating the peak area derived from the methyl group of propylene of the second unit in the three chains of each propylene unit in ¹³ C-NMR.

In the polymerization of propylene, 1,2-insertion of the propylene monomer (the methylene side is bonded to the catalyst), but rarely, 2,1-insertion may occur. The 2,1-inserted monomer forms a regio-irregular unit adjacent to a methyl group represented by the following structural formula (2) in the chain.

[0008]

Embedded image

The propylene polymer of the present invention comprises (b) a proportion P of a position irregularity unit due to 2,1-insertion of propylene.
Is in the range of 0.40 to 2.00 mol%, preferably in the range of 0.45 to 1.50 mol%, more preferably 0.1 to 0.1 mol%.
50 to 1.30 mol%, more preferably 0.5 to 1.30 mol%.
In the range of 0 to 1.20 mol%, even more preferably 0.1 to 2.0 mol%.
In the range of 60 to 1.00 mol%, particularly preferably 0.60
~ 0.90 mol%, most preferably from 0.60 to 0.90 mol%.
It is in the range of 0.85 mol%. If the proportion P of the regio-irregular units due to 2,1-insertion of propylene is less than 0.40 mol%, the workability is poor, and if it exceeds 2.00 mol%, the rigidity is reduced.

Position based on 2,1-insertion of propylene
The ratio P (mol%) of the irregular units is ¹³C-NMR measurement
It can be determined based on the results. Methyl of the above (a)
The peak derived from the group is 1 based on tetramethylsilane.
Appears at 6.5 to 18.0 ppm (multiple occurrences
There is). Therefore, the area of all peaks appearing in this range
And a peak derived from all methyl groups (16.5 to 22.5
(appearing in the range of ppm) according to the following equation (3).
Can be calculated. In addition, the methyl group was adjacent
2. One unit of irregular position based on the insertion is formed.
The peak derived from the methyl group in (a) is
Is formed. Therefore, P = (0.5 × I_a / I_t ) × (100-F) (3)_a Is the peak derived from the methyl group in (a)
Area and I_t Is the area of the peak derived from all methyl groups
And F is the content of α-olefins other than propylene
(Mol%)).

The propylene polymer of the present invention has (c) a ratio Mw / Mn of the weight average molecular weight Mw to the number average molecular weight Mn of 2.00 or more, preferably 2.50 to 10.0,
More preferably, it is in the range of 2.60 to 5.00, even more preferably in the range of 2.70 to 4.50, even more preferably in the range of 2.80 to 4.50, and particularly preferably 2.90.
~ 4.50, most preferably between 3.00 and 4.50.
Range. If Mw / Mn is out of the above range, rigidity is reduced and workability is reduced.

The propylene polymer of the present invention comprises (d) 13
The intrinsic viscosity [η] measured in decalin at 5 ° C. is 0.1 to
It is in the range of 4.50 dl / g, preferably 0.2 to
In the range of 3.50 dl / g, more preferably 0.30 dl / g
2.50 dl / g range, more preferably 0.40 to
Range of 2.30 dl / g, even more preferably 0.5.
0 to 2.25 dl / g, particularly preferably 0.60
~ .20 dl / g, most preferably 0.70-
2. The range is 10 dl / g. When the intrinsic viscosity [η] is 0.
If it is less than 1 dl / g, rigidity and impact resistance will be reduced. If it exceeds 4.50 dl / g, workability and rigidity are reduced. The weight average molecular weight M corresponding to the intrinsic viscosity is
w is the Journal of physical chemistry, 63 , 2002 (195
As described in 9), it can be obtained from the following equation (4).

[Η] = K × Mw ^α (4) (where K and α are constants, and K = 1.10 × 1
^0-4 , α = 0.80) The propylene polymer of the present invention has (e) a xylene-soluble component Xs at 25 ° C. of 2.0% by weight or less, preferably 1.0% by weight or less, More preferably 0.80% by weight or less, further preferably 0.60% by weight or less, still more preferably 0.50% by weight or less, particularly preferably 0.4% by weight or less.
0% by weight or less, most preferably 0.30% by weight or less. 2.0 wt% of xylene solubles Xs at 25 ° C.
If it exceeds, the rigidity decreases.

The propylene polymer of the present invention has (f) a content F of α-olefin other than propylene of 1.0 mol%.
Or less, preferably 0.5 mol% or less, and most preferably 0 mol%, that is, a propylene homopolymer. When the content F of the α-olefin other than propylene exceeds 1.0 mol%, the rigidity decreases. The propylene polymer of the present invention may have a position irregularity unit based on 1,3-insertion of propylene of 1.0 mol% or less, and its value is usually 0.5 mol% or less. egoism,
Preferably less than 0.4 mol%, more preferably less than 0.3 mol%, even more preferably less than 0.2 mol%, even more preferably 0.15 mol% or less, particularly preferably 0.10 mol% or less. , Most preferably 0.05 mol%
It is as follows.

The propylene polymer of the present invention generally has a melting point Tm of 140.0 to
The temperature is preferably in the range of 160.0 ° C., preferably 14 ° C.
4.0 to 155.0 ° C, more preferably 145.0 to 1
54.5 ° C, more preferably 146.0 to 154.0.
° C, more preferably 147.0-153.
0 ° C. range, particularly preferably 147.5 to 152.0 ° C.
, Most preferably in the range of 148.0 to 152.0 ° C. If the melting point exceeds the above range, workability may decrease, and if it is less than the above range, rigidity may decrease.

Further, the propylene polymer of the present invention preferably has a melting point Tm and an α-olefin content F satisfying the following formula (5): 145.0 <Tm + 5.5 × F <156.0 (5) More preferably, the following formula (6) is satisfied: 146.0 <Tm + 5.5 × F <155.0 (6), and particularly preferably, the following formula (7): 147.0 <Tm + 5.5 × F <153.0 ( 7) Satisfy

If the value of Tm + 5.5 × F is 145.0 or less, the rigidity may decrease. If it is 156.0 or more, workability may be reduced. The propylene polymer of the present invention has a triad tacticity [mm] (mol%) of a head-to-tail bonded propylene unit chain and a melting point Tm (° C.) measured by a differential scanning calorimeter according to the following formula (1). 0.0 ≦ Tm ≦ [mm] +60.0 (1) When [mm] and Tm do not satisfy the relationship of Expression (1), workability is reduced. [Mm] and Tm
Preferably satisfies the relationship of the following formula (8): 143.0 ≦ Tm ≦ [mm] +58.0 (8), and more preferably the following formula (9): 145.0 ≦ Tm ≦ [mm] +56.0 ( 9), and most preferably the following expression (10): 147.0 ≦ Tm ≦ [mm] +54.0 (10)

Next, a method for producing the propylene polymer of the present invention will be described. The propylene polymer of the present invention is produced by homopolymerizing propylene using a solid catalyst comprising a metallocene compound and a cocatalyst component, or by copolymerizing propylene with another olefin. When a soluble catalyst is used, it is difficult to obtain the propylene polymer of the present invention.

It can be used for producing the propylene polymer of the present invention.
As an effective metallocene compound, propylene is sterically regulated.
There is no particular limitation as long as it is polymerized in a more specific manner.
In general, bis (2,3-dimethylcyclopentadienyl)
Ruzirconium) dimethylsilane zirconium dichlora
Id, bis (2,4-dimethylcyclopentadienyldi
Ruconium) dimethylsilane zirconium dichlori
De, bis (2,3,5-trimethylcyclopentadieni
Ruzirconium) dimethylsilane zirconium dichlora
Id, (3-t-butylcyclopentadienyl) [4-
t-butyl- (η ^Five -1-indenyl)] dimethylsila
Zirconium dichloride, (3-t-butylcyclo
Pentadienyl) (η^Five -9-Fluorenyl) dimethyl
Silane zirconium dichloride, bis [2-methyl-
(Η^Five -1-indenyl)] dimethylsilanezirconium
Mudichloride, bis [2,4,7-trimethyl- (η
^Five -1-indenyl)] dimethylsilanezirconiumdi
Chloride, bis [2,4-dimethyl- (η^Five -1-b
Ndenyl)] dimethylsilane zirconium dichlori
De, bis [2-methyl-4,5-benzo (η^Five -1-b
Ndenyl)] dimethylsilane zirconium dichlori
De, bis [2-methyl-4-phenyl- (η^Five -1-b
Ndenyl)] dimethylsilane zirconium dichlori
De, bis [2-methyl-4- (1-naphthyl)-(η^Five 
-1-indenyl)] dimethylsilanezirconiumdic
Chloride, bis [2-methyl-4- (2-naphthyl)-
(Η^Five -1-indenyl)] dimethylsilanezirconium
Mudichloride, bis [2-methyl-4- (9-ant
Racenyl)-(η^Five -1-indenyl)] dimethylsila
Zirconium dichloride, bis [2-methyl-4-
(9-phenanthryl)-(η^Five-1-indenyl)]
Dimethylsilane zirconium dichloride, bis [2-
Methyl-4- (3,5-di-i-propylphenyl)-
(Η^Five -1-indenyl)] dimethylsilanezirconium
Mudichloride, 1,2-bis [2-methyl- (η ^Five −
1-indenyl)] ethanezirconium dichloride,
1,2-bis [2,4-dimethyl- (η^Five -1- Inde
Nyl)] ethanezirconium dichloride, 1,2-bi
[2,4,7-trimethyl- (η^Five -1- Indeni
Le)] ethane zirconium dichloride, 1,2-bis
[2-ethyl- (η^Five -1-indenyl)] ethandyl
Conium dichloride, 1,2-bis [2-n-propyl
Le-(η ^Five -1-indenyl)] ethanezirconiumdi
Chloride, 2- (3-t-butylcyclopentadienyl)
Ru) -2- [4-t-butyl- (η^Five -1- Indeni
)] Propane zirconium dichloride, 2- (3-
Methylcyclopentadienyl) -2- (η^Five -9-full
Olenyl) propane zirconium dichloride, 2-
(3-t-butylcyclopentadienyl) -2- (η^Five 
-9-Fluorenyl) propane zirconium dichlorai
Can be used, among which the 2-position of the indenyl group
Has an alkyl group and an aryl group at positions 4 and 4, respectively.
And especially [2-methyl-4,5-ben
Zo (η^Five -1-indenyl)] dimethylsilanezirconi
Um dichloride, [2-methyl-4-phenyl- (η
^Five -1-indenyl)] dimethylsilanezirconiumdi
Chloride, [2-methyl-4- (1-naphthyl)-
(Η^Five -1-indenyl)] dimethylsilanezirconium
Mudichloride is preferred.

In these metallocene compounds, zirconium is replaced by another metal such as titanium or hafnium, and the chlorine atom is replaced by a carbon atom such as another halogen atom, hydrogen atom, amide group, alkoxy group, methyl group or benzyl group. What substituted for the hydrogen group can be used without any limitation. As the cocatalyst component used with the metallocene compound, any one can be used. For example, aluminoxane compounds such as methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, methylisobutylaluminoxane, Lewis acidic organic boron compounds, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, triphenylcarbenium tetrakis (pentafluorophenyl) borate, tri-n-butylammonium tetrakis (pentafluorophenyl) borate, triethyloxonium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium [4- (trichlorosilyl) -2,
3,5,6-tetrafluorophenyl] tris (pentafluorophenyl) borate, N, N-dimethylanilinium [4- (chlorodimethylsilyl) -2,3,5
Non-coordinating anion-containing compounds such as [6-tetrafluorophenyl] tris (pentafluorophenyl) borate. Among them, methylaluminoxane,
N, N, -dimethylanilinium tetrakis (pentafluorophenyl) borate, triphenylcarbenium tetrakis (pentafluorophenyl) borate,
N-Dimethylanilinium [4- (chlorodimethylsilyl) -2,3,5,6-tetrafluorophenyl] tris (pentafluorophenyl) borate is preferred. These can be used alone or in combination of two or more as necessary.

The metallocene catalyst may be used together with an organic metal compound such as an organic aluminum compound for the purpose of activating the metallocene compound or removing impurities in the polymerization system. As the organic aluminum compound,
For example, trialkyl aluminum such as trimethyl aluminum, triethyl aluminum, tri-n-propyl aluminum, tri-n-butyl aluminum, tri-i-butyl aluminum, tri-n-hexyl aluminum, tri-n-octyl aluminum, and diethyl aluminum Examples thereof include dialkylaluminum halides such as dichloride and ethylaluminum dichloride, dialkylaluminum hydrides such as alkylaluminum dihalide and diisobutylaluminum hydride, diethylaluminum ethoxide, and diethylaluminum phenoxide. Among them, trialkylaluminum is preferred. These can be used alone or in combination of two or more as necessary.

In the production of the propylene polymer of the present invention, these are used in the form of a solid catalyst, and specifically, those in which these are supported on a fine particle carrier are used. Useful fine particle carriers include metal oxides, metal halides, metal hydroxides, metal alkoxides, carbonates, sulfates, acetates, silicates and organic high molecular compounds. These can be used alone or in combination of two or more as necessary.

Examples of the above-mentioned metal oxide include silica, alumina, titania, magnesia, zirconia, calcia, zinc oxide and the like. Examples of metal halides include, for example, magnesium chloride, calcium chloride,
Barium chloride, sodium chloride and the like can be mentioned. Examples of the metal hydroxide include aluminum hydroxide and magnesium hydroxide. Examples of the metal alkoxide include magnesium ethoxide, magnesium methoxide and the like. Examples of the carbonate include calcium carbonate, basic calcium carbonate, magnesium carbonate, basic magnesium carbonate, barium carbonate and the like. Examples of the sulfate include calcium sulfate, magnesium sulfate, barium sulfate and the like. Examples of the acetate include calcium acetate, magnesium acetate and the like. Further, as the silicate, for example, mica,
Examples thereof include magnesium silicate such as talc, calcium silicate, and sodium silicate. Among these, preferred are silica, alumina, silicates such as magnesium silicate such as mica and talc, calcium silicate and sodium silicate.

Examples of the organic polymer compound include polyethylene, propylene polymer, ethylene-propylene copolymer, ethylene-vinyl ester copolymer, partially or completely saponified ethylene-vinyl ester copolymer, and the like. And modified resins thereof, such as thermoplastic resins such as polyamide, polycarbonate and polyester, and thermosetting resins such as phenolic resin, epoxy resin, urea resin and melamine resin.

The average particle size of these fine particle carriers is not particularly limited, but is generally preferably in the range of 0.1 to 2,000 μm, preferably 1 to 1,000 μm, more preferably 5 to 100 μm. Range. The specific surface area is not particularly limited, but is usually 0.1 to 2,000 m ² /
g, preferably 10 to 1,500.
m ² / g, and more preferably 100 to 1,000.
m ² / g.

The metallocene compound and the cocatalyst component can be supported on the fine particle carrier by bringing them into contact with each other by any method, and they may be directly contacted in the absence of an organic solvent. The contact may be made with. Examples of the organic solvent used here include aliphatic hydrocarbons such as hexane and heptane, aromatic hydrocarbons such as toluene and xylene, halogenated hydrocarbons such as methylene chloride and chlorobenzene, and mixtures thereof. The contact between the metallocene compound or the cocatalyst component and the fine particle carrier can be performed at any temperature, and is usually from −80 ° C. to + 300 ° C.
It is good to be carried out in the range of ° C.

The amount of the metallocene compound to be used in the fine particle carrier is not particularly limited, but usually, the metallocene compound is used in an amount of 0.0001 to 1,1 per 100 parts by weight of the fine particle carrier.
It is preferably in the range of 1,000,000 parts by weight, more preferably in the range of 0.1 to 10,000 parts by weight, and still more preferably in the range of 1 to 1,000 parts by weight. The amount of the co-catalyst component to be used with respect to the metallocene compound is not particularly limited. Usually, the amount of boron or aluminum contained in the co-catalyst component is 0 to 1 mol of transition metal such as zirconium contained in the metallocene compound. .01 to 100,00
0 mol, preferably 0.1 to 10,000.
0 mol, more preferably 1.0 to 3,000 mol, particularly preferably 1.0 to 1,000 mol.

The propylene polymer of the present invention can be produced by homopolymerizing propylene or copolymerizing it with another olefin by an arbitrary polymerization method using the above-mentioned catalyst or the like. It can be produced by bulk polymerization performed in propylene, solution polymerization performed in a liquid phase in the presence of an inert solvent, slurry polymerization, or gas phase polymerization performed in a gas phase monomer. The polymerization temperature is not particularly limited,
Usually, the temperature is in the range of 35 to 95 ° C, preferably 5 to 95 ° C.
The range is from 0 to 80 ° C. The pressure during the polymerization is from normal pressure to 7 MPa in the polymerization in the liquid phase, and from normal pressure to 5 MPa in the gas phase.
Is a general range, and an appropriate range can be selected in consideration of the properties and productivity of the propylene polymer. At the time of polymerization, the molecular weight can be adjusted by any means such as introduction of hydrogen and selection of temperature and pressure.

Next, the propylene polymer composition of the present invention will be described. In a first embodiment of the propylene polymer composition of the present invention, 100 parts by weight of the propylene polymer (A) and (B) one of a heat-resistant stabilizer and a weather-resistant stabilizer are used.
A propylene polymer composition comprising 0.001 to 5 parts by weight of the above additives. As the heat stabilizer, β- (3,
Stearyl 5-di-t-butyl-4-hydroxyphenyl) propionate, tetrakis [methylene-3- (3,
5-di-t-butyl-4-hydroxyphenyl) propionate] methane, tris (3,5-di-t-butyl-
4-hydroxybenzyl) isocyanurate, 1,3
5-trimethyl-2,4,6-tris (3,5-di-t
-Butyl-4-hydroxybenzyl) benzene, tris (2,6-dimethyl-3-hydroxy-4-t-butylbenzyl) isocyanurate, tris [(3,5-di-
t-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate, 3,9-bis [1,
1′-dimethyl-2- {β- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy}
Phenols such as ethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, bis (2,4-di-t-butylphenyl) -4,4′-biphenylenediphospho Knight, bis (2,6-di-t-
Butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite and the like, dilauryl thiopropionate, dimyristyl thiopropion Known compounds such as a sulfur-based compound such as catenate and distearylthiopropionate can be used.

As the weathering stabilizer, bis (2,2,6,
6-tetramethyl-4-piperidyl) sebacate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, dimethyl-1- (2-succinate) -Hydroxyethyl)
-4-hydroxy-2,2,6,6-tetramethyl-4
And hindered amine-based compounds such as piperidine polycondensate.

These may be used alone or in combination of two or more. These blending amounts are
Usually, it is preferably 0.001 to 3.0 parts by weight, preferably 0.005 to 1.0 part by weight, more preferably 0.1 to 1.0 part by weight.
01 to 1.0 part by weight, more preferably 0.02 to 1.0 part by weight
0.9 parts by weight, particularly preferably 0.03 to 0.8 parts by weight, most preferably 0.05 to 0.5 parts by weight. Within the above range, the desired effect can be improved without problems such as a decrease in rigidity and strength and coloring.

A second embodiment of the propylene polymer composition of the present invention is a propylene polymer composition comprising 99 to 20 parts by weight of the propylene polymer (A) and 1 to 80 parts by weight of the elastomer (C). Known elastomers can be used as the elastomer, and olefin copolymer elastomers, conjugated diene elastomers, olefin-conjugated diene copolymer elastomers, vinyl aromatic compound-olefin copolymer elastomers, vinyl aromatic compounds -Conjugated diene copolymer elastomers and hydrogenated products thereof.

Specific examples of these elastomers include:
Ethylene-α-olefin-non-conjugated diene copolymer elastomer such as ethylene-propylene-ethylidene norbornene copolymer elastomer, ethylene-propylene-dicyclopentadiene copolymer elastomer, ethylene-butene copolymer elastomer, ethylene-propylene copolymer Polymer elastomers, ethylene-octene copolymer elastomers, ethylene-α-olefin copolymer elastomers such as ethylene-hexene copolymer elastomers,
Propylene-α- such as propylene-butene copolymer elastomer and propylene-hexene copolymer elastomer
Olefin copolymer elastomer, olefin-conjugated diene copolymer elastomer such as isoprene-isobutylene copolymer elastomer, styrene-butadiene copolymer elastomer, styrene-conjugated diene copolymer elastomer such as styrene-isoprene copolymer elastomer, and Its hydrogenated product, 1,2-polybutadiene, 1,
Examples thereof include diene-based elastomers such as 4-polybutadiene, polychloroprene and polyisoprene, and mixtures thereof. Of these, ethylene-
α-olefin copolymer elastomers, styrene-conjugated diene copolymer elastomers and hydrogenated products thereof are preferred.

The MFR of these elastomers such as ethylene-α-olefin copolymer elastomer, isoprene-isobutylene copolymer elastomer, and styrene copolymer elastomer (according to JIS K7210, 230
° C, measured at a load of 2.16 kg) is not particularly limited,
Usually, the range is preferably 0.001 to 200 g / 10 minutes. Further, it is preferably in the range of 0.1 to 100 g / 10 min, and more preferably in the range of 0.5 to 50 g / 10 min.

These may be used alone or in combination of two or more. The amount of these compounds is 1
To 80 parts by weight, preferably 3 to 70 parts by weight, more preferably 5 to 60 parts by weight, and still more preferably 7 to 50 parts by weight.
Parts by weight, more preferably 10 to 40 parts by weight, particularly preferably 12 to 35 parts by weight, most preferably 15 to 3 parts by weight.
0 parts by weight. Within the above range, the impact resistance can be improved without lowering the rigidity.

A third embodiment of the propylene polymer composition of the present invention is a propylene polymer comprising 99 to 70 parts by weight of the propylene polymer (A) and 1 to 30 parts by weight of an inorganic or organic filler (D). A composition. The rigidity of the propylene polymer of the present invention can be further improved by adding a filler. The amount of filler added is preferably 2
To 25 parts by weight, more preferably 3 to 20 parts by weight, still more preferably 4 to 20 parts by weight,
It is even more preferably in the range of 5 to 18 parts by weight, particularly preferably in the range of 5 to 15 parts by weight. If the amount of the filler exceeds the above range, problems such as a decrease in impact resistance and a decrease in workability occur. If the amount of the filler is less than the above range, the rigidity may not be improved.

The filler may be inorganic or organic, and may have a plate-like, spherical, fibrous, or irregular shape. Specific examples thereof include natural silica such as quartz, synthetic silica produced by a wet or dry method, clay, diatomaceous earth, kaolin, mica, talc, natural silicates such as asbestos, aluminum silicate, and silicate. Synthetic silicates such as calcium, metal hydroxides such as magnesium hydroxide and aluminum hydroxide, metal oxides such as alumina and titania, metal salts such as magnesium carbonate, calcium carbonate, calcium sulfate, aluminum sulfate and barium sulfate; Metal powder such as aluminum and bronze, wood powder, carbon black, graphite, shirasu balloon, glass beads, glass fiber, carbon fiber, aramid fiber, inorganic fiber or organic fiber such as alumina fiber, polymer liquid crystal substance, potassium titanate whisker,
Whisker such as magnesium sulfate whisker, magnesium borate whisker, aluminum borate whisker, calcium carbonate whisker, zinc oxide whisker, silicon carbide whisker, silicon nitride whisker, sapphire whisker, beryllia whisker, etc., and these are two or more kinds. May be used together. These may be surface-treated with a coupling agent such as a silane coupling agent, a surfactant, or the like, and commercially available products may be used.

The propylene polymer composition of the present invention comprises the propylene polymer (A), (B) one or more additives of a heat-resistant stabilizer or a weather-resistant stabilizer, (C) an elastomer or (D) an inorganic Alternatively, it can be produced by blending predetermined amounts of organic fillers and mixing them by a known method. Specifically, after blending the above components and other components as necessary with a Henschel mixer or the like,
It is manufactured by kneading at a temperature of about 100 to 300 ° C. using a kneader such as a single-screw or twin-screw extruder, a Banbury mixer or a kneader.

The molded article of the present invention is obtained by molding the above-mentioned propylene polymer composition by an arbitrary method, and specifically includes an injection molded article, an extruded article such as a film or a sheet, and a press molded article. And preferably an injection-molded body. The production of the injection molded article is obtained by injection molding the propylene polymer composition by a known method.
It is possible to perform injection molding at 00 ° C. The resulting injection-molded article has excellent rigidity, impact resistance, transparency, etc., and is used as containers for food packaging such as cups and trays, miscellaneous goods such as containers, parts for home appliances, automobile exterior materials and interior materials, etc. can do.

There is no particular limitation on the method for producing an extruded product such as a film or sheet, and any known method can be employed without any limitation. For example, in the case of an unstretched film,
The propylene polymer is mixed with a predetermined additive such as an antioxidant and the like, kneaded by a single screw extruder or the like, and formed into a film by an extruder equipped with a T die or the like. The thickness of the extruded product is not limited, but usually the thickness of the film is in the range of 3 to 150 µm, and the thickness of the sheet is in the range of 50 to 10000 µm.
Further, other films or sheets may be laminated on these.

Such films and sheets are used for various applications as they are or through secondary processing such as uniaxial or biaxial stretching, heat sealing, vacuum forming or pressure forming, lamination, etc., but they have high rigidity and low melting point. Since a propylene polymer is used, the above-mentioned secondary workability is also good, and a molded article having excellent rigidity can be easily obtained.

As described above, the propylene polymer composition of the present invention has a high stereoregularity and a high rigidity.
Various molded bodies having excellent rigidity can be easily provided.
Furthermore, since a propylene polymer having a low melting point is used, the resulting molded article can be easily subjected to secondary processing and can be used for various purposes.

Further, in the present invention, since a propylene polymer having a low melting point is used, kneading at a lower temperature,
That is, kneading in a state where the viscosity of the propylene polymer is high is possible. Therefore, it is possible to produce a composition having good dispersibility, such as an elastomer or a filler, and it is possible to mix these in a large amount. for that reason,
The composition of the present invention can be suitably used for the production of various molded articles, in combination with the fact that the molded article obtained from this composition has a good rigidity or a good balance between rigidity and impact resistance, and has good workability. It is.

[0044]

EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited to these examples without departing from the spirit of the present invention. Measurement of ¹³ C-NMR The measurement was performed by JNM-GSX400 manufactured by JEOL Ltd.

Measurement mode: proton decoupling method,
Pulse width: 8.0 μs, pulse repetition time: 3.0
s, number of accumulation: 20,000 times, measurement temperature: 120 ° C., internal standard: hexamethyldisiloxane, solvent: 1, 2, 4,
-Trichlorobenzene / benzene-d6 (volume ratio 3 /
1), Sample concentration: 0.1 g / ml Triad tacticity [m
The decision Hei 7-196734 JP-m] with reference, ¹³ C-NM
It was calculated from the measurement result of R by the following equation (11).

[Mm] = 100 × I _mm / I _CH3 (11) I _mm : Area of peaks appearing at 21.4 to 22.2 ppm (attributable to mm) I _CH3 : 19.0 to 22.4 pp
Area of peak appearing in m (attributable to mm, mr and rr) Determination of ratio of position irregular units based on 2,1-insertion of propylene Based on the measurement result of ¹³ C-NMR, the following formula (3) It was calculated from:

P = (0.5 × I _a / I _t ) × (100−F) (3) I _a : Area of peak derived from methyl group of (a) I _t : Peak derived from all methyl groups F: α-olefin content other than propylene (mol%) Measurement of intrinsic viscosity [η] Measured in decalin at 135 ° C.

The ratio of the weight average molecular weight to the number average molecular weight (Mw
/ Mn) 1) Preparation of calibration curve 0.1% by weight of BHT (2,6-di-t-butyl-4-
2 mg of each of three kinds of standard polystyrene samples (manufactured by Showa Denko KK) in 10 ml of 1,2,4-trichlorobenzene containing methylphenol) were dissolved in a dark place at room temperature for 1 hour. The elution time of the peak top was measured by the measurement. This measurement was repeated, and a calibration curve was prepared by a cubic approximation based on the molecular weights at a total of 12 points (molecular weight of 580 to 8.5 million) and the elution time at the peak top.

2) Measurement of weight average molecular weight (Mw) and number average molecular weight (Mn) 5 ml of 1,2,2 containing 0.1% by weight of BHT was placed in a test tube.
4-Trichlorobenzene was taken, and about 2.5 mg of a propylene polymer (sample) was added thereto. After stoppering the test tube, the sample was dissolved in a constant temperature bath at 160 ° C. for 2 hours. After the obtained solution was filtered with a sintering filter, the filtrate was measured using a gel permeation chromatography device 150C manufactured by Waters, and Mw and Mn were obtained from the obtained chromatogram, and the ratio Mw of these molecular weights was obtained. / Mn was calculated. In addition, other measurement conditions of GPC are as follows.

Detector: Differential refractometer Column: Shodex HT-G (1 manufactured by Showa Denko KK)
Book) and Shodex HT-80 manufactured by Showa Denko KK
6M (two) connected in series Column temperature: 140 ° C Solvent: 1,2,4-trichlorobenzene (BHT 0.1
(Including% by weight) Sample injection amount: 0.5 ml Solvent flow rate: 1 ml / min Sample injection waiting time in the apparatus: 30 minutes (5 minutes for polystyrene) Measurement of xylene solubles Xs About 2 g of propylene polymer accurately Weigh (this is W
(G)) and dissolved in 250 ml of boiling xylene under a nitrogen stream. Thereafter, the solution was cooled to 25 ° C., left for 30 minutes, and the formed precipitate was promptly filtered. 100 ml of the obtained filtrate was collected, placed in an aluminum container whose constant weight was determined, and heated under a nitrogen stream to evaporate xylene. The weight of the evaporation residue (m (g)) was determined, and the xylene-soluble component Xs of the propylene polymer was determined by the following equation (12).

Xs (% by weight) = m × 250 / W (12) Measurement of Curvature Elasticity Using a test piece injection-molded at 210 ° C.
Tensilon UTM250 manufactured by Toyo Baldwin Co., Ltd.
According to 0, it measured at 23 degreeC according to JISK7203. Measurement of Impact Resistance Using a test piece injection molded at 210 ° C., JIS K71
The Izod impact strength was measured at 23 ° C. in accordance with No. 10.

Example 1 1) Preparation of Metallocene Catalyst Silica (948, manufactured by Fuji Devison Co., Ltd., 1.5 ml at 1.5 torr) was used as a fine particle carrier in 5 ml of o-dichlorobenzene.
1.0 g (dried at 10 ° C. for 5 hours) was added. Next, N, N-dimethylanilinium [4
-(Trichlorosilyl) -2,3,5,6-tetrafluorophenyl] tris (pentafluorophenyl) borate (0.5 g) dissolved in o-dichlorobenzene (30 ml) was added, and the mixture was added at room temperature for 1 hour and 90 ° C. For 3 hours. Then, 3m of phenyldimethylchlorosilane
was added over 5 minutes, and the mixture was further stirred at 90 ° C. for 2 hours.
The suspension was cooled to room temperature, and after removing the supernatant, the suspension was washed four times with dichloromethane and twice with hexane, and dried under reduced pressure to obtain a pale yellow promoter component.

To 250 mg of this promoter component was added 5.0 mmol / l of bis [2-methyl-
4.5-benzo (η ⁵ -1-indenyl)] dimethylsilanezirconium dichloride (hereinafter abbreviated as MBIZ) in 3.0 ml of dichloromethane was added, and the mixture was stirred at room temperature for 5 minutes. Then, dichloromethane was distilled off under reduced pressure,
A light yellow solid catalyst component was obtained. Next, 30 mg of this solid catalyst component was collected in a nitrogen-purged flask, and 0.5 mol / l of tri-n-hexylaluminum (hereinafter abbreviated to TNHA) in hexane solution as an organometallic compound was added in an amount of 1.0 m.
and stirred at 25 ° C. for 20 minutes to prepare a solid catalyst.

2) Production of Propylene Polymer Into a 1.5-liter autoclave, 2 ml of a toluene solution of tri-n-butylaluminum (hereinafter abbreviated as TNBA) as a 0.5 mol / l organometallic compound and 8 mol of propylene were introduced. . Then, the metallocene catalyst 10
0 mg was injected into an autoclave, heated to 60 ° C., and polymerized for 60 minutes to obtain a propylene polymer. Triad tacticity fraction [mm] of 3 chains of propylene units in the obtained propylene polymer,
Percentage of irregular units based on insertion, ratio of molecular weight Mw
Table 1 shows / Mn and xylene solubles Xs.

As a heat stabilizer and / or a weather stabilizer, tetrakis [methylene-3-) was added to the obtained polymer.
(3,5-di-t-butyl-4-hydroxyphenyl)
Propionate] methane and bis (2,2,6,6-
Tetramethyl-4-piperidyl) sebacate was added in the amount shown in Table 1, respectively, and the mixture was added by a single screw extruder to 210
The mixture was kneaded at ℃ to obtain a propylene polymer composition. This composition was injection molded at 210 ° C., and its physical properties were evaluated. Table 1 shows the results.

Example 2 As a metallocene compound, bis [2-
Methyl-4-phenyl- (η5-1-indenyl)] dimethylsilanezirconium dichloride, hydrogen 3
A propylene polymer was obtained in the same manner as in Example 1 except that 00 ml was added. Preparation of a composition and injection molding were performed in the same manner as in Example 1 from the obtained polymer, and physical properties were evaluated. Table 1 shows the results.

Examples 3 and 4 The procedure of Example 2 was repeated except that the polymerization was carried out at 70 ° C. to obtain a propylene polymer. Preparation of a composition and injection molding were performed in the same manner as in Example 1 from the obtained polymer, and physical properties were evaluated. Table 1 shows the results. Comparative Example 1 1) Preparation of Metallocene Catalyst In a 30 ml flask, 4 ml of a toluene solution of methylaluminoxane (0.5 mol / l) as a cocatalyst component, and a toluene solution of MPIZ as a metallocene compound (0.5 mol / l)
1 mmol) and stirred at room temperature for 3 minutes.
A metallocene catalyst was obtained.

2) Production of propylene polymer In a 1.5 liter autoclave, 300 m
1, 2 ml of a 0.5 mol / l TIBA toluene solution as an organometallic compound, 4 mol of propylene and 300 mol of hydrogen
ml was introduced. Thereafter, the propylene polymerization catalyst was pressed into an autoclave, and polymerization was performed at 20 ° C. for 10 minutes to obtain a propylene polymer. Table 1 shows the measurement results of the physical properties of the obtained propylene polymer. Preparation of a composition and injection molding were performed in the same manner as in Example 1 from the obtained polymer, and physical properties were evaluated. Table 1 shows the results.

Comparative Example 2 1) Preparation of Solid Titanium Catalyst Component A 200 ml three-necked flask equipped with a thermometer and a stirrer was sufficiently purged with nitrogen, and then anhydrous magnesium chloride 9.5 was added.
g, 100 ml of n-decane and 47 ml (300 mmol) of 2-ethylhexyl alcohol were stirred for 1 hour.
After heating at 25 ° C. for 2 hours, 5.5 g (37.5 mmol) of phthalic anhydride was added to the mixture, and further heated at 125 ° C. for 1 hour with stirring to obtain a homogeneous solution.
After the solution was cooled to room temperature, the whole amount was dropped into 400 ml (3.6 mol) of titanium tetrachloride cooled to -20 ° C over 1 hour. Next, this solution was heated to 110 ° C. over 2 hours, and when it reached 110 ° C., di-i-
After adding 5.4 ml (25 mmol) of butyl phthalate, the reaction was carried out with stirring at this temperature for 2 hours. After the completion of the reaction, a solid portion was collected by filtration under heating, and this solid portion was suspended again in 2000 ml of titanium tetrachloride, and then reacted again at 110 ° C. for 2 hours. After completion of the reaction, a solid portion was collected by hot filtration, and washed with n-decane until no titanium was detected in the washing solution to obtain a solid titanium catalyst component.

2) Preparation of Propylene Polymerization Catalyst A 200 ml flask purged with nitrogen was charged with 100 m of hexane.
l, triethylaluminum 10 as organometallic compound
After the addition of 0.2 g of the solid titanium catalyst component (10 mmol of titanium atom), propylene gas was introduced at 10 ° C. at a rate of 2 g / hour for 1 hour. After removing the supernatant, the solid portion was washed with hexane to obtain a prepolymerized catalyst. Then, 1.64 mmol of triethylaluminum and 0.16 of cyclohexylmethyldimethoxysilane
4 mmol was added to obtain a propylene polymerization catalyst.

3) Production of Propylene Polymer 8 mol of propylene and 1 l of hydrogen were introduced into a 2-liter autoclave, the temperature was raised to 70 ° C., and the above-mentioned catalyst for propylene polymerization was injected to initiate polymerization. After polymerization was performed for 10 minutes, methanol was injected under pressure to stop the polymerization, and unreacted propylene was removed to obtain a propylene polymer. Table 1 shows the measurement results of physical properties of the obtained propylene polymer. Preparation of a composition and injection molding were performed in the same manner as in Example 1 from the obtained polymer, and physical properties were evaluated. Table 1 shows the results.

[0062] Using 1,2-bis [(η ⁵ -1- indenyl)] ethane hafnium dichloride in place of Comparative Example 3 MPIZ, 60 ℃
Was carried out in the same manner as in Example 3 except that the polymerization was carried out to obtain a propylene polymer. Table 1 shows the measurement results of the physical properties of the obtained propylene polymer. Preparation of a composition and injection molding were performed in the same manner as in Example 1 from the obtained polymer, and physical properties were evaluated. Table 1 shows the results.

Comparative Example 4 1) Preparation of Propylene Polymerization Catalyst A 1.5-liter autoclave was charged with 200 ml of hexane, 3.5 g of titanium trichloride and 50 mmol of diethylaluminum chloride. Next, propylene gas was introduced at a rate of 5 g / hour at 15 ° C. for 30 minutes.
Thereafter, unreacted propylene was removed by nitrogen purge, and the obtained solid was washed three times with hexane to obtain a propylene polymerization catalyst in which 2.7 g of propylene was polymerized per 1 g of titanium trichloride.

2) Preparation of Propylene Polymer 0.5 mmol of diethylaluminum chloride, 8 mol of propylene and hydrogen
00 ml (volume at normal pressure) were introduced. Thereafter, the temperature was raised to 65 ° C. while stirring, 10 mg of the above-mentioned propylene polymerization catalyst was introduced in terms of titanium trichloride, and polymerization was carried out for 120 minutes to obtain a propylene polymer. Table 1 shows the measurement results of the physical properties of the obtained propylene polymer. Preparation of a composition and injection molding were performed in the same manner as in Example 1 from the obtained polymer, and physical properties were evaluated. Table 1 shows the results.

[0065]

[Table 1]

Examples 5 to 7 Ethylene-propylene copolymer elastomer (EPR) or hydrogenated styrene-butadiene-styrene block copolymer elastomer (SEBS) was added to the propylene polymer obtained in Example 3 as an elastomer component. Table 2
And kneaded at 230 ° C. with a single screw extruder to obtain a propylene polymer composition. This composition is
Injection molding was performed at 10 ° C., and the physical properties were evaluated. Table 2 shows the results
Shown in

Comparative Examples 5 to 8 Each of the propylene polymers obtained in Comparative Examples 1 to 4 was blended with an ethylene-propylene copolymer elastomer as an elastomer component in an amount shown in Table 2, and a single screw extruder was used. To obtain a propylene polymer composition. This composition was injection molded at 210 ° C., and its physical properties were evaluated. Table 2 shows the results.

[0068]

[Table 2]

Examples 8 to 10 The propylene polymer obtained in Example 3 was mixed with talc or calcium carbonate in the amount shown in Table 3 as a filler component, and kneaded at 230 ° C. with a single screw extruder. Thus, a propylene polymer composition was obtained. This composition was injection molded at 210 ° C., and its physical properties were evaluated. Table 3 shows the results.

Comparative Examples 9 to 12 Each of the propylene polymers obtained in Comparative Examples 1 to 4 was mixed with talc as a filler component in an amount shown in Table 3 and kneaded at 230 ° C. by a single screw extruder. Thus, a propylene polymer composition was obtained. This composition was injection molded at 210 ° C., and its physical properties were evaluated. Table 3 shows the results.

[0071]

[Table 3]

[0072]

According to the present invention, there are provided a molded article having excellent rigidity, a propylene polymer having a high rigidity, a low melting point and a good processability, and a composition thereof suitable for the production thereof. You.

Continued on the front page F-term (reference) 4F071 AA14 AA15X AA20 AA20X AA81 AA84 AA88 AB21 AB26 AE05 AE17 AF11 BB05 4J002 AC03X AC06X AC08X AC09X BB05X BB12W BB14X BB15X FD010 FD060 DA04FA10 DA04 DA01 DA04

Claims (7)

[Claims] (A) (a) A triad tacticity [mm] of a head-to-tail bonded propylene unit chain is 9
5.0 mol% or more, and (b) 2,1-
The ratio P of the position irregularity unit due to insertion is 0.40 to 2.
(C) a ratio Mw / Mn of the weight average molecular weight to the number average molecular weight of 2.0 or more, and (d) 135 ° C.
Has an intrinsic viscosity [η] of 0.1 to 4.
(E) the xylene-soluble component Xs at 25 ° C. is 2.0% by weight or less, (f) the content F of α-olefin other than propylene is 1.0% by mole or less, (G) The triad tacticity [mm] (mol%) of the head-to-tail bonded propylene unit chain and the melting point Tm (° C.) measured by a differential scanning calorimeter are as follows: (1) 140.0 ≦ Tm ≦ [Mm] +60.0 A propylene polymer satisfying the following relationship: 2. A propylene polymer comprising 100 parts by weight of the propylene polymer (A) according to claim 1 and (B) 0.001 to 5 parts by weight of one or more additives of a heat-resistant stabilizer or a weather-resistant stabilizer. Coalescing composition. 3. A propylene polymer composition comprising 99 to 20 parts by weight of the propylene polymer (A) according to claim 1 and 1 to 80 parts by weight of an olefin elastomer (C). 4. A propylene polymer composition comprising 99 to 70 parts by weight of the propylene polymer (A) according to claim 1 and 1 to 30 parts by weight of an inorganic or organic filler (D). 5. A molded article obtained by molding the propylene polymer composition according to claim 2. 6. A molded product obtained by molding the propylene polymer composition according to claim 3. 7. A molded article obtained by molding the propylene polymer composition according to claim 4.