JP3895341B2 - Polypropylene composition - Google Patents

Description

  The present invention relates to a polypropylene composition that is excellent in flexibility and impact resistance, and also excellent in heat resistance and low temperature heat sealability.

  Conventionally, polypropylene has been widely used as a thermoplastic molding material excellent in rigidity, heat resistance, transparency and the like. Since this polypropylene is inferior in flexibility and impact resistance, a soft rubber component is usually blended with polypropylene.

  Thus, when a soft rubber component is blended with polypropylene, a polypropylene composition having improved flexibility and impact resistance can be obtained, but there is a problem that heat resistance is lowered. In addition, such a polypropylene composition is also desired to improve low-temperature heat sealability.

  For this reason, the appearance of a polypropylene composition having excellent flexibility and impact resistance, as well as excellent heat resistance and low temperature heat sealability has been desired. The present inventors have examined a polypropylene composition comprising polypropylene and a rubber component in view of such a conventional technique, and a polypropylene composition comprising polypropylene and a specific novel propylene-based elastomer exhibits such characteristics. I found out. That is, as this propylene-based elastomer, the triad tacticity of the propylene chain portion composed of the head-to-tail bond (head-to-tail bond and all the methyl group branching directions are the same) is high, and the propylene monomer has 2, 1-Polypropylene / 1-butene elastomer or propylene / ethylene elastomer with a high degree of stereoregularity with a specific proportion of position irregular units (also referred to as heterogeneous bonds or inversion) due to insertion, flexibility and impact resistance As a result, a polypropylene composition having excellent heat resistance and low temperature heat sealability is formed. And it discovered that such a propylene-type elastomer could be manufactured using a specific metallocene compound catalyst component, and came to complete this invention.

  An object of this invention is to provide the polypropylene composition which was excellent in the softness | flexibility and impact resistance, and excellent in heat resistance and low-temperature heat-sealing property.

The polypropylene composition according to the present invention is:
[A] polypropylene; 5 to 95% by weight;
[B] The following propylene-based elastomer [B-2] : 95 to 5% by weight.
[B-2] (1) Containing a structural unit derived from propylene in an amount of 50 to 95 mol% and a structural unit derived from ethylene in an amount of 5 to 50 mol%,
(2) The triad tacticity measured by a ¹³ C-NMR spectrum of the propylene unit chain part bonded head-to-tail is 90% or more,
(3) The proportion of position irregular units based on 2,1-insertion of propylene monomer in all propylene constituent units measured by ¹³ C-NMR is 0.05% or more,
(4) A propylene / ethylene elastomer having an intrinsic viscosity measured in decalin at 135 ° C. of 0.1 to 12 dl / g.

  As said [A] polypropylene, the random copolymer of the propylene and other olefin which contain the unit guide | induced from olefins other than propylene in the quantity of 10 mol% or less is used preferably.

  The polypropylene composition according to the present invention is excellent in flexibility and impact resistance as well as heat resistance and low temperature heat sealability. Such a polypropylene composition can be suitably used for heat-sealable OPP, injection molded articles such as containers with improved impact resistance, stretch blow molded articles, retort tableware containers, films, sheets and the like.

  Further, the polypropylene composition according to the present invention can be used for a wide range of uses other than the above, and for home appliances such as housings and washing tubs, for example, automotive interior uses such as trims, instrument panels and column covers, fenders, bumpers, etc. It can also be used for automobile exterior applications such as side moldings, mudguards, and mirror covers, and general miscellaneous goods.

  Hereinafter, the polypropylene composition according to the present invention will be specifically described. The polypropylene composition according to the present invention comprises the following polypropylene and a specific propylene-based elastomer.

[A] Polypropylene In the present invention, conventionally known polypropylene is widely used as the polypropylene. This polypropylene may be a homopolypropylene or a propylene random copolymer containing units derived from propylene and a small amount of olefin other than propylene, for example, less than 10 mol%, preferably less than 5 mol%. Of these, a propylene random copolymer is preferably used.

  Specific examples of the other olefins forming the propylene random copolymer include α-olefins having 2 to 20 carbon atoms other than propylene, such as ethylene, 1-butene, 1-pentene, 1-hexene, 1-hexene, Examples include heptene, 1-octene, 1-decene, 1-dodecene, 1-hexadecene and 4-methyl-1-pentene.

  The polypropylene used in the present invention is preferably a polypropylene produced by a known method using a conventionally known solid titanium catalyst component. Polypropylene obtained using a metallocene compound catalyst component can also be used.

  The polypropylene used in the present invention has a melting point (Tm) of 100 to 165 ° C, preferably 120 to 165 ° C. Among polypropylenes having such a melting point, when forming a polypropylene composition, it is desirable to use a polypropylene having a melting point higher than that of a propylene-based elastomer described later.

This polypropylene has a melt flow rate MFR (ASTM D1238; 230).
C., under 2.16 kg load) is usually 0.1 to 400 g / 10 min, preferably 1 to 100 g / 10 min, and the molecular weight distribution (Mw / Mn) is more than 3 and preferably 4 to 15. It is desirable.

Further, this polypropylene [A] usually has higher hardness than the propylene-based elastomer [B] described later.
[B] Propylene-based elastomer In the present invention, it is a novel propylene-based elastomer
[B-1] Propylene / 1-butene elastomer, or
[B-2] Propylene / ethylene elastomer is used, and these may be used in combination.

The propylene elastomer used in the present invention will be described below.
[B-1] Propylene / 1-butene elastomer
(1) The propylene-based elastomer used in the present invention is a random copolymer of propylene and 1-butene,
Units derived from propylene in an amount of 50 to 95 mol%, preferably 60 to 93 mol%, more preferably 70 to 90 mol%,
The unit derived from 1-butene is contained in an amount of 5-50 mol%, preferably 7-40 mol%, more preferably 10-30 mol%.

This propylene / 1-butene elastomer may contain a small amount of structural units derived from olefins other than propylene and 1-butene such as ethylene in an amount of 10 mol% or less.
(2) Stereoregularity of propylene / 1-butene elastomer (Triad tacticity mm fraction)
The stereoregularity of the propylene-based elastomer used in the present invention can be evaluated by triad tacticity (mm fraction).

This mm fraction is defined as the ratio in which the branching directions of the methyl groups are the same when the three head-to-tail bonded propylene unit chains present in the polymer chain are represented by a surface zigzag structure. In ¹³ C-NMR spectrum.

When the mm fraction of the propylene / 1-butene elastomer is determined from a ¹³ C-NMR spectrum, specifically, as a three chain including propylene units present in the polymer chain,
(i) a triple chain of head-to-tail bonded propylene units, and
(ii) The mm fraction is measured for a propylene unit / butene unit three-chain consisting of propylene units and butene units bonded head-to-tail and the second unit being a propylene unit.

The mm fraction is determined from the peak intensity of the side chain methyl group of the second unit (propylene unit) in these three chains (i) and (ii). This will be described in detail below.
The ¹³ C-NMR spectrum of the propylene elastomer was measured by a proton complete decoupling method at 120 ° C. after completely dissolving it in hexachlorobutadiene containing a small amount of deuterated benzene using the propylene elastomer as a lock solvent in a sample tube. Is done. Measurement conditions, a flip angle and 45 °, a pulse interval 3.4T ₁ or more (T ₁ is the longest value among spin-lattice relaxation time of methyl groups) and. Since T ₁ of the methylene group and methine group is shorter than the methyl group, the recovery of the magnetization of all the carbon in the sample is 99% or more under this condition. The chemical shift was determined based on the methyl group carbon peak of the third unit of 5-chain (mmmm) propylene units bonded head-to-tail with respect to tetramethylsilane as 21.593 ppm, and the other carbon peaks were based on this.

Of the ¹³ C-NMR spectrum of the propylene / 1-butene elastomer thus measured, the methyl carbon region (about 19.5 to 21.9 ppm) in which the side chain methyl group of the propylene unit is observed is
First peak area (about 21.0 to 21.9 ppm),
Second peak area (about 20.2 to 21.0 ppm),
It is classified into the third peak region (about 19.5 to 20.2 ppm).

  In each of these regions, a side-chain methyl group peak of the second unit (propylene unit) in the trimolecular chain (i) and (ii) having head-to-tail bonds as shown in Table 1 is observed.

In the table, P represents a structural unit derived from propylene, and B represents a structural unit derived from 1-butene.
Of the three head-to-tail linkages (i) and (ii) shown in Table 1, (i) the methyl group for PPP (mm), PPP (mr), and PPP (rr) in which all three linkages are composed of propylene units. The direction is illustrated in a surface zigzag structure below, but (ii) mm, mr, and rr bonds of three-chain (PPB, BPB) containing a butene unit conform to this PPP.

In the first region, the methyl group of the second unit (propylene unit) in the mm-bonded PPP, PPB, BPB3 chain resonates.
In the second region, the methyl group of the second unit (propylene unit) in the mr-bonded PPP, PPB, BPB3 chain and the methyl group of the second unit (propylene unit) in the rr-bonded PPB, BPB3 chain are resonant. To do.

In the third region, the methyl group of the second unit (propylene unit) of the rr-bonded PPP3 chain resonates.
Therefore, the triad tacticity (mm fraction) of the propylene-based elastomer is
(i) a triple chain of head-to-tail bonded propylene units, or
(ii) a propylene / butene triad consisting of a propylene unit and a butene unit bonded head-to-tail and containing a propylene unit in the second unit;
When the side chain methyl group of the second propylene unit in the three chains was measured by ¹³ C-NMR spectrum (hexachlorobutadiene solution, based on tetramethylsilane),
When the total area of the peak appearing in 19.5-21.9ppm (methyl carbon region) is 100%,
The ratio (percentage) of the area of the peak appearing in 21.0 to 21.9 ppm (first region) is obtained from the following formula (1).

In the propylene elastomer according to the present invention, the mm fraction thus determined is 90% or more, preferably 92% or more, more preferably 94% or more.
The propylene-based elastomer is not limited to the head-to-tail three-linkage (i) and (ii) as described above, but is a position irregular unit as shown by the following structures (iii), (iv) and (v) The peak derived from the side chain methyl group of the propylene unit by such other bonds is also observed in the methyl carbon region (19.5 to 21.9 ppm).

Of the methyl groups derived from the above structures (iii), (iv) and (v), the methyl group carbon A and the methyl group carbon B resonate at 17.3 ppm and 17.0 ppm, respectively. The peak based on B does not appear in the first to third regions (19.5 to 21.9 ppm). Further, since both carbon A and carbon B do not participate in propylene trilinkage based on the head-to-tail bond, it is not necessary to consider in the calculation of the triad tacticity (mm fraction).

The peak based on the methyl group carbon C, the peak based on the methyl group carbon D, and the peak based on the methyl group carbon D ′ appear in the second region, and the peak based on the methyl group carbon E and the peak based on the methyl group carbon E ′ are Appears in the third region.

Therefore, the 1st to 3rd methyl carbon regions include PPE-methyl group (side chain methyl group in propylene-propylene-ethylene chain) (around 20.7 ppm), EPE-methyl group (side in ethylene-propylene-ethylene chain). (Chain methyl group) (around 19.8 ppm), peaks based on methyl group C, methyl group D, methyl group D ′, methyl group E, and methyl group E ′ appear.

  In this way, in the methyl carbon region, peaks of methyl groups that are not based on the head-to-tail bond triple chain (i) and (ii) are also observed. It is corrected as follows.

The peak area based on the PPE-methyl group can be determined from the peak area of the PPE-methine group (resonant at around 30.6 ppm), and the peak area based on the EPE-methyl group is determined based on the EPE-methine group (around 32.9 ppm). Resonance) peak area.

The peak area based on the methyl group C can be determined from the peak area of the adjacent methine group (resonance near 31.3 ppm).
The peak area based on the methyl group D can be obtained from ½ of the sum of the peak areas based on the αβ methylene carbon of the structure (iv) (resonance at resonance around 34.3 ppm and around 34.5 ppm). The peak area based on the methyl group D ′ can be determined from the area of the peak (resonance around 33.3 ppm) based on the methine group adjacent to the methyl group of the methyl group E ′ in the structure (v).

The peak area based on the methyl group E can be obtained from the peak area of the adjacent methine carbon (resonant at around 33.7 ppm), and the peak area based on the methyl group E ′ is calculated at the adjacent methine carbon (around 33.3 ppm). Resonance) peak area.

  Therefore, by subtracting these peak areas from the total peak areas of the second region and the third region, the peak area of the methyl group based on the head-to-tail three-linked propylene units (i) and (ii) can be obtained. .

As described above, the peak area of the methyl group based on the head-to-tail bonded propylene unit triple chain (i) and (ii) can be evaluated, and the mm fraction can be determined according to the above formula.
Each carbon peak in the spectrum can be assigned with reference to literature (Polymer, 30 , 1350 (1989)).

(3) Intrinsic viscosity [η]
The intrinsic viscosity [η] measured in decalin at 135 ° C. of the propylene / 1-butene elastomer used in the present invention is 0.1 to 12 dl / g, preferably 0.5 to 12 dl / g, more preferably 1 to 1. 12 dl / g.

(4) Molecular weight distribution The molecular weight distribution (Mw / Mn) determined by gel permeation chromatography GPC of the propylene / 1-butene elastomer used in the present invention is 3 or less, preferably 1.8 to 3.0. More preferably, it is 1.9 to 2.5.

(5) Randomness The parameter B value indicating the randomness of the copolymerization monomer chain distribution of the propylene / 1-butene elastomer used in the present invention is 1.0 to 1.5, preferably 1.0 to 1.3. Preferably it is 1.0-1.2.

This parameter B value is proposed by Coleman et al. (BDCole-man and TGFox, J. Polym. Sci., Al , 3183 (1963)) and is defined as follows.
B = P ₁₂ / (2P ₁ · P ₂ )
Here, P ₁ and P ₂ are the first monomer and second monomer content fractions, respectively, and P ₁₂ is the ratio of (first monomer)-(second monomer) linkage in the chain in all two molecules.

The B value follows Bernoulli statistics when 1, indicates that the copolymer is block-like when B <1, is alternating when B> 1, and is a cross-copolymer when B = 2. .
Further, the propylene / 1-butene elastomer [B-1] used in the present invention is:
(6) The melting point Tm measured by a differential scanning calorimeter is preferably 60 to 140 ° C., preferably 80 to 130 ° C., and the melting point Tm and the 1-butene constituent unit content M (mol%) The relationship is −2.6M + 130 ≦ Tm ≦ −2.3M + 155
It is desirable that
(7) The relationship between the degree of crystallinity C measured by X-ray diffraction and the 1-butene constituent unit content M (mol%) is preferably C ≧ −1.5M + 75.

  The propylene / 1-butene elastomer [B-1] according to the present invention as described above is a heterogeneous bond unit (position irregularity) based on 2,1-insertion or 1,3-insertion of propylene present in a propylene chain. It may have a small amount of structure containing (unit).

During polymerization, propylene is usually 1,2-inserted (methylene side is bound to the catalyst) to form a head-to-tail coupled propylene chain as described above. May be inserted. 2,1-inserted and 1,3-inserted propylene form regioregular units as shown in structures (iii), (iv) and (v) in the polymer. The proportions of 2,1-insertion and 1,3-insertion of propylene in the polymer structural unit are shown in Polymer, 30 , 1350 (1989) using the ¹³ C-NMR spectrum in the same manner as the stereoregularity described above. Can be obtained from the following equation.

  The ratio of regioregular units based on 2,1-insertion of propylene can be obtained from the following formula.

In addition, when it is difficult to obtain an area such as Iαβ directly from the spectrum due to overlapping peaks, it can be corrected with a carbon peak having a corresponding area.
The propylene / 1-butene-based elastomer [B-1] according to the present invention includes heterogeneous bond units based on 2,1-insertion of propylene present in the propylene chain obtained as described above in all propylene constituent units. It may be included at a ratio of 0.01% or more, specifically about 0.01 to 0.3%.

Further, the ratio of the position irregular unit based on 1,3-insertion of propylene in the propylene / 1-butene elastomer [B-1] can be obtained from the βγ peak (resonance at around 27.4 ppm).

In the propylene-based elastomer according to the present invention, the proportion of heterogeneous bonds based on 1,3-insertion of propylene may be 0.05% or less.
[B-2] Propylene / ethylene elastomer
(1) The propylene / ethylene elastomer used in the present invention is a random copolymer of propylene and ethylene,
The structural unit derived from propylene is in the amount of 50 to 95 mol%, preferably 60 to 93 mol%, more preferably 70 to 90 mol%,
The structural unit derived from ethylene is contained in an amount of 5 to 50 mol%, preferably 7 to 40 mol%, more preferably 10 to 30 mol%.

This propylene / ethylene elastomer may contain a small amount of structural units derived from olefins other than propylene and ethylene, for example, in an amount of 10 mol% or less.
(2) The propylene / ethylene-based elastomer used in the present invention has a triad tacticity of 90% or more, preferably 92% or more, more preferably measured by a ¹³ C-NMR spectrum of a propylene unit chain unit bonded head-to-tail. 95% or more.

The triad tacticity (mm fraction) of the propylene / ethylene elastomer is the same as that of the propylene / 1-butene elastomer [B-1], but the strength (area) of the methyl group in the ¹³ C-NMR spectrum of the elastomer. ) From the following equation (2).

(Wherein, PPP (mm), PPP (mr), and PPP (rr) represent the same propylene tri-chain as the propylene / 1-butene elastomer [B-1].)
The methyl carbon region (19 ppm to 23 ppm) in the ¹³ C-NMR spectrum of this propylene / ethylene elastomer is divided into the first region (21.2 to 21.9 ppm) and the second region (20.3).
˜21.0 ppm) and the third region (19.5 to 20.3 ppm). Table 2 shows methyl group peaks appearing in each region.

In the table, P represents a structural unit derived from propylene.
In the first region, the side chain methyl group of the second unit in the three propylene unit chains represented by PPP (mm) resonates.

In the second region, the side chain methyl group of the second unit of the three propylene units represented by PPP (mr) resonates.
In the third region, the side chain methyl group of the second unit of the three propylene units represented by PPP (rr) resonates.

From the peak intensity of these methyl groups, the mm fraction can be determined by the above formula (2).
In addition, in the methyl carbon region, in addition to the side chain methyl group of the propylene unit in the head-to-tail coupled propylene 3 chain as described above, the peak derived from the side chain methyl group in the other propylene unit as described below. Is observed.

That is, a peak derived from the side chain methyl group of the second unit (propylene unit) in the PPE3 chain in which propylene is head-to-tail bonded is observed in the second region,
A peak derived from the side chain methyl group of the second unit (propylene unit) in the EPE3 chain is observed in the third region. (E represents a unit derived from ethylene.) In addition, the propylene / 1-butene elastomer is the same as that shown in structures (i) and (ii) in the propylene / 1-butene elastomer [B-1]. A small amount of a partial structure containing irregular position units.

Among them, the methyl group A peak and the methyl group A ′ peak are observed in the second region, and the methyl group B peak and the methyl group B ′ peak are observed in the third region. In this way, in the methyl carbon region, peaks of methyl groups that are not based on three chains of propylene units are also observed, but these are corrected as follows when the mm fraction is obtained by the above formula (2).

The peak area based on the side chain methyl group of the second unit (propylene unit) in the PPE3 chain was evaluated from the peak area of the methine group (resonance at around 30.6 ppm) of the second unit (propylene unit) in the PPE chain. The peak area based on the side chain methyl group of the second unit (propylene unit) in the EPE3 chain is the methine group of the second unit (propylene unit) in the EPE chain (32.
It can be evaluated from the peak area of resonance at around 9 ppm.

  The peak areas based on the methyl group A, methyl group A ′, methyl group B, and methyl group B ′ are evaluated in the same manner as the propylene / 1-butene elastomer [B-1]. Therefore, when these peak areas are subtracted from the peak areas of the second and third regions, the peak area of the methyl group based on the head-to-tail bonded propylene triad can be obtained, so the mm fraction is obtained according to the above formula. be able to.

Each peak in the spectrum was assigned with reference to literature (Polymer, 30 (1989) 1350).
(3) In the propylene / ethylene elastomer used in the present invention, the ratio of position irregular units based on 2,1-insertion of propylene monomer in all propylene constituent units measured by ¹³ C-NMR is 0.05%. More preferably 0.05-0.8% or more, more preferably 0.05-0.7.
%.

The ratio of the position irregular units based on the 2,1-insertion can be obtained in the same manner as the propylene / 1-butene elastomer [B-1].
The propylene / ethylene elastomer used in the present invention has 0.05% or less of position irregular units based on the (1,2-) / (1,3-) / (1,2-) insertion of propylene monomer. Preferably there is.

  (4) The propylene / ethylene elastomer used in the present invention has an intrinsic viscosity measured in decalin at 135 ° C. of 0.1-12 dl / g, preferably 0.5-12 dl / g, more preferably 1-12 dl / g. g.

The propylene-based elastomer [B] used in the present invention as described above has less so-called solid component than conventionally known rubber.
The propylene-based elastomer used in the present invention as described above is
[I] a specific transition metal compound as described below;
[II] [II-a] organoaluminum oxy compound, and / or
[II-b] a compound that reacts with the transition metal compound [I] to form an ion pair;
If desired, using a catalyst for olefin polymerization comprising [III] an organoaluminum compound,
[B-1] In the case of a propylene / 1-butene elastomer, by copolymerizing propylene and 1-butene,
[B-2] Propylene / ethylene elastomer is produced by copolymerizing propylene and ethylene.

Hereinafter, the olefin polymerization catalyst used in producing the propylene-based elastomer in the present invention will be described.
The transition metal compound [I] (hereinafter sometimes referred to as “component [I]”) that forms the olefin polymerization catalyst used in the present invention is represented by the following general formula (I).

  In the formula, M is a transition metal of groups IVa, Va and VIa of the periodic table, specifically, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, preferably titanium, Zirconium and hafnium are preferable, and zirconium is particularly preferable.

[Substituents R ¹ and R ² ]
R ¹ and R ² are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, an oxygen-containing group, or a sulfur-containing group. A nitrogen-containing group or a phosphorus-containing group.

Specifically, examples of the halogen atom include fluorine, chlorine, bromine, and iodine.
As the hydrocarbon group having 1 to 20 carbon atoms,
Alkyl groups such as methyl, ethyl, propyl, butyl, hexyl, cyclohexyl, octyl, nonyl, dodecyl, eicosyl, norbornyl, adamantyl,
Alkenyl groups such as vinyl, propenyl, cyclohexenyl,
Arylalkyl groups such as benzyl, phenylethyl, phenylpropyl,
And aryl groups such as phenyl, tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl, propylphenyl, biphenyl, naphthyl, methylnaphthyl, anthracenyl, phenanthryl, etc.
Examples of the halogenated hydrocarbon group include groups in which these hydrocarbon groups are substituted with halogen atoms.

Also, monohydrocarbon-substituted silyl such as methylsilyl and phenylsilyl, dihydrocarbon-substituted silyl such as dimethylsilyl and diphenylsilyl, trimethylsilyl, triethylsilyl, tripropylsilyl, tricyclohexylsilyl, triphenylsilyl, dimethylphenylsilyl, methyldiphenylsilyl Silicon-containing substitutions such as tri-hydrocarbon-substituted silyls such as tritolylsilyl, trinaphthylsilyl, hydrocarbon-substituted silyl silyl ethers such as trimethylsilyl ether, silicon-substituted alkyl groups such as trimethylsilylmethyl, silicon-substituted aryl groups such as trimethylphenyl Group,
Oxygen-containing substituents such as hydroxy groups, alkoxy groups such as methoxy, ethoxy, propoxy, butoxy, aryloxy groups such as phenoxy, methylphenoxy, dimethylphenoxy, naphthoxy, arylalkoxy groups such as phenylmethoxy, phenylethoxy,
A sulfur-containing group in which oxygen of the oxygen-containing compound is substituted with sulfur,
Amino group, alkylamino group such as methylamino, dimethylamino, diethylamino, dipropylamino, dibutylamino, dicyclohexylamino, arylamino group such as phenylamino, diphenylamino, ditolylamino, dinaphthylamino, methylphenylamino or alkylarylamino Nitrogen-containing groups such as groups,
Examples thereof include phosphorus-containing groups such as phosphino groups such as dimethylphosphino and diphenylphosphino.

Among these, R ¹ is preferably a hydrogen atom, a methyl group, a hydrocarbon group having 2 to 6 carbon atoms, an aromatic group, or the like, and particularly preferably a methyl group or a hydrocarbon group having 2 to 6 carbon atoms.
R ² is preferably a hydrogen atom or a hydrocarbon group, and particularly preferably a hydrogen atom.

[Substituent R ³ ]
R ³ is a group substituted with a hydrocarbon group having 1 to 20 carbon atoms, a halogen atom thereof, or a silicon-containing group, and among them, a secondary or tertiary alkyl group having 3 to 20 carbon atoms or an aromatic group. desirable.

Specifically, as the secondary or tertiary alkyl group, i-propyl, i-butyl, sec-butyl, tert-butyl, 1,2-dimethylpropyl, 2,3-dimethylbutyl, iso-pentyl, tert -Pentyl, neopentyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, iso-hexyl, norbornyl, adamantyl, etc.
Aromatic groups include phenyl, tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl, propylphenyl, biphenyl, α- or β-naphthyl, methylnaphthyl, anthracenyl, phenanthryl, benzylphenyl, pyrenyl, acenaphthyl, phenalenyl, aceanthrylenyl Aryl groups such as tetrahydronaphthyl, indanyl, biphenylyl,
Examples thereof include arylalkyl groups such as benzyl, phenylethyl, phenylpropyl, tolylmethyl and the like, and these may contain a double bond or a triple bond.

These groups may be substituted with a halogen atom, a silicon-containing group or the like as represented by R ¹ .
[Substituent R ⁴ ]
R ⁴ is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.

  Specific examples of the alkyl group include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, tert-butyl, pentyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, dodecyl. , Chain alkyl groups such as eicosyl, norbornyl, adamantyl and cyclic alkyl groups.

These groups may be substituted with a halogen atom or a silicon-containing group as represented by R ¹ .
[X ¹ and X ² ]
X ¹ and X ² are a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group or a sulfur-containing group.

Specifically, the halogen atom, the oxygen-containing group, the hydrocarbon group having 1 to 20 carbon atoms, and the halogenated hydrocarbon group having 1 to 20 carbon atoms are the same as R ¹ described above.
Examples of the sulfur-containing group include methyl sulfonate, trifluoromethane sulfonate, phenyl sulfonate, benzyl sulfonate, p-toluene sulfonate, trimethylbenzene sulfonate, triisobutyl together with the group represented by R ^1. Sulfonate groups such as benzene sulfonate, p-chlorobenzene sulfonate, pentafluorobenzene sulfonate, methyl sulfinate, phenyl sulfinate, benzene sulfinate, p-toluene sulfinate, trimethylbenzene sulfite Examples thereof include sulfinate groups such as nate and pentafluorobenzene sulfinate.

[Y]
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, and a divalent tin content. group, -O -, - CO -, - S -, - SO -, - SO 2 -, - NR 5 -, - P (R 5) -, - P (O) (R 5) -, - BR 5 — Or —AlR ⁵ — [wherein R ⁵ is a hydrogen atom, a halogen atom, or one carbon atom.
-20 hydrocarbon group, halogenated hydrocarbon group having 1 to 20 carbon atoms], specifically,
Alkylene groups such as methylene, dimethylmethylene, 1,2-ethylene, dimethyl-1,2-ethylene, 1,3-trimethylene, 1,4-tetramethylene, 1,2-cyclohexylene, 1,4-cyclohexylene, A divalent hydrocarbon group having 1 to 20 carbon atoms such as an arylalkylene group such as diphenylmethylene and diphenyl-1,2-ethylene;
A halogenated hydrocarbon group obtained by halogenating the divalent hydrocarbon group having 1 to 20 carbon atoms such as chloromethylene,
Methylsilylene, dimethylsilylene, diethylsilylene, di (n-propyl) silylene, di (i-propyl) silylene, di (cyclohexyl) silylene, methylphenylsilylene, diphenylsilylene, di (p-tolyl) silylene, di (p- 2 such as alkylsilylene such as chlorophenyl) silylene, alkylarylsilylene, arylsilylene group, alkyldisilyl such as tetramethyl-1,2-disilyl, tetraphenyl-1,2-disilyl, alkylaryldisilyl, arylsilyl group Valent silicon-containing groups,
A divalent germanium-containing group obtained by replacing the silicon of the divalent silicon-containing group with germanium,
A divalent tin-containing group substituent in which the silicon of the divalent silicon-containing group is substituted with tin, and the like,
R ⁵ is the same halogen atom as R ¹ , a hydrocarbon group having 1 to 20 carbon atoms, and 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 preferred, and a divalent silicon-containing group is more preferred. Of these, alkylsilylene and alkylarylsilylene are particularly preferred. Arylsilylene is preferred.

Specific examples of the transition metal compound represented by the general formula (I) are shown below.
rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-ethylindenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-n-propylindenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-i-propylindenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-n-butylindenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-sec-butylindenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-t-butylindenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-n-pentylindenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-n-hexylindenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-cyclohexylindenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-methylcyclohexylindenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-phenylethylindenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-phenyldichloromethylindenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-chloromethylindenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-trimethylsilylenemethylindenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-trimethylsiloxymethylindenyl)} zirconium dichloride,
rac-diethylsilylene-bis {1- (2,7-dimethyl-4-i-propylindenyl)} zirconium dichloride,
rac-di (i-propyl) silylenebis {1- (2,7-dimethyl-4-i-propylindenyl)}
Zirconium dichloride,
rac-di (n-butyl) silylenebis {1- (2,7-dimethyl-4-i-propylindenyl)} zirconium dichloride,
rac-di (cyclohexyl) silylenebis {1- (2,7-dimethyl-4-i-propylindenyl)} zirconium dichloride,
rac-methylphenylsilylenebis {1- (2,7-dimethyl-4-i-propylindenyl)} zirconium dichloride,
rac-methylphenylsilylenebis {1- (2,7-dimethyl-4-t-butylindenyl)} zirconium dichloride,
rac-diphenylsilylenebis {1- (2,7-dimethyl-4-t-butylindenyl)} zirconium dichloride,
rac-diphenylsilylenebis {1- (2,7-dimethyl-4-i-propylindenyl)} zirconium dichloride,
rac-diphenylsilylenebis {1- (2,7-dimethyl-4-ethylindenyl)} zirconium dichloride,
rac-di (p-tolyl) silylenebis {1- (2,7-dimethyl-4-i-propylindenyl)} zirconium dichloride,
rac-di (p-chlorophenyl) silylenebis {1- (2,7-dimethyl-4-i-propylindenyl)} zirconium dichloride,
rac-Dimethylsilylenebis {1- (2-methyl-4-i-propyl-7-ethylindenyl)} zirconium dibromide
rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-i-propylindenyl)} zirconium dimethyl,
rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-i-propylindenyl)} zirconium methyl chloride,
rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-i-propylindenyl)} zirconium-bis (trifluoromethanesulfonate),
rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-i-propylindenyl)} zirconium-bis (p-phenylsulfinato),
rac-dimethylsilylene-bis {1- (2-phenyl-4-i-propyl-7-methylindenyl)}
Zirconium dichloride etc.

  In the present invention, among the transition metal compounds represented by the above formula (I), a transition metal compound represented by the following formula (Ia) is particularly preferably used.

(In the formula, M, X ¹ , X ² , R ¹ , R ³ and Y are the same as those in formula (I), but preferably R ¹ is a hydrogen atom, a methyl group or an aromatic group.)
Preferred examples of such transition metal compounds represented by the formula (Ia) are shown below.

rac-dimethylsilylene-bis {1- (4-phenylindenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-methyl-4- (α-naphthyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-methyl-4- (β-naphthyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-methyl-4- (1-anthracenyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-methyl-4- (2-anthracenyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-methyl-4- (9-anthracenyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-methyl-4- (9-phenanthryl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-methyl-4- (p-fluorophenyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-methyl-4- (pentafluorophenyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-methyl-4- (p-chlorophenyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-methyl-4- (m-chlorophenyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-methyl-4- (o-chlorophenyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-methyl-4- (o, p-dichlorophenyl) phenylindenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-methyl-4- (p-bromophenyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-methyl-4- (p-tolyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-methyl-4- (m-tolyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-methyl-4- (o-tolyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-methyl-4- (o, o'-dimethylphenyl) indenyl)
} Zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-methyl-4- (p-ethylphenyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-methyl-4- (pi-propylphenyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-methyl-4- (p-benzylphenyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-methyl-4- (p-biphenyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-methyl-4- (m-biphenyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-methyl-4- (p-trimethylsilylenephenyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-methyl-4- (m-trimethylsilylenephenyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-phenyl-4-phenylindenyl)} zirconium dichloride,
rac-diethylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride,
rac-di- (i-propyl) silylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride,
rac-di- (n-butyl) silylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride,
rac-dicyclohexylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride,
rac-methylphenylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride,
rac-diphenylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride,
rac-di (p-tolyl) silylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride,
rac-di (p-chlorophenyl) silylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride,
rac-methylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride,
rac-ethylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride,
rac-dimethylgermylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride,
rac-dimethylstannylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dibromide,
rac-dimethylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dimethyl,
rac-dimethylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium methyl chloride,
rac-dimethylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium chloride SO ₂ Me,
rac-dimethylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium chloride OSO ₂ Me,
rac-dimethylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium monochloride mono (trifluoromethanesulfonate),
rac-dimethylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium di (trifluoromethanesulfonate),
rac-dimethylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium di (P-toluenesulfonate),
rac-dimethylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium di (methylsulfonate),
rac-dimethylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium di (trifluoromethanesulfinate),
rac-dimethylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium di (trifluoroacetate),
rac-dimethylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium monochloride mono (n-butoxide),
rac-dimethylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium di (n-butoxide),
rac-dimethylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium monochloride mono (phenoxide),
rac-dimethylsilylene-bis {1- (2-methyl-4-phenylindenyl)} titanium dichloride,
rac-dimethylsilylene-bis {1- (2-methyl-4-phenylindenyl)} hafnium dichloride and the like.

Of the above, compounds in which R ¹ is a methyl group are particularly preferred.
In the above formula (Ia), a transition metal compound in which R ¹ is a hydrocarbon group having 2 to 6 carbon atoms and R ³ is an aryl group having 6 to 16 carbon atoms is also preferably used. Of the compounds represented by the formula (I), such preferred compounds are exemplified below.

rac-dimethylsilylene-bis {1- (2-ethyl-4-phenylindenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-ethyl-4- (α-naphthyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-ethyl-4- (β-naphthyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-ethyl-4- (2-methyl-1-naphthyl) indenyl)
} Zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-ethyl-4- (5-acenaphthyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-ethyl-4- (9-anthracenyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-ethyl-4- (9-phenanthryl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-ethyl-4- (o-methylphenyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-ethyl-4- (m-methylphenyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-ethyl-4- (p-methylphenyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-ethyl-4- (2,3-dimethylphenyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-ethyl-4- (2,4-dimethylphenyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-ethyl-4- (2,5-dimethylphenyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-ethyl-4- (2,4,6-trimethylphenyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-ethyl-4- (o-chlorophenyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-ethyl-4- (m-chlorophenyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-ethyl-4- (p-chlorophenyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-ethyl-4- (2,3-dichlorophenyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-ethyl-4- (2,6-dichlorophenyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-ethyl-4- (3,5-dichlorophenyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-ethyl-4- (2-bromophenyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-ethyl-4- (3-bromophenyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-ethyl-4- (4-bromophenyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-ethyl-4- (4-biphenylyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-ethyl-4- (4-trimethylsilylenephenyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-n-propyl-4-phenylindenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-n-propyl-4- (α-naphthyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-n-propyl-4- (β-naphthyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-n-propyl-4- (2-methyl-1-naphthyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-n-propyl-4- (5-acenaphthyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-n-propyl-4- (9-anthracenyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-n-propyl-4- (9-phenanthryl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-i-propyl-4-phenylindenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-i-propyl-4- (α-naphthyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-i-propyl-4- (β-naphthyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-i-propyl-4- (2-methyl-1-naphthyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-i-propyl-4- (5-acenaphthyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-i-propyl-4- (9-anthracenyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-i-propyl-4- (9-phenanthryl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-s-butyl-4-phenylindenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-s-butyl-4- (α-naphthyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-s-butyl-4- (β-naphthyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-s-butyl-4- (8-methyl-9-naphthyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-s-butyl-4- (5-acenaphthyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-s-butyl-4- (9-anthracenyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-s-butyl-4- (9-phenanthryl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-n-pentyl-4-phenylindenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-n-pentyl-4- (α-naphthyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-n-butyl-4-phenylindenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-n-butyl-4- (α-naphthyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-n-butyl-4- (β-naphthyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-n-butyl-4- (2-methyl-1-naphthyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-n-butyl-4- (5-acenaphthyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-n-butyl-4- (9-anthracenyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-n-butyl-4- (9-phenanthryl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-i-butyl-4-phenylindenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-i-butyl-4- (α-naphthyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-i-butyl-4- (β-naphthyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-i-butyl-4- (2-methyl-1-naphthyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-i-butyl-4- (5-acenaphthyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-i-butyl-4- (9-anthracenyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-i-butyl-4- (9-phenanthryl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-neopentyl-4-phenylindenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-neopentyl-4- (α-naphthyl) indenyl)}
Zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-n-hexyl-4-phenylindenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-n-hexyl-4- (α-naphthyl) indenyl)} zirconium dichloride,
rac-methylphenylsilylene-bis {1- (2-ethyl-4-phenylindenyl)} zirconium dichloride,
rac-methylphenylsilylene-bis {1- (2-ethyl-4- (α-naphthyl) indenyl)}
Zirconium dichloride,
rac-methylphenylsilylene-bis {1- (2-ethyl-4- (9-anthracenyl) indenyl)} zirconium dichloride,
rac-methylphenylsilylene-bis {1- (2-ethyl-4- (9-phenanthryl) indenyl)} zirconium dichloride,
rac-diphenylsilylene-bis {1- (2-ethyl-4-phenylindenyl)} zirconium dichloride,
rac-diphenylsilylene-bis {1- (2-ethyl-4- (α-naphthyl) indenyl)} zirconium dichloride,
rac-diphenylsilylene-bis {1- (2-ethyl-4- (9-anthracenyl) indenyl)} zirconium dichloride,
rac-diphenylsilylene-bis {1- (2-ethyl-4- (9-phenanthryl) indenyl)} zirconium dichloride,
rac-diphenylsilylene-bis {1- (2-ethyl-4- (4-biferinyl) indenyl)} zirconium dichloride,
rac-methylene-bis {1- (2-ethyl-4-phenylindenyl)} zirconium dichloride,
rac-methylene-bis {1- (2-ethyl-4- (α-naphthyl) indenyl)} zirconium dichloride,
rac-ethylene-bis {1- (2-ethyl-4-phenylindenyl)} zirconium dichloride,
rac-ethylene-bis {1- (2-ethyl-4- (α-naphthyl) indenyl)} zirconium dichloride,
rac-ethylene-bis {1- (2-n-propyl-4- (α-naphthyl) indenyl)} zirconium dichloride,
rac-dimethylgermylene-bis {1- (2-ethyl-4-phenylindenyl)} zirconium dichloride,
rac-dimethylgermylene-bis {1- (2-ethyl-4- (α-naphthyl) indenyl)} zirconium dichloride,
rac-dimethylgermylene-bis {1- (2-n-propyl-4-phenylindenyl)} zirconium dichloride,
rac-dimethylstannylene-bis {1- (2-ethyl-4-phenylindenyl)} zirconium dichloride,
rac-dimethylstannylene-bis {1- (2-ethyl-4- (α-naphthyl) indenyl)} zirconium dichloride,
rac-dimethylstannylene-bis {1- (2-n-ethyl-4- (9-phenanthryl) indenyl)} zirconium dichloride,
rac-dimethylstannylene-bis {1- (2-n-propyl-4-phenylindenyl)} zirconium dichloride and the like.

  In the present invention, a transition metal compound in which zirconium metal is replaced with titanium metal, hafnium metal, vanadium metal, niobium metal, tantalum metal, chromium metal, molybdenum metal, or tungsten metal in the above-described compounds can also be used.

The transition metal compound is usually used as a catalyst component for olefin polymerization as a racemate, but R-type or S-type can also be used.
The transition metal compound according to the present invention as described above is exemplified by, for example, the formula [Ia] according to Journal of Organometallic Chem. 288 (1985), pp. 63-67, European Patent Application No. 0,320,762 and Examples. The compound shown by can be manufactured as follows.

  The [II-a] organoaluminum oxy compound (hereinafter sometimes referred to as “component [II-a]”) that forms the olefin polymerization catalyst used in the present invention may be a conventionally known aluminoxane. Also, a benzene-insoluble organoaluminum oxy compound as exemplified in JP-A-2-78687 may be used.

A conventionally well-known aluminoxane can be manufactured by the following methods, for example.
(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, first cerium chloride hydrate, etc. A method in which an organoaluminum compound such as trialkylaluminum is added to and reacted with a suspension of the hydrocarbon in
(2) A method of allowing water, ice or water vapor to act directly on an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether or tetrahydrofuran.
(3) A method in which an organotin oxide such as dimethyltin oxide or dibutyltin oxide is reacted with an organoaluminum compound such as trialkylaluminum in a medium such as decane, benzene, or toluene.

  The aluminoxane may contain a small amount of an organometallic component. Further, after removing the solvent or unreacted organoaluminum compound from the recovered aluminoxane solution by distillation, it may be redissolved in a solvent or suspended in a poor aluminoxane solvent.

Specific examples of organoaluminum compounds used in the preparation of aluminoxane include trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, trisec-butylaluminum, trialuminum. trialkylaluminums such as tert-butylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum,
Tricycloalkylaluminum such as tricyclohexylaluminum, tricyclooctylaluminum,
Dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, diethylaluminum bromide, diisobutylaluminum chloride,
Dialkylaluminum hydrides such as diethylaluminum hydride and diisobutylaluminum hydride,
Dialkylaluminum alkoxides such as dimethylaluminum methoxide and diethylaluminum ethoxide,
Examples thereof include dialkylaluminum aryloxides such as diethylaluminum phenoxide.

Of these, trialkylaluminum and tricycloalkylaluminum are preferable, and trimethylaluminum is particularly preferable.
Moreover, the isoprenyl aluminum represented by the following general formula can also be used as an organoaluminum compound used when preparing an aluminoxane.

_{(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.)
The organoaluminum compounds as described above are used alone or in combination.

Solvents used in aluminoxane solutions or suspensions include aromatic hydrocarbons such as benzene, toluene, xylene, cumene, and cymene, and aliphatic carbonization such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane, and octadecane. Hydrogen, cyclopentane, cyclohexane, cyclooctane, methylcyclopentane, and other alicyclic hydrocarbons, petroleum fractions such as gasoline, kerosene, and light oil, or halogens of the above aromatic hydrocarbons, aliphatic hydrocarbons, and alicyclic hydrocarbons Among them, hydrocarbon solvents such as chlorinated products and brominated products are mentioned. In addition, ethers such as ethyl ether and tetrahydrofuran can also be used. Of these solvents, aromatic hydrocarbons or aliphatic hydrocarbons are particularly preferable.

  [II-b] forming an olefin polymerization catalyst used in the present invention [II-b] a compound that reacts with the transition metal compound [I] to form an ion pair (hereinafter sometimes referred to as “component [II-b]”) Are disclosed in JP-A-1-501950, JP-A-1-502036, JP-A-3-179905, JP-A-3-179006, JP-A-3-207703, JP-A-3-207704. And Lewis acids, ionic compounds, and carborane compounds described in US Pat. No. 5,547,718.

Lewis acids include triphenylboron, tris (4-fluorophenyl) boron, tris (p-tolyl) boron, tris (o-tolyl) boron, tris (3,5-dimethylphenyl) boron, tris (pentafluorophenyl) ) Boron, MgCl ₂ , Al ₂ O ₃ , SiO ₂ —Al ₂ O _{3 and the} like.

  Examples of ionic compounds include triphenylcarbenium tetrakis (pentafluorophenyl) borate, tri-n-butylammonium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, ferrocenium tetra Examples include (pentafluorophenyl) borate.

The carborane compounds include dodecaborane, 1-carbaundecaborane, bis n-butylammonium (1-carbedodeca) borate, tri-n-butylammonium (7,8-dicarboundeca) borate, tri-n-butylammonium (trideca Examples thereof include hydride-7-carbaoundeca borate.

The compound [II-b] that forms an ion pair by reacting with the transition metal compound [I] as described above can be used in combination of two or more.
The [III] organoaluminum compound (hereinafter sometimes referred to as “component [III]”) forming the olefin polymerization catalyst used in the present invention is, for example, an organoaluminum represented by the following general formula (III) A compound can be illustrated.

R ⁹ _n AlX _3-n (III)
(In the formula, R ⁹ is a hydrocarbon group having 1 to 12 carbon atoms, X is a halogen atom or a hydrogen atom, and n is 1 to 3).
In the general formula [III], R ⁹ is a hydrocarbon group having 1 to 12 carbon atoms such as an alkyl group,
Cycloalkyl group or aryl group, specifically, methyl group, ethyl group, n-propyl group, isopropyl group, isobutyl group, pentyl group, hexyl group, octyl group, cyclopentyl group, cyclohexyl group, phenyl group, Such as a tolyl group.

Specific examples of the organoaluminum compound [III] include the following compounds.
Trialkylaluminum such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trioctylaluminum, tri (2-ethylhexyl) aluminum, tridecylaluminum,
Alkenyl aluminum such as isoprenyl aluminum,
Dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, diisopropylaluminum chloride, diisobutylaluminum chloride, dimethylaluminum bromide,
Alkylaluminum sesquichlorides such as methylaluminum sesquichloride, ethylaluminum sesquichloride, isopropylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquibromide,
Alkylaluminum dihalides such as methylaluminum dichloride, ethylaluminum dichloride, isopropylaluminum dichloride, ethylaluminum dibromide,
Alkyl aluminum hydrides such as diethyl aluminum hydride and diisobutyl aluminum hydride.

As the organoaluminum compound [III], a compound represented by the following general formula (IV) can also be used.
R ⁹ _n AlL _3-n (IV)
(Wherein R ⁹ is the same as above, and L is —OR ¹⁰ group, —OSiR ¹¹ ₃ group, —OAlR ¹² ₂ group, —NR ¹³ ₂ group, —SiR ¹⁴ ₃ group or —N (R ¹⁵ ) AlR ¹⁶ ₂ group, n is 1-2,
R ¹⁰ , R ¹¹ , R ¹² and R ¹⁶ are a methyl group, an ethyl group, an isopropyl group, an isobutyl group, a cyclohexyl group, a phenyl group, etc., and R ¹³ is a hydrogen atom, a methyl group, an ethyl group, an isopropyl group, a phenyl group. A trimethylsilyl group, and R ¹⁴ and R ¹⁵ are a methyl group, an ethyl group, and the like. )
Among these organoaluminum compounds,
A compound represented by R ⁷ _n Al (OAlR ¹⁰ ₂ ) _{3 -n} , for example, Et ₂ AlOAlEt ₂ , (iso-Bu) ₂ AlOA (iso-Bu) _{2 and the} like is preferable.

Among the organoaluminum compounds represented by the general formulas (III) and (IV), a compound represented by the general formula R ⁷ ₃ Al is preferable, and a compound in which R is an isoalkyl group is particularly preferable.

The olefin polymerization catalyst used in the present invention comprises component [I], component [II-a] (or component [II-b]) and optionally component [III] in an inert hydrocarbon solvent or olefin solvent. It can be prepared by mixing.

  Specific examples of the inert hydrocarbon solvent used for the preparation of the olefin polymerization catalyst include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene, cyclopentane, cyclohexane, and methyl. Examples thereof include alicyclic hydrocarbons such as cyclopentane, aromatic hydrocarbons such as benzene, toluene and xylene, halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane, and mixtures thereof.

The order of mixing the components in preparing the olefin polymerization catalyst is arbitrary, but the component [II-a] or the component [II-b]) and the component [I] are mixed,
Mixing component [II-a] and component [III], then mixing component [I],
Mixing component [I] with component [II-a] (or component [II-b]) and then mixing component [III], or
It is preferable to mix component [I] and component [III], and then mix component component [II-a] (or component [II-b]).

When mixing the above components, the atomic ratio (Al / transition metal) of aluminum in component [II-a] and transition metal in component [I] is usually 10 to 10,000, preferably 20 to 5000. The concentration of component (A) is in the range of about 10 ⁻⁸ to 10 ⁻¹ mol / liter, preferably 10 ^{−7 to} 5 × 10 ⁻² mol / liter.

When component [II-b] is used, the molar ratio of component [I] to component [II-b] (component [I] / component [II-b]) is usually 0.01 to 10, preferably 0. The concentration of component [I] is in the range of 1 to 5.
The range is about 10 ⁻⁸ to 10 ⁻¹ mol / liter, preferably 10 ^{−7 to} 5 × 10 ⁻² mol / liter.

When component [III] is used, the atomic ratio (Al _C / Al _B-1 ) of the aluminum atom (Al _C ) in component [III] and the aluminum atom (Al _B-1 ) in component [II-a] ) Is usually 0.02 to 2
It is 0, preferably in the range of 0.2-10.

Each of the above catalyst components may be mixed in a polymerization vessel, or those previously mixed may be added to the polymerization vessel.
The mixing temperature at the time of premixing is usually −50 to 150 ° C., preferably −20 to 120 ° C., and the contact time is 1 to 1000 minutes, preferably 5 to 600 minutes. Further, the mixing temperature may be changed during the mixing contact.

The catalyst for olefin polymerization used in the present invention is an inorganic or organic particulate carrier which is a granular or particulate solid, and at least one of component [I], component [II] and component [III]. It may be a solid olefin polymerization catalyst on which a component is supported.

The inorganic carrier is preferably a porous oxide, and examples thereof include SiO ₂ and Al ₂ O ₃ .
Examples of the granular or fine particle solid of the organic compound include polymers or copolymers produced mainly from α-olefins such as ethylene, propylene and 1-butene, or styrene.

The olefin polymerization catalyst used in the present invention includes the fine particle carrier, component [I], component [II], an olefin polymer produced by prepolymerization, and optionally component [III].
It may be an olefin polymerization catalyst formed from

As the olefin used for the prepolymerization, olefins such as propylene, ethylene and 1-butene are used, but a mixture of these with other olefins may be used.
The olefin polymerization catalyst used in the present invention may contain other components useful for olefin polymerization, such as water as a catalyst component, in addition to the above components.

  The propylene-based elastomer of the present invention is produced by copolymerizing propylene and 1-butene or propylene and ethylene in the presence of the above-mentioned olefin polymerization catalyst so that the final composition ratio is obtained. be able to. The polymerization can be carried out by either a liquid phase polymerization method such as suspension polymerization or solution polymerization, or a gas phase polymerization method.

In the liquid phase polymerization method, the same inert hydrocarbon solvent used in the catalyst preparation described above can be used, and propylene can also be used as a solvent.
The polymerization temperature is usually in the range of −50 to 100 ° C., preferably 0 to 90 ° C. when the suspension polymerization method is performed, and is usually 0 to 250 when the solution polymerization method is performed. It is desirable that the temperature be in the range of 20 ° C., preferably 20 to 200 ° C. In 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 from normal pressure to 100 kg / cm ² , preferably from normal pressure to 50 kg / cm ² , and the polymerization reaction is carried out in any of batch, semi-continuous and continuous methods. Can do. Further, the polymerization can be carried out in two or more stages having different reaction conditions.

The molecular weight of the resulting propylene-based elastomer can be adjusted by allowing hydrogen to be present in the polymerization system or changing the polymerization temperature and polymerization pressure.
[Polypropylene composition]
The polypropylene composition according to the present invention comprises [A] polypropylene as described above in an amount of 5 to 95% by weight, preferably 20 to 90% by weight, more preferably 40 to 85% by weight,
[B] The propylene-based elastomer is contained in an amount of 95 to 5% by weight, preferably 80 to 10% by weight, more preferably 60 to 15% by weight.

  The polypropylene composition is produced by a method generally known as a method for preparing a resin composition, for example, by melt-kneading polypropylene [A] and propylene-based elastomer [B].

Such a polypropylene composition has a melt flow rate MFR of 0.1 to 400 g / 10 minutes, preferably 1 to 100 g / 10 minutes.
The melting point is 60 to 165 ° C, preferably 80 to 160 ° C.

The polypropylene composition according to the present invention may contain other additives, resins, and the like within a range not impairing the object of the present invention, together with polypropylene and a propylene-based elastomer.
Other additives include nucleating agents, antioxidants, hydrochloric acid absorbers, heat stabilizers, light stabilizers, UV absorbers, lubricants, antistatic agents, flame retardants, pigments, dyes, dispersants, copper damage inhibitors And additives such as a flow improver such as a neutralizer, a foaming agent, a plasticizer, an anti-bubble agent, a crosslinking agent and a peroxide, and a weld strength improver.

As the antioxidant, a phenol-based antioxidant, a sulfur-based antioxidant, a phosphorus-based antioxidant, or the like can be used.
Examples of phenolic antioxidants include 2,6-di-tert-butyl-p-cresol, stearyl (3,3-dimethyl-4-hydroxybenzyl) thioglycolate, stearyl-β- (4-
Hydroxy-3,5-di-tert-butylphenol) propionate, distearyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, 2,4,6-tris (3 ', 5'-di-tert -Butyl-4'-hydroxybenzylthio) -1,3,5-triazine, distearyl (4-hydroxy-3-methyl-5-tert-butylbenzyl) malonate, 2,2'-methylenebis (4-methyl- 6-tert-butylphenol), 4,4'-methylenebis (2,6-di-tert-butylphenol), 2,2'-methylenebis [6- (1-methylcyclohexyl) p-cresol], bis [3,5 -Bis [4-hydroxy-3-tert-butylphenyl) butyric acid] glycol ester, 4,4'-butylidenebis (6-tert-butyl-m-cresol), 1,1,3-tris (2-methyl) -4-hydroxy-5-tert-butylphenyl) butane, bis [2-tert-butyl-4-methyl-6- (2-hydroxy-3-tert-butyl-5-methylbenzyl) ) Phenyl] terephthalate, 1,3,5-tris (2,6-dimethyl-3-hydroxy-4-tert-butyl) benzyl isocyanurate, 1,3,5-tris (3,5-di-tert-butyl) -4-hydroxybenzyl) -2,4,6-trimethylbenzene, tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane, 1,3,5-tris ( 3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris [(3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate, 2 -Octylthio-4,6-di (4-hydroxy-3,5-di-tert-butyl) phenoxy-1,3,5-triazine, 4,4'-thiobis (6-tert-butyl-m-cresol) Such as phenols and carbonic acid oligoesters of 4,4'-butylidenebis (2-tert-butyl-5-methylphenol) (eg, degree of polymerization 2-10) Phenol oligoesters are exemplified carbonate.

Examples of sulfur-based antioxidants include dialkylthiodipropionates such as dilauryl-, dimyristyl-, and distearyl- and polyhydric alcohols of alkylthiopropionic acids such as butyl-, octyl-, lauryl-, stearyl- (for example, glycerin, And esters of trimethylolethane, trimethylolpropane, pentaerythritol, trishydroxyethyl isocyanurate) (for example, pentaerythritol tetralaurylthiopropionate).

Examples of phosphorus antioxidants include trioctyl phosphite, trilauryl phosphite, tridecyl phosphite, octyl-diphenyl phosphite, tris (2,4-di-tert-butylphenyl) phosphite, triphenyl phosphite. Phyto, tris (butoxyethyl) phosphite, tris (nonylphenyl) phosphite, distearyl pentaerythritol diphosphite, tetra (tridecyl) -1,1,3-tris (2-methyl-5-tert-butyl-4 - hydroxyphenyl) butane diphosphite, tetra (C ₁₂ -C ₁₅ mixed alkyl) -4,4'-isopropylidene diphenyl diphosphite, tetra (tridecyl) -4,4'-butylidene bis (3-methyl-6- tert-butylphenol) diphosphite, tris (3,5-di-tert-butyl-4-hydroxyphenyl) phosphite, tris ( Mono-dimixed nonylphenyl) phosphite, hydrogenated-4,4'-isopropylidene diphenol polyphosphite, bis (octylphenyl) bis [4,4'-butylidenebis (3-methyl-6-tert-butylphenol) )], 1,6-hexanediol diphosphite, phenyl, 4,4'-isopropylidenediphenol, pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, Bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, tris [4,4′-isopropylidenebis (2-tert-butylphenol)] phosphite, phenyl diisodecyl phosphite, Di (nonylphenyl) pentaerythritol diphosphite), tris (1,3-di-stearoyloxyisopropyl) phosphite, 4,4 '-Isopropylidenebis (2-tert-butylphenol) di (nonylphenyl) phosphite, 9,10-di-hydro-9-oxa-9-oxa-10-phosphaphenanthrene-10-oxide, tetrakis (2,4-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite.

Still other antioxidants include 6-hydroxychroman derivatives such as various tocopherols of α, β, γ, δ or mixtures thereof, 2- (4-methyl-pent-3-enyl) -6-hydroxychroman 2, 5-dimethyl substituted, 2,5,8-trimethyl substituted, 2,5,7,8-tetramethyl substituted, 2,2,7-trimethyl-5-tert-butyl-6-hydroxychroman, 2, 2,5-trimethyl-7-tert-butyl-6-hydroxychroman, 2,2,5-trimethyl-6-tert-butyl-6-hydroxychroman, 2,2-dimethyl-5-tert-butyl-6- Hydroxychroman and the like can also be used.

The general formula MxAly (OH) 2x + 3y- 2z (A) z · aH 2 O (M is Mg, Ca or Zn, A is an anion other than hydroxyl group, x, y, z are positive numbers, a is 0 Or a positive compound) such as Mg ₆ Al ₂ (OH) ₁₆ CO ₃ .4H ₂ O,
Mg ₆ Al ₂ (OH) ₂₀ CO ₃ .5H ₂ O,
Mg ₅ Al ₂ (OH) ₁₄ CO ₃ .4H ₂ O,
_{Mg 10 Al 2 (OH) 22} (CO 3) 2 · 4H 2 O,
Mg ₆ Al ₂ (OH) ₁₆ HPO ₄ · 4H ₂ O,
Ca ₆ Al ₂ (OH) ₁₆ CO ₃ .4H ₂ O,
Zn ₆ Al ₂ (OH) ₁₆ CO ₃ .4H ₂ O,
Zn ₆ Al ₂ (OH) ₁₆ SO ₄ .4H ₂ O,
Mg ₆ Al ₂ (OH) ₁₆ SO ₃ .4H ₂ O,
Mg ₆ Al ₂ (OH) ₁₂ CO ₃ .3H ₂ O can be used as a hydrochloric acid absorbent, for example.

Examples of the light stabilizer include 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone-2,2′-di-hydroxy-4-methoxybenzophenone, and 2,4-dihydroxybenzophenone. Hydroxybenzophenones, 2- (2'-hydroxy-3'-t
ert-Butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2'-Hydroxy-5'-
Benzotriazoles such as methylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-amylphenyl) benzotriazole, phenyl salicylate, p-tert-
Benzoates such as butylphenyl salicylate, 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoate 2,2'-thiobis (4-tert-octylphenol) Ni salt, [2,2'-thiobis (4-tert-octylphenolate)]-n-butylamine Ni, (3,5-di-tert-butyl -4-hydroxybenzyl) nickel compounds such as phosphonic acid monoethyl ester Ni salt,
Substituted acrylonitriles such as methyl α-cyano-β-methyl-β- (p-methoxyphenyl) acrylate and N'-2-ethylphenyl-N-ethoxy-5-tert-butylphenyloxalic acid diamide, N-2 Oxalic acid dianilides such as 2-ethylphenyl-N'-2-ethoxyphenyloxalic acid diamide, bis (2,2,6,6-tetramethyl-4-piperidine) sebacate, poly [{(6- (1,1 , 3,3-tetramethylbutyl) imino} -1,3,5-triazine-2,4-diyl {4- (2,2,6,6-tetramethylpiperidyl) imino} hexamethylene], 2- ( 4-Hydroxy-2,2,6,6-tetramethyl-1-piperidyl) hindered amine compounds such as a condensate of ethanol and dimethyl succinate.

  Examples of the lubricant include aliphatic hydrocarbons such as paraffin wax, polyethylene wax, and polypropylene wax, capric acids, higher fatty acids such as lauric acid, myristic acid, palmitic acid, margaric acid, stearic acid, arachidic acid, and behenic acid, or These metal salts (for example, lithium salt, calcium salt, sodium salt, magnesium salt, potassium salt), aliphatic alcohols such as palmityl alcohol, cetyl alcohol, stearyl alcohol, capron amide, caprylic amide, capric amide, Aliphatic amides such as lauric acid amide, myristic acid amide, palmitic acid amide, stearic acid amide, esters of aliphatic and alcohol, fluoroalkylcarboxylic acid or metal salt thereof, fluoroalkyl Fluorine compounds such as sulfonic acid metal salts.

The additive as described above may be contained in the polypropylene composition in an amount of 0.0001 wt% to 10 wt%. The polypropylene composition according to the present invention comprises a molded article having further improved physical property balance, durability, paintability, printability, scratch resistance, molding processability and the like by containing the additives as described above. Can be formed.

Moreover, the polypropylene composition according to the present invention may contain a nucleating agent as described above.
As the nucleating agent, various conventionally known nucleating agents are used without particular limitation, and among them, the nucleating agents such as aromatic phosphate ester salts and dibenzylidene sorbitol described below are preferable.

(Wherein R ¹ is oxygen, sulfur or a hydrocarbon group having 1 to 10 carbon atoms, R ² and R ³ are hydrogen or a hydrocarbon group having 1 to 10 carbon atoms, and R ² and R ³ are the same kind. may be heterologous even, R ² to each other, may have a ring by bonding R ³ s or R ² and R ^3, M is a monovalent to trivalent metal atom, n represents It is an integer from 1 to 3.)
Specifically, sodium-2,2′-methylene-bis (4,6-di-t-butylphenyl) phosphate, sodium-2,2′-ethylidene-bis (4,6-di-t-butyl) Phenyl) phosphate,
Lithium-2,2'-methylene-bis- (4,6-di-t-butylphenyl) phosphate, lithium-2,2'-ethylidene-bis (4,6-di-t-butylphenyl) phosphate Sodium-2,2'-ethylidene-bis (4-i-propyl-6-t-butylphenyl) phosphate, lithium-2,2'-methylene-bis (4-methyl-6-t-butylphenyl) Phosphate, lithium-2,2'-methylene-bis (4-ethyl-6-t-butylphenyl) phosphate, calcium-bis [2,2'-thiobis (4-methyl-6-t-butylphenyl) Phosphate], calcium-bis [2,2'-thiobis (4-ethyl-6-t-butylphenyl) phosphate], calcium-bis [2,2'-thiobis- (4,6-di-t- Butylphenyl) phosphate], magnesium-bis [2,2'-thiobis (4,6-di-t-butylphenyl) phosphate], magnesium-bis [2,2'-thiobis- (4-t -Octylphenyl) phosphate], sodium-2,2'-butylidene-bis (4,6-di-methylphenyl) phosphate, sodium-2,2'-butylidene-bis (4,6-di-t- Butylphenyl) phosphate, sodium-2,2'-t-octylmethylene-bis (4,6-di-methylphenyl) phosphate, sodium-2,2'-t-octylmethylene-bis (4,6- Di-t-butylphenyl) phosphate, calcium-bis- (2,2'-methylene-bis (4,6-di-t-butylphenyl) phosphate), magnesium-bis [2,2'-methylene- Screw (4,6-di-t-
Butylphenyl) phosphate], barium-bis [2,2'-methylene-bis (4,6-di-t-butylphenyl) phosphate], sodium-2,2'-methylene-bis (4-methyl- 6-t-butylphenyl) phosphate, sodium-2,2'-methylene-bis (4-ethyl-6-t-butylphenyl) phosphate, sodium (4,4'-dimethyl-5,6'-di -t-butyl-2,2'-biphenyl) phosphate, calcium-bis [(4,4'-dimethyl-6,6'-di-t-butyl-2,2'-biphenyl) phosphate], sodium -2,2'-ethylidene-bis (4-m-butyl-6-t-butylphenyl) phosphate, sodium-2,2'-methylene-bis (4,6-di-methylphenyl) phosphate, sodium -2,2'-methylene-bis (4,6-di-ethylphenyl) phosphate, potassium-2,2'-ethylidene-bis (4,6-di-t-butylphenyl) phosphate, cal Cium-bis [2,2'-ethylidene-bis (4,6-di-t-butylphenyl) phosphate], magnesium-bis [2,2'-ethylidene-bis (4,6-di-t-butylphenyl) ) Phosphate], barium-bis [2,2'-ethylidene-bis (4,6-di-t-butylphenyl) phosphate], aluminum-tris [2,2'-methylene-bis (4,6- Di-t-butylfel) phosphate] and aluminum-tris [2,2′-ethylidene-bis (4,6-di-t-butylphenyl) phosphate] and combinations thereof can be exemplified. Of these, sodium-2,2′-methylene-bis (4,6-di-t-butylphenyl) phosphate is preferred.

(Wherein R ⁴ is hydrogen or a hydrocarbon group having 1 to 10 carbon atoms, M is a 1 to 3 valent metal atom, and n is an integer of 1 to 3)
Specifically, sodium-bis (4-t-butylphenyl) phosphate, sodium-bis (4-methylphenyl) phosphate, sodium-bis (4-ethylphenyl) phosphate, sodium-bis (4-i -Propylphenyl) phosphate, sodium-bis (4-t-octylphenyl) phosphate, potassium-bis (4-t-butylphenyl) phosphate, calcium-bis (4-t-butylphenyl) phosphate, magnesium -Bis (4-t-butylphenyl) phosphate, lithium-bis (4-t-butylphenyl) phosphate, aluminum-bis (4-t-butylphenyl) phosphate and combinations thereof can be exemplified . Of these, sodium-bis (4-t-butylphenyl) phosphate is preferred.

(In the formula, R ⁵ is hydrogen or a hydrocarbon group having 1 to 10 carbon atoms.)
Specifically, 1,3,2,4-dibenzylidene sorbitol, 1,3-benzylidene-2,4-p-methylbenzylidene sorbitol, 1,3-benzylidene-2,4-p-ethylbenzylidene sorbitol, 1 , 3-p-methylbenzylidene-2,4-benzylidene sorbitol, 1,3-p-ethylbenzylidene-2,4-benzylidene sorbitol, 1,3-p-methylbenzylidene-2,4-p-ethylbenzylidene sorbitol, 1,3-p-ethylbenzylidene-2,4-p-methylbenzylidenesorbitol, 1,3,2,4-di (p-methylbenzylidene) sorbitol, 1,3,2,4-di (p-ethylbenzylidene) ) Sorbitol, 1,3,2,4-di (pn-propylbenzylidene) sorbitol, 1,3,2,4-di (pi-propylbenzylidene) sorbitol, 1,3,2,4-di (pn-butyl) Benzylidene) sorbitol, 1,3,2,4-di (ps-butylbenzylidene) sorbitol, 1,3,2,4-di (pt-butylbenzyl) Den) sorbitol, 1,3,2,4-di (2 ', 4'-dimethylbenzylidene) sorbitol, 1,3,2,4-di (p-methoxybenzylidene) sorbitol, 1,3,2,4- Di (p-ethoxybenzylidene) sorbitol, 1,3-benzylidene-2-4-p-chlorobenzylidene sorbitol, 1,3-p-chlorobenzylidene-2,4-benzylidenesorbitol, 1,3-p-chlorobenzylidene- 2,4-p-methylbenzylidene sorbitol, 1,3-p-chlorobenzylidene-2,4-p-ethylbenzylidene sorbitol, 1,3-p-methylbenzylidene-2,4-p-chlorobenzylidene sorbitol, 1, 3-p-ethylbenzylidene-2,4-p-chlorobenzylidenesorbitol and 1,3,2,4-
Di (p-chlorobenzylidene) sorbitol and combinations thereof can be exemplified. Among these, 1,3,2,4-dibenzylidene sorbitol, 1,3,2,4-di (p-methylbenzylidene) sorbitol, 1,3,2,4-di (p-ethylbenzylidene) sorbitol 1,3-p-chlorobenzylidene-2,4-p-methylbenzylidene sorbitol, 1,3,2,4-di (p-chlorobenzylidene) sorbitol and combinations thereof are preferred.

  Furthermore, as the nucleating agent, a metal salt of an aromatic carboxylic acid or a metal salt of an aliphatic carboxylic acid can be used. Specifically, an aluminum benzoate, an aluminum pt-butylbenzoate, a sodium adipate, thio Examples thereof include sodium phenecarboxylate and sodium pyrolecarboxylate.

An inorganic compound such as talc can also be used as a nucleating agent.
The nucleating agent as described above is contained in the polypropylene composition [A] in an amount of 0.001 to 10% by weight, preferably 0.01 to 5% by weight, particularly preferably 0.1 to 3% by weight. May be.

When the nucleating agent as described above is contained, the crystallization speed of the polypropylene composition is improved, the crystal particles can be refined during crystallization, and molding can be performed at a higher speed.

As other resins, thermoplastic resins or thermosetting resins can be used. Specifically, α-olefin homopolymers such as polyethylene and poly-1-butene, α-olefin copolymers, α-olefin copolymers, A copolymer of an olefin and a vinyl monomer, a modified olefin polymer such as maleic anhydride-modified polypropylene, nylon, polycarbonate, ABS, polystyrene, polyvinyl chloride, polyphenylene oxide, petroleum resin, phenol resin, and the like can be used.

Furthermore, the polypropylene composition according to the present invention may contain an inorganic filler.
As an inorganic filler, specifically,
Natural silicates or silicates such as fine powder talc, kaolinite, calcined clay, vilophyllite, sericite, wollastonite, carbonates such as precipitated calcium carbonate, heavy calcium carbonate, magnesium carbonate, aluminum hydroxide, hydroxide Hydroxides such as magnesium, oxides such as zinc oxide, zinc white, magnesium oxide, powdered fillers such as hydrous calcium silicate, hydrous aluminum silicate, hydrous silicic acid, anhydrous silicic acid and other synthetic silicic acid or silicates,
Flaky filler such as mica,
Basic magnesium sulfate whisker, calcium titanate whisker, aluminum borate whisker, sepiolite, PMF (Processed Mineral Fiber), zonotlite,
Fibrous fillers such as potassium titanate and elastadite,
Balun-like fillers such as glass balun and fly ash balun can be used.

Of these, fine powder talc is preferably used in the present invention, and in particular, the average particle size is 0.2.
Fine powder talc of ˜3 μm and further 0.2 to 2.5 μm is preferably used.
The talc preferably has a content of particles having an average particle size of 5 μm or more of 10% by weight or less, preferably 8% by weight or less.

The average particle diameter of talc can be measured by a liquid phase precipitation method.
In the present invention, among such talc, talc having an average value of aspect ratio (indicating a ratio of length or thickness in either length or width) of 3 or more, particularly 4 or more is preferably used.

  The inorganic filler used in the present invention, particularly talc, may be untreated or may be surface-treated in advance. As an example of this surface treatment, specifically, a chemical or physical treatment using a treatment agent such as a silane coupling agent, a higher fatty acid, a fatty acid metal salt, an unsaturated organic acid, an organic titanate, a resin acid, or polyethylene glycol. Is mentioned.

When an inorganic filler such as talc subjected to such surface treatment is used, a polypropylene composition excellent in weld strength, paintability, and moldability can be obtained.
Two or more inorganic fillers as described above may be used in combination. Moreover, in this invention, organic fillers, such as high styrenes, lignin, a re-rubber, can also be used with such an inorganic filler as needed.
[Example]
EXAMPLES Next, although an Example demonstrates this invention concretely, this invention is not limited to these Examples.
(Physical property measurement method)
[1-butene content]
^It calculated | required using < ¹³ > C-NMR.

[Intrinsic viscosity [η]]
Measured in 135 ° C. decalin and expressed in dl / g.
[Molecular weight distribution (Mw / Mn)]
The molecular weight distribution (Mw / Mn) was measured as follows using GPC-150C manufactured by Millipore.

The separation column is TSK GNH HT, the column size is 27 mm in diameter and 600 mm in length, the column temperature is 140 ° C., the mobile phase is o-dichlorobenzene (Wako Pure Chemical Industries) and BHT ( (Takeda Pharmaceutical) using 0.025 wt%, moving at 1.0 ml / min, sample concentration 0.1 wt%, sample injection volume 500 microliters,
A differential refractometer was used as a detector. Standard polystyrene, using a Tosoh Corporation on the molecular weight of Mw <1000 and ^{Mw> 4 × 10 6, 1000} < for Mw <4 × 10 ⁶ was used Pressure Chemical Corporation.

[B value]
The composition distribution B value is a ¹³ C-NMR spectrum of a sample in which about 200 mg of copolymer is uniformly dissolved in 1 ml of hexachlorobutadiene in a 10 mmφ sample tube, usually at a measurement temperature of 120 ° C. and a measurement frequency. Measured under measurement conditions of 25.05 MHz, spectrum width 1500 Hz, filter width 1500 Hz, pulse repetition time 4.2 sec, integration number 2000 to 5000 times, and calculated by obtaining P _E , P _o , and P _OE from this spectrum did.

[Triad Tacty City]
A ¹³ C-NMR spectrum was measured with a hexachlorobutadiene solution (based on tetramethylsilane), and 21.0 with respect to the total area (100%) of the peak appearing at 19.5 to 21.9 ppm.
The ratio (%) of the area of the peak appearing at ˜21.9 ppm was determined.

[Percentage of heterogeneous bonds based on 2,1-insertion]
Polymer, 30 , 1350 (1989)) with reference to ¹³ C-NMR spectrum by the method described above.

[Melting point (Tm)]
About 5 mg of sample is packed in an aluminum pan, heated to 200 ° C. at 10 ° C./minute, held at 200 ° C. for 5 minutes, then cooled to room temperature at 20 ° C./minute, and then endothermic when heated at 10 ° C./minute. Obtained from the curve. For the measurement, a DSC-7 type apparatus manufactured by Perkin Elmer was used.

[Crystallinity]
It was determined by X-ray diffraction measurement of a 1.0 mm thick press sheet that had passed at least 24 hours after molding.

[Heat seal strength]
The laminated film obtained in the following examples was tested as a sample.
After a laminated film formed of a polypropylene composition and stretched homopolypropylene is overlapped on the sides of the polypropylene composition and heat sealed at a temperature of ² mm / cm ² with a seal bar having a width of 5 mm for 1 second at each temperature. , Allowed to cool.

  Next, a test piece having a width of 15 mm was cut from the sample, and the temperature at which the strength reached 300 g / 15 mm when the seat heel part was peeled off at a crosshead speed of 200 mm / min was defined as the heat seal start temperature.

[Haze]
A film formed in accordance with ASTM D1003 was aged in an air oven at 50 ° C. for 1 day. The haze before and after aging was measured.

[Slip property]
A film formed in accordance with ASTM D1894 was aged in an air oven at 50 ° C. for 1 day. The static friction coefficient and dynamic friction coefficient before and after aging were measured.

[Blocking resistance]
Evaluation was performed according to ASTM D1893.
Cut the sample film for measuring (1) heat seal strength to a width of 10 cm and a length of 15 cm, and stack the surfaces on which the polypropylene composition is laminated. Leave in an air oven at 50 ° C. One day later, a sample was taken out, the peel strength was measured with a universal testing machine, and the peel strength per 1 cm was taken as a blocking value.

Below, the polypropylene and propylene-type elastomer used by the Example and comparative example of this invention are shown.
In the examples and comparative examples of the present invention, as polypropylene, the following polypropylene polymerized using a general-purpose solid titanium catalyst component was used.

Polypropylene-1; homopolymer of propylene (intrinsic viscosity [η]; 2.9 dl / g, DSC melting point; 164 ° C., crystallinity; 62%)
Polypropylene-2; propylene random copolymer (composition of propylene 96.4 mol%, ethylene 2.1 mol%, 1-butene 1.5 mol%, intrinsic viscosity [η]; 2.1 dl / g, DSC melting point; 142 ° C, crystallinity: 56%)
Next, synthesis examples of catalyst components used in producing the propylene-based elastomer [B] and production examples of the propylene-based elastomer [B] are shown. Table 3 shows the characteristics of the propylene-based elastomer (PBR) obtained in the production examples.
[Synthesis Example 1]
Synthesis of rac-dimethylsilylene-bis {1- (2-ethyl-4-phenylindenyl)} zirconium dichloride [Synthesis of 3- (2-biphenylyl) -2-ethylpropionic acid]
To a 500 ml 4-neck round bottom flask (stirrer, Dimroth condenser, dropping funnel, equipped with thermometer) was added 13.46 g (120 mmol) of potassium tert-butoxide, 100 ml of toluene and 20 ml of N-methylpyrrolidone, and the mixture was added in a nitrogen atmosphere. A solution prepared by dissolving 20.7 g (110 mmol) of diethyl ethylmalonate in 50 ml of toluene was added dropwise while heating to ° C. After completion of the dropwise addition, the reaction was carried out at the same temperature for 1 hour. Then 2-phenylbenzyl bromide at the same temperature 20.
A solution of 27 g (100 mmol) dissolved in 30 ml of toluene was added dropwise. After completion of the dropwise addition, the temperature was raised and refluxed for 2 hours. The reaction mixture was poured into 200 ml of water, and 2N-HCl was added to pH = 1. The organic phase was separated and the aqueous phase was extracted three more times with 100 ml of toluene. The combined organic phases were washed with saturated brine until neutral and dried over anhydrous Na ₂ SO ₄ . The solvent was concentrated under reduced pressure to obtain 36.7 g of a yellow-orange liquid concentrate.

In a 1 liter 4-neck round bottom flask (stirrer, Dimroth condenser, dropping funnel, equipped with thermometer), potassium hydroxide 67.3 g (1.02 mol) and methanol aqueous solution 160 ml (methanol / water = 4/1 (= v / V)) was added. A solution prepared by dissolving the above concentrate in 50 ml of methanol aqueous solution (methanol / water = 4/1 (= v / v)) was added dropwise in a nitrogen atmosphere at room temperature. After dropping, the temperature was raised and refluxed for 4 hours. Then, it cooled to room temperature and filtered the depositing solid. The filtrate was dissolved in water, acidified with sulfuric acid (pH = 1), and extracted five times with 100 ml of methylene chloride. The combined organic phases were dried over anhydrous Na ₂ SO ₄ . The solvent was concentrated under reduced pressure to obtain 24.2 g of a white solid product.

Next, 24.2 g of the above white solid, 56 ml of acetic acid, 37 ml of water and 13.1 ml of concentrated sulfuric acid are added to a 300 ml 3-neck round bottom flask (stirrer chip, Dimroth condenser, with thermometer), and refluxed in a nitrogen atmosphere for 6 hours. It was. After completion of the reaction, acetic acid was distilled off under reduced pressure, 50 ml of water was added, and the mixture was extracted 3 times with 50 ml of methylene chloride. The combined organic phases were washed with 50 ml of saturated brine and then dried over anhydrous Na ₂ SO ₄ . The solvent was distilled off under reduced pressure, and the residue was separated and purified by silica gel chromatography (development with hexane / ethyl acetate = 2/1 → 1/1 volume part) to obtain a white solid 13.7 (yield: 54%). ). The physical properties of the obtained product are shown below.

FD-MS: 254 (M ⁺ )
mp. : 91.2-94.0 ° C
NMR (CDCl ₃ , 90 Hz):
δ = 0.71 (t, J = 7.2 Hz, 3H, CH ₃ );
1.16 to 1.58 (m, 2H);
2.32 (bquin, J = 7.0 Hz, 1H,>CH−);
2.61-2.99 (m, 2H);
6.89-7.47 (m, 9H)
IR (KBr disk): 1696 cm ⁻¹ (ν _{C = O} )
[Synthesis of 3- (2-biphenylyl) -2-ethylpropionyl chloride]
3-ml (2-biphenylyl) -2-ethylpropionic acid 13.3 g (52.4 mmol) and thionyl chloride 25.9 ml in a 100 ml 3-neck round bottom flask (stirrer tip, Dimroth condenser, thermometer, NaOH trap) (355 mmol) and 2.
Heated to reflux for 5 hours. After completion of the reaction, unreacted thionyl chloride was distilled under reduced pressure to obtain 15.2 g of a crude product as a yellow-orange liquid. This acid chloride was used in the next reaction without further purification. The physical properties of the obtained product are shown below.

IR (Neat): 1786 cm ⁻¹ (ν _{c = o} )
[Synthesis of 4-ethyl-2-phenyl-1-indanone]
To a 200 ml 3-neck round bottom flask (stirrer tip, Dimroth condenser, dropping funnel, thermometer, NaOH trap) was added 8.04 g (60.3 mmol) of anhydrous aluminum chloride and 50 ml of carbon disulfide. A solution of 15.2 g (52.4 mmol) of 3- (2-biphenylyl) -2-ethylpropionyl chloride obtained above in an atmosphere was added dropwise in 21 ml of carbon disulfide. After completion of the dropwise addition, the internal temperature was raised to room temperature and reacted for 1 hour. The reaction solution was decomposed by pouring into 200 ml of ice water and extracted twice with 100 ml of ether. The combined organic phases were washed with 100 ml saturated NaHCO ₃ water and then with 100 ml saturated brine and dried over anhydrous Na ₂ SO ₄ . The solvent was distilled off under reduced pressure, and the residue was separated and purified by silica gel chromatography (development with hexane / ethyl acetate = 10/1 volume part) to obtain 10.8 g of the desired product as a yellow solid (yield: 88%). . The physical properties of the obtained product are shown below.

NMR (CDCl ₃ , 90 Hz):
δ = 0.98 (t, J = 7.2 Hz, 3H, CH ₃ );
1.60-2.20 (m, 2H);
2.42-2.82 (m, IH,>CH-);
2.80 (dd, J = 3.8 Hz, 16.5 Hz, 1H);
3.36 (dd, J = 7.6 Hz, 16.5 Hz, 1H);
7.09 to 7.91 (m, 8H)
IR (Neat): 1705 cm ⁻¹ (ν _{C = O} )
[Synthesis of 2-ethyl-1-hydroxy-4-phenylindane]
To a 200 ml 3-neck round bottom flask (stirrer tip, Dimroth condenser, dropping funnel, equipped with thermometer) were added 0.85 g (22.6 mmol) of sodium borohydride and 28 ml of ethanol, and 2-ethyl at room temperature under a nitrogen atmosphere. -4-phenyl-1-indanone 10.6 g (
45.1 mmol) in 20 ml ethanol was added dropwise. After completion of dripping
The temperature was raised to 50 ° C., and the reaction was further continued for 3.5 hours. After the reaction, the reaction mixture was cooled, and unreacted sodium borohydride was decomposed by adding acetone dropwise. Next, the reaction mixture was concentrated under reduced pressure, and extracted by adding 50 ml of water and 50 ml of ether. After separating the organic phase, the aqueous phase was extracted twice with 50 ml of ether. The combined organic phases were washed with 100 ml of saturated brine and dried over anhydrous Na ₂ SO ₄ . The solvent was distilled off under reduced pressure to give a viscous pale yellow liquid target product (a mixture of two isomers).
67 g was obtained (yield: 99%). The physical properties of the obtained product are shown below.

NMR (CDCl ₃ , 90 Hz):
δ = 1.02 (t, J = 7.1 Hz, 3H, CH ₃ );
1.31-3.28 (m, 5H);
4.86, 5.03 (each d, each J = 6.4 Hz,
J = 5.1 Hz, combined IH,>CH—O—);
7.10-7.66 (m, 8H)
IR (Neat): 3340 cm ⁻¹ (ν _OH )
[Synthesis of 2-ethyl-4-phenylindene]
To a 300 ml 4-neck round bottom flask (stirrer tip, dropping funnel, equipped with thermometer), 9.78 g (41.3 mmol) of 2-ethyl-1-hydroxy-4-phenylindane and 17.2 ml (123.8 mmol) of triethylamine ), 0.25 g (2.1 mmol) of 4-dimethylaminopyridine and 98 ml of methylene chloride were added. Under ice cooling, a solution of 6.4 ml (82.5 mmol) of methanesulfonyl chloride in 6.5 ml of methylene chloride was slowly added dropwise in a nitrogen atmosphere. After completion of the dropwise addition, the reaction was further continued at the same temperature for 3.5 hours. The reaction mixture is ice water 250
After pouring into ml, the organic phase was separated and the aqueous phase was extracted twice more with 50 ml of methylene chloride. The combined organic phases were washed with saturated aqueous NaHCO ₃ and then with saturated brine, followed by anhydrous Na ₂ SO ₄
And dried. The solvent was distilled off under reduced pressure, and the residue was separated and purified by silica gel chromatography (developed with hexane) to obtain 6.56 g of the desired product (a mixture of two isomers) as a pale yellow liquid (yield: 73%). . The physical properties of the obtained product are shown below.

NMR (CDCl ₃ , 90 MHz):
δ = 1.20 (t, J = 7.6 Hz, 3H, CH ₃ );
2.49 (q, J = 7.6 Hz, 2H);
3.41 (s, 2H);
6.61, 6.72 (each bs, combined 1H);
7.09-8.01 (m, 8H)
[Synthesis of dimethylsilylene-bis (2-ethyl-4-phenylindene)]
In a 200 ml-3 neck round bottom flask (stirrer tip, Dimroth condenser, dropping funnel, equipped with thermometer), 2-ethyl-4-phenylindene (5.0 g, 22.8 mmol) and copper thiocyanate (80 mg, 0.63 mmol) Then, 15.7 ml (25.1 mmol) of a 1.6 M concentration n-butyllithium hexane solution was slowly added dropwise under ice cooling in a nitrogen atmosphere. After completion of the dropwise addition, the temperature was raised to room temperature and the reaction was further continued for 1 hour. Next, a solution obtained by dissolving 1.52 ml (12.6 mmol) of dimethyldichlorosilane in 4.5 ml of anhydrous ether was slowly added dropwise. After completion of the dropwise addition, the reaction was further continued at room temperature for 12 hours. The reaction mixture was filtered through celite, and the filtrate was poured into 50 ml of saturated aqueous ammonium chloride. After separating the organic phase, the aqueous phase was extracted with 50 ml of ether. The combined organic phases were washed with saturated brine and dried over anhydrous Na ₂ SO ₄ . The solvent was distilled off under reduced pressure, and the residue was separated by silica gel column chromatography (development with hexane → hexane / methylene chloride = 20/1 part by volume) to give the desired product (mixture of two isomers) as a pale yellow solid. 4.5 g was obtained (yield 80%). The physical properties of the obtained product are shown below.

NMR (CDCl ₃ , 90 Hz):
δ = −0.23, −0.17 (s, respectively 6H, Si—CH ₃ );
1.12, 1.19 (each t, each J = 7.4 Hz,
Combined 6H, CH ₃ );
2.44, (bq, J = 7.4 Hz, 4H);
3.81 (s, 2H,>CH-Si-);
6.75 (bs, 2H, 3-H-Ind);
6.88-7.74 (m, 16H)
[Synthesis of rac-dimethylsilylene-bis {1- (2-ethyl-4-phenyl-1-indenyl)} zirconium dichloride]
In a 50 ml 3-neck round bottom flask (stirrer tip, ball-filled condenser, dropping funnel, equipped with thermometer), 0.84 g (1.69 mmol) of dimethylsilylene-bis (2-ethyl-4-phenylindene) was added in an argon atmosphere. Add 17 ml of anhydrous ether and add 1.58M n-
2.25 ml (3.56 mmol) of butyllithium in hexane was slowly added dropwise. After dropping, the reaction was further continued for 13.5 hours. The obtained reaction solution was dried ice to acetone bath.
After cooling to 70 ° C., 0.395 g (1.69 mmol) of ZrCl ₄ powder was gradually added. After the addition was complete, the mixture was left overnight with continued stirring. Next, the solvent was distilled off under reduced pressure at room temperature. After adding 30 ml of methylene chloride, insoluble matters were filtered, and the filtrate was concentrated and crystallized at room temperature. The precipitated solid was filtered, washed twice with 3 ml of anhydrous ether, and dried under reduced pressure to obtain 0.17 g of the desired product as an orange-yellow solid (yield: 15%). The physical properties of the obtained product are shown below.

NMR (CDCl ₃ , 90 MHz):
δ = 1.09 (t, J = 7.3 Hz, 6H, CH ₃ );
1.34 (s, 6H, Si- CH 3);
2.46 (quin, J = 7.3 Hz, 2H);
2.73 (quin, J = 7.3 Hz, 2H);
6.96 (s, 2H, 3-H-Ind);
699-7.88 (m, 16H)
[Production Example 1]
A 2 liter autoclave thoroughly purged with nitrogen is charged with 900 ml of hexane and 60 g of 1-butene, 1 mmol of triisobutylaluminum is added, the temperature is raised to 70 ° C., propylene is supplied, and the total pressure is 7 kg / cm ^2. -G, 0.330 mmol of methylaluminoxane and rac-dimethylsilylene-bis {1- (2-methyl-4-phenyl-1-indenyl)} zirconium dichloride synthesized in the same manner as in the above synthesis example as Zr atom In conversion, 0.001 mmol was added, and propylene was continuously supplied to carry out polymerization for 30 minutes while maintaining the total pressure at 7 kg / cm ² -G. After the polymerization, the polymer was degassed and the polymer was recovered in a large amount of methanol and dried under reduced pressure at 110 ° C. for 12 hours.

The obtained polymer was 39.7 g, polymerization activity was 79 kg-polymer / mmol Zr · hr, 1-butene content was 26.4 mol%, [η] = 1.60 dl / g, melting point was 88.4 ° C. The proportion of heterogeneous bonds based on 2,1-insertion was about 0.02%. Other physical properties are shown in Table 3.
[Production Example 2]
A 2 liter autoclave thoroughly purged with nitrogen is charged with 900 ml of hexane and 60 g of 1-butene, 1 mmol of triisobutylaluminum is added, the temperature is raised to 70 ° C., propylene is supplied, and the total pressure is 7 kg / cm ^2. -G, 0.330 mmol of methylaluminoxane, and rac-dimethylsilylene-bis {1- (2-methyl-4-phenyl-1-indenyl)} zirconium dichloride synthesized in the same manner as in the above synthesis example as a Zr atom. In conversion, 0.001 mmol was added, and propylene was continuously supplied to carry out polymerization for 30 minutes while maintaining the total pressure at 7 kg / cm ² -G. After the polymerization, the polymer was degassed and the polymer was recovered in a large amount of methanol and dried under reduced pressure at 110 ° C. for 12 hours.

The obtained polymer was 45.2 g, the polymerization activity was 90 kg-polymer / mmol Zr · hr, the 1-butene content was 20.2 mol%, [η] = 1.90 dl / g, the melting point was 101.5 ° C. The proportion of heterogeneous bonds based on 2,1-insertion was about 0.02%.
[Production Example 3]
A 2 liter autoclave thoroughly purged with nitrogen is charged with 950 ml of hexane and 30 g of 1-butene, 1 mmol of triisobutylaluminum is added, the temperature is raised to 70 ° C., propylene is supplied, and the total pressure is 7 kg / cm ^2. -G, 0.330 mmol of methylaluminoxane, and rac-dimethylsilylene-bis {1- (2-methyl-4-phenyl-1-indenyl)} zirconium dichloride synthesized in the same manner as in the above synthesis example at the Zr atom. In conversion, 0.001 mmol was added, and propylene was continuously supplied to carry out polymerization for 30 minutes while maintaining the total pressure at 7 kg / cm ² -G. After the polymerization, the polymer was degassed and the polymer was recovered in a large amount of methanol and dried under reduced pressure at 110 ° C. for 12 hours.

The obtained polymer was 52.1 g, and the polymerization activity was 104 kg-polymer / mmol Zr.
Hr, 1-butene content is 13.9 mol%, [η] = 2.51 dl / g, melting point is 116.3 ° C, and the proportion of heterogeneous bonds based on 2,1-insertion is about 0.02% Met.
[Comparative Production Example 4]
A 2 liter autoclave thoroughly purged with nitrogen is charged with 830 ml of hexane and 100 g of 1-butene, 1 mmol of triisobutylaluminum is added, the temperature is raised to 70 ° C., propylene is supplied, and the total pressure is 7 kg / cm ^2. -G, 1 mmol of triethylaluminum and 0.005 mmol of titanium catalyst supported on magnesium chloride in terms of Ti atoms are added, and propylene is continuously fed to maintain the total pressure at 7 kg / cm ² -G. The polymerization was carried out for 30 minutes. After the polymerization, the polymer was degassed and the polymer was recovered in a large amount of methanol and dried under reduced pressure at 110 ° C. for 12 hours.

  The obtained polymer was 33.7 g, the polymerization activity was 14 kg-polymer / mmol Ti · hr, the 1-butene content was 25.3 mol%, [η] = 1.89 dl / g, and the melting point was 110.0 ° C. The proportion of heterogeneous bonds based on 2,1-insertion was below the detection limit.

[ Reference Examples 1 to 6 ]
Polypropylene-1 is melted in an extruder and extruded from a T-die at a resin temperature of 250 ° C., cooled and solidified into a sheet, and then passed through a heating roll to be stretched in the longitudinal direction so that the stretch ratio is 5 times. Thus, a uniaxial sheet of polypropylene-1 (crystalline polypropylene) was formed.

Using this uniaxially stretched sheet of polypropylene as a base material layer, on one side of this sheet,
Each polypropylene composition layer as shown in Table 4 was laminated as follows.
The polypropylene composition layer shown in Table 4 was melt-kneaded with an extruder different from the above, and a molten film extruded at a resin temperature of 230 ° C. with another T-die in the molten state was laminated on the base material layer. A base material layer (thickness: 22 μm) made of crystalline polypropylene biaxially stretched by continuously passing the laminated sheet through a heated tenter and stretching it in the transverse direction so that the stretching ratio is 10 times. And the laminated film which consists of a layer (thickness 3 micrometers) which consists of a polypropylene composition extended | stretched uniaxially was obtained.

Table 4 shows the results of evaluating the obtained laminated film as described above.
[Comparative Reference Examples 1 and 2]
In Reference Example 1 , a laminated film was obtained in the same manner as Reference Example 1 except that a polypropylene composition as shown in Table 4 was used. The results are shown in Table 4.

[Synthesis Example 2]
Synthesis of rac-dimethylsilylene-bis {1- (4-isopropyl-2,7-dimethylindenyl)} zirconium dichloride [Synthesis of (4-isopropyl-2,7-dimethyl) indene (compound (1))]
In a 1 liter reactor sufficiently purged with nitrogen, 90 g (0.67 mol) of aluminum chloride,
150 ml of carbon disulfide was charged, and a solution prepared by mixing 47 ml (0.30 mol) of p-cymene and 33 ml (0.3 mol) of methacryloyl chloride with 30 ml of carbon disulfide was added dropwise at 20 to 25 ° C. After reacting at room temperature for 12 hours, the mixture was added to 1 kg of ice and extracted with ether. The obtained ether solution was washed with saturated aqueous sodium hydrogen carbonate, the ether layer was further washed with water, and the ether layer was concentrated to obtain 68 g of oil. This oil was purified by silica gel column chromatography (developing solvent: n-hexane) and a mixture of 2,4-dimethyl-7-propyl-1-indanone and 2,7-dimethyl-4-isopropyl-1-indanone ( 42 g of mixture (1) was obtained (yield: 67%).

A 1 liter reactor thoroughly purged with nitrogen was charged with 2.82 g (0.075 mol) of lithium aluminum hydride and 200 ml of ether, into which 36.5 g (0.18 mol) of mixture (1) and 150 ml of ether were added. The mixture was added dropwise under ice cooling. After completion of dropping, the mixture was stirred at room temperature for 30 minutes and then refluxed for 1 hour. After completion of the reaction, normal post-treatment was performed and ether extraction was performed. The obtained ether solution was washed with saturated aqueous sodium hydrogen carbonate and water and dried over anhydrous sodium sulfate, and then the ether layer was concentrated to obtain 36 g of a solid. This solid was reslurried with 100 ml of n-hexane to obtain 30 g of a mixture of 2,4-dimethyl-7-isopropyl-1-indanol and 2,7-dimethyl-4-isopropyl-1-indanol (mixture (2)). It was. (Yield: 82%)
A 1 liter reactor sufficiently purged with nitrogen was charged with 25 g (0.12 mol) of the mixture (2) and 500 ml of benzene, and 50 mg (0.55 mmol) of paratoluenesulfonic acid monohydrate was added to the reactor. Reflux for hours. After completion of the reaction, the mixture was poured into 300 ml of saturated aqueous sodium hydrogen carbonate, washed with the organic layer, and then dried over anhydrous sodium sulfate. The organic layer was concentrated, and the obtained oil was distilled (bp .: 90 ° C./1 mmHg) to obtain 20 g of the desired compound (1) (yield: 90%).

[Synthesis of 1,1'-dimethylsilylene-bis (4-isopropyl-2,7-dimethylindene) (compound (2))]
Into a 200 ml reactor sufficiently purged with nitrogen, 9.5 g (51 mmol) of compound (1), 7.7 ml (51 mmol) of tetramethylethylenediamine and 60 ml of diethyl ether were charged and cooled to −10 ° C. To this solution was added n-butyllithium hexane solution (51 mmol). After heating up to room temperature, it cooled again to -10 degreeC, and dimethyldichlorosilane 3.1ml (25.5 mmol) was dripped in 30 minutes, and reaction was performed for 1 hour. After completion of the reaction, the reaction mixture was added to 40 ml of a saturated aqueous ammonium chloride solution, extracted with n-hexane, washed with water and dried over magnesium sulfate. The yellow oil obtained by removing the salt and concentrating the organic layer under reduced pressure was purified by silica gel column chromatography (developing solvent: n-hexane) to obtain 5.4 g of Compound (2) as a colorless amorphous substance ( Yield: 50%).

[Synthesis of rac-dimethylsilylene-bis {1- (4-isopropyl-2,7-dimethylindenyl)} zirconium dichloride (compound (3))]
5.4 g (12.6 mmol) of compound (2) and 100 ml of tetrahydrofuran were charged into a 300 ml reactor sufficiently purged with nitrogen, cooled to −78 ° C., and stirred. To this, 16 ml of n-butyllithium (n-hexane solution, 1.58N, 25.2 mmol) was added dropwise over 20 minutes, and the mixture was further stirred for 1 hour while maintaining the temperature to prepare an anion solution. Thereafter, the temperature was slowly raised to room temperature.

At the same time, 100 ml of tetrahydrofuran was charged into a 300 ml reactor sufficiently purged with nitrogen, cooled to −78 ° C., and stirred. To this was slowly added 2.94 g (12.6 mmol) of zirconium tetrachloride, and then the temperature was raised to room temperature. The above-mentioned anion solution was dropped into this over 30 minutes and stirred at room temperature for 12 hours. After completion of the reaction, the mixture was concentrated under reduced pressure, and the precipitated solid was washed three times with 300 ml of hexane to remove insoluble matters. The obtained hexane solution was concentrated to about 50 ml and cooled at 6 ° C. for 12 hours. When the obtained solid was analyzed by ¹ H-NMR, it was 1.78 g of a mixture of racemic and meso forms (4: 1) (yield: 24%). To this mixture, 100 ml of hexane was added, and recrystallization was performed again to obtain yellow columnar crystals 0.2 of compound (3).
2 g was obtained (yield: 3%). In addition, the result of FD mass spectrometry of the compound (3) was 588 (M ⁺ ).

[Production Example 5]
A 2 liter autoclave fully purged with nitrogen was charged with 900 ml of hexane, 1 mmol of triisobutylaluminum was added, the temperature was raised to 70 ° C., ethylene was fed and pressurized to 2.0 kg / cm ² , and propylene was fed. The total pressure is 8 kg / cm ² -G, 0.3 mmol of methylaluminoxane, rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-isopropylindenyl)} zirconium dichloride is converted to Zr atoms. 0.0
Polymerization was carried out for 10 minutes while maintaining a total pressure of 8 kg / cm ² -G by adding 01 mmol and continuously feeding propylene. After the polymerization, the polymer was degassed and the polymer was recovered in a large amount of methanol and dried under reduced pressure at 110 ° C. for 10 hours.

The obtained polymer was 16.8 g, the polymerization activity was 16.8 kg polymer / mmol Zr, the intrinsic viscosity [η] was 1.7 dl / g, the ethylene content was 8.5 mol%, The triad tacticity of the propylene chain consisting of the tail bond is 95.6%, the proportion of regioregular units based on 2,1-insertion of the propylene monomer is 0.62%, 3-The percentage of irregular units based on insertion was 0.05% or less.
The results are shown in Table 6.

In Production Example 5 and Production Example 6, the stereoregularity (mm fraction) is about 5 mg φ in a mixed solvent of 0.5 ml o-dichlorobenzene (or hexachlorobutadiene) and 0.1 ml deuterated benzene. After complete dissolution in an NMR sample tube at about 120 ° C., measurement is performed by GX500 NMR (measurement nuclide; ¹³ C, measurement mode; proton complete decoupling, measurement temperature: 120 ° C.) manufactured by JEOL. It was.

Further, the proportion of the heterogeneous bond based on the 2,1-insertion and 1,3-insertion of the propylene monomer present in the propylene chain was determined from the following formula by ¹³ C-NMR spectrum.

Where Iαα is the total area of the αα carbon peak (resonates around 42.0 ppm and 46.2 ppm), Iαβ is the total area of the αβ carbon peak (resonates around 30.2 ppm and 35.6 ppm), and Iαδ is αδ It is the area of the carbon peak (resonates around 37.1 ppm). The peaks such as αα were named according to Carman's classification (CJ Carman and CE Wilkes, Rubber Chem. Technol., 44, 781 (1971)).
[Production Example 6]
In a gas flow-through glass polymerizer with an internal volume of 500 ml that has been sufficiently purged with nitrogen, 250 ml of toluene is placed, cooled to 0 ° C., propylene is passed at 140 liter / hr, ethylene is passed at 60 liter / hr, and the system is fully Saturated. Next, 0.25 mmol of triisobutylaluminum, 0.5 mmol of methylaluminoxane in terms of Al atom, rac-dimethylsilylene-bis {1- (2-ethyl-4-phenylindenyl)} zirconium dichloride is converted to Zr. In terms of atoms, 0.001 mmol was added, and polymerization was carried out for 10 minutes while maintaining the system at 0 ° C. The polymerization was stopped by adding a small amount of methanol. The polymerization suspension was placed in 2 liters of methanol to which a small amount of hydrochloric acid had been added, stirred well, and filtered. The polymer was washed with a large amount of methanol and dried at 80 ° C. for 10 hours.

  The obtained polymer was 5.62 g, and the polymerization activity was equivalent to 33.7 kg-polymer / mmol Zr · hr. The ethylene content is 3.9 mol%, [η] is 1.80 dl / g, Mw / Mn is 2.15, triad tacticity is 99.3%, The ratio of position irregular units based on 1-insertion was 0.12%, and the ratio of position irregular units based on 1,3-insertion of propylene monomer was less than the lower detection limit (less than 0.03). The results are shown in Table 6.

[Examples 1 and 2, Reference Example 7-8]
A laminated film was molded and evaluated in the same manner as in Reference Examples 1 to 6 using Polypropylene-1, Polypropylene-2 and the propylene / ethylene elastomer obtained in Production Examples 5 to 6 . The results are shown in Table 7.

Claims (2)

[A] polypropylene; 5 to 25 % by weight;
[B] The following propylene-based elastomer [B-2] ; a polypropylene composition comprising 95 to 75 % by weight:
[B-2] (1) Containing a structural unit derived from propylene in an amount of 50 to 95 mol% and a structural unit derived from ethylene in an amount of 5 to 50 mol%,
(2) Measured with a ¹³ C-NMR spectrum of a propylene unit chain unit bonded head-to-tail.
Triad tacticity is over 90%,
(3) Propylene monomer in all propylene structural units measured by ¹³ C-NMR
% Of position irregular units based on 2,1-insertion of
(4) A propylene / ethylene elastomer having an intrinsic viscosity measured in decalin at 135 ° C. of 0.1 to 12 dl / g.   The [A] polypropylene is a random copolymer of propylene and another olefin containing a unit derived from an olefin other than propylene in an amount of 10 mol% or less. Polypropylene composition.