JP5010802B2 - Highly rigid polypropylene-based composition and production method - Google Patents

Description

  The present invention relates to a high-rigidity propylene-based composition and a process for producing the same, and more specifically, improved rigidity and heat resistance containing a low-molecular weight polypropylene component having specific properties and a specific polypropylene component having a higher molecular weight. The present invention relates to a highly rigid polypropylene composition and a method for producing the same.

  Conventionally, polypropylene is excellent in rigidity and strength, and has been widely used for various injection molding, blow molding, film, sheet molding methods and the like. However, it cannot be said that the rigidity and strength are still sufficient depending on the application, and many studies have been made so far for further improving the rigidity of polypropylene. Among them, the method for increasing the rigidity by controlling the molecular weight of polypropylene is excellent in terms of cost in that it is not necessary to use an expensive additive substance, and is preferable from the viewpoint of recyclability that has become important in recent years. It can be said.

  Examples of the composition whose rigidity is improved by controlling the molecular weight include, for example, a high molecular weight polypropylene having an isotacticity of 97.5 wt% or more having an intrinsic viscosity of 1.8 to 10 and an intrinsic viscosity of 0.6 to 1.2. It is disclosed that a composition for producing a low molecular weight polypropylene by two-stage polymerization is excellent in rigidity (for example, see Patent Document 1). In addition, it is disclosed that polypropylene produced by polymerizing propylene in multiple stages and having a polymer produced in the first stage and the second and subsequent stages such that the MFR satisfies a specific relational expression is excellent in rigidity (for example, (See Patent Document 2). However, these methods require a large amount of components having extremely high intrinsic viscosity or extremely low MFR. In such a case, a decrease in fluidity is unavoidable, and good fluidity such as injection molding is required. It cannot be used in fields where safety is required.

On the other hand, a low molecular weight component having a molecular weight of 2,000 to 26,000 in polypropylene is a component that contributes to improvement in rigidity, and a method for controlling this amount within a specific range is disclosed (for example, Patent Document 3). reference.). However, when a Ziegler-Natta catalyst used conventionally is used, the lower the molecular weight, the lower the stereoregularity of the polypropylene, and as a result, more soft components that lower the rigidity. Therefore, in this method, the improvement in rigidity is not sufficient, or in order to obtain a high rigidity, it is necessary to extract a solvent-soluble component or use a thermal decomposition method to obtain a low molecular weight component, which is costly. There was a problem of getting higher.
In addition, a polyolefin component having a narrow molecular weight distribution, a molecular weight of 1,000 to 50,000 and a melting point of 120 to 160 ° C., and a polyolefin component having a molecular weight of 100,000 or more (the olefin component constituting this component is a composition of a low molecular weight polyolefin component) A technique for obtaining a highly rigid polyolefin is disclosed (for example, see Patent Literature 4). However, in this technique, since the stereoregularity of the low molecular weight component is not yet sufficiently high, a large amount of a low molecular weight component having a molecular weight of 1,000 to 50,000 is used in order to sufficiently increase the rigidity of the composition. There is a need. When a large amount of low molecular weight component is used, there is a problem that the material becomes extremely brittle.

Furthermore, 90 to 99.9 parts by weight of a high molecular weight polypropylene having an intrinsic viscosity of 1.0 dl / g or more, an mmmm Pendant fraction having an intrinsic viscosity of 0.1 to 0.8 dl / g and measured by ¹³ C-NMR Has disclosed a polypropylene composition comprising 0.1 to 10 parts by weight of a low molecular weight polypropylene having a N of 93% or more (for example, see Patent Document 5). In this technique, since the blending amount of the low molecular weight polypropylene is small, the effect of improving the rigidity is not sufficient. Further, in this technique, a manufacturing method by melt-kneading is used to obtain the effect of improving the rigidity. At this time, if the mixing proceeds sufficiently uniformly, the effect of improving the rigidity may not be obtained. It is said. The reason for this has not been clarified, but one presumption is that the low-molecular-weight components are present to some extent inhomogeneously, resulting in non-uniform regions of high and low crystallization rates in the composition. Since the region having high crystallinity and high rigidity exists specifically, it can be interpreted that the rigidity is improved. However, such material non-uniformity not only adversely affects transparency and moldability, but also may adversely affect stretchability and toughness.
JP 59-172507 A JP-A-1-254706 JP-A-4-356511 JP-A-6-9829 JP-A-6-248133

  In view of the circumstances as described above, an object of the present invention is to provide a high-rigidity polypropylene composition excellent in rigidity, particularly rigidity and heat resistance, and a method for producing the same.

  As a result of diligent studies to solve the above-mentioned problems, the present inventors have a sufficiently high stereoregularity as a low molecular weight component having an effect of improving rigidity and satisfy certain specific physical properties. Even when the proportion of low molecular weight components in the entire material is relatively low, the polypropylene resin has sufficient rigidity, especially rigidity and heat resistance. The inventors have found that an effect of increasing can be obtained, and have reached the present invention.

That is, according to the first aspect of the present invention, the following (a-i) ~ possess the characteristics of (a-iv), propylene polymers produced by metallocene catalyst (a) 10 to 50 wt%, And a propylene homopolymer or propylene / α-olefin copolymer (b) having the following properties (b-i) to (b-ii): 90 to 50% by weight A composition is provided.
Component (a): Propylene polymer (ai) Weight average molecular weight Mw _(a) obtained by gel permeation chromatography (GPC ₎ is 1,000-60,000 (a-ii) Molecular weight distribution ( Mw _(a) / Mn _(a) ) is 1.5 to 4.0 (a-iii) Melting point Tm _(a) obtained by differential scanning calorimetry (DSC) is a relational expression of the following formula (1) Satisfying 155 × (Mw _(a) −582) / (Mw _(a) −99) ≦ Tm _(a) (1)
(A-iv) mm of propylene chain portion obtained by ¹³ C-NMR is greater than 98.0% Component (b): propylene homopolymer or propylene / α-olefin copolymer (bi ) The weight average molecular weight Mw _(b) obtained by GPC is 60,000 to 1,000,000 (b-ii) The melting point Tm _(b) obtained by DSC is 120 to 170 ° C.

  According to the second invention of the present invention, in the first invention, the positional irregularity based on 2,1-insertion of component (a) is 0.01 to 2.00%, 1,3-insertion. A highly rigid polypropylene-based composition characterized in that the positional irregularity based on is 0.06 to 0.40% is provided.

Further, according to the third aspect of the present invention, in the invention of the first or 2, wherein the metallocene catalyst is characterized in that it consists of the following components (A), component (B) and component (C) A high stiffness polypropylene-based composition is provided.
Component (A): Transition metal compound represented by the following general formula (I)
Component (B): a solid component containing one or more selected from the following (b-1) to (b-4)
(B-1) A particulate carrier carrying an aluminum oxy compound
(B-2) Particulate carrier carrying an ionic compound or Lewis acid capable of reacting with component (A) to convert component (A) into a cation
(B-3) Solid acid fine particles
(B-4) Ion exchange layered compound
Component (C): Organoaluminum compound

  Further, according to the fourth aspect of the present invention, the component (b) is first melt-kneaded and then melted and kneaded in the melted component (b) by using a melt-kneader in at least two stages. There is provided a method for producing a high-rigidity polypropylene composition according to any one of the first to third aspects, wherein the component (a) is added to the composition and further melt-kneaded.

  According to a fifth aspect of the present invention, in the fourth aspect, the melt kneader is an extruder, and after the component (b) is fed and melt-kneaded upstream, the component (a ) Is introduced into the melt-kneaded component (b) from different feed ports and continuously melt-kneaded, thereby providing a method for producing a highly rigid polypropylene composition.

  The high-rigidity polypropylene composition of the present invention is a composition containing a low-molecular weight polypropylene component having specific properties and a specific polypropylene component having a higher molecular weight than that, and the ratio of the low-molecular weight component can be reduced. Compared with general polypropylene resins, it can be expected to have an effect of suppressing embrittlement of the resin, and since the high stereoregularity of the low molecular weight component will further improve the rigidity of the material and heat resistance. And improved rigidity, particularly rigidity and heat resistance.

  The present invention relates to a propylene polymer (a) having the following properties (ai) to (a-iv) and a propylene homopolymer or propylene-polymer having the following properties (bi) to (b-ii): A high-rigidity polypropylene composition containing an α-olefin copolymer (b) and a method for producing the same. Hereinafter, in order to describe the invention group in the present invention in detail, embodiments of the invention will be described in detail.

1. High Stiffness Polypropylene Composition (1) Component (a) Propylene Polymer The component (a) used in the high rigidity polypropylene composition of the present invention is propylene having the following properties (ai) to (ai). Based polymer. Component (a) is preferably a homopolymer of propylene because it is necessary to use one having extremely high melting point and stereoregularity. However, as long as various physical properties disclosed in the present invention are satisfied, carbon A copolymer obtained by copolymerizing a small amount of α-olefin of 2 to 10 excluding Formula 3 within a range of 3% by weight or less.

Characteristic (ai) Weight average molecular weight Mw _(a)
The weight average molecular weight Mw _(a) measured by gel permeation chromatography (GPC) of the component (a) is 1,000 to 60,000, preferably 5,000 to 50,000, more preferably. Is in the range of 8,000 to 45,000. If the range of Mw _(a) is lower than this, it is difficult to produce industrially, and the embrittlement of the whole material becomes large, which is not preferable. When exceeding this range, the effect of improving rigidity cannot be obtained.
The measurement by GPC is measured by a conventionally known method, and is obtained by conversion using a calibration curve with a standard sample having a known molecular weight.

Characteristic (a-ii) Molecular weight distribution The molecular weight distribution of component (a) is defined by the ratio of the weight average molecular weight Mw _(a) and the number average molecular weight Mn _(a) measured by gel permeation chromatography (GPC), The range is 1.5 to 4.0, preferably 1.8 to 3.7. When the molecular weight distribution is larger, it means that components having a molecular weight much larger or smaller than the molecular weight defined by the average molecular weight are produced, and these adversely affect physical properties such as rigidity. In addition, those having a molecular weight distribution smaller than the above range are practically difficult to produce.
Here, the measuring method of molecular weight and molecular weight distribution by GPC is as follows.
Apparatus: Waters GPC (ALC / GPC 150C)
Detector: MIRAN 1A IR detector manufactured by FOXBORO (measurement wavelength: 3.42 μm)
Column: AD806M / S (3 pieces) manufactured by Showa Denko KK
Mobile phase solvent: o-dichlorobenzene Measurement temperature: 140 ° C
Flow rate: 1.0 ml / min Injection volume: 0.2 ml
Sample preparation: Prepare a 1 mg / mL solution using ODCB (containing 0.5 mg / mL BHT) and dissolve at 140 ° C. for about 1 hour.
The baseline and section of the obtained chromatogram are performed as shown in FIG.
Further, the conversion from the retention capacity obtained by GPC measurement to the molecular weight is performed using a standard curve prepared in advance by standard polystyrene. Standard polystyrenes used are the following brands manufactured by Tosoh Corporation.
F380, F288, F128, F80, F40, F20, F10, F4, F1, A5000, A2500, A1000
A calibration curve is created by injecting 0.2 mL of a solution dissolved in ODCB (containing 0.5 mg / mL BHT) so that each is 0.5 mg / mL. The calibration curve uses a cubic equation obtained by approximation by the least square method.
The following numerical value is used for the viscosity formula [η] = K × M ^α used for conversion to molecular weight.
PS: K = 1.38 × 10 ⁻⁴ , α = 0.7
PP: K = 1.03 × 10 ⁻⁴ , α = 0.78

Characteristic (a-iii) Melting point Tm _(a)
The melting point Tm _(a) obtained by differential scanning calorimetry (DSC) of the component (a) is preferably as high as possible in order to increase the rigidity of the composition and increase the heat resistance. Therefore, the range of the melting point Tm _(a) of the component (a) needs to satisfy the following formula (1):
155 × (Mw _(a) −582) / (Mw _(a) −99) ≦ Tm _(a) (1)
Preferably, the following formula (2) is satisfied, and more preferably, the formula (3) is satisfied.
155 × (Mw _(a) −582) / (Mw _(a) −99) ≦ Tm _(a) ≦ 168 × (Mw _(a) −582) / (Mw _(a) −99) (2)
157 × (Mw _(a) −582) / (Mw _(a) −99) ≦ Tm _(a) ≦ 166 × (Mw _(a) −582) / (Mw _(a) −99) (3)
As a measuring method, a commercially available differential scanning calorimeter (DSC) was used, and a sample of 5.0 mg was taken, held at 200 ° C. for 5 minutes, and then crystallized to 40 ° C. at a rate of temperature decrease of 10 ° C./min. The melting peak temperature when melted at a heating rate of 10 ° C./min is defined as Tm _(a) (unit: ° C.).

The reason for defining Tm _(a) by the relational expression with the molecular weight is as follows.
Usually, the melting point of polypropylene is usually used as an index of the stereoregularity of molecules, but in reality it varies not only by the regularity of molecules but also by factors such as the thickness of lamellae. Is a well-known fact. In particular, when the molecular weight is small, the proportion of molecular ends in the material is relatively increased, and this increases the surface free energy of the crystalline lamella, so that the apparent melting point obtained by DSC or the like is the molecular rule. Decrease regardless of sex (see, for example, “Polypropylene Handbook” by Edward P. Moore Jr, Industrial Research Committee, 1998, P147). In the range of molecular weight as in the component (a) disclosed in the present invention, the stereoregularity of the component is defined by the melting point value obtained by DSC measurement at a normal temperature rising rate (about 10 to 30 ° C./min). This is quite inadequate, and the range must always be defined in consideration of the relationship with the molecular weight.

On the other hand, regarding the molecular weight and melting point of the crystalline polymer, according to Flory and Vrij (J. Am. Chem. Soc. 85, 3548 (1963)), or Wunderlich and Czornyj (Macromolecules 10, 906 (1977)), etc. Most simply, it is shown that it can be well described by the following relational expression.
Tm = Tm0 (x + a) / (x + b)
Here, x is the length of the chain and is a number proportional to the molecular weight, so the above equation can be rewritten as follows.
Tm = Tm0 (Mw + a ′) / (Mw + b ′)
Tm0 is a melting point when the molecular weight is assumed to be infinite under the adopted DSC measurement conditions. That is, equation (1) defines the melting point of the low molecular weight component in consideration of the relationship between the melting point and the molecular weight, and the coefficient 155 on the left side or the coefficient 168 on the right side of equation (1) is disclosed in the present invention. This corresponds to the melting point when the low molecular weight component is assumed to have a sufficiently high molecular weight with the same regularity. Other constants described in Equation (1) are obtained experimentally.
When the melting point of the component (a) is below the lower limit of this formula, the regularity of the low molecular weight component is insufficient, and an effective improvement effect of rigidity and heat resistance cannot be obtained. The melting point of the propylene polymer is preferably equal to or less than the value calculated by 168 × (Mw _(a) −582) / (Mw _(a) −99) because of difficulty in production thereof, and 166 × (Mw _{( a)} −582) / (Mw _(a) −99) or less is more preferable.

Characteristic (a-iv) mm of propylene chain portion by ¹³ C-NMR
For component (a), as described above, it is not sufficient to specify the regularity of the low molecular weight component, but it is not sufficient to specify the melting point, so it is also necessary to specify the isotactic index mm by ¹³ C-NMR. is there. The low molecular weight component of the present invention is required to have a mm larger than 98.0%, preferably 98.5% or more.
The mm fraction is the ratio of three propylene unit chains in which the direction of methyl branching in each propylene unit is the same among arbitrary three propylene unit chains composed of head-to-tail bonds in the polymer chain. This mm fraction is a value indicating that the three-dimensional structure of the methyl group in the polypropylene molecular chain is controlled isotactically, and the higher the value, the higher the level.

Here, the mm fraction is a value measured according to the following ¹³ C-NMR spectrum measurement method. ^{The 13} C-NMR spectrum was obtained by completely dissolving 250 mg of the sample in a 10 mmφ NMR sample tube in a solvent obtained by adding 0.5 ml of deuterated benzene as a lock solvent to 2 ml of o-dichlorobenzene. Measured by proton complete decoupling at ℃. The measurement conditions are a flip angle of 90 ° and a pulse interval of 15 seconds. For quantification of trace components, integration is performed 5,000 times or more using an NMR apparatus having a resonance frequency of carbon nuclei of 100 MHz or more. The chemical shift is a head-to-tail bond, and the methyl group of the third unit of the 5-unit propylene unit having the same methyl branching direction is set as 21.8 ppm, and the chemical shifts of other carbon peaks are based on this. . According to this standard, the peak based on the methyl group of the second unit in the three propylene unit chain represented by mm is in the range of 21.2 to 22.5 ppm, and the second unit unit in the three propylene unit chain represented by mr. The peak based on the methyl group in the range of 20.5 to less than 21.2 ppm, and the peak based on the methyl group of the second unit in the three propylene units chain represented by rr is less than 19.5 to 20.5 ppm Appears in the range of.
Here, mm, mr, and rr are each represented by the following chemical structure.

The mm fraction is calculated from the ratio of each structure of mm, mr, rr by the following formula.
mm fraction (%) = PPP [mm] / (PPP [mm] + PPP [mr] + PPP [rr]) × 100
However, PPP [mm], PPP [mr] and PPP [rr] represent the ratio of each structure of mm, mr and rr in each of the three linked propylene units linked head-to-tail, and the area of the region attributed to each peak It is evaluated from.

Here, when the polymer contains ethylene as a comonomer, the second unit (propylene unit) of the three chain (PPE) in which ethylene is bonded to the two propylene units in the mr region as a partial structure including an ethylene unit. Of the methyl group (PPE-methyl group) resonates (around 20.9 ppm). In addition, in the rr region, the methyl group (EPE-methyl group) of the second unit (propylene unit) of the triple chain (EPE) in which all the units adjacent to the propylene unit are ethylene units is resonant (around 20.2 ppm). To do. Therefore, it is necessary to reduce the peak area based on the PPE-methyl group and the peak area based on the EPE-methyl group.
The peak area based on the PPE-methyl group can be evaluated by the peak area of the corresponding methine group (resonance at around 31.0 ppm), and the peak area based on the EPE-methyl group is resonant at the corresponding methine group (around 33.3 ppm). ) Peak area.

  Moreover, as a partial structure containing a position irregular unit, it may have the following structure (i), structure (ii), structure (iii), and structure (iv).

  Among them, carbon A, A ′, A ″ peaks appear in the mr region, carbon B, B ′ peaks appear in the rr region. Further, carbon C, C ′ peaks appear in 16.8 to 17.8 ppm. Among these peaks, peaks that are not based on the head-to-tail three-linked propylene unit chain are PPE-methyl group, EPE-methyl group, carbon A, A ′, A ″, B, B ′, C, and carbon C ′. It is a peak based on. Therefore, it is necessary to reduce the peak area based on carbon A, A ′, A ″, B, B ′.

The peak area based on carbon A can be evaluated from the peak area of carbon F (resonance in the vicinity of 38.7 ppm) of the position irregular partial structure [structure (i)].
The peak area based on carbon A ′ can be evaluated by double the peak area of the position irregular substructure [carbon J of structure (ii) (resonance near 34.1 ppm).
The peak area based on carbon A ″ can be evaluated by the peak area of carbon L (resonance at around 27.7 ppm).

The peak area based on carbon B can be evaluated by carbon J. Moreover, the peak area based on carbon B ′ can be evaluated by carbon K (resonance at around 33.7 ppm).
The carbon C peak and the carbon C ′ peak need not be considered because they are generated in a region different from the peak of the head-to-tail bonded propylene unit triple chain (PPP).
Since the peak areas of mm, mr, and rr can be evaluated as described above, the isotactic triad fraction mm of the propylene unit chain portion composed of the head-to-tail bond can be obtained according to the above formula.

(2) Production of component (a) In order to obtain component (a) having a high melting point, high stereoregularity and a narrow molecular weight distribution as described above, it is preferable to use a metallocene catalyst as the catalyst. Conventionally used Ziegler-Natta catalysts are considered to have a plurality of active sites, and it is inevitable that atactic components with low regularity are generated. Moreover, it is known that the regularity generally decreases with a low molecular weight component, and it is difficult to obtain a low molecular weight component with a high melting point. In addition, since a Ziegler-Natta catalyst generally has a large molecular weight distribution, undesired components may be produced in improving physical properties such as rigidity for the reasons described above.

A preferred metallocene catalyst is preferably produced from a specific metallocene catalyst from the viewpoint of stereoregularity related to the melting point and polymerization stability. Specifically, it is preferable to (co) polymerize propylene in the presence of a catalyst comprising the following component (A), component (B) and, if necessary, component (C).
Component (A): Transition metal compound represented by general formula (I) Component (B): Solid component containing one or more selected from the following (b-1) to (b-4) (b-1) Particulate carrier carrying aluminum oxy compound (b-2) Particulate carrier carrying ionic compound or Lewis acid capable of reacting with component (A) to convert component (A) into cation b-3) Solid acid fine particles (b-4) Ion exchange layered compound Component (C): Organoaluminum compound

(I) Component (A)
As a typical example, the transition metal compound (A) used in the present invention is a metallocene complex composed of a transition metal belonging to Group 4 of the periodic table (short-period type) having two conjugated five-membered ring ligands. These are preferable, and those represented by the following general formula (I) are preferable.

  Here, in the formula (I), A and A ′ representing the conjugated five-membered ring ligand may be the same or different, and at least the 2-position and 4-position thereof are indenyl having the specific substituent described below. Group, an azulenyl group, or a hydrogenated azulenyl group. The substituent at the 2-position is a hydrocarbon group having 1 to 6 carbon atoms which may contain a hetero atom such as halogen, silicon, oxygen or sulfur, preferably an alkyl group such as methyl, ethyl or propyl group. . The substituent at the 4-position is an aryl group represented by the following general formula, and R ′ is a hydrocarbon group having 1 to 20 carbon atoms which may contain a heteroatom such as a halogen atom, or an organic silicon having 1 to 20 carbon atoms. A group or a halogen atom. However, at least one R ′ present at the 3-position, 4-position and 5-position of the aryl group is a branched hydrocarbon group having 4 to 10 carbon atoms which may contain a halogen atom, preferably a halogen atom. Or a tertiary branched hydrocarbon group having 4 to 7 carbon atoms, or an organic silicon group having 3 to 10 carbon atoms that may contain a halogen atom, preferably containing a halogen atom. It may be a tertiary organic silicon group having 3 to 6 carbon atoms. Here, the plurality of substituents of each hydrocarbon group or organosilicon group may be the same as or different from each other. Specific examples of at least one R ′ present at the 3-position, 4-position, and 5-position of the aryl group include a trifluoromethyl group, a trimethylsilyl group, a t-butyl group, a t-pentyl group, a phenyl group, and triethyl. Although a silyl group etc. can be illustrated, a trimethylsilyl group, t-butyl group, t-pentyl group, and a triethylsilyl group are preferable. Two or more adjacent R's may be connected. n is in the range of 1-4.

  Among these, particularly preferred is a conjugated five-membered ring ligand A or A ′ or both having an alkyl group having 2 to 4 carbon atoms at the 2-position and represented by the above general formula at the 4-position. An aryl group, and in the aryl group, at least one of R′n present at the 3-position, 4-position, and 5-position of the aryl group may contain a halogen atom and has 4 to 7 carbon atoms A tertiary branched hydrocarbon group or a tertiary organic silicon group having 3 to 6 carbon atoms which may contain a halogen atom, and substitution other than the branched hydrocarbon group and the organic silicon group The group is an indenyl group, an azulenyl group, or a hydrogenated azulenyl group having at least one substituent selected from a methyl group and a halogen atom. Particularly preferred is an azulenyl group. n is preferably 2 or 3.

  It is considered that the substituents at the 2nd and 4th positions in the metallocene complex having a bridged indenyl skeleton or an azulenyl skeleton function as follows. In addition, this does not limit the action / effect of the present invention. That is, the substituent at the 2-position is known to affect the terminal structure of the polymer bonded to the coordination monomer and the central metal, but by selecting an appropriate bulky substituent, reverse insertion of the monomer Reactions and chain transfer reactions can be suppressed, which is effective in reducing heterogeneous bonds and increasing molecular weight.

  Further, the substituent at the 4-position is known to affect the stereoselectivity of the coordination monomer and the polymer terminal structure bonded to the central metal sterically, but has a substituent at the 2-position, In addition, by selecting a substituent having an aryl structure at the 4-position, the arrangement of the polymer terminal structure can be controlled, and a smooth insertion (polymerization) reaction proceeds with high stereoselectivity, as in the present invention. High mesotriad fraction (mm) and high molecular weight polymer can be obtained with high activity. In other words, selecting the substituents at the 2-position and 4-position makes it possible to obtain a polymer having a high molecular weight and a high melting point. In the polymerization by a catalyst using such a metallocene complex, it is possible to easily produce even a low molecular weight PP such as (a) having a molecular weight by adding hydrogen as a chain transfer agent. There are no features.

Q represents a binding group that bridges at any position between ligands such as two conjugated five-membered rings, and is preferably directly bonded to the conjugated five-membered ring, a hydrocarbon group having 1 to 20 carbon atoms, A silicon-containing hydrocarbon group or a germanium-containing hydrocarbon group is preferred. Specifically, it is a substituted or unsubstituted alkylene group, a silylene group or a germylene group, preferably a substituted silylene group or a substituted germylene group. The substituent bonded to silicon and germanium is preferably a hydrocarbon group having 1 to 6 carbon atoms, and two substituents may be linked.
M is a metal atom of a transition metal selected from Group 4 of the periodic table, and zirconium and hafnium are preferred.

  X and Y are auxiliary ligands which react with the cocatalyst of component (B) to produce an active metallocene having olefin polymerization ability. Therefore, as long as this object is achieved, X and Y are not limited in the type of ligand, and each may be a hydrogen atom, a halogen atom, a hydrocarbon group, or a hydrocarbon group optionally having a heteroatom. Etc. can be exemplified. Of these, a hydrocarbon group having 1 to 10 carbon atoms or a halogen atom is preferred.

  Specific examples of the compound include dichloro {1,1′-dimethylsilylenebis (2-ethyl-4-phenyl-4-hydroazurenyl)} hafnium, dichloro [1,1′-dimethylsilylenebis {2-ethyl- 4- (4-Chlorophenyl) -4-hydroazurenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-ethyl-4- (4-tert-butylphenyl) -4hydroazurenyl}] hafnium, dichloro [1 , 1'-dimethylsilylenebis {2-ethyl-4- (4-trimethylsilylphenyl) -4-hydroazulenyl}] hafnium, dichloro [1,1'-dimethylsilylenebis {2-ethyl-4- (3-chloro- 4-t-butylphenyl) -4-hydroazurenyl}] hafnium, dichloro [1,1′-dimethylsilyl Bis {2-ethyl-4- (3-methyl-4-t-butylphenyl) -4-hydroazulenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-ethyl-4- (3-chloro- 4-trimethylsilylphenyl) -4-hydroazurenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-ethyl-4- (3-methyl-4-trimethylsilylphenyl) -4-hydroazurenyl}] hafnium, dichloro [ 1,1′dimethylsilylenebis {2-ethyl-4- (3,5-dichloro-4-trimethylsilylphenyl) -4-hydroazurenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-ethyl-4 -(2-Naphtyl) -4-hydroazulenyl}] hafnium, dichloro [1,1′-dimethyl Rylenebis {2-ethyl-4- (2-fluoro-4-biphenyl) -4-hydroazulenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-ethyl-4- (2-chloro-4-biphenyl) ) -4-hydroazurenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-ethyl-4- (9-phenanthryl) -4-hydroazurenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis { 2-ethyl-4- (4-chloro-2-naphthyl) -4-hydroazurenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-i-propyl-4- (4-chlorophenyl) -4- Hydroazurenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-n-propyl-4- (3-chloro) -4-trimethylsilylphenyl) -4-hydroazurenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (3-chloro-4-t-butylphenyl) -4-hydroazurenyl}] hafnium Dichloro [1,1′-dimethylgermylenebis {2-ethyl-4- (2-fluoro-4-biphenyl) -4-hydroazulenyl}] hafnium, dichloro [1,1′-dimethylgermylenebis {2- Ethyl-4- (4-t-butylphenyl) -4-hydroazurenyl}] hafnium, dichloro [1,1 ′-(9-silafluorene-9,9-diyl) bis {2-i-propyl-4- ( 4-chlorophenyl) -4-hydroazurenyl}] hafnium, dichloro [1,1 ′-(9-silafluorene-9,9-diyl) bis 2-ethyl-4- (3,5-dichloro-4-trimethylsilylphenyl) -4-hydroazulenyl}] hafnium, dichloro [1,1 ′-(9-silafluorene-9,9-diyl) bis {2-ethyl -4- (3,5-dimethyl-4-trimethylsilylphenyl) -4-hydroazurenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-ethyl-4- (4-t-butylphenyl) -4 , 5,6,7,8-pentahydroazulenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-ethyl-4- (4-trimethylsilylphenyl) -4,5,6,7,8 -Pentahydroazurenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-ethyl-4- (2-fluoro-4-biphenyl) -4,5 6,7,8-pentahydroazurenyl}] hafnium, dichloro (1,1′-dimethylsilylenebis [2-ethyl-4- {4-chloro-2- (5,6,7,8-tetrahydronaphthyl)] -4,5,6,7,8-pentahydroazulenyl}] hafnium and the like.

  The above-mentioned compound avoids many complicated examples and describes only typical exemplary compounds, and a compound in which the central metal is hafnium is described, but it goes without saying that similar zirconium compounds can also be used. It is obvious that various ligands, crosslinking groups or auxiliary ligands can be used arbitrarily.

(B) Component (B)
As the component (B), at least one of the components selected from the above-described (b-1) to (b-4) is used. Each of these components is known, and specific examples and production methods thereof are not described repeatedly, but for example, detailed disclosure is made in JP-A-2002-284808.
In short, aluminoxane or the like is used as the aluminum oxy compound of (b-1), and the compound of (b-2) reacts with component (A) to convert component (A) into a cation. Possible ionic compounds or Lewis acids, such ionic compounds include cations such as carbonium cations, ammonium cations, triphenylboron, tris (3,5-difluorophenyl) boron, tris (penta And a complex with an organic boron compound such as (fluorophenyl) boron. Examples of the Lewis acid as described above include various organic boron compounds such as tris (pentafluorophenyl) boron. Examples of the solid acid (b-3) include alumina, silica-alumina, and silica-magnesia. The ion-exchange layered compound (b-4) occupies most of the clay mineral, and is preferably an ion-exchange layered silicate.
Among the above components (B), preferred is the ion-exchange layered silicate of (b-4). For example, Japanese Patent Application Laid-Open No. 2002-53609, Japanese Patent Application Laid-Open No. 2002-69116, or Japanese Patent Application Laid-Open No. 2003-105015 discloses specific examples and detailed manufacturing methods.

(C) Component (C)
Component (C) is an organoaluminum compound. The organoaluminum compound used as the component (C) in the present invention is suitably a compound represented by the general formula AlR _p X _3-p . In the present invention, it goes without saying that the compounds represented by this formula can be used singly or in combination. In this formula, R represents a hydrocarbon group having 1 to 20 carbon atoms, and X represents a halogen, hydrogen, an alkoxy group, or an amino group. p is a number greater than 0 and up to 3. R is preferably an alkyl group, and X is chlorine when it is a halogen, an alkoxy group having 1 to 8 carbon atoms when it is an alkoxy group, and 1 to 8 carbon atoms when it is an amino group. An amino group is preferred. Accordingly, specific examples of preferred compounds include trimethylaluminum, triethylaluminum, trinormalpropylaluminum, trinormalbutylaluminum, triisobutylaluminum, trinormalhexylaluminum, trinormaloctylaluminum, diethylaluminum chloride, diethylaluminum sesquichloride, diethyl Examples thereof include aluminum hydride, diethylaluminum ethoxide, diethylaluminum dimethylamide, diisobutylaluminum hydride, diisobutylaluminum chloride and the like. Of these, trialkylaluminum and dialkylaluminum hydride are preferable.

The catalyst can be formed by contacting the above-described components in a (preliminary) polymerization tank simultaneously or continuously, or once or multiple times. The contact of each component is usually carried out in an aliphatic hydrocarbon or aromatic hydrocarbon solvent. Although a contact temperature is not specifically limited, It is preferable to carry out between -20 degreeC and 150 degreeC.
Arbitrary combinations according to the purpose are possible as the contact order. When using an ion-exchange layered silicate as the component (B), a preferred embodiment is a method of contacting the component (C) with the component (B) before bringing the component (A) and the component (B) into contact. In that case, the excess component (C) can be removed by washing. Moreover, the component (C) can use the same or different kind of component (C) several times.

The usage-amount of component (A), (B) and (C) is arbitrary. For example, when an ion-exchange layered silicate is used as the component (B), the amount of the component (A) used is preferably 0.1 to 1000 micromol, particularly preferably 0 to 1 g of the component (B). The range is from 5 micromolar to 500 micromolar. The amount of the component (C) used relative to the component (B) is preferably in the range of 0.1 mmol to 5000 mmol, particularly preferably 0.5 mmol to 1000 mmol, with respect to 1 g of the component (B). is there. Therefore, the amount of the component (C) relative to the component (A) is preferably in the range of 0.1 to 5 × 10 ⁷ , particularly preferably 1 to 2 × 10 ⁶ in terms of molar ratio.

It is preferable that the catalyst is subjected to a prepolymerization treatment in which the olefin is brought into contact with the catalyst and polymerized in a small amount. The olefin used is preferably propylene. The olefin can be supplied by any method, such as a supply method for maintaining the olefin at a constant speed or in a constant pressure state, a combination thereof, or a stepwise change. The prepolymerization temperature and time are not particularly limited, but are preferably in the range of −20 ° C. to 100 ° C. and 5 minutes to 24 hours, respectively. The amount of prepolymerization is such that the amount of prepolymerized polymer is in a weight ratio with respect to component (B), preferably 0.01 to 100, more preferably 0.1 to 50. Moreover, a component (C) can also be added or added at the time of prepolymerization.
After completion of the prepolymerization, the catalyst can be used as it is, depending on the usage form of the catalyst. However, if necessary, drying can be performed. When drying is performed, it is preferable to add the component (C) in order to prevent poisoning due to impurities.
A method of coexisting a polymer such as polyethylene or polypropylene or a solid of an inorganic oxide such as silica or titania at the time of or after the contact of the above components is also possible.

Here, in order to manufacture the component (a) which comprises the composition of this invention using a metallocene catalyst, it is important to select a catalyst and polymerization conditions appropriately as follows.
In general, when the polymerization temperature is increased, the metallocene catalyst has a lower molecular weight and a lower melting point due to a decrease in stereoregularity (for example, mesotriad). Therefore, the polymerization temperature condition should be appropriately selected according to the performance of the catalyst. Depending on the catalyst to be selected, if the monomer partial pressure (concentration) is low, the stereoregularity of the resulting polymer may be lowered or the molecular weight may be lowered. Therefore, the polymerization pressure should be appropriately selected. . For example, when using a complex or a catalyst having low performance, it may be possible to compensate for poor catalyst performance by setting the polymerization pressure to a higher condition. In order to control the molecular weight (MFR is used as an index), hydrogen can be used as a known molecular weight adjusting method, for example, a chain transfer agent, in addition to the selection of the polymerization temperature described above.

  The component (a) polymerized using such a catalyst has a large isotactic triad fraction mm, but has a positional irregularity based on 2,1-insertion or 1,3-insertion. The range is 0.01 to 2.00%, preferably 0.01 to 1.00% in the former, 0.06 to 0.40% in the latter, preferably 0.00. It is 06 to 0.30%. In the case of production using a conventional Ziegler-Natta catalyst, this positional irregularity is hardly observed.

  The 2,1-bond content (the amount of heterogeneous bonds due to 2,1-insertion) is determined according to the following formula.

The symbols in the above formula mean the following.
αβ (i): Peak intensity derived from αβ methylene carbon (G and G ′ carbon in the structure diagram) included in structure (i), and occurs as a doublet in the vicinity of 36.0 ppm.
αβ (ii): peak intensity derived from methylene carbon (H and I carbons in the structure diagram) contained in structure (ii), and occurs as a doublet near 34.8 ppm.
CH (iii): Intensity of a peak derived from methine carbon (K carbon in the structure diagram) contained in structure (iii), and occurs around 33.7 ppm.
αα: Peak intensity derived from methylene carbon sandwiched between two 1,2-linked propylene chains, occurring around 45.5 to 47.0 ppm.
αγ + αδ: peak intensity derived from methylene carbon that is directly bonded to methine carbon, and the position of the nearest methine carbon opposite to the directly bonded methine carbon is at the γ position or earlier, and 37.2 to 38. It occurs around 4 ppm.
βγ: peak intensity derived from the methylene carbon L of the structure (iii), which occurs around 27.7 ppm.

  The 1,3-bond content (the amount of heterogeneous bonds due to 1,3-insertion) is determined according to the following formula.

（上式中の記号の意味は前記したとおりである。）

(The meaning of the symbols in the above formula is as described above.)

(3) Component (b) Propylene homopolymer or propylene / α-olefin copolymer Component (b) used in the highly rigid polypropylene-based composition of the present invention has the following characteristics (bi) to (b-ii): A propylene homopolymer or a propylene / α-olefin copolymer. The propylene and α-olefin copolymer may be a so-called random copolymer or a so-called block copolymer obtained by multistage polymerization. As the α-olefin used for the copolymerization, any one in the range of 2 to 10 excluding 3 carbon atoms can be used, and among them, ethylene is preferably used. The copolymer may be a stereoblock copolymer obtained by controlling the stereoregularity of PP.

Characteristic (b-1) Mw _(b)
The range of Mw _(b) obtained by GPC of component (b) is 60,000 to 1,000,000, preferably 100,000 to 800,000, more preferably 150,000 to 600,000. When the molecular weight range of the component (b) exceeds this range, the fluidity of the composition is lowered or blisters are liable to occur. On the other hand, if it falls below this range, the fluidity of the composition will be out of the practical range, which is not preferable.
Here, the molecular weight is measured by the same method as in the case of component (a).

Characteristic (b-2) Tm _(b)
The range of melting | fusing point Tm _(b) obtained by DSC of a component (b) is 120-170 degreeC, Preferably it is 150-169 degreeC, More preferably, it is 160-168 degreeC. Those below this range do not have sufficiently high rigidity, and are outside the scope of the present invention. Moreover, what exceeds this range is practically difficult to manufacture. In the range of the molecular weight of the component (b), the melting point obtained by ordinary measurement is not affected by the molecular weight so much, and thus it can be specified in such a range.
Here, the measuring method of Tm _(b) is the same as the case of component (a).

  The catalyst for producing the component (b) is not particularly limited, and a conventionally known Ziegler-Natta catalyst, metallocene catalyst, or the like can be used, but the resin composition of the present invention is highly rigid. Since it is a characteristic, it is desirable to select a catalyst system that can produce a polypropylene resin having a relatively high melting point. Therefore, when the component (b) is also produced by a metallocene catalyst, it is preferably produced by the same catalyst as that for producing the component (a).

(4) Composition ratio of component (a) and component (b) The weight fraction of component (a) with respect to the entire high-rigidity polypropylene composition of the present invention is 10 to 50% by weight, preferably 15 to 45% by weight. %. When the proportion of component (a) is below this range, the rigidity improving effect is not sufficient, and when it exceeds, the fluidity is in a range not suitable for practical use, or the material becomes brittle, which is not preferable. Thereby, the range of the component (b) with respect to the whole composition is the range of 90-50 weight%, Preferably it is the range of 85-55 weight%.

2. Production of High-Rigidity Polypropylene Composition The high-rigidity polypropylene composition of the present invention essentially comprises two components of the above component (a) and component (b), a high molecular weight component and a low molecular weight component. There are no particular restrictions on the method used in the production of the method, a method of producing two components by multistage polymerization, a method of producing different molecular weight components using a plurality of catalysts, and a single catalyst having two different active points. Examples thereof include a production method, a method of removing the solvent after mixing the two components in the presence of the solvent, and a method of melt-kneading with an extruder or a brabender. In the case of a composition in which a component having a very low molecular weight and a component having a large molecular weight coexist as disclosed in the present invention, it is generally difficult to obtain a uniform composition. And when obtaining this composition, it is easy to obtain a more uniform composition. In general, when the resin composition is obtained by a melt kneading method used for producing a resin composition, the following method is preferably used.

  In producing this composition by melt-kneading, a method of melt-kneading in at least two stages using a melt-kneader is used to first melt-knead component (b) and then add component (a). Furthermore, a method of manufacturing by melt kneading is preferably used. This is because the composition disclosed in the present invention contains a component (a) having a very low molecular weight, and such a composition is prepared by dry blending the powders or pellets of both components and then by ordinary melt kneading. In this case, the component (a) having a low molecular weight and a low viscosity is melted in the kneader prior to the component (b), which is sufficient for the component (b) having a high molecular weight and a high viscosity compared to the component (a). This is because the shearing is not applied and the component (b) may not be dispersed in the component (a). In such a case, not only the effect of improving the rigidity is not sufficient, but also the problem that the final composition is fuzzy and the stretchability and toughness are extremely deteriorated is caused. In order to avoid such a phenomenon, as described above, the component (b) having a high viscosity is first melt-kneaded, and the component (a) in the form of powder or pellets is added to the molten component (b). It is preferable to do. At this time, since the component (b) having a high viscosity is melt-kneaded first, the component (a) added thereto is subjected to a large shear via the component (b), so that the dispersibility is greatly improved. .

As a method of melt kneading, using an extruder, first, the component (b) is fed upstream and melt kneaded, and then the component (a) is melt melt kneaded on the downstream side in the component (b). It is preferable that it is introduced from the mouth and continuously melted and kneaded.
As the extruder used at this time, a single-screw, twin-screw or other continuous extruder can be used, and two or more extruders can be connected and used. At this time, in order to melt and knead the component (b) and further disperse the component (a) sufficiently, at least two mixing zones are provided, and the component (b) is fed first in the first mixing zone. It is preferable to produce the mixture by melt-kneading, feeding the component (a) through a feed hole provided behind the first mixing zone, and melt-mixing both components in the second and subsequent mixing zones.
The temperature range at the time of melt kneading (mixing zone) is larger than 150 ° C. and not higher than 300 ° C., preferably 160 ° C. to 280 ° C.
Here, the most preferably used is a meshing twin screw extruder of L / D ≧ 30 (where L is the screw length and D is the screw diameter), and feeds at two or more locations upstream and downstream. It has a mouth.
That is, when a single screw extruder is used, if the component (a) is fed after the component (b) is melt-kneaded, the feed port has no friction from the cylinder wall, so that the transfer is poor and vent-up is likely to occur. There's a problem. On the other hand, the meshing twin-screw extruder has the advantage that it is excellent in kneading ability and high dispersibility because it is difficult to cause vent-up because volume transfer works in addition to shearing, and various kneading segments can be provided.

A typical example of a twin-screw kneader that is suitably used is shown in FIG. In FIG. 2, the twin-screw kneader 1 is composed of a screw element portion and a temperature control portion, and 2, 3 are feed ports. In the screw element section, 4, 4 ′, 4 ″ are full flight screws, 5 and 5 ′ are mixing zones, and 6 and 6 ′ are reverse threads. A zone temperature control unit, 17 is an adapter, and 18 is a strand die temperature control unit, where the mixing zone is a screw element of a twin-screw extruder, kneading or dispersing compared to a full flight screw. It is a portion provided with an element having an excellent effect, and an element generally used in a twin-screw extruder such as a so-called kneading disk or a rotor can be used.
Further, as the screw configuration, in order to knead the resin as well as possible in the mixing zone, it is preferable to use a reverse screw at the end of the mixing zone. In addition, when the component (a) is fed after the component (b) is melt-kneaded, it is desirable to adopt a structure having as high a transfer capability as possible in order to vent up when the pressure rises. The full flight screw is used to transfer the resin, and the addition of the component (a) is preferably performed in the region where the molten resin is transferred by the full flight screw after the first mixing zone. The temperature of this region needs to be controlled within a range where the component (b) does not solidify in order to prevent the powder or pellet of the component (a) from being melted and adhered near the feed port. It is preferable that it is a temperature of 60 degreeC, Preferably 60-150 degreeC.

Selection of the number and type of kneading discs and other screw elements is optional depending on the type of twin-screw extruder used as long as the purpose of sufficiently melting and kneading components (a) and (b) can be achieved. You can choose. Similarly, the extruder rotational speed may be arbitrarily set.
However, when selecting the twin-screw kneader, it is preferable to change the temperature in the vicinity of the mixing zone and the second feed port 3 as described above, so select an apparatus that can be controlled at different temperatures depending on the position of the barrel. It is preferable.
Specifically, for example, the component (b) is fed and kneaded at a temperature-controlled portion of a kneader at 50 to 160 ° C., preferably 60 to 150 ° C., and further 150 to 300 ° C., preferably 160 It is kneaded and transferred to a site whose temperature is controlled at ˜280 ° C. and melt-kneaded. And, when kneaded and transferred to a site whose temperature is controlled to 50 to 160 ° C., preferably 60 to 150 ° C., after component (a) is added and kneaded to the component (b), 150 to 300 ° C., Preferably, the component (b) and the component (a) are melt-kneaded by being kneaded and transferred to a site whose temperature is controlled at 160 to 280 ° C.
The ratio of the component (a) in the composition can be estimated from the ability of the feeder that has been measured in advance, or the weight average molecular weight Mw of the component (a), the component (b), and the total composition produced. It is also possible to calculate from the measurement of _{(a + b)} by the following equation.
Wa = [logMw _{(a + b)} −logMw _(b) ] / [logMw _{( a)} −logMw _(b) ] × 100

The high-rigidity propylene-based composition of the present invention can be suitably used for various molded products such as sheets, films, injection-molded products, textile products, and packaging materials, but is particularly suitable for use in high-rigidity injection-molded products. Can be used.
When used for these applications, the molding method is not particularly limited, and various known molding methods such as an injection molding method and a melt extrusion molding method can be used. In forming, unless the main point of the present invention is impaired, conventionally known additives such as stabilizers, antioxidants, nucleating agents, UV absorbers, photoprotective agents, metal deactivators, free radical scavengers are used. , Fillers and reinforcing agents, compatibilizers, plasticizers, lubricants, emulsifiers, fluorescent whitening agents, flame retardants, pigments, antistatic agents, foaming agents and the like may be added.

  In the following, the present invention will be described in more detail by way of examples and further in comparison with comparative examples. The following examples are intended to explain the present invention more specifically, so it is clear that the present invention is not limited by these examples. In the following Examples and Comparative Examples, various physical property measurement methods, composition production methods, composition evaluation methods, and used component production methods are as follows.

1. Measurement of resin physical properties (1) GPC: Measured according to the method described above.
(2) DSC: Using a Seiko DSC, take 5.0 mg of sample, hold at 200 ° C. for 5 minutes, crystallize to 40 ° C. at a rate of temperature decrease of 10 ° C./minute, and further increase by 10 ° C./minute. The melting peak temperature when melting at a temperature rate was defined as Tm (unit: ° C.).
(3) MFR: Measured according to the melt flow rate (conditions: 230 ° C., load 2.16 kgf) of the polypropylene test method of JIS K6758. The unit is g / 10 minutes.
(4) Weight fraction wa of component (a): Calculated from the ability of each feeder to add component (a) and component (b) in the granulation step with a twin screw extruder.
(5) mm and amount of heterogeneous bonds: measured according to the method described above.

2. Production of composition Melting and kneading under the following conditions, the molten resin extruded from the strand die is taken out while being cooled and solidified in a cooling water tank, and the strand is cut into a diameter of about 2 mm and a length of about 3 mm using a strand cutter. Resin composition raw material pellets were obtained.
Component (b) was introduced from the feed port 2 in FIG. 2 using a screw feeder, and component (a) was added to the feed port 3 in FIG. 2 by a screw feeder. Feeder capacity (added amount of resin per hour) was measured in advance for each, and from this, the ratio of component (a) and component (b) in the composition was determined.

Extruder: KZW-15-45-MG twin screw extruder manufactured by Technobel Co., Ltd. Screw: 15 mm in diameter L / D45
Screw configuration: As shown in FIG. 2 Extruder set temperature: From below the hopper 100, 180, 200, 130, 190, 190, 190, 190 (die) ° C.
Screw rotation speed: 400rpm
Die: 3 mm diameter strand die Number of holes 2 The kneader used here is a meshing twin-screw extruder, and the temperature can be controlled independently at 8 locations from the bottom of the hopper to the die. The used screw element is as shown in FIG. 2, and the component (b) charged from the hopper is kneaded at a temperature controlled to 180 ° C. and 200 ° C. in the region extending over the temperature control units 12 and 13 in FIG. . A kneading block is arranged in the kneading section. A welding block is a plurality of kneading discs having the same cross-sectional shape, in which the geometric centers of the discs are located on a common straight line, and a predetermined angle with respect to each other in a certain direction around the straight line. It has a shape that is shifted and overlapped sequentially with a shift. The kneading block has a 90 ° difference between the type in which the kneading disk is displaced in the direction in which the resin is transferred in the direction of the die as the screw rotates (forward screw type). There is a type (neutral type) and a type (reverse screw type) that is arranged in a direction to transfer the resin in the direction of the hopper as the screw rotates. Here, two forward screw types and four neutral types from the hopper side A total of 6 pieces of 2 reverse screw types were used. At the end of the kneading part, a reverse flight full flight screw was arranged to increase the residence time so that stronger kneading was achieved.
The component (a) is charged by the temperature controller 14 (feed port 3) in FIG. 2 controlled to 130 ° C. and transferred to the temperature controller 15 in FIG. 2 controlled to 190 ° C. by the full flight screw 4 ′. Both components are kneaded. Here, the kneading block uses two forward screw types, three neutral types, and two reverse screw types. A reverse flight full flight screw is placed at the end of the kneading section to increase the residence time and achieve stronger mixing. It was made to be.

3. Preparation of physical property test piece The obtained composition pellet was injection-molded under the following conditions to obtain a flat test piece for physical property evaluation.
Standard number: JIS-7152 (ISO294-1)
Molding machine: Toshiba EC20 injection molding machine Setting temperature: 80, 80, 160, 200, 200, 200 ° C from below the hopper
Mold temperature: 40 ℃
Injection speed: 200 mm / s (speed in the mold cavity)
Mold shape: flat plate (thickness 2 mm, width 30 mm, length 90 mm, thickness 4 mm, width 10 mm, length 80 mm)

4). Method for measuring composition physical properties (1) Flexural modulus: The flexural modulus of the obtained composition was evaluated under the following conditions.
Standard number: Compliant with JIS K-7171 (ISO178) Testing machine: Precision universal testing machine Autograph AG-20kNG (manufactured by Shimadzu Corporation)
Specimen sampling direction: Flow direction Specimen shape: Thickness 2.0 mm, width 25.0 mm, length 40.0 mm
Test piece preparation method: Injection-molded flat plate is punched to the above dimensions.
Condition adjustment: left in a temperature-controlled room adjusted to room temperature 23 ° C. and humidity 50% for more than 24 hours Test room: temperature-controlled room temperature adjusted to 23 ° C. and humidity 50% Number of test pieces: 5
Distance between fulcrums: 32.0mm
Test speed: 1.0 mm / min
(2) Heat resistance: Heat resistance was evaluated by heat distortion temperature (HDT). HDT was measured flat-wise under the condition of 0.45 MPa in accordance with JIS K7191-1 using an injection-molded piece having a thickness of 4 mm. However, as a test piece state adjustment before measurement, after injection molding, an operation of annealing at 100 ° C. for 30 minutes and cooling to room temperature is performed.

5. Production of component (a) and component (b) (Production Example 1)
(1) Synthesis of metallocene complex (r) -dichloro [1,1′-dimethylsilylenebis {2-ethyl-4- (3-chloro-4-trimethylsilylphenyl) -4-hydroazurenyl}] hafnium (a) 3- Synthesis of chloro-4-trimethylsilylbromobenzene 3-Chloro-4-iodo-bromobenzene (3.1 g) was dissolved in diethyl ether (100 ml), and a hexane solution of n-butyllithium (1.59 M 6 at −78 ° C. 0.1 ml) was added dropwise. After stirring at that temperature for 30 minutes, trimethylsilyl trifluoromethanesulfonate (3.77 ml; 17.4 mmol) was added dropwise and stirred for 1 hour. After completion of the reaction, water was added little by little in an ice bath, followed by extraction with ether, the organic phase was dried over magnesium sulfate, and the solvent was distilled off under reduced pressure. The obtained crude product was purified twice by column chromatography (silica gel, hexane manufactured by Merck & Co., Inc.) to obtain the desired product (2.3 g) (yield 90%).
¹ H-NMR (CDCl ₃ )
δ: 0.35 (s, 9H, TMS), 7.3-7.4 (m, 2H, arom), 7.50 (s, 1H, arom)

(B) Synthesis of ligand 3-Chloro-4-trimethylsilyl-bromobenzene obtained in (a) above was dissolved in a mixed solvent of hexane (50 ml) and diethyl ether (50 ml), and t-butyllithium was dissolved. A pentane solution (1.51M 11.6 ml) was added dropwise at -78 ° C. After stirring at −78 ° C. for 30 minutes, the temperature was raised to 0 ° C., and 2-ethylazulene (1.29 g) was added in one portion, and then the temperature was immediately raised to room temperature and stirred for 1 hour. Tetrahydrofuran (50 ml) and N-methylimidazole (0.02 ml) were added, and dimethylsilyl dichloride (0.42 ml) was added dropwise at -5 ° C. After stirring at that temperature for 1.5 hours, distilled water was added to the reaction solution and extracted with diethyl ether. The organic layer was dried over magnesium sulfate, and the solvent was distilled off under reduced pressure. The obtained crude product was purified by column chromatography (silica gel, hexane / methylene chloride, manufactured by Merck), and dimethylsilylene bis {2-ethyl-4- (3-chloro-4-trimethylsilylphenyl) -1,4- Dihydroazulene} (2.5 g) was obtained (yield 98%).

(C) Synthesis of complex The ligand (2.5 g) obtained in (b) above was dissolved in diethyl ether (15 ml), and an n-hexane solution of n-butyllithium (1.59M, 4.3 ml). Was added dropwise at -78 ° C. After heating to 0 ° C. and stirring for 1 hour, toluene (120 ml) was added, the mixture was cooled again to −78 ° C., and hafnium tetrachloride (1.09 g) was added. The temperature was slowly raised and the mixture was stirred at room temperature for 6 hours. The obtained reaction solution was concentrated once, extracted with hexane, and concentrated again to dryness. The solid was further extracted with hexane at −78 ° C., concentrated to dryness, and washed repeatedly with n-pentane. Further, it was washed with a mixed solvent of diethyl ether-hexane (1: 3) and extracted with methylene chloride. As a result, 0.20 g (yield 6%) of the racemic dichloro [1,1′-dimethylsilylenebis {2-ethyl-4- (3-chloro-4-trimethylsilylphenyl) -4-hydroazurenyl}] hafnium as a target. )
¹ H-NMR (CDCl ₃ )
δ: 0.36 (s, 18H, TMS), 1.00 (s, 6H, SiMe ₂ ), 1.05 (t, J = 5.6 Hz, 6H, 2-CH ₂ CH ₃ ), 2.5 −2.7 (m, 4H, 2-CH ₂ CH ₃ ), 5.00 (d, J = 3.0 Hz, 2H, 4-H), 5.8-6.1 (m, 6H), 5 .99 (s, 2H), 6.79 (d, J = 6.0 Hz, 2H, 7-H), 7.2-7.4 (m, 6H, arom)

(D) Preparation of ion-exchangeable layered silicate (i) Chemical treatment:
Into a 3 L separable flask equipped with a stirring blade and a reflux apparatus, 500 g of ion-exchanged water is added, and 249 g (5.93 mol) of lithium hydroxide monohydrate is added and stirred. Separately, 581 g (5.93 mol) of sulfuric acid is diluted with 500 g of ion-exchanged water and added dropwise to the lithium hydroxide aqueous solution using a dropping funnel. At this time, a part of the sulfuric acid is consumed in the neutralization reaction to form a lithium sulfate salt in the system, and when the sulfuric acid becomes excessive, it becomes an acidic solution. Further, 350 g of commercially available granulated montmorillonite (Mizusawa Chemical Co., Ltd., Benclay SL, average particle size: 24.3 μm) is added and stirred. Thereafter, the temperature is raised to 108 ° C. over 30 minutes and maintained for 150 minutes. Then, it cooled to 50 degreeC over 1 hour. The slurry was filtered under reduced pressure using a device in which an aspirator was connected to Nutsche and a suction bottle. The cake was collected, 5.0 L of pure water was added to reslurry, and filtration was performed. This operation was repeated four more times. All filtrations were completed in less than a few minutes. The pH of the final washing liquid (filtrate) was 5. The collected cake was dried at 110 ° C. overnight under a nitrogen atmosphere. As a result, 275 g of a chemically treated product was obtained. When composition analysis was performed by fluorescent X-ray, the molar ratio of the constituent elements to silicon as the main component was Al / Si = 0.20, Mg / Si = 0.043, and Fe / Si = 0.021. . Furthermore, in order to remove water contained in a small amount, drying was performed at 200 ° C. for 2 hours under reduced pressure.
(Ii) Chemically treated montmorillonite organoaluminum treatment:
10.0 g of the chemically treated montmorillonite obtained above was weighed into a flask having an internal volume of 1 L, 64.6 ml of heptane and 35.4 ml (25 mmol) of a heptane solution of triisobutylaluminum were added, and the mixture was stirred at room temperature for 1 hour. Thereafter, it was washed with heptane, and finally the amount of slurry was adjusted to 100 ml.

(E) Preparation of catalyst 0.43 ml (0.304 mmol) of a triisobutylaluminum heptane solution was added to the triisobutylaluminum-treated montmorillonite heptane slurry prepared above and stirred for 10 minutes at room temperature. In another flask (volume 200 mL), the dichloro [1,1′-dimethylsilylenebis {2-ethyl-4- (3-chloro-4-trimethylsilylphenyl) -4-hydroazurenyl}] hafnium synthesized above was added. Toluene (30 ml) was added to the racemate (0.150 mmol), added to the above 1 L flask, and stirred at room temperature for 60 minutes. Next, 370 ml of heptane was further added to the mixed reaction product of montmorillonite and metallocene complex, and the mixture was introduced into a stirring autoclave having an internal volume of 1 liter. When the temperature in the autoclave was stabilized at 40 ° C., the above prepared metallocene complex solution was added, and then propylene was supplied at a constant rate of 238 mmol / hour (10 g / hour) for 120 minutes. After the completion of the propylene supply, the temperature was raised to 50 ° C. and maintained for 2 hours, after which the remaining gas was purged and the prepolymerized catalyst slurry was recovered from the autoclave. The recovered prepolymerized catalyst slurry was allowed to stand, and the supernatant liquid was extracted. To the remaining solid, 8.5 ml (6.0 mmol) of a heptane solution of triisobutylaluminum was added at room temperature, stirred at room temperature for 10 minutes, and then dried under reduced pressure to recover 31.6 g of a solid catalyst. The prepolymerization ratio (a value obtained by dividing the amount of the prepolymerized polymer by the amount of the solid catalyst) was 2.08.

(2) Polymerization After sufficiently replacing the inside of the polymerization tank (autoclave with a stirrer with an internal volume of 3 liters) with propylene, 2.76 ml (2.02 mmol) of a heptane solution of triisobutylaluminum was added, followed by 2500 ml of hydrogen, followed by liquid propylene 1500 ml was introduced and the temperature was raised to 65 ° C. Polymerization was started by injecting 20 mg of the previously prepared prepolymerized catalyst as a solid catalyst (amount of net solid catalyst excluding prepolymerized polymer). The temperature inside the tank was maintained at 65 ° C., and polymerization was carried out for 0.5 hour. The residual monomer was purged to terminate the polymerization, and the recovered polymer was dried at 90 ° C. under a nitrogen stream for 1 hour.
As a result, the obtained propylene polymer was 189 g, and the amount of polymer produced per 1 g of solid component / hour was 18900 g. Mw by GPC was 21,400 and Mw / Mn was 2.83. The polymer had a mm of 98.8%, a 2,1 bond content of 0.12 mol%, and a 1,3 bond content of 0.19 mol%.

(Production Example 2)
After fully replacing the inside of the polymerization tank (autoclave with an internal volume of 3 liters with a stirrer) with propylene, 2.76 ml (2.02 mmol) of a heptane solution of triisobutylaluminum was added, and 500 ml of hydrogen and then 1500 ml of liquid propylene were introduced. The temperature was raised to 65 ° C. 20 mg (the amount of the net solid catalyst excluding the prepolymerized polymer) of the prepolymerized catalyst prepared in Polymerization Example 1 was injected as a solid catalyst to initiate polymerization. The temperature in the tank was maintained at 65 ° C., and a hydrogen mixed gas diluted with argon gas (concentration: 20 vol%) was supplied as hydrogen at 890 ml / hour. The polymerization was carried out for 1 hour. The residual monomer was purged to terminate the polymerization, and the recovered polymer was dried at 90 ° C. under a nitrogen stream for 1 hour.
As a result, the obtained propylene polymer was 386 g, Mw by GPC was 44,100, and Mw / Mn was 2.53. The polymer had a mm of 99.0%, a 2,1 bond content of 0.10 mol%, and a 1,3 bond content of 0.17 mol%.

(Production Example 3)
The same procedure as in Production Example 1 was carried out except that the hydrogenation amount was 600 ml, the solid catalyst amount was 30 mg, and the polymerization time was 1 hour. As a result, the obtained propylene polymer was 300 g, Mw by GPC was 76,400, and Mw / Mn was 3.17. The polymer had a mm of 99.4%, a 2,1 bond content of 0.10 mol%, and a 1,3 bond content of 0.17 mol%.

(Production Example 4)
The same procedure as in Production Example 1 was carried out except that the hydrogenation amount was 90 ml, the solid catalyst amount was 40 mg, and the polymerization time was 1 hour. As a result, the obtained propylene polymer was 220 g, Mw by GPC was 379,000, and Mw / Mn was 3.65. The polymer had a mm of 99.5%, a 2,1 bond content of 0.09 mol%, and a 1,3 bond content of 0.15 mol%.

(Production Example 5)
The same procedure as in Production Example 1 was carried out except that the hydrogenation amount was 300 ml, the solid catalyst amount was 30 mg, and the polymerization time was 1 hour. As a result, the obtained propylene polymer was 260 g, Mw by GPC was 179,000, and Mw / Mn was 3.81. The polymer had a mm of 99.7%, a 2,1 bond content of 0.10 mol%, and a 1,3 bond content of 0.15 mol%.

(Production Example 6)
Component (a) was produced using a prepolymerized catalyst obtained by the method described in Example 1 of JP-A-10-139955 as the metallocene catalyst. In the polymerization, the inside of the polymerization tank (autoclave with a stirrer having an internal volume of 3 liters) was sufficiently replaced with propylene, and then 2.76 ml (2.02 mmol) of a heptane solution of triisobutylaluminum was added, followed by 1500 ml of n-heptane, An additional 500 ml of hydrogen is added. The temperature increase was started, and propylene was intermittently added in parallel, and the internal pressure was adjusted to 65 MPa at 65 ° C. Polymerization was initiated by injecting 100 mg (the amount of the net solid catalyst excluding the prepolymerized polymer) of the previously prepared prepolymerized catalyst as a solid catalyst. Polymerization was carried out for 3 hours while maintaining the tank temperature at 65 ° C. and the internal pressure at 0.5 MPa. The residual monomer was purged to terminate the polymerization, and the recovered polymer slurry was recovered by filtration under reduced pressure, and the polymer was dried at 90 ° C. under reduced pressure for 2 hours. As a result, the obtained propylene polymer was 230 g, Mw by GPC was 25,000, and Mw / Mn = 2.20. The mm of this polymer was 95.8%.

(Examples 1-4, Comparative Examples 1-4, 6)
The polymer obtained in the production example was used as component (a) and component (b) as described in Table 1, and the feed amount was adjusted so that component (a) would have the ratio described in Table 1 during granulation. The composition was prepared according to the method described above, and a test piece was prepared by injection molding. As additives, antioxidants: tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane 500 ppm, tris (2,4-di-t- (Butylphenyl) phosphite 500 ppm, neutralizing agent: calcium stearate 500 ppm. The results are shown in Table 1. What is described as not being used in the table is one in which the component (a) is not added and only the component (b) is granulated and molded to evaluate the physical properties.

(Example 5)
Production example 1 as component (a), propylene-ethylene block copolymer polymerized with Ziegler-Natta catalyst as component (b) (propylene homopolymerization component: 77 wt%, propylene-ethylene random copolymer component: 23 wt. %, Ethylene content in the propylene-ethylene random copolymer component: 40 wt%, total MFR: 30 g / 10 min), and so that the component (a) has the ratio shown in Table 1 during granulation, A feed amount was adjusted, a composition was produced according to the above method, and injection molding was performed to prepare a test piece. Various physical property values are shown in Table 1.

(Comparative Example 5)
Performed in the same manner as in Example 5 except that component (a) was not added. Various physical property values are shown in Table 1.

As is clear from the comparison with Examples and Comparative Examples, the rigidity and heat resistance of the composition containing the component (a) satisfying various physical property values disclosed in the present invention are clearly improved as compared with the case where it is not added. Yes. As is clear from Comparative Example 2, when the molecular weight range of component (a) is a large molecular weight that does not satisfy the requirements of the present invention, the effect of improving rigidity and heat resistance is not observed.
As is clear from the comparison between Example 5 and Comparative Example 5, even when a copolymer is used as the component (b), a remarkable effect of improving rigidity and heat resistance is obtained.
From the comparison between Examples 3 and 4 and Comparative Example 6, when the melting point and mm of component (a) are not sufficiently high, although the effect of improving the rigidity is seen, it is not remarkable, and almost no HDT is added. It can be seen that the heat resistance is not improved.

  The high-rigidity polypropylene composition of the present invention has improved rigidity, particularly rigidity and heat resistance, compared to general polypropylene resins, and is used in various applications such as sheets, films, injection molded products, textile products, and packaging materials. Can be suitably used. Especially, it can use suitably for an injection molded product.

It is a figure of the description of the baseline of a chromatogram in GPC, and an area. It is explanatory drawing of the twin-screw kneader used by this invention.

Explanation of symbols

1 Twin-screw kneader 2, 3 Feed port 4, 4 ', 4 "Full flight screw 5, 5' Mixing zone 6, 6 'Reverse screw 11-18 Temperature controller

Claims (5)

Following (a-i) ~ possess the characteristics of (a-iv), propylene polymers produced by metallocene catalyst (a) 10 to 50 wt%, and the following (b-i) ~ (b -ii) A high-rigidity polypropylene composition comprising 90 to 50% by weight of a propylene homopolymer or propylene / α-olefin copolymer (b) having the following characteristics:
Component (a): Propylene polymer (ai) Weight average molecular weight Mw _(a) obtained by gel permeation chromatography (GPC ₎ is 1,000-60,000 (a-ii) Molecular weight distribution ( Mw _(a) / Mn _(a) ) is 1.5 to 4.0 (a-iii) Melting point Tm _(a) obtained by differential scanning calorimetry (DSC) is a relational expression of the following formula (1) Satisfying 155 × (Mw _(a) −582) / (Mw _(a) −99) ≦ Tm _(a) (1)
(A-iv) mm of propylene chain portion obtained by ¹³ C-NMR is greater than 98.0% Component (b): propylene homopolymer or propylene / α-olefin copolymer (bi ) The weight average molecular weight Mw _(b) obtained by GPC is 60,000 to 1,000,000 (b-ii) The melting point Tm _(b) obtained by DSC is 120 to 170 ° C.   The positional irregularity based on 2,1-insertion of component (a) is 0.01-2.00%, and the positional irregularity based on 1,3-insertion is 0.06-0.40%. The high-rigidity polypropylene-based composition according to claim 1, characterized in that it is characterized. The said metallocene catalyst consists of the following component (A), a component (B), and a component (C) , The highly rigid polypropylene-type composition of Claim 1 or 2 characterized by the above-mentioned.
Component (A): Transition metal compound represented by the following general formula (I)

[In the formula (I), A and A ′ represent a conjugated five-membered ring ligand, which may be the same or different, and is an indenyl group, azulenyl group having substituents at the 2-position and 4-position, or The hydrogenated azulenyl group, the substituent at the 2-position is a hydrocarbon group having 1 to 6 carbon atoms which may contain halogen, silicon, oxygen or sulfur, and the substituent at the 4-position has the following general formula And R ′ is a hydrocarbon group having 1 to 20 carbon atoms, an organosilicon group having 1 to 20 carbon atoms or a halogen atom which may contain a halogen atom. However, at least one R ′ present at the 3-position, 4-position and 5-position of the aryl group contains a branched hydrocarbon group having 4 to 10 carbon atoms which may contain a halogen atom or a halogen atom. Or an organosilicon group having 3 to 10 carbon atoms, and two or more adjacent R's may be linked. n is in the range of 1-4. Q is a binding group that bridges two conjugated five-membered ring ligands, and is a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group, or a germanium-containing hydrocarbon group. M is zirconium or hafnium. X and Y are auxiliary ligands that react with the cocatalyst of component (B) to generate an active metallocene having olefin polymerization ability, and have a hydrogen atom, a halogen atom, a hydrocarbon group, or a heteroatom. It may be a hydrocarbon group. ]

Component (B): a solid component containing one or more selected from the following (b-1) to (b-4)
(B-1) A particulate carrier carrying an aluminum oxy compound
(B-2) Particulate carrier carrying an ionic compound or Lewis acid capable of reacting with component (A) to convert component (A) into a cation
(B-3) Solid acid fine particles
(B-4) Ion exchange layered compound
Component (C): Organoaluminum compound   Using a melt-kneading machine, a method of melt-kneading in at least two stages, first melt-kneading component (b), then adding component (a) to the melted component (b), and further melt-kneading The method for producing a high-rigidity polypropylene-based composition according to any one of claims 1 to 3, wherein the production method is performed.   The melt kneader is an extruder, and after the component (b) is fed and melt-kneaded on the upstream side, the component (a) is melt-kneaded on the downstream side and fed into the component (b) from different feed ports, The method for producing a high-rigidity polypropylene composition according to claim 4, wherein the melt-kneading is continuously performed.

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