JP2000017019A - High rigidity polypropylene resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a propylene resin excellent in rigidity, heat resistance, moldability or the like. SOLUTION: The objective propylene resin meets the equation: FM>=1,300 tan-1 (1.31×PI) [wherein PI is a product of multiplying the reciprocal of the storage elastic modulus value (unit: Pa) at the intersection point Gc of a frequency ω dependent curve G' (ω) of storage elastic modulus and a frequency ωdependent curve G'' (ω) of less elastic modulus by dynamic viscoelasticity measurement by 105; and FM (unit: MPa) is a modulus in flexure according to JIS K7203].

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a propylene-based resin excellent in rigidity, heat resistance, moldability and the like. More specifically, the present invention relates to a high-rigidity polypropylene in which an index relating to dynamic viscoelasticity and a flexural modulus satisfy a specific relational expression.

[0002]

2. Description of the Related Art Crystalline polypropylene has advantages such as high mechanical strength, high usable temperature, excellent chemical resistance, and excellent electrical insulation. Films, sheets, blow molded products, and injection molded products. It is useful as a raw material resin. However, these properties may not be sufficient for some applications. In particular, the rigidity is inferior to amorphous resins such as polystyrene and ABS, so that the usable application fields are limited. Several proposals have been made to date to overcome this disadvantage.

[0003] Among them, there has been proposed to increase the crystallinity of crystalline polypropylene by focusing on the crystallinity characteristic of polypropylene as compared with amorphous resins such as polystyrene and ABS. Compositions to which a crystal nucleating agent is added in order to enhance the crystallinity (for example, see JP-A-62-2
No. 09151), compositions to which various fillers such as fibers are added (for example, JP-A-2-77459), and a method of heat treatment after molding (for example, JP-A-62-256837) have been attempted. I have. However, when crystallizing under commonly used molding conditions, since the crystallization rate of polypropylene is low, a high degree of crystallinity cannot be obtained, and it cannot be said that the mechanical strength or rigidity of polypropylene has been sufficiently improved. Further, it is hard to say that the widening of the usable temperature range and the improvement of the heat resistance have been sufficiently improved.

For the same purpose, JP-A-8-325327 discloses a polypropylene having a specific stereoregularity focusing on stereoregularity, but having a molecular weight distribution (Mw / Mn) of 1.5.
Since it is as small as 3.8, it is not suitable for a processing method involving high-speed viscous flow such as injection molding, since problems such as flow marks occur. Further, in order to eliminate this disadvantage, as a method of controlling the molecular weight distribution by combining polymers having different molecular weights, a polypropylene having an intrinsic viscosity [η] as a viscoelasticity index and having a value of 0.55 to 1.2 dl / g is used. And a polypropylene having an intrinsic viscosity [η] of 1.4 to 5 dl / g (Japanese Patent Publication No. 50-37696), and an intrinsic viscosity [η] of 0.6 to 1.2 dl / g and 1.8 to 10 dl / g, respectively.
(Japanese Patent Application Laid-Open No. Sho 59-172507), a method in which the molecular weight of a low molecular weight component having high crystallinity and the amount of addition thereof are defined by an intrinsic viscosity [η] (Japanese Patent Application Laid-Open No. No.-356511), Mw / Mn is used as the molecular weight distribution based on the molecular weight instead of the viscoelastic index, and the value is 1.8 to 4.0, and the weight average molecular weight Mw is greater than 1000 to 50,000 and 100,000, respectively. Composition combining polyolefin) (JP-A-6-9829)
Publication No.) and the like. However, it is hard to say that the rigidity of these polypropylenes has been sufficiently improved, and they are not suitable for molding because the intrinsic viscosity is too high. Further, in the method of adjusting the molecular weight distribution by the molecular weight of the low molecular weight component and the amount thereof added, there is a problem in moldability such as generation of a silver mark caused by a low molecular weight component, and it cannot be said that rigidity has been sufficiently improved. .

[0005] WO 97/454 is an index for the melt viscoelasticity.
63 shows polypropylene specified by the loss tangent etc. measured in a specific frequency region, but this is no different from the control by the conventional intrinsic viscosity that physically shows Newton's viscosity, and this also has sufficient rigidity. It is hard to say that heat resistance and moldability have been improved.

With respect to the weight average molecular weight, an attempt has been made to improve the rigidity by controlling the molecular weight by using a high molecular weight region generally showing non-Newtonian properties. For example, JP-A-3-7704 discloses that the weight average molecular weight is 150
A method of reducing the molecular weight from 7,000,000 to 7,000,000 is described. However, if the molecular weight is large, the fluidity is low, and the easiness of the molding process inherently possessed by polypropylene is significantly reduced, and only the cutting process can be performed. Further, simply having a large molecular weight by weight causes a decrease in crystallinity, and it is difficult to say that the polypropylene achieves both original easy moldability and sufficient rigidity.

[0007]

SUMMARY OF THE INVENTION In view of the above state of the art, the present invention has been made to solve the above-mentioned problems, and in particular, to provide a polypropylene having excellent flexural modulus, heat resistance and moldability. Aim.

[0008]

SUMMARY OF THE INVENTION The present inventors have determined the real part (dynamic dynamic modulus G) of the complex modulus defined as the ratio of stress to sinusoidal strain in the viscoelastic behavior of a non-Newtonian polymer melt. ') And the imaginary part (loss modulus G ") at the intersection of the respective frequency-dependent curves and the value of the flexural modulus have a specific relationship, the rigidity,
The inventors have found that a propylene-based resin excellent in heat resistance and moldability can be obtained, and completed the present invention.

That is, the propylene-based resin of the present invention comprises: 1) a frequency ω dependence curve G ′ (ω) of storage modulus and a frequency ω dependence curve G ″ of loss modulus obtained by dynamic viscoelasticity measurement.
When the reciprocal of the value of the storage modulus at the intersection Gc with (ω) (unit: Pa) is 10 ⁵ times the PI, and the flexural modulus according to JIS K7203 is FM (the unit: MPa), the equation (1) is obtained.

## EQU3 ## A propylene resin satisfying FM ≧ 1300 tan ^-1 (1.31 × PI) (1), preferably 2) Formula (2)

(4) a propylene resin satisfying FM ≧ 1300 tan ^-1 (1.33 × PI) (2); 3) a propylene resin according to the above (1) or (2), wherein PI is 4 or more; 4) xylene The propylene-based resin according to any one of the above-mentioned items 1 to 3, wherein the proportion (XI) of the extract-insoluble component is 98.0% by weight or more. 5) The isotactic pentad fraction (IP) by ¹³ C nuclear magnetic resonance spectrum analysis is 98.0% or more, the average isotactic chain length (N) is 500 or more, and the average chain length (Nf) of each fraction is 800 or more according to the column fractionation method for the insoluble portion of xylene extraction, and the total is 10% by weight or more of all the fractions 5. The propylene-based resin according to any one of the above items 1 to 4.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION In the propylene-based resin of the present invention, a frequency ω dependence curve G ′ (ω) of storage modulus and a frequency ω dependence curve G ″ of loss modulus obtained by dynamic viscoelasticity measurement.
(Omega) the value of storage modulus at the intersection Gc of (unit: Pa) 10 ⁵ times the reciprocal of the PI, a flexural modulus according to JISK7203 FM (Unit: MPa) when the said formula (1) Satisfaction is required.

In the present invention, the dynamic viscoelasticity measurement refers to the measurement of the dynamic viscoelasticity of a polymer melt, which can be measured by an ordinary device for measuring dynamic viscoelasticity. Examples of an apparatus for measuring dynamic viscoelasticity include, but are not limited to, a so-called mechanical spectrometer manufactured by Rheometrics and Iwamoto Seisakusho.

The measurement of the dynamic viscoelasticity is performed in a molten state, and the strain and stress generally called a gap loading method are measured. As the gap, there is a cylindrical type, a conical and disk type, a parallel disk type, etc., and there is no particular limitation, but since a polymer melt is generally treated as a viscoelastic material, it is measured with a parallel disk. Can be. When the viscosity of the polymer melt is as low as that of the low molecular weight, it can be measured by using a cylinder type, a cone and a disk type or the like so that the measurement sample does not flow away.

In general, in the step of finishing a polymer material into a product, that is, in the forming process, the viscoelastic behavior of the polymer melt at the forming temperature is important. For example, when stretched at a high speed, a thin and long stretch may be obtained, or when extruded from a thin tube, the liquid may shrink in a streamline direction, and a ballast effect may be observed. This appears as a defect such as silver or a flow mark in injection molding. It is believed that such phenomena result from rheological properties, particularly elasticity, long relaxation times, and even greater non-Newtonian properties.

In this viscoelastic phenomenology, a case is considered in which a liquid of a high-viscosity polymer melt is packed and shifted between two parallel plates (shear strain). After giving a constant strain: γ = γ ₀ at time: t = 0, the stress G (t) maintaining this constant strain amount decreases exponentially with time. This time indicates the speed at which the stress inherent in the high-viscosity liquid relaxes, and is referred to as the relaxation time, and indicates a value unique to the substance. The ratio of the relaxing stress σ (t) to the initially applied constant strain γ ₀ changes with time. Elastic modulus G (t) = σ
(T) / γ ₀ is called the relaxation modulus. When the constant strain is a strain that vibrates sinusoidally at the angular frequency ω, the elastic modulus G ^* (ω) defined as the ratio between the stress and the sinusoidal strain becomes a complex number and is called a complex elastic modulus. The real part is called dynamic elastic modulus or storage elastic modulus G ', and the imaginary part is loss elastic modulus G ", whereby the non-Newtonian property of the polymer melt can be evaluated. When the mechanical strain is applied, the stress has the same frequency but the phase is changed.The phase of the stress is advanced by δ with respect to the strain by tan δ = G ′ / G ″ = 1 / ωτ. .

The viscoelasticity of general polypropylene is plotted on the frequency axis ω of sinusoidal strain on the horizontal axis, and the measured storage modulus and loss modulus are plotted on the vertical axis, and the frequency dependence curve G ′ (ω) and frequency FIG. 1 shows the dependency curve G ″ (ω).
Frequency range from 0.01 rad / sec to 150 rad / s
When the intersection of the frequency dependence curve G ′ (ω) of the dynamic elastic modulus measured at ec and the frequency dependence curve G ″ (ω) of the loss elastic modulus is Gc, the value of the storage elastic modulus at Gc (unit: A value obtained by multiplying the reciprocal of Pa) by 10 ⁵ was determined as an index PI regarding viscoelasticity (Reference: edited by Edward P. Moore Jr., translated by Yasuda et al., Polypropylene Handbook, 1998, Industrial Research Committee). In the present invention, the frequency dependence curves of the storage modulus and the loss modulus include straight lines.

Depending on the measurement conditions, G ′ (ω) and G ″
Although each curve of (ω) may not have an intersection, the intersection can be obtained by appropriately selecting the measurement conditions. Generally, Gc can be determined at a measurement temperature of 150 to 250 ° C. In the present invention, Gc is usually measured at 210 ° C., but a propylene-based resin sample having an MFR of 2 g / 10 minutes or less is measured at 230 ° C. and has an MFR of 2 g / 10 min.
It is preferable to measure a propylene-based resin sample exceeding 210 minutes at 210 ° C. Further, when the content of the low molecular weight substance is large and the viscosity is Newtonian, or when the polypropylene has a melt flow rate (hereinafter also referred to as MFR) (temperature 230).
C., a low molecular weight with a load of 2.16 kgf) exceeding 100 g / 10 min can be measured at a lower temperature, for example, at 180 ° C., and the frequency range is 0.01 rad / sec.
G '(ω) and G "at 150 rad / sec from
Each curve of (ω) can have an intersection.
When the viscosity is further low, the frequency dependence of the complex elastic modulus can be obtained by measuring using a conical or cylindrical type. Here, the Newton property indicates that a straight line is obtained when plotting as shown in FIG. 1 (Reference: edited by The Rheological Society of Japan, Lectures / Rheology (1992); Nemoto et al., Journal of the Rheology Society, Vol. 119, 181 pages (1991
Year)).

The index PI defining the propylene-based resin of the present invention is a useful index because it can easily represent polypropylene having a more wide-ranging and complicated molecular weight distribution form. That is, when controlling the molecular weight distribution by combining polymers having different molecular weights, for example, general gel permeation chromatography (hereinafter, GP)
Also called C. In the case of a combination of a low-molecular-weight compound with a molecular weight of about 5,000 or less, which is difficult to measure in), and an ultra-high-molecular-weight compound with a molecular weight of several million or more, which is unsuitable for GPC measurement due to the limitation from the exclusion limit volume of the column, It is useful to use PI instead of molecular weight. Also, for example, GP
Avoid unclear expressions such as "become bimodal", "bimodal", "has shoulders", "pull the tail", and "camel-type distribution" in molecular weight distribution curves such as C It is useful because it can.

In the present invention, the value of the PI may be any value as long as the expression (1) is satisfied. In general, commercially available polypropylene does not show large non-Newtonian viscosity in dynamic viscoelasticity measurement, and G ″ increases linearly with an increase in frequency, and the value of G ′ at the intersection with G ′ increases.
Its PI value is about three. On the other hand, a propylene-based resin satisfying the formula (1) shows a large non-Newtonian property in dynamic viscoelasticity measurement, and the frequency dependence of G ′ becomes small or negative, so the intersection of G ′ and G ″ , The PI value increases.

The propylene-based resin of the present invention has a long relaxation time and a high loss elastic modulus in a low frequency region (higher equilibrium compliance), and therefore has a Gc in a lower frequency region. Is thought to be higher. In the present invention, the larger the PI value, the better, specifically, usually 4 or more, more preferably 5 or more.
If it is less than 4, rigidity and heat resistance may be insufficient. At this time, the dynamic viscoelasticity is set in a temperature range of 180 to 230.
It is preferable that the PI value is 4 or more when measured at a temperature in the range of 0.01 to 150 rad / sec.

The index PI in the present invention represents the properties of the entire propylene resin, and is limited to only the bimodal control based on the composition ratio of the low molecular weight compound and the high molecular weight compound and the respective molecular weights as described in the prior art. It is not something to be done. In addition, the propylene-based resin of the present invention does not show flow mark, defects such as silver, a decrease in mechanical properties, and difficulty in molding due to too much high molecular weight or too high viscosity. Absent.

In the present invention, the flexural modulus FM (unit: MPa) satisfying the expression (1) can be obtained according to JIS K7203. The propylene-based resin of the present invention,
It is desirable that the FM value and the PI value satisfy the relationship of the above formula (1), preferably the relationship of the above formula (2).

More preferably, it is desirable to satisfy the relationship of the following expression (3), and more preferably to satisfy the relationship of the following expression (4).

(5) FM ≧ 1600 tan ⁻¹ (1.31 × PI) (3) FM ≧ 1600 tan ⁻¹ (1.33 × PI) (4)

"Tan ^-1 " in the equation (1) of the present invention is an inverse function of a tangent of a trigonometric function, and is a dimensionless number (radian). If the relationship of the formula (1) is not satisfied, it is difficult to achieve balanced, excellent rigidity, heat resistance and moldability.

The propylene resin of the present invention satisfies the relational expression of the formula (1), but has an FM of 1800 MPa or more, preferably 2400 MPa or more, more preferably 2800 MPa or more.
Particularly preferably, the one having 3000 MPa or more can achieve good moldability as well as high rigidity, excellent mechanical properties and heat resistance.

The propylene-based resin of the present invention preferably contains isotactic polypropylene having a high stereoregularity, and the ratio (XI) of the xylene-extracted insoluble content in all the polymers is preferably at least 98.0% by weight. Here, XI is the weight% of the polymer insoluble in xylene at 25 ° C.
Specifically, it is the weight percent of the polymer precipitated at 25 ° C. after being dissolved in ortho-xylene at 135 ° C. Preferred XI is 99.0% by weight or more, and XI is 98.0% by weight.
If it is less than the above, the effect of the present invention tends to decrease.

The propylene resin of the present invention has an isotactic pentad fraction (IP) of at least 98.0%, an average isotactic chain length (N) of at least 500 as determined by ¹³ C nuclear magnetic resonance spectrum, and is insoluble in xylene extraction. The average chain length (Nf) of each fraction by the column fractionation method of
It is desirable that the total of 00 or more is 10% by weight or more of the total fraction. When the IP is less than 98.0%, the solubility in xylene becomes high, so that XI is 98.0% by weight.
However, the effects of the present invention tend to decrease. Further, if N is less than 500 or the total of Nf 800 or more is less than 10% by weight, the crystallizable isotactic chain length in the entire propylene-based resin becomes short, resulting in a crystal structure having many racemic structures. Therefore, the effect of the present invention tends to decrease. N is 500 or more and Nf
If the weight fraction is less than 10% by weight even if the value is 800 or more, the formula (1) may not be satisfied even if the PI is high.
Even when N and Nf are extremely low, the effect of the present invention tends to be reduced. When the isotactic pentad fraction (IP) is less than 98%, XI also becomes less than 98% by weight, and the effect of the present invention tends to be reduced.

The IP mentioned here is based on the method described in Macromolecules, vol. 6, p. 925 (1973). That is, IP refers to an isotactic fraction in pentad units in a propylene-based polymer molecular chain measured using a nuclear magnetic resonance spectrum ( ¹³ C-NMR) of isotope carbon. Incidentally, IP referred to in the present invention is a measured value of polypropylene itself obtained by polymerization, the xylene extraction, other extraction,
It is not the measured value of polypropylene after fractionation. Peak assignments were made by Macromolecules (Macromol
Based on a revised version of the above document described in Ecules, Vol. 8, p. 687 (1975), IP was measured based on the intensity fraction of the mmmm peak among all the absorption peaks in the methyl carbon region of the ¹³ C-NMR spectrum. .

The average isotactic chain length N is the average isotactic chain length of a methyl group in a polypropylene molecule, and is described in Chapter 2 (1977) of Polymer Sequence Distribution.
Annual) (Academic Press New York (Academic
Press, New York)). C. Randall (J.
C. Randall). Specifically, polypropylene is dissolved in a mixed solvent of 1,2,4-trichlorobenzene / heavy benzene by heating to a temperature of 120 ° C. so that the polymer concentration becomes about 10% by weight. This solution is
The sample is put in a φ glass sample tube, and ¹³ C-NMR is measured under the same measurement conditions as the above isotactic pentad fraction (IP).

[0029] Polymer Journa
l) The definition of the two-site model described in Vol. 15 (No. 12), pages 859 to 868 (1983), that is, it is assumed that there are two types of active sites during polymerization. One of them is called catalyst-controlled polymerization and the other is called terminal-controlled polymerization. (For the catalyst-controlled polymerization and terminal-controlled polymerization, Junji Furukawa; Essences and Topics of Polymers 2, “Polymer Synthesis”, p. 73) , Issued by Kagaku Dojin (1986).) The two-site model is as follows: α: Probability of addition of D-form and L-form due to catalyst-controlled polymerization (indicator of the degree of disorder in isotactic components); σ: Terminal-controlled polymerization (Bernoulli process) Probability that a meso body is formed; ω: ratio of α site; In the propylene homopolymer, the methyl group splits into ten peaks in pentad units due to stereoregularity. However, α, σ,
ω is determined by the method of least squares, and each pentad unit is determined by the equation shown in Table 1.

[0030]

[Table 1]

Next, the definition formula of the isotactic average chain length (N) described in the above-mentioned Randall document N 1 = A _{1 to} A ₇ which is obtained by calculating N = chain length of meso form / number of units of meso form. Applying each pentad unit of

N = (A ₁ + A ₂ + A ₃ +0.5 (A ₄ + A ₅ + A ₆ +
A ₇₎₎ / 0.5 can be calculated average chain length (N) by _{(A 4 + A 5 + A} 6 + A 7). The N value in the present invention is a measured value of the polypropylene itself obtained by polymerization, not a measured value of the polypropylene after the above-mentioned xylene extraction, other extraction, fractionation and the like.

In general, the ¹³ C-NMR signal of polypropylene has three main peaks of methylene, methine and methyl, of which the peak in the methyl region indicates the form of the asymmetric bond. The average crystallizable isotactic chain length may be considered to be inversely related to the number of asymmetric bonds. The greater the number of irregular bonds, that is, the more racemic structures that cut the mm mm structure, the shorter the average chain length (N).
The average chain length (N) obtained in this way represents the length of the sequence of the crystallizable isotactic structure as described above, so that the longer the length (ie, the smaller the number of asymmetric bonds), It is considered that physical properties such as rigidity of the propylene-based polymer are improved.

Isotactic average chain length (Nf) of each fraction by column fractionation of xylene-extracted insolubles
Means that the xylene-extracted insoluble polypropylene obtained at the time of XI measurement is dissolved in para-xylene at a temperature of 130 ° C., celite is added, the temperature is lowered to 30 ° C. at a rate of 10 ° C./hour, and adhered to the celite. Fill the column,
The temperature was raised from a temperature of 70 to 130 ° C. every 2.5 ° C., fractionated by fraction, the average isotactic chain length was determined for each fraction by the above method, and this was determined by isotacticity of each fraction. Average chain length (Nf)
And

When the propylene resin of the present invention satisfies the requirements described below, the effects of the present invention can be further enhanced. Although the number average molecular weight (Mn) of the propylene-based resin of the present invention is not particularly limited, it is preferably 30,000 or more, and the weight average molecular weight (Mw) is not particularly limited. Less than ten thousand,
It is preferably 250,000 or more and less than 1,000,000, and the Z-average molecular weight (Mz) is not particularly limited.
10,000 or more is preferable. Further, Mw / Mn is not particularly limited, but is preferably 7.0 or more, and Mz / Mw
Is not particularly limited, but is preferably 7.0 or more.

In the propylene-based resin of the present invention, the proportion of those having a molecular weight of 1,000,000 or more in all the molecules is not particularly limited, but is preferably 5.0% by weight or more. In addition, the intrinsic viscosity (also referred to as intrinsic viscosity and represented by [η]) is not particularly limited, but a value obtained by measuring at 135 ° C. in tetralin may exceed 4.0 dl / g. preferable.

The temperature of the propylene resin of the present invention is 230
° C, melt flow rate (MF at 2.16 kgf load)
R) is not particularly limited, but is 0.01 to 300.
g / 10 minutes is preferable, and the thing of 0.1-150 g / 10 minutes is suitable. If the ratio is outside the above range, the moldability is poor.

The method for producing the propylene resin of the present invention is not particularly limited as long as it can be prepared so as to satisfy the above formula (1). For example, it can be produced by polymerization of propylene using a Ziegler-Natta catalyst. In particular, it can be obtained by adjusting the polymerization conditions using a catalyst that gives isotactic polypropylene. Moreover, it can also be obtained by mixing at least two types obtained by individual polymerization.

The catalyst used in the production of the propylene-based resin of the present invention is not particularly limited. For example, a catalyst obtained by combining the olefin polymerization catalyst component obtained by the following preparation method with an organometallic component is used. Can be. That is, the catalyst component for olefin polymerization is (1) a method of co-milling magnesium chloride / alkoxysilane adduct, titanium tetrachloride / electron-donating compound complex, a titanium compound and an electron-donating compound, (2) magnesium chloride / alkoxysilane.
A method in which an alkoxysilane adduct is brought into contact with a titanium tetrachloride / electron donating compound complex and then treated simultaneously with a titanium compound and an electron donating compound. (3) Magnesium chloride / alkoxysilane adduct and titanium tetrachloride / electron It can be prepared by, for example, a method of bringing a titanium compound and an electron-donating compound into contact with each other after contacting with a donor compound complex. The catalyst component for olefin polymerization thus obtained may be used as it is for the production of an olefin polymer, but may also be used after removing unreacted substances and by-products by operations such as filtration and washing.

The titanium compound is preferably a titanium halide such as titanium tetrachloride, titanium trichloride, titanium tetrabromide, etc., more preferably a tetravalent titanium compound containing halogen, particularly preferably tetrachloride. It is titanium.

As the electron donating compound, it is preferable to use at least one compound selected from an organosilicon compound having an alkoxy group, a nitrogen-containing compound, a phosphorus-containing compound and an oxygen-containing compound. Among these, it is particularly preferable to use an organosilicon compound having an alkoxy group. The amount of the electron donating compound used is a molar ratio of 0.001 to the organoaluminum compound.
5, preferably in the range of 0.01 to 1.

Specific examples of the organosilicon compound having an alkoxy group include tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, tetraisobutoxysilane, trimethylmethoxysilane, trimethylethoxysilane, triethylmethoxysilane, and triethylethoxysilane. , Ethyl isopropyl dimethoxy silane, propyl isopropyl dimethoxy silane, diisopropyl dimethoxy silane, diisobutyl dimethoxy silane, isopropyl isobutyl dimethoxy silane, di-te
rt-butyldimethoxysilane, tert-butylmethyldimethoxysilane, tert-butylethyldimethoxysilane,
tert-butyl-n-propyldimethoxysilane, tert-
Butyl isopropyl dimethoxy silane, tert-butyl normal butyl dimethoxy silane, tert-butyl isobutyl dimethoxy silane, tert-butyl (sec-butyl) dimethoxy silane, tert-butyl amyl dimethoxy silane, tert-butyl hexyl dimethoxy silane, tert-butyl heptyl dimethoxy Silane, tert-butyloctyldimethoxysilane, tert-butylnonyldimethoxysilane, tert-butyldecyldimethoxysilane, tert-butyl (3,3,3-trifluoromethylpropyl) dimethoxysilane, tert-butyl (cyclopentyl) dimethoxysilane, tert-butyl (cyclohexyl) dimethoxysilane, dicyclopentyldimethoxysilane, bis (2
-Methylcyclopentyl) dimethoxysilane, bis (2,3-dimethylcyclopentyl) dimethoxysilane, diphenyldimethoxysilane, phenyltriethoxysilane, mesityltrimethoxysilane, ethyltrimethoxysilane, n-propyltrimethoxysilane, isopropyltrimethoxysilane Butyltrimethoxysilane, isobutyltrimethoxysilane, tert-butyltrimethoxysilane, sec-butyltrimethoxysilane, amyltrimethoxysilane, isoamyltrimethoxysilane, cyclopentyltrimethoxysilane, cyclohexyltrimethoxysilane, norbornanetrimethoxysilane, Indenyltrimethoxysilane, 2-methylcyclopentyltrimethoxysilane, cyclopentyl (tert-
Butoxy) dimethoxysilane, isopropyl (tert-butoxy) dimethoxysilane, tert-butyl (isobutoxy) dimethoxysilane, tert-butyl (tert-butoxy) dimethoxysilane, texyltrimethoxysilane,
Texyl (isopropoxy) dimethoxysilane, texyl (tert-butoxy) dimethoxysilane, and the like.

As the nitrogen-containing compound, specifically,
2,6-diisopropylpiperidine, 2,6-diisopropyl-4-methylpiperidine, N-methyl-2,2,
2,6-substituted piperidines such as 6,6-tetramethylpiperidine, 2,5-diisopropylpyrrolidine, N-
2,5-substituted pyrrolidines such as methyl-2,2,5,5-tetramethylpyrrolidine, N, N, N ', N'-tetramethylmethylenediamine, N, N, N', N'-tetraethylmethylene Substituted methylene diamines such as diamines; and substituted imidazolines such as 1,3-dibenzylimidazolidine and 1,3-dibenzyl-2-phenylimidazolidine.

Specific examples of the phosphorus-containing compound include triethyl phosphite, trinormal propyl phosphite, triisopropyl phosphite, trinormal butyl phosphite, triisobutyl phosphite, diethyl normal butyl phosphite, and diethyl phenyl phosphite. And the like.

As the oxygen-containing compound, specifically,
2,2,6,6-tetramethyltetrahydrofuran,
2,6-substituted tetrahydrofurans such as 2,2,6,6-tetraethyltetrahydrofuran, 1,1-dimethoxy-2,3,4,5-tetrachlorocyclopentadiene, 9,9-dimethoxyfluorene, diphenyldimethoxymethane and the like And the like. However, it is not limited to these.

As the organometallic component, for example, organoaluminum compounds represented by the following formulas (5) to (8) can be used.

[0046]

Embedded image

The above equations (5), (6), (7) and (8)
In the formula, R ³ , R ⁴ , and R ⁵ may be the same or different, and are a hydrocarbon group having at most 12 carbon atoms, a halogen atom or a hydrogen atom, and at least one of them is a hydrocarbon group; R ⁶ , R ⁷ , R ⁸ and R ⁹ may be the same or different and are a hydrocarbon group having at most 12 carbon atoms.
R ¹⁰ is a hydrocarbon group having at most 12 carbon atoms, and k is an integer of 1 or more.

Representative examples of the organoaluminum compound represented by the formula (5) include trialkylaluminums such as triethylaluminum, tripropylaluminum, tributylaluminum, triisobutylaluminum, trihexylaluminum and trioctylaluminum. Furthermore, alkyl aluminum hydrides such as diethyl aluminum hydride and diisobutyl aluminum hydride, and alkyl aluminum halides such as diethyl aluminum chloride, diethyl aluminum bromide and ethyl aluminum sesquichloride can be mentioned.

Representative examples of the organoaluminum compound represented by the formula (6) include alkyldialuminoxanes such as tetraethyldialuminoxane and tetrabutyldialuminoxane.

Formulas (7) and (8) represent aluminoxanes, which are polymers of aluminium compounds. R ¹⁰ includes a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group and the like, and is preferably a methyl group or an ethyl group. k
Is preferably 1 to 10.

Of these organoaluminum compounds,
Trialkylaluminums, alkylaluminum halides and alkylaluminoxanes are preferred, and trialkylaluminums are particularly preferred.

In the production of the olefin polymer, the amount of the organoaluminum compound used in the polymerization system is generally 10 ^-4 mmol / l or more, and 10 ^-2 mmol / l.
The above is preferable. In addition, the usage ratio to the titanium atom in the solid catalyst component for olefin polymerization is generally a molar ratio.
0.5 or more, preferably 2 or more, particularly preferably 10 or more. If the amount of the organoaluminum compound is too small, the polymerization activity is significantly reduced.
When the amount of the organoaluminum compound used in the polymerization system is 20 mmol / l or more and the ratio to the titanium atom is 1000 or more in molar ratio, the catalyst performance is further improved even if these values are further increased. There is no.

The propylene-based resin of the present invention is obtained by polymerizing propylene alone, but can be obtained by copolymerizing propylene with ethylene or α-olefin. As an α-olefin,
Examples thereof include 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, and 4-methyl-1-pentene. These two or more comonomers may be mixed and used for copolymerization with propylene.

The propylene-based resin of the present invention has a single-stage polymerization,
It can be produced by multi-stage polymerization or continuous multi-stage polymerization. The polymerization can be carried out by a slurry polymerization method, a gas phase polymerization method, a combination of the slurry polymerization method and the gas phase polymerization method, or the like. Further, the propylene-based resin of the present invention can be obtained by combining single-stage polymerized products, a single-stage polymerized product and a multi-stage polymerized product, or a multi-stage polymerized product and mixing the respective components. The mixing can be performed by combining two or more kinds of plural components.

A specific production method for producing the propylene resin of the present invention by continuous multistage polymerization is as follows.
The first step is slurry polymerization or gas phase polymerization, using Ziegler-Natta catalyst, using hydrogen as a molecular weight controller,
Hydrogen concentration 0 ~ 0.008mol%, polymerization pressure 30 ~ 50kg
/ Cm ² , polymerization temperature 70-80 ° C., high load melt flow rate (temperature 230 ° C., load 21.6 kgf MF
R; hereinafter abbreviated as HLMFR. ) Is 0.1 to 20 g /
A propylene-based polymer was obtained for 10 minutes, and hydrogen was used as a molecular weight control agent in the second stage, at a polymerization pressure of 30 to 50 kg / cm.
² , at a polymerization temperature of 70 to 80 ° C. and an MFR of 5 to 300 g /
A propylene-based polymer for 10 minutes was obtained, and in the third step, a slurry method polymerization or a gas phase method polymerization was used, a hydrogen was used as a molecular weight controller with a Ziegler-Natta catalyst, and a hydrogen concentration of 0 was obtained.
0.010.01 mol%, polymerization pressure 30-50 kg / cm ² , polymerization temperature 70-80 ° C., HLMFR 1-50 g / 10
Propylene-based polymer is obtained. Also, the polymerization temperature,
The propylene-based polymer can be obtained even in a polymerization facility in which a molecular weight controlling agent can be added and removed at an arbitrary time.

In the case of producing the propylene-based resin of the present invention by mixing a plurality of polymerization components, known techniques can be used as they are. For example, a method of mixing the powder and the granulated pellets obtained by polymerization in a batch system such as a mixer or a tumbler, and a method of continuously adding and mixing the powder and granulated pellets to a pneumatic conveying device or the like by using a measuring device can be used. A melt mixing method is used to increase the degree of mixing. For example, powder and granulated pellets melt kneading machine, for example,
There is a method of melting and mixing with a kneader, a roll, a Brabender, an extruder, etc., and pelletizing with a granulator. Although not particularly limited, an extruder is generally used in order to improve productivity, and particularly preferably, a twin-screw extruder having a rotor portion, and a melt-mixing machine in which molecular weights and melt viscosities are significantly different are further mixed. In this case, a tandem extruder in which two extruders are connected in series is more preferable.

As an example of a specific component ratio when mixing, the component (A): weight average molecular weight Mw is 5.0 × 10 ⁴ to
15.0 × 10 ⁴ , more preferably 7.0 × 10 ^{4 to} 13.0 × 10 ⁴
70% by weight to 97% by weight of a propylene-based polymer, component (B): a weight average molecular weight Mw of 100 × 10 ^{4 to} 900
× 10 ⁴ , more preferably 150 × 10 ^{4 to} 500 × 10
⁴ of the propylene polymer 3 wt% to 30 wt%, and component (C): Weight average molecular weight Mw of 15.0 × 10 ⁴ to exceed 100 × 10 below ^4, more preferably 18.0 × 10 ⁴ ~80.0
× 10 ⁴ propylene-based polymer in 0% by weight to 10% by weight
Is mentioned. By mixing such components, the effects of the present invention can be sufficiently exhibited. In addition, each of the above components can be produced by multistage polymerization or continuous multistage polymerization.

The propylene resin according to the present invention may contain various additives, compounding agents, and the like, as long as the properties of the resin are not impaired.
Fillers and the like can be used. If these are specifically shown, antioxidants, heat stabilizers, ultraviolet absorbers, light stabilizers, weather resistance stabilizers, antistatic agents, antifogging agents, flame retardants, lubricants, slip agents, antiblocking agents, plasticizers Agents, release agents, foaming agents, filler-based inorganic fillers such as talc and silica, fiber-based inorganic fillers such as glass fiber and carbon fiber, organic fillers, reinforcing agents, coloring agents, dyes, pigments, fragrances, etc. No. Further, various thermoplastic resins and the like can be added.

Various nucleating agents may be added to the propylene resin of the present invention as needed. Examples thereof include inorganic compounds such as metal salts of carboxylic acids, dibenzylidene sorbitol derivatives, phosphate metal salts, talc, and silica. Specific examples include sodium benzoate,
Aluminum adipate, sodium thiophenecarboxylate, 1,3,2,4-dibenzylidenesorbitol,
1,3,2,4-di- (p-methylbenzylidene) sorbitol, 1,3-p-chlorobenzylidene-2,4-
p-Methylbenzylidene sorbitol, sodium-bis- (4-t-butylphenyl) phosphate, sodium-bis- (4-methylphenyl) phosphate, potassium-bis- (4-t-butylphenyl) phosphate, sodium -2,2'-methylene-bis-
(4,6-di-t-butylphenyl) phosphate,
Sodium-2,2'-ethylidene-bis (4,6-di-t-butylphenyl) phosphate; talc; calcium carbonate; These nucleating agents may be used alone or in combination of two or more.

The amount of the nucleating agent to be added depends on the amount of the propylene resin or the resin composition 1 containing the propylene resin.
The amount is preferably 0.01 to 2.0 parts by weight with respect to 00 parts by weight.
Preferably, 0.05 to 1.0 part by weight, particularly preferably 0.06
It is in the range of ~ 0.4 parts by weight. If the amount of the crystal nucleating agent is less than 0.01 part by weight, the effect of improving rigidity and heat resistance is poor, and if it exceeds 2.0 parts by weight, the effect may be saturated and the cost is increased.

The propylene-based resin of the present invention and a composition containing the propylene-based resin can be supplied to a product having a desired shape by using a known molding technique generally used in the field of synthetic resins. The molding technology is not particularly limited, but there are injection molding, hollow molding, and extrusion molding depending on the molding machine shape, and further, depending on the shape of the molded resin product, film molding, tenter molding, sheet molding, vacuum molding, extrusion lamination. Molding, calender molding, profile molding, fiber spinning, non-woven fabric, compression molding, foam molding and the like. These can be combined with one or more molding techniques to provide a product having a desired shape.

For example, in the case of injection molding, the method is not particularly limited as long as it is a method used as a known technique.
It can be performed by cooling and solidifying in a mold through a holding pressure. Injection molding machines include plunger-type injection molding machines, screw pre-plasticization molding machines, in-line screw injection molding machines, vent-type injection molding machines, gas-assisted injection molding machines, injection compression molding machines, and injection stretch molding machines. ,
An injection blow molding machine and the like can be mentioned. In general, injection molding is excellent in dimensional accuracy, has a short molding cycle, and is suitable for mass-producing products with complicated shapes.The propylene-based resin used in the molding process is a flow mark caused by resin flow during filling. Those which do not generate silver or silver are more preferable.

As a combination of a plurality of molding techniques, for example, in vacuum molding, a sheet produced by T-die extrusion molding, calender molding or the like is heated and softened while clamping both ends thereof, and the gap between the female mold and the clamp is vacuumed. The plasticized and softened sheet is formed in close contact with a mold by using a plug, compressed air, or the like, and the molded article can be mass-produced at low cost by removing the molded article from the mold after cooling. As the propylene resin used in the molding process, it is generally preferred to add an ethylene resin in order to avoid drawdown such as sagging or deformation due to the weight of the sheet during softening by heating. Since the addition of a series resin inevitably causes a decrease in rigidity and heat resistance, it is most preferable to suppress the occurrence of drawdown only with a propylene series resin.

[0064]

The present invention will be specifically described below with reference to examples. The physical properties of the polymers in Examples and Comparative Examples were measured by the following methods.

Measurement of dynamic viscoelasticity: A propylene-based resin was compression-molded by a press at 230 ° C. for 5 minutes so as to prevent bubbles from entering into a disk-shaped measurement sample having a thickness of 1.5 mm and a diameter of 25 mm. Measurements are made using Rheometrics
s) Rheometer (RMS800) manufactured by the company
Was performed using Using a parallel disk having a diameter of 25 mm and a gap of 1.4 mm, an MFR of 2 g /
A sample of 10 minutes or less has an MFR of 2 g / l at 230 ° C.
The storage modulus (G ′) and the loss modulus (G ″) of the sample exceeding 0 minutes were measured at 210 ° C. and in the frequency range of 0.01 rad / sec to 150 rad / sec. PI was defined as 10 ⁵ times the reciprocal of the storage elastic modulus (unit: Pa) at the point Gc where G and (") intersect.

Bending elastic modulus: JIS of test specimens by injection molding
Prepared according to the method described in K6758. The flexural modulus was measured according to JIS K7203.

Xylene extraction insoluble content ratio (XI): About 2 g of a powdery propylene-based resin is precisely weighed to obtain a sample.
A sample and 250 ml of o-xylene were heated in a 300 ml flask equipped with an Aline cooler and a thermometer.
Heating was performed at 135 ° C. for 30 minutes. Then, it was left to cool to 25 ° C. Thereafter, the solid was filtered, and the solid was dried by heating at 140 ° C. for 30 minutes under a nitrogen atmosphere. After allowing the mixture to cool sufficiently, it was weighed to determine the ratio (% by weight) of the xylene-insoluble matter.

Weight analysis of each fraction of the xylene-extracted insoluble fraction by column fractionation: The above xylene-extracted insoluble fraction was dissolved in p-xylene at a temperature of 130 ° C, celite was added, and the mixture was cooled to 30 ° C at a temperature gradient of 10 ° C / hr. Then, the xylene-extracted insoluble matter was adsorbed on Celite. The adsorbate was packed in a cylindrical column, and the temperature was increased from 70 ° C. to 130 ° C. every 2.5 ° C. while flowing p-xylene as a developing solution, and fractionated into fractions at each temperature. The developing solution is evaporated, and the solid substance is heated at 140 ° C. 3 under a nitrogen atmosphere.
It was dried by heating for 0 minutes. After allowing the mixture to cool sufficiently, it was weighed to determine the weight ratio (% by weight) of each fraction.

Isotactic pentad fraction (IP)
And measurement of the isotactic average chain length (N) and the isotactic average chain length (Nf) of each fraction: The measurement was performed using JNM-GSX400 ( ^13C nuclear resonance frequency 100 MHz) manufactured by JEOL Ltd. The measurement was performed under the following measurement conditions. IP is Macromolecule
s) According to the method described in Volume 6, page 925 (published in 1973),
N and Nf are based on Polymer Sequence Distribution, Chapter 2 (1977).
Annual) (Academic Press New York (Academic
Press, New York)). C. Randall (J.
C. Randall). Measurement mode: Proton decoupling method, pulse width: 8.0 μs, pulse repetition time: 3.0 μs, number of integration: 20,000 times, solvent: 1,2,4-trichlorobenzene / deuterated benzene mixed solvent (75/25 weight Ratio), internal standard compound: hexamethyldisiloxane, sample concentration: 300 mg / 3.0 ml (solvent), measurement temperature: 120 ° C.

MFR and HLMFR: JIS K721
0, and measured at a temperature of 230 ° C.

Heat resistance: Heat resistance is determined by the deflection temperature under load (HD
T) was measured according to JIS K7207.

Molecular weight (Mw): Measured using GPC. Preparation of calibration curve 1,2,4-trichlorobenzene 10 containing 0.1% by weight of 2,6-di-t-butyl-p-cresol (BHT)
2 mg each of three kinds of standard polystyrene samples (manufactured by Showa Denko KK) having different molecular weights,
After dissolving in a dark place for 1 hour, the elution time of the peak top was measured by GPC measurement. This measurement was repeated, and a calibration curve was prepared from the molecular weights at a total of 12 points (molecular weight of 580 to 8.5 million) and the elution time at the peak top by linear approximation. Measurement of Sample 2 mg of a sample was placed in 5 ml of 1,2,4-trichlorobenzene containing 0.1% by weight of BHT, and dissolved while stirring at 160 ° C. for 2 hours, and then GPC measurement was performed. Other measurement conditions : 150C manufactured by Waters, moving bed: 1,2,4-trichlorobenzene (BHT 0.1
Column): Showdex HT-G manufactured by Showa Denko KK
(1), Showdex HT-806M (2), Measurement temperature: 140 ° C, Sample preparation: About 2 mg at 160 ° C in 3.5 ml of 1,2,4-trichlorobenzene (including 0.1% by weight of BHT).
For 2 hours. Sample injection volume: 0.5 ml, flow rate: 1.0 ml / min.

Evaluation of moldability: compatibility with vacuum molding is 2
g / 10 min or less low MFR propylene resin, 50mm width 50mm thickness 50μm length 1
A 50 mm sheet was prepared, and the drawdown property and the appearance of the molded product were evaluated using a cup-shaped mold using our simple vacuum forming apparatus. The suitability for injection molding is as follows. For this propylene-based resin exceeding 2 g / 10 minutes, a large flat plate (600 × 150 × 0.5 mm) having a large flow aspect is molded using a 500T injection molding machine manufactured by Toshiba Machine Co., Ltd. The appearance of the molded article was evaluated.

Example 1 Preparation of catalyst component for olefin polymerization: (1) Preparation of solid component 568 g (5.97 mol) of anhydrous magnesium chloride was added to 1.0 kg (1.74 mol) of anhydrous ethanol, and Vaseline oil CP15N 5.0 manufactured by Idemitsu Kosan Co., Ltd. Liter and silicone oil KF96 manufactured by Shin-Etsu Silicone Co., Ltd. were completely dissolved at 120 ° C. in a nitrogen atmosphere at 5.0 ° C. This mixture was stirred for 3 minutes at 120 ° C. and 3000 rpm using a TK homomixer manufactured by Tokushu Kika Kogyo Co., Ltd. While maintaining agitation, in 20 liters of anhydrous heptane at 0 ° C.
Transported so as not to exceed. The obtained white solid was sufficiently washed with anhydrous heptane and dried in vacuum at room temperature. 300 g of the obtained spherical solid of MgCl ₂ .2.5 C ₂ H ₅ OH was suspended in 2.0 liters of anhydrous heptane. While stirring at 0 ° C., 5.0 liter (45 mol) of titanium tetrachloride was added dropwise over 1 hour. Next, heating was started, and when the temperature reached 40 ° C., 49.6 g of diisobutyl phthalate (178 mmol
1) was added and the temperature was raised to 100 ° C. in about 1 hour. 1
After reacting at 00 ° C. for 2 hours, a solid portion was collected by hot filtration. Thereafter, 5.0 liters (45 mol) of titanium tetrachloride was suspended in the reaction product, and the reaction was performed at 120 ° C. for 1 hour. After the completion of the reaction, a solid portion was collected again by hot filtration. Then, with 10 liters of hexane at 60 ° C, 7
This was washed three times with 10 liters of hexane at room temperature three times to obtain a solid component.

(2) TiCl ₄ [C ₆ H ₄ (COOiC
Preparation of ₄ H ₉ ) ₂ ] Hexane 1 containing 190 g (1.0 mol) of titanium tetrachloride
278 g of diisobutyl phthalate (1.
0 mol) was added dropwise over about 30 minutes while maintaining the temperature at 0 ° C. After completion of the dropwise addition, the temperature was raised to 40 ° C., and the reaction was performed for 30 minutes.
After completion of the reaction, a solid portion was collected and washed three times with 5.0 liters of hexane to obtain an intended product.

(3) TiCl ₄ [C ₆ H ₄ (COOiC
₄ H ₉ ) ₂ ] 400 g of the solid component obtained in the above (1) was suspended in 6.0 liters of toluene, and TiCl ₄ [C ₆ H ₄ (CO 2
OiC ₄ H ₉ ) ₂ ] was treated with 103 g (220 mmol) for 1 hour to be supported. After the completion of the loading, a solid portion was collected by filtration. After that, 6.0 l of toluene and 200 ml (1.8 mol) of titanium tetrachloride were suspended in the reaction product, and reacted at 90 ° C. for 2 hours. After the completion of the reaction, a solid portion was collected again by hot filtration. Subsequently, the solid was washed five times with 10 liters of toluene at 90 ° C. and three times with 10 liters of hexane at room temperature to obtain a solid catalyst component for olefin polymerization.

Pre-polymerization: Under nitrogen atmosphere, inner volume 5
In a 0 liter autoclave, 10 liters of n-heptane and 120 g of triethylaluminum (1.6 mol
l), 78 g of dicyclopentyldimethoxysilane (34
0 mmol) and 200 g of the solid catalyst component for olefin polymerization obtained in (3) above, and the mixture was stirred for 5 minutes in a temperature range of 0 to 5 ° C. Next, 10 g / g of the solid catalyst component
Propylene was fed into the autoclave so that g of propylene was polymerized, and prepolymerized for 1 hour in a temperature range of 0 to 5 ° C. The obtained prepolymerized catalyst was washed three times with 10 liters of n-heptane and used for the production of the following propylene-based resin.

First stage propylene polymerization: internal volume 290
In a liter reactor equipped with a stirrer, propylene 95 kg /
Time, 10 g / h of the above prepolymerized catalyst, 59 g / h of triethylaluminum (520 mmol / h), 35.3 g / h of dicyclopentyldimethoxysilane (155 m / h)
mol / hour), and hydrogen for polymerization adjustment is 0.0030 mol% and H
The LMFR was continuously supplied while being adjusted to 1 g / 10 minutes. The reactor was kept at 80 ° C., and lumped slurry polymerization with liquefied propylene was performed to polymerize propylene. HLM as planned
Propylene polymer having an FR of 1 g / 10 min (P-1-
1) was obtained.

Second stage propylene polymerization: Internal volume 580
The propylene-based polymer (P-1-2) in the second stage only was supplied with 95 kg / hour of propylene and 1.3 mol% of hydrogen for polymerization adjustment while supplying the polymer of the first stage to a liter reactor equipped with a stirrer. ) Was supplied while adjusting the MFR to 10 g / 10 minutes. The reactor was kept at 80 ° C. to perform bulk slurry polymerization with liquefied propylene,
The polymer (P-1) in the entire two-stage polymerization including the polymer in the first stage and the polymer in the second stage (MFR of 0.48 g / 1
0 min). The polymer (P-
1) Tris (2,4-di-t-
Butylphenyl) phosphite 0.09 parts by weight, pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] 0.15 parts by weight, calcium stearate 0.08 parts by weight, sodium 2,2 ′ -Methylene bis (4,6-di-t-butylphenyl) phosphate (trade name, manufactured by Asahi Denka Kogyo Co., Ltd.)
NA-11) 0.2 parts by weight of an additive was added by melt-kneading and pelletized to obtain a propylene-based resin (P-1-R).
The obtained propylene-based resin (P-1-R) contains 33 parts by weight of the first-stage propylene-based polymer and 67 parts by weight of the second-stage propylene-based polymer. It was shown to. Table 2 shows the MFR, Mw, composition ratio, and the like of the polymer of each component and the entire resin (the same applies to the following examples). When the suitability for vacuum forming was evaluated using this propylene-based resin (P-1-R), it was possible to form sufficiently with little drawdown.

Example 2 First-stage propylene polymerization: Performed in the same manner as in Example 1.
A propylene-based polymer (P-2-1) was obtained. Second-stage propylene polymerization: 95 kg / hour of propylene and 1.6 g of hydrogen for polymerization adjustment were supplied to a reactor with an internal volume of 580 liters equipped with a stirrer while supplying the first-stage polymer.
mol% of the propylene polymer (P
It was supplied while adjusting the MFR of -2-2) to be 100 g / 10 minutes. The reactor was kept at 80 ° C., and bulk slurry polymerization with liquefied propylene was performed to obtain a polymer in the entire second-stage polymerization including the first-stage polymer and the second-stage polymer. Third-stage propylene polymerization: 95 kg / hour of propylene was supplied to the reactor with the stirrer having an internal volume of 290 liters while supplying the polymer in the first and second stages (the polymer in the entire second-stage polymerization). 2.0mol of hydrogen for polymerization adjustment
MF of polymer (P-2-3) in the third stage only at 1%
It was supplied while adjusting R to be 300 g / 10 minutes. The reactor was kept at 80 ° C., and bulk slurry polymerization with liquefied propylene was performed to obtain a polymer in the entire three-stage polymerization including the polymers in the first, second, and third stages. As a result, the polymer (P-2) in the entire three-stage polymerization
(MFR: 81.3 g / 10 minutes). Further, based on 100 parts by weight of the polymer (P-2) in the entire three-stage polymerization, 0.09 parts by weight of tris (2,4-di-t-butylphenyl) phosphite and pentaerythrityl-tetrakis [3- ( 3,5-di-t-butyl-4-hydroxyphenyl) propionate] 0.15 parts by weight, calcium stearate 0.08 parts by weight, sodium 2,2'-methylenebis (4,6-di-t-butylphenyl) phosphate (Asahi Denka Kogyo Co., Ltd., trade name NA-11) 0.2 parts by weight of an additive was melt-kneaded and pelletized to obtain a propylene-based resin (P-2-R). In the obtained propylene-based resin (P-2-R), the first-stage propylene-based polymer (P-2-1) contained 15 parts by weight, and the second-stage propylene-based polymer (P-2-2) was used. 20 parts by weight, 65 parts by weight of the third-stage propylene-based polymer (P-2-3) was contained, and the physical properties are shown in Table 3. When the suitability for injection molding was evaluated using this propylene-based resin (P-2-R), a flat plate having a beautiful appearance without problems such as Flowmark Silver was obtained.

Example 3 95 kg / hour of propylene, 10 g / hour of the prepolymerized catalyst, 59 g / hour of triethylaluminum (520 mmol / hour)
Time), 35.3 g / hour of dicyclopentyldimethoxysilane (155 mmol / hour), and 1.9 m of hydrogen for adjusting the polymerization.
It was continuously supplied while controlling the MFR to be 203 g / 10 min in ol%. The reactor was kept at 70 ° C., and lumped slurry polymerization was performed using liquefied propylene to polymerize propylene to obtain a propylene-based polymer (P-3-1). Next, the propylene polymer (P-3-1) 80
Parts by weight, propylene-based polymer (P-1) 20 of Example 1
Parts by weight, 0.09 parts by weight of tris (2,4-di-t-butylphenyl) phosphite, 0.15 parts by weight of pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] Parts, calcium stearate 0.08 parts by weight, sodium 2,2'-methylenebis (4,6-di-t-butylphenyl) phosphate (manufactured by Asahi Denka Kogyo KK, trade name: NA-11) 0.2
The weight part is a twin screw extruder (KTX series made by Kobe Steel)
Was melt-kneaded at 210 ° C. and 300 rpm to obtain a propylene-based resin (P-3-R) having an MFR of 31.9 g / 10 min. The obtained propylene resin (P
Table 3 shows the physical properties of -3-R). When the suitability for injection molding was evaluated using this propylene-based resin, a flat plate having a beautiful appearance without problems such as flow mark silver was obtained.

Example 4 95 kg / h of propylene, 10 g / h of the above prepolymerized catalyst, 59 g / h of triethylaluminum (520 mmol / h) were placed in a 290 liter reactor equipped with a stirrer.
Hours), 35.3 g / hour (155 mmol / hour) of dicyclopentyldimethoxysilane, and 0.040 hydrogen for polymerization adjustment.
It was continuously supplied while adjusting the MFR to 1 g / 10 min in mol%. The reactor was kept at 75 ° C., and lumped slurry polymerization with liquefied propylene was performed to polymerize propylene to obtain a propylene-based polymer (P-4-1).
Next, 50 parts by weight of the propylene-based polymer (P-4-1), 50 parts by weight of the propylene-based polymer (P-1) of Example 1, and tris (2,4-di-t-butylphenyl) phospho 0.09 parts by weight of phytate, 0.15 parts by weight of pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 0.08 parts by weight of calcium stearate, sodium 2,2'-methylenebis (4 , 6-di-t-butylphenyl) phosphate (manufactured by Asahi Denka Kogyo Co., Ltd., trade name: NA-11) in an amount of 0.2 parts by weight was fed into a twin-screw extruder (Kobe Steel, KTX series).
Was melt-kneaded at 210 ° C. and 300 rpm to obtain a propylene-based resin (P-4-R) having an MFR of 0.7 g / 10 min. The obtained propylene resin (P
The physical properties of -4-R) are shown in Table 3. When the suitability for vacuum molding was evaluated using this propylene-based resin, it was possible to mold sufficiently with little drawdown.

Example 5 95 kg / h of propylene, 10 g / h of the above prepolymerized catalyst, 59 g / h of triethylaluminum (520 mmol / h)
Time), 35.3 g / hour of dicyclopentyldimethoxysilane (155 mmol / hour), and 1.0 m of hydrogen for adjusting polymerization.
It was continuously supplied while adjusting the MFR to 100 g / 10 min in ol%. The reactor was kept at 80 ° C., and lumped slurry polymerization with liquefied propylene was performed to polymerize propylene to obtain a propylene-based polymer (P-5-1). Next, the propylene-based polymer (P-5-1) 85
Parts by weight, 15 parts by weight of the propylene-based polymer (P-1-1) obtained by the polymerization in the first stage of Example 1, and 0.1 parts of tris (2,4-di-t-butylphenyl) phosphite.
09 parts by weight, pentaerythrityl-tetrakis [3-
(3,5-di-t-butyl-4-hydroxyphenyl)
Propionate] 0.15 parts by weight, calcium stearate
0.08 parts by weight, sodium 2,2′-methylenebis (4,4
0.2 parts by weight of 6-di-t-butylphenyl) phosphate (manufactured by Asahi Denka Kogyo KK, trade name: NA-11)
Using a twin screw extruder (KTX series, manufactured by Kobe Steel, Ltd.), melt kneading at 210 ° C. rotation speed and 300 rpm, and MF
A propylene-based resin having an R of 0.7 g / 10 minutes (P-5
R) was obtained. Obtained propylene-based resin (P-5-R)
The physical properties of are shown in Table 3. When the suitability for injection molding was evaluated using this propylene-based resin, a flat plate having a beautiful appearance without problems such as flow mark silver was obtained.

Comparative Example 1 Preliminary polymerization was carried out in the same manner as in Example 1 except that the solid component obtained by adjusting (1) the solid component in Example 1 was used as a polymerization catalyst. Next, the HLMFR of the first-stage propylene-based polymer (Q-1-1) was adjusted to 50 g / 10 minutes by setting the polymerization preparation hydrogen in the first-stage propylene polymerization to 0.020 mol%, and Assuming that the hydrogen for polymerization preparation in the polymerization of propylene in the second step was 0.20 mol%, the MFR of the propylene-based polymer (Q-1-2) in the second stage alone was 10 g / 1.
0 minutes, and the first-stage polymer (Q-1-
A propylene-based polymer (Q-1) having an MFR of 0.5 g / 10 minutes in the entire two-stage polymerization, including the polymer (Q-1-2) in the first stage and the polymer in the second stage. Example 1
The same additives as described above were added by melt-kneading to pelletize in the same manner as in Example 1 to obtain a propylene-based resin (Q-1-R).
Table 3 shows the physical properties of the obtained propylene-based resin (Q-1-R).
It was shown to. When the suitability for vacuum molding was evaluated using this propylene-based resin, the drawdown was large and molding was impossible.

Comparative Example 2 Prepolymerization was carried out in the same manner as in Example 1 except that the solid component obtained in (1) Preparation of Solid Component in Example 1 was used as a polymerization catalyst. Next, the MFR of the first-stage propylene-based polymer (Q-2-1) was adjusted to 10 g / 10 minutes by setting the polymerization preparation hydrogen in the first-stage propylene polymerization to 0.20 mol%. The hydrogen for preparation in the second propylene polymerization was set to 2.0 mol%, and the MFR of the propylene-based polymer (Q-2-2) in the second stage alone was adjusted to 300 g / 10 min. MFR of the polymer in the entire two-stage polymerization, including the coalesced and the polymer in the second stage
Is 24.2 g / 10 minutes propylene-based polymer (Q-
2) was obtained. The same additives as in Example 1 were added by melt-kneading and pelletized as in Example 1 to obtain a propylene-based resin (Q-2-R). The obtained propylene resin (Q
Table 3 shows the physical properties of -2-R). When the suitability for injection molding was evaluated using this propylene-based resin, only those that violently generated Flow Mark Silver or the like were obtained.

Comparative Example 3 In a nitrogen atmosphere, 6.0 g of AA type titanium trichloride and 23.5 g (13.5 g) of diethylaluminum chloride manufactured by Tosoh Akzo Co., Ltd. were placed in a 60-liter autoclave with a stirrer.
95 mmol), and then 18 kg of propylene are introduced.
The temperature was raised to 80 ° C., and polymerization was performed for 2 hours. Two hours later, unreacted propylene was removed to terminate the polymerization. As a result, the MFR was 0.9 g / 1.
A propylene-based polymer (Q-3) for 0 minutes was obtained. 100 parts by weight of this polymer (Q-3), tris (2,4-di-
t-butylphenyl) phosphite 0.09 parts by weight, pentaerythrityl-tetrakis [3- (3,5-di-t-
Butyl-4-hydroxyphenyl) propionate] 0.
15 parts by weight, 0.08 part by weight of calcium stearate, 0.2 part by weight of sodium 2,2'-methylenebis (4,6-di-t-butylphenyl) phosphate (manufactured by Asahi Denka Kogyo KK, trade name: NA-11) Melt kneading, MFR
Propylene resin (Q-3-R) which is 0.9 g / 10 minutes
I got Table 3 shows the physical properties of the obtained propylene-based resin (Q-3-R). When the suitability for vacuum forming was evaluated using this propylene-based resin, drawdown occurred, and the vacuum-formed product had an uneven thickness and poor appearance.

Comparative Example 4 6.0 g of AA type titanium trichloride and 23.5 g (13.5 g) of diethylaluminum chloride (manufactured by Tosoh Akzo Co., Ltd.) were placed in a 60-liter autoclave with a stirrer in a nitrogen atmosphere.
95 mmol), and then 18 kg of propylene, hydrogen was charged so as to be 0.35 mol% based on propylene, the temperature was raised to 70 ° C., and polymerization was performed for 1 hour. One hour later, unreacted propylene was removed to terminate the polymerization. As a result, a propylene-based polymer (Q-4) having an MFR of 10.0 g / 10 min was obtained. This polymer (Q-4) 1
00 parts by weight, tris (2,4-di-t-butylphenyl) phosphite 0.09 parts by weight, pentaerythrityl-
0.15 parts by weight of tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 0.08 parts by weight of calcium stearate, sodium 2,2′-methylenebis (4,6-di-t-butylphenyl) ) Phosphate (Asahi Denka Kogyo Co., Ltd., trade name: NA-1)
1) 0.2 parts by weight was melt-kneaded to obtain a propylene-based resin (Q-4-R) having an MFR of 10.0 g / 10 minutes. Table 3 shows the physical properties of the obtained propylene-based resin (Q-4-R). When the suitability for injection molding was evaluated using this propylene-based resin, there were cases where full filling was not possible, and flow mark silver occurred.

Comparative Example 5 6.0 g of AA type titanium trichloride and 23.5 g (13.5 g) of diethylaluminum chloride (manufactured by Tosoh Akzo Co., Ltd.) were placed in a 60-liter autoclave with a stirrer in a nitrogen atmosphere.
95 mmol), hydrogen was then charged so as to be 18 kg of propylene and 0.085 mol% with respect to propylene, and the temperature was raised to 70 ° C. to perform polymerization for 1 hour. 1
After an hour, unreacted propylene was removed to terminate the polymerization. As a result, a propylene-based polymer (Q-5) having an MFR of 3.0 g / 10 min was obtained. This polymer (Q-5) 1
00 parts by weight, tris (2,4-di-t-butylphenyl) phosphite 0.09 parts by weight, pentaerythrityl-
0.15 parts by weight of tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 0.08 parts by weight of calcium stearate, sodium 2,2′-methylenebis (4,6-di-t-butylphenyl) ) Phosphate (Asahi Denka Kogyo Co., Ltd., trade name: NA-1)
1) 0.2 parts by weight was melt-kneaded to obtain a propylene-based resin (Q-5-R) having an MFR of 10.0 g / 10 minutes. Table 3 shows the physical properties of the obtained propylene-based resin (Q-5-R). When the suitability for injection molding was evaluated using this propylene-based resin, there were cases where full filling was not possible, and flow mark silver occurred.

[0089]

[Table 2]

[0090]

[Table 3]

The two curves representing the relationship between the PI value and the FM value (Pa) when the equal signs on both sides of the formulas (1) and (4) are satisfied are compared with those of the propylene-based examples and the comparative examples. FIG. 2 is a graph plotting the measured values of the resin.

[0092]

The propylene resin of the present invention has a real part of a complex elastic modulus (dynamic elastic modulus G ') defined as a ratio of stress to sinusoidal strain in the viscoelastic behavior of a non-Newtonian polymer melt. And the imaginary part (loss modulus G ") at the intersection of the respective frequency dependence curves and the value of the flexural modulus have a specific relationship as defined in the claims. According to the propylene-based resin of the present invention, a sheet can be easily vacuum formed, and a molded product having excellent physical properties can be obtained. Can be obtained.

[Brief description of the drawings]

FIG. 1 shows a frequency ω dependency curve G ′ (ω) of storage modulus and a frequency ω of loss modulus obtained by dynamic viscoelasticity measurement of the present invention.
Dependency curve G "(ω).

FIG. 2 is a graph in which measured values of propylene-based resins of Examples and Comparative Examples are plotted against a relational expression between PI and FM (Pa) that defines the present invention.

Continued on the front page (72) Inventor Tadayoshi Wakasugi 2nd Nakanosu, Oita-shi, Oita Japan Polyolefin Co., Ltd. Oita Research Laboratories F-term (reference) BC16B BC25A BC25B BC26A BC26B BC32A BC32B BC34A BC34B CB44A CB44B CB47A CB47B CB53A CB73A CB73B CB74A CB74B CB75A CB75B CB88A CB88B CB92A CB92B DA02 DB01A DB02A DB03A DB04A EA01 EA02 EA03 EB01 EB02 EB03 EB04 EB05 EB08 EB09 EB10 EC01 EC02 FA01 FA04 FA09 GA01 GA04 GA05 GA06 GA15 GA21 GA26 4J100 AA03P CA01 DA39 DA41 DA47 DA49 FA09

Claims (5)

[Claims] 1. A storage modulus value at an intersection Gc of a frequency ω dependency curve G ′ (ω) of storage modulus and a frequency ω dependency curve G ″ (ω) of loss modulus by dynamic viscoelasticity measurement. The reciprocal of (unit: Pa) is 10 ⁵ times the PI and JIS K7
A propylene-based resin which satisfies the following formula (1) where the flexural modulus according to 203 is FM (unit: MPa): FM ≧ 1300 tan ⁻¹ (1.31 × PI) (1) 2. The value of the storage modulus at the intersection Gc of the frequency ω dependency curve G ′ (ω) of storage modulus and the frequency ω dependency curve G ″ (ω) of loss modulus obtained by dynamic viscoelasticity measurement. The reciprocal of (unit: Pa) is 10 ⁵ times the PI and JIS K7
2. The propylene resin according to claim 1, which satisfies the following expression (2): FM ≧ 1300 tan ⁻¹ (1.33 × PI) (2) where the flexural modulus according to 203 is FM (unit: MPa). 3. The propylene-based resin according to claim 1, wherein PI is 4 or more. 4. The ratio (XI) of the xylene-extracted insoluble content is 9
The propylene-based resin according to any one of claims 1 to 3, wherein the amount is 8.0% by weight or more. 5. An isotactic pentad fraction (IP) of at least 98.0% as determined by ¹³ C nuclear magnetic resonance spectrum analysis,
The total of those having an isotactic average chain length (N) of 500 or more and an average chain length (Nf) of 800 or more for each fraction by column fractionation of xylene-extracted insolubles is 10% by weight or more of all fractions. The propylene-based resin according to any one of claims 1 to 4, characterized in that: