SG172306A1 - Propylene-based resin composition, moldings, and container - Google Patents

Abstract

An object of the invention is to provide propylene resincompositions that can give shaped articles such as containers having excellent properties even when the thickness and weight are reduced. The composition of the invention includes a propylene polymer (A) satisfying (Al) to (A5), an ethylene/a-olefin copolymer (B) satisfying (B1) to (B3), anda nucleating agent. (Al): The propylene polymer contains 90.5 to 97.0 wt% of a decane-insoluble component (Dins01) and 3.0 to9.5 wt% of a decane-soluble component (D501). (A2): The component Dsol has nsol of 1.0 to 2.5 dl/g. (A3): The componentDs01 contains ethylene units at 25 to 35 wt%. (A4): Thecomponent Dinsol has ninscdof 0.8 to 1.1 dl/g. (A5): The propylene polymer has MFR (230°C, 2.16 kg) of 35 to 170 g/10 min. (B1): The copolymer is a copolymer made with a single-site catalyst. (B2): The copolymer has a density of 900 to 919 kg/m3. (B3): The copolymer has MFR (190°C, 2.16 kg) of 0.1 to 50 g/10 min.

Description

SF-2185 1

DESCRIPTION TITLE OF INVENTION

PROPYLENE RESIN COMPOSITION, SHAPED ARTICLE AND CONTAINER

TECHNICAL FIELD

[0001]

The present invention relates to propylene resin compositions, shaped articles formed from the compositions, and containers produced from the compositions.

BACKGROUND ART

[0002]

Packaging containers for foods such as jelly, pudding and coffee (hereinafter, also the food packaging containers) have been required to permit good visibility of contents, namely to have excellent transparency. Propylene resin compositions have excellent heat resistance, rigidity and transpareéncy and are frequently used as materials for highly transparent containers.

[0003]

Since foods are frequently handled in a low-temperature environment during storage or distribution, the food packaging containers require impact resistance not only at normal temperature but at low temperatures, namely low-temperature

SF-2185 2 impact resistance. :

[0004]

Known propylene resin compositions having excellent impact resistance contain a propylene/ethylene block copolymer, a nucleating agent, and a low-density polyethylene resin or a linear low-density polyethylene resin (for example, Patent

Literature 1).

[0005]

Literature (for example Patent Literatures 2 and 3) has disclosed propylene resin compositions of excellent low-temperature impact resistance that contain a propylene block copolymer and an ethylene resin and have specific properties,

[0006]

Recently, the containers as described above are required to be thinner and lighter from the viewpoint of reducing environmental load and costs.

[0007]

In detail, general food packaging containers range from approximately 0.7 to 0.9 mm in thickness, but the requirement is that the food packaging containers have a thickness of 0.5 mm or less.

[0008] :

However, the existing propylene resin compositions

SF-2185 3 cannot give containers such as food packaging containers showing sufficient performance when the thickness and weight are reduced from the conventional levels.

Citation List

Patent Literatures

[0009]

Patent Literature 1: JP-A-2001-26686

Patent Literature 2: JP-A-2002-18799%6

Patent Literature 3: JP-A-2002-187997

SUMMARY OF INVENTION Technical Problem

[0010] : i5 The present invention has beenmade in view of the problems in the art as described above. It is therefore an object of : the invention to provide propylene resin compositions that can give shaped articles including containers such as food packaging containers which show excellent rigidity, low-temperature impact resistance and transparency even when : the thickness and weight are reduced from the conventional levels. It is another object of the invention to provide shaped articles such as containers produced from the compositions.

SF-2185 4

Solutiecn to Problem [001%]

The present inventors studied diligently to achieve the above objects. They have then found that propylene resin compositions containing a specific propylene polymer, a specific ethylene/a-olefin copolymer and a nucleating agent can give shaped articles such as containers which show excellent rigidity, low-temperature impact resistance and transparency even when the thickness and weight are reduced from the conventional levels. The present invention has been completed Co based on the finding. -

[0012]

A propylene resin composition according to the present invention comprises 60 to 80 parts by weight of a propylene polymer (A) satisfying the following requirements (Al) to (A5), to 40 parts by weight of an ethylene/a-olefin copolymer (B) satisfying the following requirements (B1) to (B3) (wherein the total of the propylene polymer (A) and the ethylene/a-olefin copolymer (B) is 100 parts by weight), and 20 0.1 to 0.4 parts by weight of a nucleating agent; :

[0013] (Al): the propylene polymer (A) contains 90.5 to 97.0 wit of a n-decane-insoluble component (Dijnso1) and 3.0 to 9.5 wt% of a n-decane-soluble component (Dgo:) (wherein the total of

SF~2185

Dinsc1 and Dsop is 100 wt%); (A2) : the component Dg, has an intrinsic viscosity [Nse1] of 1.0 to 2.5 dl/g as measured at 135°C in tetralin; ' (A3): the component Dso: contains ethylene-derived 5 structural units at 25 to 35wt% based on 100 wt% of the component

Dso1s (Ad): the component Dingo; has an intrinsic viscosity [Ninso1] of 0.8 to 1.1 dl/g as measured at 135°C in tetralin; (A5): the propylene polymer (A) has amelt flow rate (MFR) {ASTM D-1238, measurement temperature 230°C, load 2.16 kg) of 35 to 170 g/10 min; (Bl): the ethylene/a-olefin copolymer (B) is an ethylene/a-olefin copolymer made with a single-site catalyst; (B2): the ethylene/a-olefin copolymer (B) has a density of 900 to 919 kg/m?; (B3): the ethylene/a-olefin copolymer (B) has amelt flow rate (MFR) (ASTM D-1238, measurement temperature 190°C, load 2.16 kg) of 0.1 to 50 g/10 min.

The propylene polymer (A) preferably satisfies the following requirement (A2'), and the ethylene/a-olefin copolymer (B) preferably satisfies the following requirement (B3') :

[0014] (A2') : the component Dg, has an intrinsic viscosity [Mso1]

SF-2185 6 of 1.5 to 2.5 dl/g as measured at 135°C in tetralin; (B3"): the ethylene/a-olefin copolymer (B) has a melt flow rate (MFR) (ASTM D-1238, measurement temperature 190°C, load 2.16 kg) of 1 to 10 g/10 min.

The propylene resin composition preferably has a melt flow rate (MFR) (ASTM D-1238, measurement temperature 230°C, load 2.16 kg} of 20 to 100 g/10 min. 0015]

Preferably, the ethylene/a-olefin copolymer (B) has a 16 melt flow rate (MFR) (ASTM D-1238, measurement temperature 190°C, load 2.16 kg) of 2.0 to 5.0 g/10 min.

[0016]

The propylene resin composition preferably satisfies the following requirement (X1). [C017] (X1): pellets of the propylene resin composition are injection molded using an injection molding machine with a clamping force of 100 tons, at a cylinder temperature of 200°C, a mold temperature of 40°C, a primary injection pressure of 1700 kg/cm?, an injection rate of 30 mm/sec, a primary dwell ' pressure of 350 kg/cm?, a primary dwell time of 4 sec, and a dwell rate of 4 mm/sec, thereby producing a shaped article 129 mm in length, 119 mm in width and 1 mm in thickness; the shaped article is cut into a small piece; the piece is embedded in

SF-2185 7 a resin, and the resin-embedded piece is sealed in a glass bottle together with RuC, crystal and is stained therewith; the piece is then sliced with an ultramicrotome at normal temperature; the resultant ultrathin piece is observed with TEM, and the

TEM image obtained shows that the skin layer (a layer from the surface of the shaped article to a depth of 2 to 5 pm) has a dark color phase with a width in the depth direction of not more than 0.4 pm.

The propylene resin composition preferably has a tensile elastic modulus cof 1300 to 1800 MPa. [00183

A shaped article according to the present invention is formed from the propylene resin composition.

[0019] :

A container according to the present invention is formed from the propylene resin composition.

[0020]

A food packaging container according to the present invention is formed from the propylene resin composition.

[0021]

The container of the invention is preferably obtained by injection molding or injection stretch blow molding the propylene resin composition.

SF-2185 8

The food packaging container of the invention is preferably obtained by injection melding or injection stretch blow molding the propylene resin composition.

Advantageous Effects of Invention

[0023]

The propylene resin compositions of the invention can give shaped articles including containers such as food packaging containers which show excellent rigidity, low-temperature impact resistance and transparency even when the thickness and weight are reduced from the conventional levels.

BRIEF DESCRIPTION OF DRAWINGS

[0024]

FIG. 1 is a TEM image of a skin layer of a TEM observation sample prepared from a TEM observation test piece in Example 1. The numeral 1 indicates an embedding resin.

FIG. 2 is a TEM image of a core layer of the TEM observation sample prepared from the TEM cbservation test piece in Example 1.

FIG. 3 is a TEM image of a skin layer of a TEM observation sample prepared from a TEM observation test piece in Example 5. The numeral 1 indicates an embedding resin.

SF-2185 9

FIG. 4 is a TEM image of a core layer of the TEM cbservation sample prepared from the TEM observation test piece in Example 5.

FIG. 5 is a TEM image of a skin layer of a TEM observation sample prepared froma TEM observation test piece in Comparative

Example 13. The numeral 1 indicates an embedding resin.

FIG. 6 is a TEM image of a core layer of the TEM observation sample prepared from the TEM observation test piece in

Comparative Example 13.

DESCRIPTION OF EMBODIMENTS

[0025]

The present invention will be described in detail hereinbelow.

[0026]

A propylene resin composition according to the present invention comprises 60 to 80 parts by weight of a propylene polymer (A) satisfying the following requirements (Al) to (AD), to 40 parts by weight of an ethylene/a-clefin copolymer (B) 20 satisfying the following requirements (Bl) to (B3) (wherein the total of the propylene polymer (A) and the ethylene/a-olefin copolymer (B) is 100 parts by weight), and 0.1 to 0.4 parts by weight of a nucleating agent.

SF-2185 (Al): The propylene polymer (&) contains 20.5 to 97.0 wt% of a n-decane-insoluble component (Dips) and 3.0 to 9.5 wtd of a n-decane-soluble component (Dg) (wherein the total of

Dinsor and Dgo1 is 100 wt%). > (AZ) : The component Dg; has an intrinsic viscosity [Nsoz] of 1.0 to 2.5 dl/g as measured at 135°C in tetralin. (A3}: The component Dso1 contains ethylene-derived structural units at 25 to 35 wt% based on 100 wt% of the component

Dso1. } 10 (Ad): The component Dipnso1 has an intrinsic viscosity [MNinsor] of 0.8 to 1.1 dl/g as measured at 135°C in tetralin. : (AS) : The propylene polymer (A) has a melt flow rate (MFR) (ASTM D-1238, measurement temperature 230°C, load 2.16 kg) of 35 to 170 g/10 min. (Bl): The ethylene/a-olefin copolymer (B} is an ethylene/a-olefin copolymer made with a single-site catalyst. (B2}: The ethylene/a-olefin copolymer (B) has a density of 900 to 919 kg/m. {B3): The ethylene/a-clefin copolymer (B) has a melt flow rate (MFR) (ASTM D-1238, measurement temperature 190°C, load 2.16 kg) of 0.1 to 50 g/10 min. [Propylene polymers (A)]

The propylene resin compositions of the invention contain the propylene polymers (A) satisfying the requirements (Al)

SF-2185 11 to (A5). The propylene pelymers (A) satisfying the requirements (Al) to (A5) are also referred to as the propylene polymers (A). :

[0028]

The propylene polymers (A) for use in the invention are not particularly limited as long as they satisfy the requirements (Al) to (AS). In general, they are preferably propylene copolymers that are obtained by copolymerizing propylene and ethylene and contain components mainly composed of propylene-derived structural units (hereinafter, also the propylene homopolymer component) and. components mainly composed of structural units from propylene and ethylene (hereinafter, also the propylene/ethylene copolymer component) (so-called block copolymers). The polymers may also contain structural units derived from C4-10 a-olefins as comonomer components at approximately 3 wt% or less based on 100 wt% of the propylene polymer (A).

[0029] (Requirement (Al))

The propylene polymer (A) contains 90.5 to 97.0 wi% of a n—-decane-insoluble component (Dimser) and 3.0 to 9.5 wt% of a n-decane~soluble component (Dse1) , and preferably 92.0 to 96.0 wt% of a n-decane-insoluble component (Dipso1) and 4.0 to 8.0 wt% of a n—-decane-soluble component (Dg,;} (wherein the total

SF-2185 12

OF Dinsor and Dass: is 100 wt%).

[0030]

The propylene polymers {A} used in the invention contain a n-decane-insoluble component (Dinso1) and a n—-decane-soluble component (Dg.,:) in the above range.

[0031]

In the propylene polymers (A), the n-decane-insocluble component (Dipsor) is usually a component mainly composed of propylene-derived structural units (hereinafter, also the propylene homopolymer component), and is considered to have crystallinity and high rigidity. The n-decane-soluble component (Dgo1) 1s a component mainly composed of structural units from propylene and ethylene (hereinafter, also the copolymer component). The component Die is considered to be amorphous or low crystalline and have a low glass transition temperature and provide impact resistance and compatibility.

This component is also referred to as a rubber component. The propylene polymer (A) in the invention is a propylene copolymer (so-called block copolymer} that usually includes the propylene homopolymer component and the copolymer component.

[0032] :

The propylene resin compositions of the iavention have a sea-island structure as described later in which the Dips component mainly forms the sea and the ethylene/da-olefin

SF-2185 copolymer (B) described later mainly forms islands. The component Dg, is considered to be mainly involved in the compatibilization of the component Dinse1 and the ethylene/a-olefin copolymer (B} and in the improvement of impact resistance.

[0033]

If the amount of Dingo; is below the above range and that of D:o1 exceeds the range, the proportion of the high-rigidity component Dipser 1S SO reduced that shaped articles such as containers produced from the obtainable propylene resin compositions have low rigidity. The propylene resin compositions have a sea-island structure with Dja..1 as the continuous phase as described above. The presence of Dge in excess of the above range tends to result in lowered transparency, probably because the increased islands reflect more light. On the other hand, the impact resistance of shaped articles from the propylene resin compositions tends to be lowered if the amount of Dg, is below the above range and that

Of Dinso1 exceeds the range. This is probably because such small amounts of Dg can absorb less amounts of impact energy.

[0034]

The proportions of Dinser and Dgop in the propylene polymers (A) may be determined by the following method.

SE-2185 14 200 ml of n-decane is added to 5 g of a sample of the propylene polymer (A). The polymer is dissolved by heating at 145°C for 30 minutes to give a solution (1}. Subsequently, the solution is cooled to 25°C in approximately 2 hours and is allowed to stand at 25°C for 30 minutes, resulting in a solution (2) containing a precipitate (a). The precipitate (a) is then separated from the solution (2) through a filter fabric having a mesh size of approximately 15 um.

The precipitate (a) is dried, and the weight of the precipitate (a) is measured.

The weight of the precipitate (a) is divided by the sample weight (5 g) to give a proportion of the n-decane~insoluble component (Dinso1) - Separately, the solution (2) separated from the precipitate (a) is added to an approximately 3-fold amount of acetone, and the component that has been dissolved in the n-decane is precipitated as a precipitate (B). The precipitate {(B} is filtered through a glass filter (G2, mesh size: approximately 100 to 160 pm). The precipitate (BP) is dried, and the weight thereof is measured.

The weight of the precipitate (BP) is divided by the sample weight (5 g) to give a proportion of the n-decane-soluble component (Dgp1). In the worked examples described later, the filtrate from the separation of the precipitate (pf) was concentrated to dryness, but no residues were observed.

SF-2185 15

The proportions of Dipgser and Dgo1 in the propylene polymers may be controlled as desired by adjusting the production conditions described later.

[0037]

In more detall, the proportion of Dinse1 may be increased : and that of Ds, may be decreased by increasing the polymerization Time in [Step 1] over the polymerization time in [Step 2] in the production of the propylene polymers (A) described later. Similarly, the proportion of Dipse1 may be decreased and that of Deus may be increased by performing the polymerization in [Step 21 for a longer time than the polymerization in [Step 1].

[0038] {Requirement (AZ2))

The component Dgo; has an intrinsic viscosity [Nse1] OF 1.0 to 2.5 dl/g, preferably 1.5 to 2.5 dl/g, and more preferably 1.6 to 2.0 dl/g as measured at 135°C in tetralin.

[0039]

If the intrinsic viscosity [Nso1] 1s below the above range, shaped articles such as containers produced from the obtainable propylene resin compositions tend to have lower impact resistance. This is probably because such components Ds,1 have a lower molecular weight and consequently the amounts of impact energy absorbed are reduced. If the intrinsic viscosity [Nso1l

SF-2185 16 exceeds the above range, shaped articles such as containers produced from the obtainable propylene resin compositions tend to have lower transparency, probably because such components

Dso; have an excessively high molecular weight and thus are not dispersed appropriately.

[0040]

The intrinsic viscosity [Mso1]l of Dso1 in the propylene polymer (A) at 135°C in tetralin may be determined in the following manner.

[0041]

The sample used herein may be the precipitate (B) obtained in the determination of the proportions of Dipser and Dior.

Approximately 25 mg of the sample is dissolved in 25 ml of tetralin, and the specific viscosity msp is measured in an oil bath at 135°C. The tetralin solution is diluted by addition of 5 ml of tetralin solvent, and the specific viscosity Tsp is determined in the same manner. This dilution is repeated two more times. The concentration (C) is extrapolated to zero concentration, and the value of ms/C is obtained as the intrinsic viscosity [Msoi] ©f Dso1 at 135°C in tetralin.

[0042]

The intrinsic viscosity [Mse1] OF Dgor at 135°C in tetralin may be controlled as desired by adjusting the production conditions described later.

SF-2185 17

[0043]

In detail, the intrinsic viscosity may be controlled by regulating the feed rate of hydrogen gas used as a chain transfer agent in the polymerization in [Step 2] in the production of the propylene polymers (A). In more detail, the intrinsic ~ viscosity [Nse1] may be lowered by increasing the hydrogen gas feed rate relative to the feed rate of propylene or the feed rates of propylene and ethylene when the polymerization involves propylene and ethylene. The intrinsic viscosity 10. [Mso1] may be increased by decreasing the hydrogen gas feed rate relative to the feed rate of propylene or the feed rates of propylene and ethylene when the polymerization invelves propylene and ethylene.

[0044] (Requirement (A3})

The component Ds, contains ethyliene-derived structural units at 25 to 35 wt%, preferably 25.0 to 35.0 wt%, more preferably 28 to 31 wt%, and still more preferably 28.0 to 31.0 wt% based on 100 wt®% of the component Dgoi.

[0045]

If the component Dg, contains ethylene-~derived structural units at below the above range, shaped articles such as containers produced from the obtainable propylene resin compositions tend to have poor impact resistance (in particular

SF-2185 18 low-temperature impact resistance). This is probably because the small ethylene proportion in Dg leads to a lower glass ~ transition temperature and higher crystallinity with the result that the amounts of impact energy absorbed are reduced.

[0046]

On the other hand, if the component Ds, contains ethylene-derived structural units in excess of the above range, shaped articles such as containers produced from the obtainable propylene resin compositions tend to have lower transparency.

This is probably because such components Ds,1 are less compatibie with Djuso1 and consequently the islands have an increased dispersed-particle diameter.

[0047]

The weight percentage of the ethylene-derived structural units in Dso; in the propylene polymer (A) may be calculated based on the results of C-NMR in the following manner.

[0048]

The sample used herein may be the precipitate (Pp) obtained in the determination of the proportions of Dinser and Dgs:. The precipitate (B) as the sample may be analyzed by >C-NMR under the following conditions . : [0049] 1PC-NMR conditions

Measurement apparatus: nuclear magnetic resonance

SF-2185 19 apparatus LA400 manufactured by JEQOL Ltd.

Measurement mode: BCM (bilevel complete decoupling)

Observation frequency: 100.4 MHz

Observation range: 17006.8 Hz

Pulse width: C nucleus 45° (7.8 psec)

Pulse repetition time: 5 sec

Sample tube: 5 mm diameter

Sample tube rotation speed: 12 Hz

Accumulation: 20000 scans

So Measurement temperature: 125°C

Solvents: 0.35 ml of 1,2,4-trichlorobenzene/0.2 ml of deuterated benzene

Sample amcunt: approximately 40 mg

From the spectrum obtained, the proportions of monomer sequence distributions (triad (three units) distributions) are determined in accordance with Literature (1) below, and the molar fraction (mol%) of the ethylene-derived structural units (hereinafter BE (mol%)) and the molar fraction {(mol%) of the propylene-derived structural units (hereinafter P (mol%)) in

Dgo1 in the propylene polymer are calculated. The ethylene-derived structural units are converted to wt% based on the fractions E (mol%) and P (mol%) according to the equation (Eg. 1) below, and thereby the weight percentage (wt%) of the ethylene-derived structural units (hereinafter E (wt%)) in Dae:

SF-2185 20 in the propylene polymer is calculated.

[0050]

Literature (1): Kakugo, M.; Naito, Y.; Mizunuma, K.;

Miyatake, T., Carbon-13 NMR determination of monomer sequence distribution in ethylene-propylene copolymers prepared with delta~titanium trichloride-diethylaluminum chloride.

Macromolecules 1582, 15, (4), 1150-1152

E (wt%) = E (mol%) x 28 x 100/[P (mol%) x 42 + E (mol%) x 281 --- (Eg. 1) 10 . The weight percentage of the ethylene-derived structural units in Dgo; may be controlled as desired by adjusting the production conditions described later.

[0051]

In detail, the weight percentage of the ethylene-derived structural units in Die may be increased by increasing the ethylene feed rate relative to the propylene feed rate in the polymerization in [Step 2] in the production of the propylene polymers (A). Similarly, the weight percentage of the ethylene-derived structural units in Dso may be lowered by decreasing the ethylene feed rate relative to the propylene feed rate in the polymerization in [Step 2].

[0652] (Requirement (Ad)

The component Dinse1 has an intrinsic viscosity [Nipser] of

SF-2185 21 0.8 to 1.1 dl/g as measured at 135°C in tetralin.

[0053]

If the intrinsic viscosity [Minso1] 18 below the above range, shaped articles such as containers produced from the obtainable propylene resin compositions have lower impact resistance because such components Dinse1 contain larger amounts of low-molecular weight components and consequently the amounts of impact energy absorbed are reduced. If the intrinsic viscosity [MNinso1] exceeds the above range, such components Dipsol contain larger amounts of high-molecular weight components and consequently the resins show deteriorated flowability in the production of shaped articles such as containers, making it difficult to produce the shaped articles in reduced thickness.

[0054] | :

The intrinsic viscosity [TMinser] Of Dinser in the propylene polymer (A) at 135°C in tetralin may be determined in the following manner.

[0055]

The sample used herein may be the precipitate (a) obtained in the determination of the proportions of Dipgor and Dggs-

Approximately 25 mg of the sample is dissolved in 25 mi of tetralin, and the specific viscosity ns, is measured in an oil bath at 135°C. The tetralin solution is diluted by addition of 5 ml of tetralin solvent, and the Specific viscosity msp is

SF-2185 22 determined in the same manner. This dilution is repeated two more times. The concentration (C) is extrapolated to zero concentration, and the value of 1M /C is obtained as the intrinsic viscosity [Minsor] Of Dimnsor at 135°C in tetralin.

[0056]

The intrinsic viscosity [Ninso1] Of Dinser at 135°C in tetralin may be controlled as desired by. adjusting the production conditions described later.

[0057]

In detail, the intrinsic viscosity may be controiled by regulating the feed rate of hydrogen gas used as a chain transfer agent in the polymerization in [Step 1] in the production of the propylene polymers (A). In more detail, the intrinsic viscosity [Minso1] may be lowered by increasing the hydrogen gas feed rate relative to the feed rate of propylene or the feed rates of propylene and ethylene when the polymerization involves propylene and ethylene. The intrinsic viscosity [Ninse1] may be increased by decreasing the hydrogen gas feed rate relative to the feed rate of propylene or the feed rates of propylene and ethylene when the polymerization involves propylene and ethylene.

[0058] {Requirement (AS5))

The propylene polymer (A) has amelt flow rate (MFR} (ASTM

SF-2185 23

D-1238, measurement temperature 230°C, load 2.16 kg) of 35 to 170 g/10 min, preferably 40 to 150 g/10 min, and more preferably 50 to 130 6/10 min.

[0059] :

If the melt flow rate (MFR) of the propylene polymer (A) exceeds the above range, shaped articles such as containers produced from the obtainable propylene resin compositions have poor impact resistance. If the melt flow rate (MFR) of the propylene polymer (A) is below the above range, the resin shows deteriorated flowability when the propylene resin composition is shaped into articles such as containers, making it difficult to produce the shaped articles in reduced thickness.

[0060]

The melt flow rate (MFR) of the propylene polymer (A) may be controlled as desired by adjusting the production conditions described later. g

[0061]

In detail, the melt flow rate may be controlled by regulating the feed rate of hydrogen gas used as a chain transfer agent relative to the feed rate of propylene and/or ethylene in [Step 1] and [Step 2] in the production of the propylene pelymers (A). In more detail, the melt flow rate (MFR) (ASTM

D-1238, measurement temperature 230°C, load 2.16 kg) may be increased by increasing the hydrogen feed rate relative to the

SE-2185 24 feed rate of propylene or the feed rates of prplene and ethylene when the polymerization involves propylene and ethyiene. The melt flow rate {MFR) (ASTM D-1238, measurement temperature 230°C, load 2.16 kg) may be lowered by decreasing the hydrogen feed rate relative to the feed rate of propylene or the feed rates of propylene and ethylene when the polymerization involves propylene and ethylene.

[0062]

Alternatively, the melt flow rate (MFR) (ASTM D-1238, measurement temperature 230°C, load 2.16 kg} may be contrclled by melt-kneading the propylene polymer obtained by the polymerization, in the presence of an organic peroxide. The melt flow rate {MFR} (ASTM D-1238, measurement temperature 230°C, load 2.16 kg) may be increased by melt-kneading the propylene polymer in the presence of an organic peroxide. The melt-kneading treatment in the presence of an organic peroxide can deliver a further increased melt flow rate (MFR) (ASTM

D-1238, measurement temperature 230°C, load 2.16 kg) by increasing the amount of the organic peroxide added.

[0063] :

When the propylene polymer obtained by the polymerization is melt-kneaded in the presence of an organic peroxide, the organic peroxide is desirably added in an amount between 0.005 to 0.05 parts by weight based on 100 parts by weight of the

SF-2185 25 propylene polymer.

[0064]

The organic peroxides for use in the melt-kneading treatment are not particularly limited. Examples of the organic peroxides include benzoyl peroxide, t-butyl perbenzoate, t-butyl peracetate, t-butylperoxyisopropyl carbonate, 2,5-di-methyl-2,5-di-{(benzoylpercxy)hexane, 2,5-di-methyl-2,5~di-(benzoylperoxy)hexyne-3, t-butyl-di-peradipate, t-butylperoxy-3,5,5-trimethyl hexanoate, methyl ethyl ketone peroxide, cyclohexanone peroxide, di-t-butyl peroxide, dicumyl peroxide, 2,5-di-methyl-2, 5-di- (t-butylperoxy) hexane, 2,5-di-methyl-2,5-di-(t-butylperoxy)hexyne-3, 1,3-bis-(t-butylperoxyisopropyl)benzene, t-butyl cumyl peroxide, 1l,1-bis~(t-butylperoxy)-3,3,5-trimethyicyclchexane, : 1,1-bis-(t-butylperoxy}cyclohexane, 2,2-bis-(t-butylperoxy)butane, p-menthane hydroperoxide, di-isopropylbenzene hydroperoxide, cumene hydroperoxide, t-butyl hydroperoxide, p-cymene hydroperoxide, 1,1,3,3-tetra-methyl butyl hydroperoxide and 2,5-di-methyl-2,5-di- (hydroperoxy)hexane. Of these, 2,5-di-methyl-2,5-di- (benzoylperoxy) hexane and 1,3-bis-(t-butylperoxyisopropyl)benzene are more preferred.

SF-2185 26

[0065]

The propylene polymers (A) used in the invention may be produced by any processes without limitation. They are usually produced by copolymerizing propylene and ethylene in the presence of a metallocene compound-containing catalyst or a

Ziegler-Natta catalyst.

[0066]

Since resins with a wide molecular weight distribution and good shaping properties are obtained easily, the propylene polymers (A) are preferably produced by copolymerizing propylene and ethylene in the presence of a Ziegler-Natta catalyst. :

[0067] (Metallocene compound-containing catalysts)

Examples of the metallocene compound-containing -catalysts include metallocene catalysts that contain a metallocene compound, at least one compound selected from organometallic compounds, organoaluminum oxy-compounds and compounds capable of reacting with the metallocene compound to form an ion pair, and optionally a particulate carrier.

Metallocene catalysts that can catalyze stereoregular polymerization to afford isotactic or syndiotactic structures are preferable. Suitable metallocene compounds are bridged metallocene compounds described in WO 01/27124.

SF-2185 27

[0068] [Chem. 1]

Rr? R3

R-

Ri .

Lo Mo,

Riz RS pi LL 5 nt oe oe Fr)

[0069]

In Formula [I], R', R?, R?®, R* R° RS, R’, RY, RY R'%, RM, rR, R! and RY may be the same or different from each other and are selected from a hydrogen atom, hydrocarbon groups and silicon-containing groups. Examples of the hydrocarbon groups include linear hydrocarbon groups such as methyl, ethyl, n-propyl, allyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl and n-decanyl groups; branched hydrocarbon groups such as isopropyl, tert-butyl, amyl, 3-methylpentyl, 1l,1-diethylpropyl, 1,l-dimethylbutyl, l-methyl-1-propylbutyl, 1,l-propylbutyl, 1,l1-dimethyl-2-methylpropyl and l-methyl-l-isopropyl-2-methylpropyl groups; saturated cyclic hydrocarbon groups such as cyclopentyl, cyclohexyl,

SF-2185 28 cycloheptyl, cyclooctyl, norbornyl and adamantyl groups; unsaturated cyclic hydrocarbon groups such as phenyl, tolyl, naphthyl, biphenyl, phenanthryl and anthracenyl groups: saturated hydrocarbon groups substituted with unsaturated cyclic hydrocarbon groups such as benzyl, cumyl, 1,1-diphenylethyl and triphenylmethyl groups; and hetervcatom—-containing hydrocarbon groups such as ——— ethoxy, phenoxy, furyl, N-methylaminc, N,N-dimethylamino,

N-phenylamino, pyrryl and thienyl groups. Examples of the silicon-containing groups include trimethylsilyl, triethylsilyl, dimethylphenylsilyl, diphenylmethylsilyl and triphenylsilyl groups. Adjacent groups of R® to R'? may be linked together to form a ring. Examples of such substituted fluorenyl groups include benzofluorenyl, dibenzofluorenyl, octahydrodibenzeofluorenyl, octamethyloctahydrodibenzofluorenyl and octamethyltetrahydrodicyclopentafluorenyl groups.

[0070]

In Formula [Il, R*, R?, R® and R® on the cyclopentadienyl ring are each preferably a hydrogen atom or a C1-20 hydrocarbon group. Examples of the C1-20 hydrocarbon groups include the hydrocarbon groups described above. In a more preferred embodiment, R! and R® are C1-20 hydrocarbon groups (the remaining groups are hydrogen atoms).

SE-2185 29

[0071]

In Formula [I], R® to R'? on the fluorene ring are each preferably a Cl-20 hydrccarbon group. Examples of the Cl1-20 hydrocarbon groups include the hydrocarbon groups described above. Adjacent groups of R’ to R'? may be linked together to form a ring.

[0072]

In Formula [I], Y that bridges the cyclopentadienyl ring and the fluorenyl ring is preferably a Group 14 element in the periodic table, more preferably carbon, silicon or germanium, and still more preferably a carbon atom. The substituents RY? and R'* bonding to Y are each preferably a Cl-20 hydrocarbon group, and they may be the same or different from each other and may be linked together to forma ring. Examples of the Cl-20 hydrocarbon groups include the hydrocarbon groups described above. More preferably, R*® and RY are 6-20 aryl groups.

Examples of the aryl groups include the aforementioned unsaturated cyclic hydrocarbon groups, saturated hydrocarbon groups substituted with unsaturated cyclic hydrocarbon groups, and hetercatom-containing unsaturated cyclic hydrocarbon groups. R'? and R' may be the same or different from each other and may be linked together to form a ring. Examples of such substituents include fluorenylidene, 10-hydroanthracenylidene and dibenzocycloheptadienylidene

SF~2185 30 groups.

[0073]

In Formula [I], Mis preferably a Group 4 transition metal in the periodic table, and more preferably Ti, Zr or Ef. Q is a halogen atom, a hydrocarbon group, an anionic ligand or a neutral ligand capable of coordination via a lone pair of electrons, and may be the same or different from each other.

The letter j is an integer of 1 to 4. When j is 2 or greater, the plurality of Q may be the same or different from each other.

Examples of the halogen atoms include fluorine, chlorine, bromine and iodine. Examples of the hydrocarbon groups include those described hereinabove. Examples of the anionic ligands include alkoxy groups such as methoxy, tert-butoxy and phenoxy; carboxylate groups such as acetate and benzoate; and sulfonate groups such as mesylate and tosylate. Examples of the neutral ligands capable of coordination via lone-pair electrons include organophosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine and diphenylmethylphosphine; and ethers such as tetrahydrofuran, diethylether, dioxane and 1,2-dimethoxyethane. It is preferable that at least one Q is a halogen atom or an alkyl group. 0074]

Preferred examples of the bridged metallocene compounds

SF-2185 31 include diphenylmethylene (3-tert~butyi-5-methyl-cyclopentadienyl) (fluorenyl) zirconium dichloride, diphenylmethylene (3~tert-butyl-5-methyl-cyclopentadienyl) (2,7~di-tert-butylfluorenyl) zirconium dichloride, diphenylmethylene (3-tert-butyl-5-methyl-cyclopentadienyl) (3,6-di-tert-butylfluorenyl) zirconium dichloride, (methyl) (phenyl}methylene {3-tert~-butyl-5-methyl-cyclopentadienyl) {octamethyloctahydrobenzofluorenyl) zirconium dichloride, [3=-(17,17,4r,4" 77,7" ,10" ,10" —octamethyloctahydrodibenzo [b,h]fluorenyl) (1,1,3-trimethyl-5~tert-butyl-1,2,3,3a- tetrahydropentalene) ]l zirconium dichloride (represented by : Formula [II] below), and compounds represented by Formula [III]

Dbelow.

[0075] [Chem. 21]

SF-2185 32 ® {5 1 4

A / Ci hey 17 iy 11 3 wy 2 9

FAs 5 7 ¥ - «= [113 [00763 [Chem. 3] 6

LD

L/ po

PZ

'

Cl 9 8 2 & ’ ¥ 4 ¥ LE [1 17] 5 [0077]

In the metallocene catalysts used in the production of the propylene polymers (A), the organometallic compounds, the organcaluminum oxy-compounds, the compounds capable of reacting with the transition metal compound to form an ion pair,

SF-2185 33 and the optional particulate carriers that are used together with the Group 4 transition metal compounds of Formula [I] may be those compounds disclosed in the above-cited literature {WO 01/27124) and JP-A-H11-315109.

[0078] {Ziegler-Natta catalysts)

The propylene polymers (A) used in the invention may be produced using highly stereospecific Ziegler-Natta catalysts.

The highly stereospecific Ziegler-Natta catalysts may be various known catalysts. For example, catalysts may be used which are formed of (a) a solid titanium catalyst component containing magnesium, titanium, halcgen and an electron donor, (b) an organometallic compound catalyst component, and (c) an organosilicon compound catalyst component having at least one group selected from cyclopentyl group, cyclopentenyl group, cyclopentadienyl group and derivatives thereof. ~ [0079]

The solid titanium catalyst components (a) may be prepared by contacting a magnesium compound {(a-1), a titanium compound (a-Z) and an electron donor (a-3). Examples of the magnesium compounds (a-1) include reductive magnesium compounds such as magnesium compounds having a magnesium-carbon bond or a magnesium-hydrogen bond, and non-reductive magnesium compounds such as magnesium halides,

SF-2185 34 alkoxymagnesium halides, allyloxymagnesium halides, alkoxymagnesiums, allyloxymagnesiums and magnesium carboxylate salts.

[0080]

In the preparation of the solid titanium catalyst components (a), the titanium compound (a-2) is preferably a tetravalent titanium compounds represented by, for example,

Formuia (1) below.

[0081] | Ti {OR} gq Xs—g == (1)

In Formula (1), R is a hydrocarbon group, X is a halogen atom and 0 £ g =< 4.

Specific examples of such compounds include titanium tetrahalides such as TiCl,, TiBry and TiIl,; alkoxytitanium trihalides such as Ti (OCH;3)Cls, Ti (OCyHs)Cls, Ti (0-n-CsHs)Cls,

Ti (OC;Hs) Br; and Ti (0O-iso-C4Hg) Bry; dialkoxytitanium dihalides such as Ti ({OCH3),Cl,, Ti (OC3Hs)2Cls, Ti (0-n-C4sHg)»Cls and

Ti (OCyHs) 2Bry; trialkoxytitanium monohalides such as

Ti (OCH;3)3C1l, Ti(0OCzHs5)3C1l, Ti{0-n-C4Hg)3:Cl and Ti (CC:Hs)sBr; and tetraalkoxytitaniums such as Ti (OCHi),, Ti {OC:Hg)4,

Ti (O-n-C4Hg)4a, Ti(O0-1is0-C4Hs)s and Ti(0-2-ethyihexyl),.

[0082]

Exemplary electron donors (a-3) used in the preparation of the solid titanium catalyst components (a) include alcohols,

SF-2185 35 phenols, ketones, aldehydes, organic or inorganic acid esters, organic acid halides, ethers, acid amides, acid anhydrides, ammonia, amines, nitriles, isocyanates, nitrogen-containing cyclic compounds and oxygen-—-containing cyclic compounds.

[0083] :

Other reagents such as silicon, phosphorus and aluminum may be used in the contact of the magnesium compound (a-1), the titanium compound {(a-2) and the electron donor (a-3).

Carriers may be used to prepare supported solid titanium catalyst components (a).

[0084]

Any methods including established methods may be adopted for the preparation of the solid titanium catalyst components (a). Several exemplary methods will be briefly described below. (1) A hydrocarbon solution cof the magnesium compound {a-1) that contains the electron donor (a liquefying agent) (a—3) is brought into contact with an organometallic compound and reacted therewith to precipitate a solid and thereafter, or while precipitating the solid, the titanium compound (a-2) is contacted and reacted with the system.’ (2) A complex formed of the magnesium compound (a-1) and the electron donor (a-3}) is brought into contact with an organometallic compound and reacted therewith, and thereafter

SF-2185 36 the titanium compound (a-2) is contacted and reacted with the product. {3) The titanium compound (a—-2) and the electron donor (a—-3) are brought into contact and reacted with a contact product of an inorganic carrier and the organomagnesium compound {a-l). In this method, the contact product may be contacted and reacted with a halogen-containing compound and/or an organometallic compound beforehand. (4) A mixture is prepared which contains a solution of the magnesium compound (a-1l} together with a liquefying agent and cptionally a hydrocarbon solvent, the electron donor (2-3) and a carrier. The magnesium compound (a-1} supported on the carrier is obtained from the mixture and is brought into contact with the titanium compound (a-2). (5) A carrier is contacted with a solution containing the magnesium compound (a-1), the titanium compound (a-2), the electren donor (a-3) and opticnally a hydrocarbon solvent. (6) The liquid organomagnesium compound (a-1) is contacted with the halogen-containing titanium compound (a-2).

In this method, the electron donor {a-3} is used at least one time. {7) The liquid organomagnesium compound (a-1) is brought into contact with a halegen-containing compound and thereafter with the titanium compound (2-2). In this method, the electron

SF-2185 37 donor (a-3) 1s used at least one time.

(8) The alkoxy group-containing magnesium compound (a-1) is contacted with the halogen~containing titanium compound {a-2). In this method, the electron donor (a-3) is used at least one time.

(8) A complex formed of the alkoxy group-containing magnesium compound (a-1) and the electron donor (a-3) is brought into contact with the titanium compound {a-2).

(10) A complex formed of the alkoxy group-containing magnesium compound (a-1) and the electron donor (a-3) is brought into contact with an organometallic compound and thereafter contacted and reacted with the titanium compound (a-2).

(11) The magnesium compound (a-1), the electron donor

(a—3) and the titanium compound {(a-2} are brought into contact and reacted in an arbitrary order.

Prior to the reactions, the components may be pretreated with reagents such as the electron donor (a-3), an organometallic compound and a halogen-containing silicon compound.

(12) The non-reductive liquid magnesium compound (a-1)

is reacted with the liquid titanium compound (a-2) in the presence of the electron denor (a-3) to precipitate a solid magnesium/titanium complex.

{13) The reaction product obtained in (12) is further reacted with the titanium compound (a-2).

SEF-2185 38 - (14) The reaction product obtained in (11) or {12) is further reacted with the electron donor (a-3} and the titanium compound (a-2). (15) The magnesium compound (a-1), the titanium compound (a-2) and the electron donor (a-3) are crushed to give a solid product. The solid product is treatedwith a halogen, a halogen compound or an aromatic hydrocarbon. This method may include a step in which the magnesium compound (a-1) alone is crushed, or a complex compound formed of the magnesium compound (a-1) and the electron donor (a-3) is crushed, or the magnesium compound (a-1) and the titanium compound (a-2) are crushed.

The solid product obtained by crushing may be pretreated with a reaction auxiliary and thereafter treated with a halogen or the like. Examples of the reaction auxiliaries include organometallic compounds and halogen-containing silicon compounds. } (16) The magnesium compound (a-1) is crushed and thereafter brought into contact with the titanium compound (a-2). The electron donor (a-3) and optionally a reaction auxiliary are used in the crushing of the magnesium compound (a-1) and/or the subsequent contact. {17) The compound obtained in any one of (11) to (16) is treated with a halogen, a halogen compound or an aromatic hydrocarbon.

SF-2185 39 {18) A reaction product from the contact of a metal oxide, the organomagnesium (a-1) and a halogen-containing compound is brought into contact with the electron donor (a-3) and preferably with the titanium compound (a-2). (19) The magnesium compound {a-1), for example an organic acid magnesium salt, an alkoxymagnesium or an aryloxymagnesium, is contacted with the titanium compound (a-2), the electron donor (a-3) and optionally a halogen-containing hydrocarbon. (20) A hydrocarbon solution containing the magnesium compound (a-1) and an alkoxytitanium is contacted with the electron donor (a-3) and optionally the titanium compound (a-2).

In this method, the contact preferably takes place in the presence of a halogen-containing compound, for example a halogen-containing silicon compound. (21) The non-reductive liquid magnesium compound (a-1) is reacted with an organometallic compound to precipitate a solid magnesium/metal (z2luminum) complex. The complex is then reacted with the electron donor {(a-3) and the titanium compound (a=2) .

[0085] :

The organometallic compound catalyst components (b) preferably contain metais selected from Group I to Group III in the periodic table. Specific examples include organoaluminum compounds, alkyl complex compounds of Group I

SF-2185 40 metals and aluminum, and organometallic compounds of Group TI metals. These compounds are described below.

[0086] : (b-1) Organcaluminum compounds represented by the formula R'WAL (OR?) H,Xq (wherein R! and R? are hydrocarbon groups which usually have 1 to 15 carbon atoms, and preferably 1 to 4 carbon atoms, and may be the same or different from each cther;

X indicates a halogen atom; 0 <m £3, 0 <n <3, 0 <p < 3, 0 £g<3, andm +n + p + g= 3).

[0087] (b-2) Alkyl complex compounds of Greoup I metals and aluminum represented by the formula M'AIR?, (wherein M! is Li,

Na or K, and R' is as described above).

[0088] (b-3) Dialkyl compounds of Group II or III metals represented by the formula R'R®’M? wherein R' and R? are as described above, and M? is Mg, Zn or Cd).

[0089]

Examples of the organocaluminum compounds (b-1) include compounds represented by RY;Al (OR?)3 (wherein R' and R? are as described above, and m is preferably a number of 1.5 <m < 3), compounds represented by R';Al1Xs; , (wherein R! is as described above, X is a halogen, and m is preferably 0 <m < 3), compounds represented by R4AlH;-n (wherein R! is as described above, and

SF-2185 41 m is preferably 2 £m < 3), and compounds represented by

RAL (OR?) 1Xg (wherein R! and R? are as described above, X is a halogen, 0 «m3, 0 sn<3, 0£g<3, andm +n + gq = 3). [00901

Specific examples of the crgancsilicon compound catalyst components (c¢} include organosilicon compounds represented by

Formula (2) below.

[0091]

SiR'R?, (OR?) 3m ee (2)

In Formula (2), n is 0, 1 or 2, R' is a group selected from cyclopentyl group, cyclopentenyl group, cyclopentadienyl group and derivatives thereof, and R? and R?® are hydrocarbon groups.

In Formula (2), specific examples of R! include cyclopentyl group and derivatives thereof such as cyclepentyl,

Z2-methylcyclopentyl, 3-methylcyclopentvyl,

Z2-ethylcyclopentyl, 3-propylcyclopentyl, 3-isopropylcyclopentyl, 3-butylcyclopentyl, 3-tert-butvlcyclopentvyl, 2,2-dimethylcyclopentyl, 2,3-dimethylcyclopentyl, 2,5-dimethylcyclopentyl, 2,2, 5-trimethyloyclopentyl, 2,3,4,5-tetramethylcyclopentyl, 2,2,5,5-tetramethylcyclopentyl, l-cycleopentylpropyl and l-methyl-1-cyclopentylethyl groups; cyclopentenyl group and derivatives thereof such as cyclopentenyl, 2-cyclopentenyl,

SF-2185

42 3-cyclopentenyl, 2-methyl-Il-cyclopentenyl, 2-methyl~3-cyclopentenyl, 3-methyl~3-cyclopentenyl, 2-ethyl-3-cyclopentenyl, 2,2-dimethyl-3-cyclopentenyl, 2,5-dimethyl-3-cyciopentenyl,

2,3,4,5-tetramethyl-3-cyclopentenyl and 2,2,5,5-tetramethyl-3-cyclopentenyl groups: cyclopentadienyl group and derivatives thereof such as 1l,3-cyclopentadienyl, 2,4-cyclopentadienyl, l,4-cyclepentadienyl, 2-methyl-1,3~cyclopentadienyl,

2-methyl-2,4-cyclopentadienyl, : 3-methyl-2,4-cyclopentadienyl, 2-ethyl-2,4-cyclopentadienyl, 2,2-dimethyl-2, 4-cyclopentadienyl, : 2,3-dimethyl-2, 4-cyclopentadienyl, 2,5-dimethyl-2, 4-cyclopentadienyl and

2,3,4,5-tetramethyl-2, 4-cyclopentadienyl groups; and derivatives of the cyclopentyl, cyclopentenyl or cyclopentadienyl group such as indenyl, 2-methylindenyl, 2-ethylindenyl, 2-indenyl, l-methyl-2-indenvl, 1,3-dimethyl-Z-indenyl, indanyl, 2-methylindanyl, 2-indanyl,

1,3-dimethyl-2-indanyl, 4,5,6,7-tetrahydroindenyl, 4,5,6,7~tetrahydro-2-indenvyl, 4,5,6,7-tetrahydro-1l-methyl-2~indenyl, 4,5,6,7-tetrahydro-1, 3-dimethyl-2-indenyl and fluorenyl groups.

SF-2185 43

[0092]

In Formula (2), specific examples of the hydrocarbon groups R? and R® include alkyl groups, cycloalkyl groups, aryl groups and aralkyl groups. When two or more R® or R® are present, the plurality of R? or R® may be the same or different, and R? and R® may be the same or different from each other. In Formula (2), R' and R* may be bridged via an alkylene group or the like.

[0093]

Of the organosilicon compounds, preferred organosilicoen compounds are those of Formula (2) in which R' is a cyclopentyl : group, R? is an alkyl or cyclopentyl group, and R?® is an alkyl group, in particular a methyl group or an ethyl group.

[0094] ,

Specific examples of the organosilicon compounds of

Formula (2) include trialkoxysilanes such as cyclopentyltrimethoxysilane, 2-methylcyclopentyltrimethoxysilane, 2,3-dimethylcyclopentylirimethoxysilane, 2,5-dimethylcyclopentyltrimethoxysilane, cyclopentyltriethoxysilane, cyclopentenyltrimethoxysilane, 3-cyclopentenyltrimethoxysilane, 2,4-cyclopentadienyltrimethoxysilane, indenyltrimethoxysilane and fluorenyltrimethoxysilane; dialkoxysilanes such as dicyclopentyldimethoxysilane,

: SE-2185 44 bis(2-methylcyclopentyl)dimethoxysilane, bis (3-tert-butylcyclopentyl)dimethoxysilane, bis (2, 3-dimethylcyclopentyl)dimethoxysilane, bis (2,5-dimethylcyclopentyl)dimethoxysilane, dicyclopentyldiethoxysilane, dicyclopentenyldimethoxysilane, di (3-cyclopentenyl)dimethoxysilane, bis (2,5-dimethyl-3-cyclopentenyl)dimethoxysilane, di-2,4-cyclopentadienyldimethoxysilane, bis (2,5-dimethyl-2,4~cyclopentadienyl)dimethoxysilane,

bis{l-methyl-l-cyclopentylethyl)dimethoxysilane, cyclopentylcyclopentenyldimethoxysilane, cyclopentylcyclopentadienyldimethoxysilane, diindenyldimethoxysilane, bis (l,3-dimethyl~-2-indenyl)dimethoxysilane,

cyclopentadienylindenyldimethoxysilane, difluorenyldimethoxysilane, cyclopentylfluorenyldimethoxysilane and indenylfluorenyldimethoxysilane; monoalkoxysilanes such as tricyclopentylmethoxysilane, tricyclopentenylmethoxysilane,

tricyciopentadienylmethoxysilane, tricyclopentylethoxysilane, dicyclopentylmethylmethoxysilane, dicyclopentylethylmethoxysilane, dicyclopentylmethylethoxysilane,

SF-2185 45 cyclopentyldimethylmethoxysilane, cyclopentyldiethylmethoxysilane, } cyclopentyldimethylethoxysilane, bis (2, 5-dimethylcyclopentyl)cyclopentylmethoxysilane, dicyclopentylcyclopentenylmethoxysilane, dicyclopentyleyclopentadienylmethoxysilane and diindenylcyclopentylmethoxysilane; and ethylenebiscyclopentyldimethoxysilane.

[0095]

Prepolymerization may be performed prior to the polymerization of propylene using the catalyst formed of the solid titanium catalyst component (a), the organometallic compound catalyst component (bk) and the crganosilicon compound - catalyst component (c). In the prepolymerization, an olefin is polymerized in the presence of the solid titanium catalyst component (a), the organometallic compound catalyst component (b) and opticnally the organosilicon compound catalyst component {c) as required.

[0096]

The olefins for prepolymerization may be C2-8 a~olefins.

Specific examples include linear olefins such as ethylene, propylene, l-butene and l-octene; and branched olefins such as 3-methyl-l-butene, 3-methyl-l-pentene, 3-ethyl-l-pentene, 4-methyl-1-pentene, 4-methyl-l-hexene,

SF-2185 46 4,4-dimethyl-1-hexene, 4,4-dimethyl-l-pentene, d-ethyl-l-hexene and 3-ethyl-l-hexene. These olefins may be copolymerized. + [0097]

The prepolymerization is desirably carried out so that about 0.1 to 1000 g, and preferably about 0.3 to 500 g of the polymer will be formed per 1 g of the solid titanium catalyst component (a). Excessively large amounts of the polymers prepolymerized may deteriorate the efficiency of (co)polymer production in the main polymerization. In the prepolymerization, the catalyst can be used in a considerably higher concentration than the catalyst concentration in the main polymerization system. When propylene is polymerized by continuous multistage polymerization using the catalyst described above, propylene may be copolymerized with ethylene : in some or all of the stages while still achieving the objects of the invention. :

[0098]

In the case of continuous multistage polymerization, propylene is homopolymerized or copolymerized with ethylene to afford a polypropylene in each stage. In the main polymerization, the solid titanium catalyst component (a) (or the prepolymerized catalyst) is desirably used in about 0.0001 to 50 mmol, and preferably about 0.001 to 10 mmol in terms of

SF-2185 47 titanium atoms per 1 L of the polymerization volume. The organometallic compound catalyst component (b) is desirably used in about 1 to 2000 mol, and preferably about 2 to 500 mol in terms of the metal atoms relative to 1 mol of the titanium atoms in the polymerization system. The organosilicon compound catalyst component (c)} is desirably used in about 0.001 to 50 mol, and preferably about 0.01 to 20 mol per 1 mol of the metal atoms in the organometallic compound catalyst component (b).

[00889] (Processes for producing propylene polymers (A})

The propylene polymers (A) used in the invention may be produced by copolymerizing propylene and ethylene in the presence of the metallocene compound-containing catalyst or the Ziegler-Natta catalyst described above.

[0100]

The polymerization may be made by gas-phase polymerization processes or liquid-phase polymerization processes such as solution polymerization and suspension: polymerization. Different processes may be adopted for different stages. Continuous or semi-continuous systems may be used, or each stage may involve a plurality of polymerizers, for example 2 to 10 polymerizers. Continuous polymerization is most advantageous for industrial scale production. In the

SF-2185 48 case of continuous polymerization, it is preferable that the polymerization in the second and later stages is performed using two or more polymerizers, thereby inhibiting the gelation.

[0101]

Inert hydrocarbons may be used as the polymerization media. Alternatively, liquid propylene may be used as a polymerization medium. With regard to the polymerization conditions in each stage, the polymerization temperature may be appropriately controlled in the range of about -50 to +200°C, preferably about 20 to 100°C, and the polymerization pressure in the range of atmospheric pressure to 10 MPa (gauge pressure), preferably about 0.2 to 5 MPa (gauge pressure).

[0102]

In an embodiment, the propylene polymer (A) may be produced by successively performing the following two steps (Step 1] and [Step 21) using a reaction apparatus in which two or more polymerizers are connected in series. In the : invention, [Step 1] may be carried out in two or more reactors that are connected in series to constitute a polymerization apparatus, and [Step 2] may be performed in two or more reactors that are connected in series to constitute a polymerization apparatus.

[0103]

Alternatively, [Step 1] and [Step 2] may be performed

SF-2185 . 49 separately, and the polymers obtained in these steps may be melt-kneaded together by the use of an apparatus such as a single-screw extruder, a multi-screw extruder, a kneader or a Banbury mixer to give a propylene polymer (A). Hereinbelow, a process will be described in which [Step 1] and [Step 2] are performed successively to produce the propylene polymer (A).

[0104]

In [Step 1], propylene is (co)polymerized optionally with ethylene as required at a polymerization temperature of 0 to 100°C and a polymerization pressure of atmospheric pressure to 5 MPa-G. [Step 1] is controlled by feeding ethylene at a lower rate than propylene or feeding no ethylene so that the propylene (co)polymer from [Step 1] will be the major component of Dinsor. Where necessary, chain transfer agents such as hydrogen gas may be fed to control the intrinsic viscosity [1] of the polymer formed in [Step 1].

[0105]

In [Step 2], propylene is copolymerized with ethylene at a polymerization temperature of 0 to 100°C and a polymerization pressure of atmospheric pressure to 5 MPa-G. [Step 2] is controlled by increasing the ethylene feed rate relative to propylene from the level in [Step 11 so that the propylene/ethylene copolymer rubber from [Step 2] will be the major component of Dge1. Where necessary, chain transfer agents

SF-2185 50 such as hydrogen gas may be fed to control the intrinsic viscosity [nN] of the polymer formed in [Step 2].

[0106]

The propylene polymer {A) may be obtained by successively performing [Step 1] and [Step 21 described above. The requirement (Al), namely the Dinso1 and Dse1 proportions, may be controlled by adjusting the polymerization time in [Step 1] and [Step 2]. In detail, the proportion of Dips may be increased and that of Dg, may be decreased by increasing the polymerization time in [Step 1] over the polymerization time in [Step 2]. Similarly, the proportion of Diuse1 may be decreased and that of Dg. may be increased by performing the polymerization in [Step 2] for a longer time than the polymerization in [Step 1].

[0107]

The requirement (A2) concerning Dg, may be controlled by regulating the feed rate of hydrogen gas used as a chain transfer agent in [Step 2]. In detail, the intrinsic viscosity [Mso1l may be lowered by increasing the hydrogen gas feed rate relative to the feed rate of propylene or the feed rates of propylene and ethylene when the polymerization involves propylene and ethylene. The intrinsic viscosity [Tso] may be increased by decreasing the hydrogen gas feed rate relative to the feed rate of propylene or the feed rates of propylene and ethylene when

SF-2185 51 the polymerization involves propylene and ethylene.

[0108]

The requirement (A3) concerning Dyes: may be controlled by regulating the propylene feed rate and the ethylene feed rate in [Step 2]. In detail, the weight percentage of the ethylene-derived structural units in Ds, may be increased by increasing the ethylene feed rate relative to the propylene feed rate. Similarly, the weight percentage of the : ethylene-derived structural units in Dgo; may be lowered by decreasing the ethylene feed rate relative to the propylene feed rate.

[0109]

The requirement (A4) concerning Di,s.: may be controlled by regulating the feed rate of hydrogen gas used as a chain transfer agent in [Step 1]. In detail, the intrinsic viscosity [Ninso1] may be lowered by increasing the hydrogen gas feed rate relative to the feed rate of propylene or the feed rates of propylene and ethylene when the polymerization involves propylene and ethylene. The intrinsic viscosity [finsec1] may be increased by decreasing the hydrogen gas feed rate relative to the feed rate of propylene or the feed rates of propylene and ethylene when the polymerization involves propylene and ethylene.

SF-2185 52

The requirement (A3) may be controlled by regulating the feed rate of hydrogen gas used as a chain transfer agent in [Step 11 cr [Step 2] relative to the feed rate of propylene or the feed rates of propylene and ethylene when the polymerization involves propylene and ethylene. The MFR may be increased by increasing the hydrogen feed rate relative to the feed rate of propylene or the feed rates of propylene and ethylene when the polymerization involves propylene and ethylene. The MFR may be lowered by decreasing the hydrogen feed rate relative to the feed rate of propylene or the feed rates of propylene and ethylene when the polymerization involves propylene and ethylene.

[0111]

Alternatively, the melt flow rate (MFR) (ASTM D-1238, measurement temperature 230°C, load 2.16 kg) may be controlled by melt-kneading the propylene polymer obtained by the polymerization, in the presence of an organic peroxide. The melt flow rate (MFR) (ASTM D-1238, measurement temperature 230°C, load 2.16 kg) may be increased by melt-kneading the propylene polymer in the presence of an organic peroxide. The melt-kneading treatment in the presence of an organic peroxide can deliver a further increased melt flow rate (MFR) (ASTM

D-1238, measurement temperature 230°C, load 2.16 kg) by increasing the amount of the organic peroxide added. When the

SF-2185 53 propylene polymer obtained by the polymerization is melt-kneaded in the presence of an organic peroxide, the ocrganic peroxide is desirably added in an amount between 0.005 to 0.05 parts by weight based on 100 parts by weight of the propylene polymer. The melt-kneading treatment in the presence of an organic peroxide may be carried out after the posttreatment steps described later.

[0112]

The organic peroxides for use in the melt-kneading treatment are not particularly limited. Examples of the organic peroxides include benzoyl peroxide, t-butyl perbenzoate, t-butyl peracetate, t-butylperoxyisopropyl carbonate, 2,5-di-methyl-2,5~di-~(benzoylperoxy)hexane, 2,5-di-methyl-2, 5-di- (benzoylperoxy)hexyne-3, t-butyl-di-peradipate, t-butylperoxy-3,5,5-trimethyl hexanocate, methyl ethyl ketone peroxide, cyclohexanone peroxide, di-t-butyl peroxide, dicumyl peroxide, 2,5-di-methyl-2,5~di-(t~butylperoxy)hexane, 2,5~di-methyl-2, 5-di- (t-butylperoxy)hexyne-3, : 1,3-bis~(t-butylperoxyisopropyl)benzene, t-butyl cumyl peroxide, 1,1-bis-(t-butylperoxy)-3,3,5~trimethylcyclohexane, 1, 1-bis- (t-butylperoxy) cyclohexane, 2,2-bis-(t-butylperoxy)butane, p-menthane hydroperoxide,

SF-2185 54 di-isopropylbenzene hydroperoxide, cumene hydroperoxide, t-butyl hydroperoxide, p-cymene hydroperoxide, 1,1,3,3-tetra-methyl butyl hydroperoxide and 2,5~di-methyl-2, 5-di- (hydroperoxy) hexane. Of these, 2,5-di-methyl-2,5-di-(benzoylperoxy) hexane and 1,3-bis-(t-butylperoxyisopropyl)benzene are more preferred.

[0113]

The polymerization may be followed by known posttreatment steps such as catalyst deactivation step, catalyst residue 16 removal step and drying step as reguired. By the polymerization as described above, the propylene polymers (A) are obtained as powders.

[0114] : [Ethylene/a-olefin copolymers (B)]

The propylene resin compositions of the invention contain the ethylene/a-olefin copolymers (B) satisfying the requirements (Bl) to (B3). The ethylene/ua-olefin copolymers (B) satisfying the requirements (Bl) to (B3) are also referred to as the ethylene/a-olefin copolymers (B). Preferably, the ethylene/a~olefin copolymers (B) further satisfy the requirement (B4) described later.

[0115]

The ethylene/a-olefin copolymers (B) for use in the invention are not particularly limited as long as they satisfy

SF-2185 55 the requirements (Bl) to (B3). From the viewpoint of excellence in properties such as impact resistance and transparency, copolymers cbtained by copolymerizing ethylene and C3-20 a-olefins are preferable.

[0116]

Examples of the C3-20 a-olefins include propylene, l-butene, l-pentene, 3-methyl-l-butene, l-hexene, 4-methyl-l-pentene, 3-methyl-l-pentene, l-octene, l-decene, i—-dodecene, l-tetradecene, l-hexadecene, l-octadecene and 1l-elcosene. From the viewpoints of transparency, impact resistance, rigidity and economic efficiency, C4-10 a-olefins are preferred.

[0117] (Requirement (B1l))

The ethylene/a~olefin copolymer (B) is an ethylene/a~clefin copolymer made with a single-site catalyst.

[0118]

Exemplary single-site catalysts are single-site olefin polymerization catalysts that are formed of 2 transition metal compound (a) described later, an organoaluminum oxy-compound (bY, a fine particulate carrier (c} and optionally an organoaluminum compound {d).

[0119]

When the ethylene/a-olefin copolymers (B) are

SF-2185 ; 56 single-site-catalyzed ethylene/a-olefin copolymers, the obtainable propylene resin compositions tend to achieve higher transparency. This tendency is probably because such components (B) have a more uniform composition distribution than that of Ziegler-Natta-catalyzed ethylene/a-olefin copolymers and can thus easily compatibilize with the components Dso1, and further they have a narrow molecular weight distribution and contain little low-molecular weight components which can deteriorate low-temperature impact resistance. {0120]

For the reasons as described above, the use of the single-site-catalyzed ethylene/a-olefin copolymers results in propylene resin compositions having excellent transparency and excellent low-temperature impact resistance.

[0121] oo

Examples of the single-site catalysts include catalysts containing constrained geometry complexes (also referred to as CGC (constrained geometry catalysts)), and metallocene compound-containing catalysts. Of these, metallocene compound-containing catalysts are preferable from the viewpoint of excellent low-temperature impact resistance.

[0122] (Requirement (B2))

SF-2185 57

The ethylene/a-olefin copolymer (B} has a density of 900 to 919 kg/m’.

[0123]

If the ethylene/a-olefin copolymers (B) have a density below the above range, it tends to be that shaped articles such as containers produced from the obtainable propylene resin compositions have low rigidity and transparency. This is probably because such components (B) have lower crystallinity and a larger difference in refractive index from the propylene polymers (A). On the other hand, if the ethylene/a-olefin copolymers (B) have a density exceeding the above range, shaped articles such as containers produced from the obtainable propylene resin compositions tend to have low transparency.

This tendency is also considered to be ascribed to the larger difference in refractive index between the ethylene/a-olefin copolymer (B) and the propylene polymer (A). That is, deteriorated transparency results if the density of the ethylene/a-olefin ccpolymers (B) is outside the above range.

[0124]

The density of the ethylene/a-olefin copolymers (B) may be controlled as desired by adjusting the production conditions described later.

[0125]

In detail, the density may be controlled by regulating

SF-2185 58 the feed rates of ethylene and o-clefin in the production of the ethylene/a~olefin copolymers (B) by copolymerization of ethylene and «-olefin. In more detail, the density may be lowered by increasing the a-olefin feed rate relative to the ethylene feed rate. The density may be increased by decreasing the a-olefin feed rate relative to the ethylene feed rate.

[0126]

The density of the ethylene/a-olefin copolymers (B) is : measured with respect to a strand that is obtained in the measurement of the melt flow rate (ASTM D-1238, measurement temperature 190°C, load 2.16 kg) of the ethylene/a-olefin copolymers (B). In detail, a strand sample is heat treated at 120°C for 1 hour and is gradually cooled to room temperature in 1 hour, and the sample is analyzed by a density gradient tube method to determine the density of the ethylene/a-clefin copolymer (B}.

[0127] (Requirement {(B3))

The ethylene/a-olefin copolymer (B) has a melt flow rate (MFR) (ASTM D-1238, measurement temperature 190°C, load 2.16 kg) of 0.1 to 50 g/10 min, preferably 1 to 10 g/10 min, and more preferably 2.0 to 5.0 g/10 min.

[0128]

If the melt flow rate (MFR) (ASTM D-1238, measurement

SF-2185 59 temperature 190°C, load 2.16 kg) of the ethylene/a-olefin copolymer is below the above range, the resin has so high a molecular weight that it shows bad flowability in the production of shaped articles such as containers, making it difficult to produce the shaped articles in reduced thickness. If the melt flow rate (MFR) (ASTM D-1238, measurement temperature 190°C, load 2.16 kg) of the ethylene/o-olefin copolymer exceeds the above range, the molecular weight is so low that the resin can absorb less amounts of impact energy, resulting in poor impact resistance of shaped articles such as containers produced from the obtainable propylene resin compositions.

[0129]

The melt flow rate (MFR) (ASTM D-1238, measurement temperature 190°C, load 2.16 kg) of the ethylene/a-olefin copolymer (B) may be controlled as desired by adjusting the production conditions described later.

[0130]

In detail, the melt flow rate may be controlled by regulating the feed rate of hydrogen gas relative to the feed rate of ethylene and/or a-olefin in the polymerization for the ethylene/a-olefin copolymer (B) described later. The melt flow rate (MFR) (ASTM D-1238, measurement temperature 190°C, load 2.16 kg) may be increased by increasing the hydrogen gas feed rate relative to the feed rate of ethylene gas or the feed

SF-2185 60 rates of ethylene and a-olefin when ethylene and a-olefin are fed in the polymerization. The melt flow rate (MFR) (ASTM

D-1238, measurement temperature 190°C, load 2.16 kg) may be lowered by decreasing the hydrogen gas feed rate relative to the feed rate of ethylene gas or the feed rates of ethylene and o-olefin when ethylene and a-olefin are fed.

[0131]

Hereinbelow, there will be described single-site olefin polymerization catalysts and catalyst components used in the production of the ethylene/a-olefin copolymers (B). The transition metal compounds {a} (hereinafter, also the components {a)) used inthe invention are represented by Formula (I) below. {0132] : i5 ML, ree (I)

In Formula (I}, Mis a transition metal atom selected from

Group IVB of the periodic table, in detail zirconium, titanium or hafnium, and preferably zirconium.

[0133]

The letter x is the atomic valence of the transition metal atom M and indicates the number of I coordinated to the transition metal atom. The letter L indicates a ligand coordinated to the transition metal atom M. At least two ligands L are cyclopentadienyl groups, methylcyclopentadienyl

$F-2185 61 groups, ethylcyclopentadienyl groups, or substituted cyclopentadienyl groups having at least one substituent selected from C3-10 hydrocarbon grcups. The ligands L other than the (substituted) cyclopentadienyl groups are Cl-12 hydrocarbon groups, alkoxy groups, arvloxy groups, halogen atoms, trialkylsilyl groups or hydrogen atoms.

[0134]

The substituted cyclopentadienyl groups may have two or more substituents, and the two or more substituents may be the same or different. When the substituted cyclopentadienyl groups have two or more substituents, at least one substituent is a C3-10 hydrocarbon group and the remaining substituents aremethyl, ethyl or C3-10 hydrocarbon groups. The substituted cyclopentadienyl groups coordinated to M may be the same or different from each other.

[0135] :

Examples of the C3-10 hydrocarbon groups include alkyl groups, cycloalkyl groups, aryl groups and aralkyl groups.

Specific examples include alkyl groups such as n-propvl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, pentyl, hexyl, octyl, 2-ethylhexyl and decyl groups; cycloalkyl groups such as cyclopentyl and cyclohexyl groups; aryl groups such as phenyl and tolyl groups; and aralkyl groups such as benzyl and neophyl groups.

SE-2185 62

[0136]

Of these, alkyl groups are preferred, and n-propyl and n-butyl groups are particularly preferred. In the invention, the (substituted) cyclopentadienyl groups coordinated to the transition metal are preferably substituted cyclopentadienyl groups, more preferably cyclopentadienyl groups substituted with C3 or higher alkyl groups, still more preferably disubstituted cyclopentadienyl groups, and particularly preferably 1,3-substituted cyclopentadienyl groups.

[0137]

In Fermula (I), the ligands 1 coordinated to the transition metal atom M other than the (substituted) cyclopentadienyl groups are Cl-12 hydrocarbon groups, alkoxy groups, aryloxy groups, halogen atoms, trialkylsilyl groups © 15 or hydrogen atoms.

[0138]

Examples of the Cl-12 hydrocarbon groups include alkyl groups, cycloalkyl groups, aryl groups and aralkyl groups.

Specific examples include alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, pentyl, hexyl, octyl, 2-ethylhexyl and decyl groups; cycloalkyl groups such as cyclopentyl and cyclohexyl groups; aryl groups such as phenyl and tolyl groups; and aralkyl groups such as benzyl and neophyl groups.

SF-2185 63

[0139]

Exampies of the alkoxy groups include methoxy, ethoxy, n-propoxy, liscpropoxy, n-butoxy, iscbutoxy, sec-butoxy, t-butoxy, pentoxy, hexoxy and octoxy groups.

[0140]

Examples of the aryloxy groups include phenoxy group.

Examples of the halogen atoms include fluorine, chlorine, bromine and iodine.

[0141]

Examples of the trialkyisilyl groups include trimethylsilyl, triethylsilyl and triphenylsilyl groups..

Examples of the transition metal compcunds represented by

Formula (I) include bis{cycloperntadienyl)zirconiumdichloride, bis (methylcyclopentadienyl) zirconium dichloride,

Dbis(ethylcyclopentadienyl) zirconium dichloride, bis (n=-propylcyclopentadienyl) zirconium dichloride, bis (n-butyleyclopentadienyl) zirconium dichloride, bis (n-hexylcyclopentadienyl) zirconium dichloride, bis (methyl-n~-propylcyclopentadienyl) zirconium dichloride, bis (methyl-n-butylcyclopentadienyl) zirconium dichloride, bis (dimethyl-n-butylcyclopentadienyl) zirconium dichloride, bis (n-butylcyclopentadienyl) zirconium dibromide, bis (n-butylcyclopentadienyl) zirconium methoxychloride, bis (n-butylcyclopentadienyl) zirconium ethoxychloride,

SE-2185 64 bis (n-butylcyclopentadienyl) zirconium butoxychloride, bis {n-butylcyclcpentadienyl) zirconium ethoxide, bis (n-butylcyclopentadienyl) zirconium methylchloride, bis (n-butylcyclopentadienyl} zirconium dimethyl, bis (n-butylcyclopentadienyl) zirconium benzylchloride, bis (n-butylcyclopentadienyl) zirconium dibenzyl, bis (n-butylcyclopentadienyl) zirconium phenylchloride and bis (n-butylcyclopentadienyl} zirconium hydride chloride. In these compounds, the di-substituted cyclopentadienyl rings include the 1,2-substituted ring and the 1,3-substituted ring, and the tri-substituted cyclopentadienyl rings include the 1,2,3-substituted ring and the 1,2, 4-substituted ring. In the invention, transition metal compounds corresponding to the above zirconium compounds except that the zirconium metal is replaced by titanium metal or hafnium metal may also be used.

[0142]

Of the transition metal compounds represented by Formula (I), bis(n-propylcyclopentadienyl) zirconium dichloride, bis (n-butylcyclopentadienyl) zirconium dichloride, bis (l-methyl-3-n-propylcyclopentadienyl) zirconium dichloride and bis (l-methyl-3-n—butylcyclopentadienyl) zirconium dichloride are particularly preferable.

SF-2185 65

The organocaluminum oxy-compounds (b) (hereinafter, also the components (b)) may be conventional benzene-soluble alumincoxanes or may be benzene-insoluble organoaluminum oxy-compounds as disclosed in JP-A-H02-276807.

[0144]

The conventional aluminoxanes may be produced by contacting organoaluminum compounds described later with water : such as adsorption water, crystallization water, ice or vapor, or by reacting organcaluminum compounds with organotin oxides.

[0145]

The fine particulate carriers (c¢) are solid granules or fine particles of inorganic or organic compounds with a particle diameter of 10 to 300 pum, and preferably 20 to 200 um. Porous oxides are preferable as the inorganic carriers. Examples thereof include Si0;, Al:03, MgO, Zr0,, TiO,, B03, C20, 700, BaO,

ThO;, and mixtures thereof such as $Si0;-Mg0O, $i0,-Al,0s,

Si0,-Ti0,, $102-V205, S510,~-Cr;0;3 and Si0,-Ti0,-Mg0O. A preferred carrier contains at least one of S5i0; and Al;03 as a major component.

[0146]

The inorganic oxides may contain small amounts of carbonate salts, sulfate salts, nitrate salts and oxide components such as Na,C0z3, K,C0O3, CaCOsj, MgCOs3, NapS04, Al (S04) 3,

BaS04, KNOj3, Mg (NOs3}., Al (NO3)s3, Nay0, KC and Li,O.

SF-2185 66

[0147]

The fine particulate carriers (c) have various properties depending on the types and the production processes. The fine particulate carriers used in the invention desirably have a specific surface area of 50 to 1000 m?*/g, preferably 100 to 700 m?/qg, and a pere volume of 0.3 to 2.5 em’/q. The fine particulate carriers may be calcined at 100 to 1000°C, and preferably 150 to 700°C as required.

[0148]

Solid granules or fine particles of organic compounds with a particle diameter of 10 to 300 pum may be used as the fine particulate carriers. Examples of such organic compounds include (co)peclymers containing as a main component a C2-14 a-clefin such as ethylene, propylene, l-butene or 4-methyl-1l-pentene, and polymers or copolymers containing vinylcyclohexane or styrene as a main component.

[0149]

The olefin polymerization catalysts used in the production of the ethylene/a-olefin copolymers (B) are formed of the aforementioned component (a), component (b) and fine particulate carrier (cc). Where necessary, organoaluminum compounds (d) may be used.

[0150]

Examples of the optional organcaluminum compounds {d)

SE-2185 67 (hereinafter, also the components {d)) include or gancal uml compounds represented by Formula (III) below.

[01517]: . RYL.AIXs, ~er (IIT) wherein R' denotes a C1-12 hydrocarbon group, X denotes a halogen atom or a hydrogen atom, and n ranges from 1 to 3. oo ~ In Formula (III}, R! is a C1-12 hydrocarbon group such as an alkyl group, a cycloalkyl group or an aryl group. -. Specific examples include methyl, ethyl, n-propyl, isopropyl, iscbutyl, pentyl, hexyl, octyl, cyclopentyl, cyclohexyl, ~~. phenyl and tolyl groups.

[0152]

Specific examples of the organcaluminum compounds include trialkylaluminums such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trioctylaluminum and tri-2-ethylhexylaluminum; alkenylaluminums such as isoprenylaluminum; dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, diisopropyialuminum chloride, diisobutylaluminum chloride and dimethylaluminum bromide; alkylaluminum sesquihalides such as methylaluminum sesquichloride, ethylaluminum sesquichloride, isopropylaluminum sesquichloride, butylaluminum sesquichloride and ethylaluminum sesquibromide; alkylaluminum dihalides such as

SF-2185 68 methylaluminum dichloride, ethylaluminum dichloride, isopropylaluminum dichloride and ethylaluminum dibromide; and alkylaluminum hydrides such as diethylaluminum hydride and diiscbutylaluminum hydride.

[0153]

Examples of the organcaluminum compounds (d} further include compounds represented by Formula (IV) below.

[0154]

RYMWALYso, cee (IV)

In Formula (IV), R'is a hydrocarbon group similar to RY in Formula (IIL), Y is -OR*, -0SiR%;, -OAlR%;, -NR%;, -SiR®% or -N(R7)A1RE, group, n is 1 to 2, RZ, R?, R? and R® are each methyl, : ethyl, isopropyl, isobutyl, cyclohexyl or phenyl group, R® is a hydrogen atom or methyl, ethyl, isoprecpyl, phenyl or trimethylsilyl group, and R® and R’ are each methyl or ethyl group.

Of the organocaluminum compounds, compounds represented by RAL (0OA1R%) 3. such as Et,AlOAlEt, and (iso—-Bu):;AlOCAl (iso-Bu), are preferable.

[0155]

Of the organcaluminum compounds having Formula (III) and (IV), compounds represented by RIAL are preferable; in particular compounds of the formula in which R' is an isocalkyl group are preferable.

SF-2185 69

[0156]

In the invention, the production of the ethylene/u-olafin copolymers (B) is catalyzed by catalysts that are prepared by contacting the aforementioned component (a), component (b), o fine particulate carrier (c¢) and optionally component (d).

[0157]

These components may be contacted in an inert hydrocarbon solvent. Examples of the inert hydrocarbon solvents for use in the catalyst preparation include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane and kerosine; alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclopentane; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as ethylene chloride, chlorcbenzene and dichloromethane; and mixtures of these solvents.

[0158]

In an embodiment, the production of the ethylene/a-olefin copolymers (B) may be catalyzed by a prepolymerized catalyst that is obtained by prepolymerizing an olefin in the presence of the component (a), the component (b), the fine particulate carrier (c) and optionally the component (d}. The prepolymerization may be carried out by introducing an olefin to an inert hydrocarbon solvent in the presence of the component (a), the component (b), the fine particulate carrier (c) and

SF-2185 70 optionally the component {d).

[0159]

Examples of the olefins for prepolymerization include ethylene and C3-20 a-olefins as described hereinabove. In particular, the clefin for prepolymerization is preferably the same as the olefin used in the polymerization. That is, ethylene alone or a combination of ethylene and a C3-20 aa-olefin is preferable.

[0160]

The prepolymerization may be carried out batchwise or continuously and at reduced pressure, atmospheric pressure or increased pressure. The prepolymerization is preferably performed in the presence of hydrogen so that the prepolymer obtained will at least have an intrinsic viscosity [n] at 135°C in decalin of 0.2 te 7 dl/g, and preferably 0.5 to 5 dl/g.

[0161]

The ethylene/a~olefin copolymers (B) may be obtained by polymerizing ethylene in a gas phase or copolymerizing ethylene and the C3-20 a-olefin in a gas phase in the presence of the olefinpolymerization catalyst or the prepclymerized catalyst.

Where necessary, the molecular weight of the polymer may be controlled by feeding a chain transfer agent such as hydrogen gas, and thereby the melt flow rate (MFR) {ASTM D-1238, measurement temperature 190°C, load 2.16 kg) may be controlled.

SF-2185 71

[0162]

In carrying out the polymerization, the olefin polymerization catalyst or the prepclymerized catalyst is desirably used in a concentration in terms of the transition metal atoms in the polymerization systemof 107% to 107° g atoms/L, and preferably 1077 to 10" g atoms/L.

[0163]

In the polymerization, an organcaluminum oxy-compound similar to the component (b) and/or the organcaluminum compound (d) may be added. In such cases, the atomic ratio (Al/M} of the aluminum atoms (Al) in the organcaluminum oxy-compound and the organcaluminum compound to the transition metal atoms (M) in the transition metal compound (a) is in the range of 5 to 300, preferably 10 to 200, and more preferably 15 to 150.

[0164]

The polymerization temperature is usually in the range of 0 to 120°C, and preferably 20 to 100°C. The polymerization pressure is usually atmospheric pressure to 100 kg/cm?, and preferably 2 to 50 kg/cm? The polymerization may be carried out batchwise, semi-continuously or continuously.

[0165]

It is also possible to conduct the polymerization in 2 or more stages under different reaction conditions.

SF-2185 72

The ethylene/a-olefin copolymers (B) may be produced by the steps as described above. The requirement (B2) regarding the ethylene/a-olefin copolymers (B) may be controlled by regulating the feed rates of ethylene and the a-olefin in the polymerization step. The density may be lowered by increasing the a-olefin feed rate relative to the ethylene feed rate. The density may be increased by decreasing the a~olefin feed rate relative to the ethylene feed rate.

[0167]

The requirement (B3) regarding the ethylene/a-olefin copolymers (B) may be controlled by regulating the feed rate of hydregen gas fed as a chain transfer agent relative to the feed rate of ethylene or the feed rates of ethylene and the a~olefin when ethylene and the a-clefin are fed in the polymerization step. The melt flow rate (MFR) (ASTM D-1238, measurement temperature 190°C, load 2.16 kg) of the ethylene/oa-olefin copolymer (B) may be increased by increasing the hydrogen gas feed rate relative to the feed rate of ethylene or the feed rates of ethylene and the a-oclefin when ethylene and the aa—-olefin are fed. The melt flow rate (MFR) {ASTM D-1238, measurement temperature 190°C, load 2.16 kg) of the ethylene/a-olefin copolymer (B) may be lowered by decreasing the hydrogen gas feed rate relative to the feed rate of ethylene or the feed rates of ethylene and the a-oclefin when ethylene

SF-2185 73 and the a-olefin are fed.

[0168] [Nucleating agents]

The propylene resin compositions of the invention contain nucleating agents.

[0169]

The nucleating agents used in the propylene resin compositions of the invention are not particularly limited.

Examples include sorbitol nucleating agents, phosphorus nucleating agents, metal carboxylate nucleating agents, polymer nucleating agents and inorganic compounds. Preferred nucleating agents are sorbitol nucleating agents, phosphorus nucleating agents and polymer nucleating agents.

[0170]

Examples of the sorbitol nucleating agents include nonitol 1,2,3-trideoxy-4,6:5,7-bis-0- [ (4-propylphenyl)methylene]l, 1,3,2,4-dibenzylidene sorbitol, 1,3,2,4-di-({p-methylbenzyiidene) sorbitol and 1,3-p-chlorobenzylidene-2,4-p-methylbenzylidene sorbitol.

[0171]

Examples of the phosphorus nucleating agents include sodium-bis-{4-t-butylphenyl} phosphate, potassium-bis- (4-t-butylphenyl) phosphate, sodium-2,2'-ethylidene-bis (4, 6-di-t-butylphenyl) phosphate,

SF-2185 74 sodium-2,2"'-methylene-bis(4,6-di-t-butylphenyl) phosphate and bis(2,4,8,10-tetra-t-butyl-6-hydroxy-12H-dibenzo {d,glll,3,2]dioxaphosphocin-6-oxide) aluminum hydroxide salt.

[0172]

Examples of the metal carboxylate nucleating agents include aluminum p-t-butylbenzcate, aluminum adipate and sodium benzoate.

[0173]

Preferred examples of the polymer nucleating agents include branched a—-olefin polymers. Examples of the branched a-olefin polymers include homopolymers of 3-methyl-1-butene, 3-methyl-l-pentene, 3-ethyl-l-pentene, 4-methyl-l-pentene, 4-methyl-1l-hexene, £,4-dimethyl-1-hexene, 4,4-dimethyl-1l-pentene, 4-ethyl-l-hexene and 3-ethyl-1l-hexene, copolymers of these monomers, and copolymers of these monomers with other o-olefins. In particular, 3-methyl-1-butene polymers are preferable from the viewpoints of excellent transparency, low-temperature impact resistance, rigidity and economic efficiency.

[0174]

Examples of the inorganic compounds include talc, mica and calcium carbonate.

SF-2185 75

Of the above nucleating agents, nonitol 1,2,3-trideoxy-4,6:5,7-bis-0-[ (4-propylphenyl)methylene] and/or bis(2,4,8,10- tetra t-butyl-6-hydroxy-12H-dibenzo [d,g][1,3,2]dioxaphosphocin-6-oxide} aluminum hydroxide salt is preferably used from the viewpoints of transparency, low-temperature impact resistance, rigidity and low odor.

[0176]

The nucleating agents may be used singly, or two or more kinds may be used in combination.

[0177] : Commercially available nucleating agents may be used in the invention. For example, nonitocl 1,2,3-trideoxy-4,6:5,7-bis-0O-[ (4d-propylphenyl)methylene] is marketed under the trade name of Millad NX8000C (manufactured i5 by Milliken & Company). ADK STAB NA-21 (trade name, manufactured by ADEKA CORPORATION) is a nucleating agent containing bis (2,4,8,10-tetra-t-butyl-6-hydroxy-12H-dibenzo [d,g][1,3,2]dloxaphosphocin-6-oxide) aluminum hydroxide salt as a main component.

[0178]

By containing the nucleating agents, the propylene resin compositions of the invention can give shaped articles such as containers having excellent rigidity and transparency.

This is probably because such propylene resin compositions have

SF-2185 76 a smaller spherulite size and consequently have a reduced diffuse reflection of light to result in improved transparency, and also because the crystallinity is enhanced to provide higher rigidity.

[0179]

If the amount of the nucleating agents is lower than described below, the rigidity and transparency are not improved sufficiently. Containing the nucleating agents in excess of the range described below does not deliver additional improvement effects and is not economical.

[0180] [Propylene resin compositions]

The propylene resin compositions according to the present invention include 60 to 80 parts by weight of the propylene polymer (A), 20 to 40 parts by weight of the ethylene/a-olefin copolymer (B) and 0.1 to 0.4 parts by weight of the nucleating agent (wherein the total of the propylene polymer (A) and the ethylene/a-olefin copolymer (B) is 100 parts by weight), and preferably 70 to 78 parts by weight of the propylene polymer (A), 22 to 30 parts by weight of the ethylene/a~olefin copolymer {B) and 0.15 to 0.35 parts by weight of the nucleating agent.

[0181]

The propylene resin compositions of the invention may contain additional components including additives such as

SF-2185 77 neutralizers, antioxidants, heat stabilizers, weathering stabilizers, lubricants, UV absorbers, antistatic agents, antiblocking agents, antifecgging agents, antifoaming agents, dispersants, flame retardants, antibacterial agents, fluorescent brighteners, crosslinking agents and crosslinking auxiliaries; and coloring agents such as dyes and pigments, while still achieving the objects of the invention.

[0182]

When the propylene resin compositions contain the additional compeonents, the amount of such components is in the range of 0.01 to 5 parts by weight based on 100 parts by weight of the propylene polymer (A) and the ethylene/a-olefin copolymer (B) combined.

[0183]

The propylene resin compositions preferably have a melt flow rate (MFR) (measurement temperature 230°C, load 2.16 kg) of 20 to 100 g/10 min, more preferably 30 to 80 g/10 min, and still more preferably 40 to 70 g/10 min. The propylene resin compositions having this melt flow rate shows excellent fiowability in the production of shaped articles such as containers.

[0184]

The melt flow rate (MFR) (ASTM D-1238, measurement temperature 230°C, load 2.16 kg) of the propylene resin

SF-2185 78 compositions may be controlled by appropriately selecting the melt flow rate (MFR) (ASTM D-1238, measurement temperature 230°C, load 2.16 kg) of the propylene polymer (A) or the melt flow rate (MFR) (ASTM D-1238, measurement temperature 190°C, load 2.16 kg) of the ethylene/a-olefin copolymer used in the propylene resin compositions.

[0185]

Alternatively, the melt flow rate may be controlled by using an organic peroxide when the aforementioned components are melt-kneaded in a kneader. In detail, the melt flow rate (MFR) (ASTM D-1238, measurement temperature 230°C, load 2.16 kg) of the propylene resin compositions may be increased by adding an organic peroxide in the melt-kneading or by increasing the amount of the organic peroxide added in the melt-~kneading.

The organic peroxides for use in the invention are not particularly iimited. Examples include benzoyl peroxide, t-butyl perbenzoate, t-butyl peracetate, t-butylperoxyisopropyl carbonate, 2,5-di-methyl-2,5-di-{benzoylperoxy}hexane, 2,5-di-methyl-2,5-di-(benzoylperoxy)hexyne-3, t-butyl-di-peradipate, t-butylperoxy-3,5,5-trimethyl hexanoate, methyl ethyl ketone peroxide, cyclohexanone percxide, di-t-butyl peroxide, dicumyl peroxide,

Z2,5-di-methyl-2,5-di~{t-butylperoxy)hexane,

SE-2185 79 2,5-di-methyl-2, 5-di-{t-butylperoxy)hexyne-3, 1, 3-bis-(t-butylperoxyisopropyl)benzene, t-butyl cumyl peroxide, 1,1-bis-(t-butylperoxy)-3,3,5~trimethylcyclohexane, 1,1-bis-(t~butylperoxy)cyclohexane, 2,2-bis- (t-butylperoxy)butane, p-menthane hydroperoxide, di-isopropylbenzene hydroperoxide, cumene hydroperoxide, t-butyl hydroperoxide, p-cymene hydroperoxide, 1,1,3,3-tetra-methyl butyl hydrcperoxide and 2,5-di-methyl-2, 5-di~ (hydroperoxy) hexane. Of these, 2,5-di-methyl-2, 5-di- (benzoylperoxy) hexane and 1,3-bis-{t-butylperoxyisopropyl}benzene are more preferred.

When the organic peroxides are used, the amount thereof is desirably in the range of 0.005 to 0.05 parts by weight based on 100 parts by weight of the propylene polymer (A} and the ethylene/a-olefin copolymer (B) combined.

[0186]

The propylene resin compositions preferably have a tensile elastic modulus of 1300 to 1800 MPa, and more preferably 1350 to 1700 MPa.

[0187]

For the determination of the tensile elastic modulus, the propylene resin composition is injection molded using an injection molding machine with a clamping force of 110 tons,

SF-2185 80 at a cylinder temperature of 200°C and a mold temperature of 40°C to give an ISO test piece (Type A) for testing the tensile elastic modulus. The tensile elastic modulus of the propylene resin composition is a value measured by testing the ISO test piece (Type A) by a tensile elastic modulus testing method in accordance with ISC 527-2. The tensile measurement temperature is 23°C, and the stress rate is 1 mm/min.

[0188]

The propylene resin compositions having a tensile elastic modulus in the above range can give shaped articles including containers such as food packaging containers that show high rigidity even when formed in reduced thickness and reduced weight from the conventional levels and are resistant to deformation even when subjected to a large load.

[0189]

The tensile elastic modulus of the propylene resin compositions may be controlled by controlling the content or the crystallinity of the component Dipsor. The crystallinity may be controlled by known means, for example by regulating the stereoregularity of the component Dinso1, by controiling the contents of propylene and other optional olefins, or by introducing nucleating agents. The stereoregularity may be controlled by known means such as catalyst types or polymerization temperatures.

SE-2185 81

[0190]

The propylene resin compositions have a sea-isiand structure with the component Diss; mainly as a continuous phase, namely the sea. The component Dg; and the ethylene/a-olefin copolymer (B) mainly form islands. Consequently, the propylene resin compositions of the invention achieve both high rigidity and high impact resistance.

[0191]

The propylene resin compositions of the invention preferably satisfy the following requirement (X1).

[0192] : (Requirement (X1))

A shaped article manufactured from the propylene resin composition under specific conditions has a skin layer which has a dark color phase with a width in the depth direction of not more than 0.4 um according to TEM observation. The shaped article used herein is made by injection molding pellets of the propylene resin composition using an injection molding machine with a clamping force of 100 tons, at a cylinder temperature of 200°C, a mold temperature of 40°C, a primary injection pressure of 1700 kg/cm”, an injection rate of 30 mm/sec, a primary dwell pressure of 350 kg/cm®, a primary dwell time of 4 sec, and a dwell rate of 4 mm/sec, thereby producing a shaped article 129 mm in length, 119 mm in width and 1 mm

SF-2185 82 in thickness. A test piece (ultrathin piece) for TEM observation is obtained by commen procedures as described below.

[0193]

The surface of the shaped article is cut with a knife or the like, and the cut piece is embedded in a resin by a common method. The resin-embedded piece is sealed in a glass bottle together with Ruy crystal and is stained therewith. (The component Ds, and the ethylene/a-olefin copolymer (B) component are mainly stained.) The piece is then sliced with an ultramicrotome at normal temperature to give an ultrathin piece having a thickness of about 5C to 120 nm.

[0194]

In the propylene resin compositions, it is preferred that a TEM image cof the ultrathin piece obtained above shows that the skin layer (a layer from the surface of the shaped article to a depth of 2 to 5 um) has a stained phase which has a width in a direction from its surface toward the center thereof (the depth direction} of up to 0.4 pm or less. The width in the depth direction is a value between arbitrary 2 points on a 5 pm square.

[0195]

In the above-described TEM observation of the propylene polymer compositions of the invention, the core layer (a layer from the surface of the test piece to a depth of 50 fo 60 um)

SF-2185 83 preferably has a dark color phase with a width in the depth direction of not more than 0.7 pm, more preferably from 0.2 to 0.6 um, and still more preferably from 0.3 to 0.6 um.

[0196]

The resin embedding by a common method is for the purpose of surface protection of the test piece, and is considered to have no influences on the sea-island structure of the test piece.

[0197]

The propylene resin compositions of the invention contain the propylene polymer (A), the ethylene/a-olefin copolymer (B) and the nucleating agent in the specific amounts, and tend to have the specific sea-island structure as described above.

[0198]

The propylene resin compositions satisfying the requirement (X1) can achieve rigidity, impact resistance and transparency at high level, probably because the finely dispersed sea-island structure reduces diffuse reflection of light and the sea-island interface has a large area to permit efficient impact absorption mainly by the component Dse-

[0199]

The propylene resin compositions contain the aforementioned components in the amounts described above, and can consequently give shaped articles including containers

SF-2185 84 such as food packaging containers that show excellent rigidity, low-temperature impact resistance and transparency even when formed in smaller thickness and smaller weight than the conventional levels.

[0200]

The propylene resin compositions of the invention may be produced by any processes without limitation. In an exemplary process, the components may be melt-kneaded with a kneading apparatus to give the propylene resin composition. Examples of the kneading apparatuses include single-screw kneading extruders, multi-screw kneading extruders, kneaders, Banbury mixers and Henschel mixers. The melt-kneading conditions are not particularly limited as long as the molten resins are not degraded by the shear, the heating temperature, or the heat generated by shearing in the melt-kneading. To prevent the degradation of the molten resins, it is effective that the heating temperature is set to an appropriate level or antioxidants or heat stabilizers are added.

[0201]

The propylene resin compositions of the invention may be formed into various shaped articles by known shaping methods such as injection melding, injection stretch blow molding, compression molding, injection compressionmolding, T~die film forming, stretch film forming, blown-film extrusion, sheet

SF-2185 85 forming, calendering, pressure forming, vacuum forming, pipe forming, profile extrusion, hollow molding and laminating.

[0202]

Exemplary shaped articles producible from the propylene resin compositions include containers, home electronics parts and daily goods. In view of impact resistance and rigidity, containers are preferable.

[0203]

Containers according to the present invention are formed from the propylene resin compositions described hereinabove.

The containers find wide applications, including packaging containers for liquid commodities such as shampoos, hair styling agents, cosmetics, detergents and fungicides; food packaging containers for liquids such as beverages, water and seasonings; food packaging containers for solids such as

Jellies, puddings and yogurts; packaging containers for chemicals; and packaging containers for industrial liquids.

[0204]

In particular, the containers are suitably used as food packaging containers that have been required to be reduced in thickness and weight, to permit good visibility of contents, and to have little odor.

[0205]

The containers {for example food packaging containers)

SF-2185 86 from the propylene resin compesiticns are preferably manufactured by injection molding or injection stretch biow molding.

[0206]

For example, injection molding may be performed using an injection melding machine as follows. First, the propylene ‘resin composition is placed into a hopper of the injection mechanism. The propylene resin composition is delivered to a : cylinder heated to approximately 200°C to 250°C and is kneaded and plasticized to a molten state. The molten composition is injected from a nozzle at high pressure and high speed (maximum pressure 700 to 1500 kg/cm?) into a clamped mold that is temperature-controlled at 5 to 50°C, preferably 30 to 50°C with cooling water, hot water or the like. The propylene resin 1s composition injected is cooled and solidified by cooling effected from the mold. The clamped mold is opened, and the shaped article is collected.

[0207]

In an exemplary injection stretch blow molding process, the propylene resin composition is placed inte a hopper of an injection molding machine. The resin composition is delivered to a cylinder heated to approximately 200°C to 250°C and is kneaded and plasticized to a molten state. The molten composition is injected from a nozzle at high pressure and high

SF-2185 87 speed (maximum pressure 700 to 1500 kg/cm’) into a clamped mold that is temperature-controlled at 5 to 50°C, preferably 10 to 30°C with cooling water, hot water or the like. The composition is cooled therein for 1.0 to 3.0 seconds fc give a preform.

Immediately thereafter, the mold is opened and the preform is stretched and oriented in the longitudinal direction using stretch rods and is further stretched and oriented in the traverse direction by blowing, thereby producing a molded article.

EXAMPLES

[0208]

The present invention will be described in detail by presenting examples hereinbelow without limiting the scope of the invention.

[0209] [Production of propvliene polymer (A-1)] (1} Preparation of solid catalyst component

Anhydrous magnesium chloride 95.2 g, decane 442 ml and 2~-ethylhexyl alcohol 390.6 g were reacted under heating at 130°C for 2 hours to give a homogeneous solution. Phthalic acid anhydride 21.3 g was added to the solution, and the mixture was stirred at 130°C for 1 hour, thereby dissolving the phthalic acid anhydride.

SF-2185 88

[0210]

The resultant homogeneous solution was cooled to room temperature. To 200ml of titanium tetrachloride kept at -20°C, 75 ml of the homogeneous sclution was added dropwise over a period of 1 hour. After the addition, the mixture liquid was brought to a temperature of 110°C in 4 hours. When the peuperALUTe reached 110°C, 5.22 g of diisobutyl phthalate (DIBP) was added, and the mixture was stirred at the temperature for 2 hours. i0 [0211]

After the reaction for 2 hours, the solid was collected : by hot filtration and was resuspended in 275 ml of titanium : tetrachloride, followed by heating at 110°C for 2 hours. After ‘the reaction, the solid was again collected by hot filtration and was washed sufficiently with decane and hexane at 110°C until no free titanium compounds were detected in the solution.

[0212]

Here, the free titanium compounds were detected by the following method. 10 ml of the supernatant of the solid catalyst component was collected with a syringe and was added : to a 100 ml branched Schlenk flask previously purged with nitrogen. Under a stream of nitrogen, the hexane sclvent was dried and the residue was further dried in vacuum for 30 minutes.

To the residue, 40 ml of ion exchange water and 10 ml of 50%

SF-2185 89 by volume sulfuric acid were added, followed by stirring for 30 minutes. The resultant aqueous solution was transferred through a filter paper to a 100 ml measuring flask.

Subsequently, there were added 1 ml of concentrated H3PO, as a masking agent for iron (II) ions, and 5 ml of a 3% aqueous

H;0; sclution as a coloring reagent for titanium. Ion exchange water was added to obtain a volume of 100 ml. The measuring flask was shaken. After 20 minutes, the absorbance at 420 nm was measured using UV light to detect free titanium. Washing to remove free titanium and the detection of free titanium were repeated until this absorption was not detected.

[0213]

The solid titanium catalyst component (A) prepared above was stored as a decane slurry. A portion thereof was dried to examine the catalyst composition. The solid titanium catalyst component (A) was found to contain 2.3 wt% of titanium, 61 wt% of chlorine, 19 wt% of magnesium, and 12.5 wt% of DIBP.

[0214] (2) Preparation of prepolymerized catalyst component

A 500 mi volume three-necked flask equipped with a stirrer was purged with nitrogen gas and was thereafter charged with 400 ml of dehydrated heptane, 19.2 mmol of triethylaluminum, 3.8 mmol of dicyclopentyldimethoxysilane, and 4 g of the solid titanium catalyst component (A). The inside temperature was

SF-2185 90 maintained at 20°C, and propylene was introduced with stirring.

After 1 hour, the stirring was terminated. As a result, a prepolymerized catalyst component (B) was obtained in which 2 g of propylene had been polymerized per 1 g of the solid titanium catalyst component (A}.

[0215] (3-1) Polymerization 1 (Polymerization [Step 1])

A 10 L volume stainless steel autoclave equipped with a stirrer was thoroughly dried and was purged with nitrogen.

Thereafter, the autoclave was charged with 6 L of dehydrated heptane, 12.5 mmol of triethylaluminum, and 0.6 mmol of dicyclopentyldimethoxysilane. The system was purged of nitrogen with propylene. Hydrogen was supplied at 0.30 MPa-G, and successively propylene was fed with stirring. When the system stabilized at an inside temperature of 80°C and a total pressure of 0.8 MPa-G, 20.8 ml of a heptane slurry containing 0.10 mmol in terms of Ti atoms of the prepolymerized catalyst component (B) was added. Polymerization was performed at 80°C for 3 hours while continuously supplying propylene.

[0216] . (3-2) Polymerization 2 (Polymerization [Step 2])

After the propylene homopolymerization ([Step 1]), the inside temperature was lowered to 30°C and the system was depressurized. Thereafter, hydrogen was supplied at 0.10

SF-2185 91

MPa-G, and successively a mixed gas containing propylene/ethylene = (4.0 L/min)/ (2.4 L/min) was fed.

Propylene/ethylene copolymerization was carried out at an inside temperature of 60°C and a total pressure of 0.30 MPa-G for 60 minutes.

[0217]

After the passage of the predetermined time, the reaction was terminated by adding 50 ml of methanol. The temperature was lowered, and the pressure was released. The whole contents were transferred to a filtration tank fitted with a filter, and solid-liquid separation was performed at an elevated : temperature of 60°C. Further, the solid was washed two times with 6 L of heptane at 60°C. The resultant propylene/ethylene copolymer was dried in vacuo. The propylene polymer (A-1) obtained had a melt flow rate (MFR) (ASTM D-1238, measurement temperature 230°C, load 2.16 kg) of 89 g/10 min, a Digsol proportion of 92.02 wt%, a Ds proportion of 7.98 wtd, [Nsoi] of 1.77 dl/g, a weight percentage of ethylene-derived structural units in Dge1 of 30.9 wt%, and [Minser] of 0.92 dl/g.

[0218] [Production of propylene polymer (A-2)]

Polymerization was carried cut in the same manner as in the production of the propylene polymer (A-1), except that the propylene/ethylenc copolymerization in Polymerization 2 in the

) SF-2185 92 preduction of the propylene polymer (A-1) was performed for 40 minutes. The propylene polymer (A-2) obtained had a melt flow rate (MFR) (ASTM D-1238, measurement temperature 230°C, load 2.16 kg) of 107 g/10 min, a Dinso1 proportion of 93.80 wt, a Dge1 proportion of 6.20 wt®%, [Nse1]l of 1.77 dl/g, a weight percentage of ethylene-derived structural units in Dge of 30.9 wt%, and [Minse1] of 0.89 dl/g.

[0219] [Production of propylene polymer (A-3)]

Polymerization was carried out in the same manner as in the production of the propylene polymer (A-1), except that the propylene/ethylene copolymerization in Polymerization 2 in the production of the propylene polymer (A-1) was performed for 30 minutes. The propylene polymer (2-3) obtained had a melt flow rate (MFR) (ASTM D-1238, measurement temperature 230°C, load 2.16 kg) of 55 g/10 min, a Dinsor proportion of 95.80 wt%, a Dgo1 proportion of 4.20 wt%, INso1l of 1.82 dl/g, a weight percentage of ethylene-derived structural units in Dg of 29.2 wt%, and [MNinso1] of 0.91 dl/g.

[0220] [Production of propylene polymer (A-cl)]

Polymerization was carried out in the same manner as in the production of the propylene pelymer (A~1), except that the propylene/ethylene copolymerization in Polymerization 2 in the

SF-2185 23 production of the propylene peclymer (A-1) was performed for 70 minutes. The propylene polymer (A-cl)} obtained had a melt flow rate (MFR) (ASTM D-1238, measurement temperature 230°C, load 2.16 kg) of 74 g/10 min, a Dinsor Proportion of 90.25 wt$%, a Dgo1 proportion of 9.75 wt%, [Nsex] of 1.77 dl/g, a weight percentage of ethylene-derived structural units in Dser of 30.9 wt%, and [Minse1] of 0.94 dl/g.

[0221] [Production of propylene polymer (A-c2)]

Polymerization was carried out in the same manner as in the production of the propylene polymer (A-1), except that the propylene/ethylene copolymerization in Polymerization 2 in the production of the propylene polymer (A-1) was performed at a total pressure of 0.50 MPa-G for 120 minutes. The propylene polymer (A-c2) obtained had amelt flow rate (MFR} (ASTM D-1238, measurement temperature 230°C, load 2.16 kg) of 74 g/10 min, a Dinse1 proportion of 82.50 wt%, a Dgo1 proportion of 17.50 wth, : [Msor] of 1.94 dl/g, a weight percentage of ethylene-derived structural units in Dse1 of 31.0 wt%, and [Minser] of 0.81 dl/g.

[0222] [Production of propylene polymer (A-c3)]

Polymerization was carried out in the same manner as in the production of the propylene polymer {(A-c2), except that the propylene/ethylene copolymerization in Polymerization 2

SF-2185 94 in the production of the propylene polymer (A-cZ) was performed for 90 minutes. The propylene polymer (A-c3) obtained had a melt flow rate (MFR) (ASTM D-1238, measurement temperature 230°C, load 2.16 kg) of 89 g/10 min, a Dinser proportion of 85.70 wt%, a Dg proportion of 14.30 wt%, [Nser] of 1.%4 dl/g, a weight percentage of ethylene—-derived structural units in Dge; of 31.0 wt%, and [Minser] of 0.81 dl/g.

[0223] [Production of propylene polymer (A-cd)]

Polymerization was carried out in the same manner as in the production of the propylene polymer (A-c2), except that the propylene/ethylene copolymerization in Polymerization 2 in the production of the propylene polymer (A-c2) was performed for 60 minutes. The propylene polymer (A-c4) obtained had a melt flow rate (MFR) (ASTM D-1238, measurement temperature 230°C, load 2.16 kg) of 107 g/10 min, a Dinso: proportion of 88.80 wt%, a Dgo1 proportion of 11.20 wt%, [nse] of 1.94 d1/g, a weight percentage of ethylene~derived structural units in Dg of 31.0 wt%, and [Minse1] of 0.81 dl/g.

[0224] [Production of propylene polymer (A-c5}]

Polymerization was carried out in the same manner as in the production of the propylene polymer (A-1), except that the amount of hydrogen supplied in Polymerization 1 (propylene

SF-2185 95 homopolymerization) in the production of the propylene polymer (A-1) was changed to 0.20 MPa-G and that the propylene/ethylene copolymerization in Polymerization 2 was performed for 30 minutes by feeding a mixed gas containing propylene/ethylene = (4.0 L/min) /(2.0 L/min). The propylene polymer (A-c5) obtained had a melt flow rate (MFR) (ASTM D-1238, measurement temperature 230°C, load 2.16 kg) of 102 g/10 min, a Dinscli proportion of 95.03 wt%, a Dso1 proportion of 4.97 wt%, [TNseil of 1.83 dl/g, a weight percentage of ethylene-derived structural units in Dg of 24.1 wt%, and [TMinser] of 1.10 dl/g.

[0225] [Production of propylene polymer (A-c6)]

Polymerization was carried out in the same manner as in the production of the propylene polymer (A-1), except that the amount of hydrogen supplied in Polymerization 1 (propylene homopolymerization) in the production of the propylene polymer (A-1) was changed to 0.20 MPa-G and that Polymerization 2 was performed for 30 minutes by supplying hydrogen at 0.1 MPa-G and successively feeding a mixed gas containing propylene/ethylene = (4.0 L/min) /{2.4 L/min) to a total pressure of 0.50 MPa-G. The propylene polymer {A-cb6b) obtained had amelt flow rate (MFR) (ASTM D-1238, measurement temperature 230°C, load 2.16 kg) of 55 ¢g/10 min, a Dipso1 proportion of 95.80 wt%, a Dgo1 proportion of 4.20 wt$%, [Ns] of 2.35 dl/g, a weight

SF-2185 96 percentage of ethylene-derived structural units in Dee of 29.2 wt%, and [MNinso1] of 1.08 dl/g.

[0226] : [Production of propylene polymer (A-4)] (1} Preparation of solid titanium catalyst component

Avibrationmill was provided which was equipped with four 4 L volume milling pots containing 9 kg of steel balls 12 mm in diameter. In a nitrogen atmosphere, 300 g of magnesium chloride, 115 ml of diisobutyl phthalate and 60 ml of titanium tetrachloride were added to each pot and were milled for 40 hours.

[0227]

The resultant milled mixture weighing 75 g was placed to a 5 L flask and was combined with 1.5 L of toluene, followed by stirring at 114°C for 30 minutes. The mixture obtained was allowed to stand, and the supernatant was removed. The solid was washed three times with 1.5 L of n-heptane at 20°C and was dispersed in 1.5 L of n-heptane toc give a slurry of the transition metal catalyst component. The transition metal catalyst component contained 2 wt% of titanium and 18 wt% of diiscbutyl phthalate.

[0228] (2) Preparation of prepolymerized catalyst

A 200 IL, volume autoclave equipped with a stirrer was

SF-2185 97 charged with 115 g of the transition metal catalyst component, 65.6 ml of triethylaluminum, 22.1 ml of

Z-isobutyl-2-isopropyl-1, 3-dimethoxypropane and 115 L of heptane. The inside temperature was maintained at 5°C, and 1150 g of propylene was introduced. Reaction was carried cut with stirring for 60 minutes. After the polymerization, 15.8 ml of titanium tetrachloride was added, thereby producing a prepolymerized catalyst. The prepolymerized catalyst contained 10 g of polypropylene per 1 g of the transition metal catalyst component.

[0229] (3) Main polymerization

A 1000 L volume polymerization vessel equipped with a stirrer was continuously charged with 140 kg/h of propylene, 1.2 g/h of the prepolymerized catalyst in terms of the transition metal catalyst component, 20.9 ml/h of triethylaluminum, and 2.3 ml/h of dicyclopentyldimethoxysilane. Hydrogen was supplied to a hydrogen concentration of 13.0 mol% in the gas phase.

Polymerization was carried out at a temperature of 67.5°C and a pressure of 3.5 MPa /G.

[0230]

The slurry obtained was delivered to a 500 IL volume polymerization vessel equipped with a stirrer, and

SF-2185 98 polymerization was further conducted therein. To the polymerization vessel, propylene was supplied at 30 kg/h and hydrogen was fed to a hydrogen concentration of 8.9 mol% in the gas phase. Polymerization was carried out at a temperature of 68°C and a pressure of 3.4 MPa/G.

[0231]

The slurry obtained was delivered to a 500 L volume polymerization vessel equipped with a stirrer, and polymerization was further conducted therein. To the polymerization vessel, propylene was supplied at 20 kg/h and hydrogen was fed to a hydrogen concentration of 7.3 mol% in the gas phase. Polymerization was carried out at a temperature of 68.5°C and a pressure of 3.3 MPa/G.

[0232]

The siurry obtained was delivered to a 500 L volume polymerization vessel equipped with a stirrer, and polymerization was further conducted therein. To the polymerization vessel, propylene was supplied at 15 kg/h and hydrogen was fed to a hydrogen concentration of 7.2 mol% in the gas phase. Ethylene was fed such that the polymerization temperature was 60°C and the pressure was 3.2 MPa/G.

Diethylene glycol ethyl acetate was added in a molar amount 100 times that of the Ti component in the transition metal catalyst component.

SE-2185 99

[0233]

The slurry obtained was deactivated, gasified and subjected to gas-solid separation. The propylene polymer was obtained at 78 kg/h. The propylene polymer obtained was introduced to a dryer and was vacuum dried at 80°C.

[0234]

The propylene polymer (A-£) obtained had a melt flow rate (MFR) (ASTM D-1238, measurement temperature 230°C, load 2.16 kg) of 120 g/1l0 min, a Dips: proportion of 93.90 wt%, a Dsa1 proportion of 6.10 wt%, [Msoi] of 1.40 d1l/g, a weight percentage of ethylene-derived structural units in Dg of 26.7 wt%, and [Minso1] of 0.89 dl/g.

[0235] : [Production of propylene polymer (A-5)]

Polymerization was carried out in the same manner as in the production of the propylene polymer {A-4) except for the following.

[0236] {1) Main polymerization

A 1000 L volume polymerization vessel equipped with a stirrer was continuously charged with 140 kg/h of propylene, 1.2 g/h of the prepolymerized catalyst in terms of the transition metal catalyst component, 20.9 ml/h of triethylaluminum, and 2.3 ml/h of

SF-2185 100 dicyclopentyldimethoxysilane. Hydrogen was supplied to a hydrogen concentration of 12.5 mol% in the gas phase.

Polymerization was carried out at a temperature of 67.5°C and a pressure of 3.5 MPa/G.

[0237]

The slurry obtained was delivered to a 500 L volume polymerization vessel equipped with a stirrer, and polymerization was further conducted therein. To the polymerization vessel, propylene was supplied at 30 kg/h and hydrogen was fed to a hydrogen concentration of 8.5 mol% in the gas phase. Polymerization was carried out at a temperature of 68°C and a pressure of 3.4 MPa/G.

[6238]

The slurry obtained was delivered toc a 500 L volume polymerization vessel equipped with a stirrer, and : polymerization was further conducted therein. To the polymerization vessel, propylene was supplied at 20 kg/h and hydrogen was fed to a hydrogen concentration of 6.9 mol% in the gas phase. Polymerization was carried out at a temperature of 68.5°C and a pressure of 3.3 MPa/G.

[0239]

The slurry obtained was delivered to a 500 1 volume polymerization vessel equipped with a stirrer, and polymerization was further conducted therein. To the

SF-2185 101 polymerization vessel, propylene was supplied at 15 kg/h and hydrogen was fed to a hydrogen concentration of 6.7 mol% in the gas phase. Ethylene was fed such that the polymerization temperature was 57°C and the pressure was 3.2 MPa/G.

Diethylene glycol ethyl acetate was added in a molar amount 108 times that of the Ti component in the transition metal catalyst component. :

[0240]

The slurry obtained was deactivated, gasified and subjected to gas-solid separation. The propylene polymer was cbtained at 77 kg/h. The propylene polymer obtained was introduced to a dryer and was vacuum dried at 80°C.

[0241]

The propylene polymer (A-5} obtained had a melt flow rate (MFR) (ASTM D-1238, measurement temperature 230°C, load 2.16 kg) of 118 g/10 min, a Dinso1 proportion of 94.60 wt%, a Dso1 proportion of 5.40 wt%, [Mso:] of 1.45 dl/g, a weight percentage of ethylene-derived structural units in Dg of 30.0 wt%, and [Minso1] of 0.88 di/g.

[0242] [Production of propylene polymer (A-6)]

Polymerization was carried cut in the same manner as in the production of the propylene polymer (A-4) except for the following.

SF-2185 102

[0243] (1) Main polymerization

A 1000 L volume polymerization vessel equipped with a stirrer was continuously charged with 140 kg/h of propylene, 1.2 g/h of the prepclymerized catalyst in terms of the transition metal catalyst component, 20.9 ml/h of triethylaluminum, and 2.3 ml/h of dicyclopentyldimethoxysilane. Hydrogen was supplied to a hydrogen concentration of 11.85 mol% in the gas phase.

Polymerization was carried out at a temperature of 67.5°C and a pressure of 3.4 MPa/G.

[0244]

The siurry obtained was delivered to a 500 L volume polymerization vessel equipped with a stirrer, and polymerization was further conducted therein. To the polymerization vessel, propylene was supplied at 30 kg/h and hydrogen was fed to a hydrogen concentration of 8.0 mol% in the gas phase. Polymerization was carried out at a temperature of 68°C and a pressure of 3.3 MPa/G.

[0245]

The slurry obtained was delivered to a 500 L volume polymerization vessel equipped with a stirrer, and pelymerization was further conducted therein. To the polymerization vessel, propylene was supplied at 20 kg/h and

SE-2185 103 hydrogen was fed to a hydrogen concentration of 6.5 mol% in the gas phase. Polymerization was carried out at a temperature of 68.5°C and a pressure of 3.2 MPa/G.

[0246]

The slurry obtained was delivered to a 500 L volume polymerization vessel equipped with a stirrer, and polymerization was further conducted therein. To the polymerization vessel, propylene was supplied at 15 kg/h and hydrogen was fed to a hydrogen concentration of 2.3 mol% in the gas phase. Ethylene was fed such that the polymerization temperature was 60°C and the pressure was 3.0 MPa/G.

Diethylene glycol ethyl acetate was added in a molar amount 109 times that of the Ti component in the transition metal catalyst component.

[0247]

The slurry obtained was deactivated, gasified and subjected to gas-solid separation. The propylene polymer was obtained at 77 kg/h. The propylene polymer obtained was introduced to a dryer and was vacuum dried at 80°C.

[0248]

The propylene polymer (A-6) obtained had a melt flow rate (MFR) (ASTM D-1238, measurement temperature 230°C, load 2.16 kg) of 105 g/10 min, a Dinsor proportion of 94.70 wt%, a Dsa proportion of 5.30 wt%, [Mse1] of 2.30d1/g, a weight percentage

SF-2185 104 of ethylene~derived structural units in Ds of 26.5 wt%, and [Minso1] of 0.90 dl/g.

[0249] [Production of propylene polymer {(A-7)]

Polymerization was carried out in the same manner as in the production of the propylene polymer (A-£4} except for the following.

[0250] (1) Main polymerization

A 1000 L volume polymerization vessel equipped with a stirrer was continuously charged with 140 kg/h of propylene, 1.2 g/h of the prepolymerized catalyst in terms of the transition metal catalyst component, 20.9 ml/h of triethyialuminum, and 2.3 ml/h of dicyclopentyldimethoxysilane. Hydrogen was supplied to a hydrogen concentration of 13.5 mol% in the gas phase.

Polymerization was carried out at a temperature of 67.5°C and a pressure of 3.5 MPa/G.

[0251]

The slurry obtained was delivered to a 500 L volume polymerization vessel equipped with a stirrer, and polymerization was further conducted therein. To the polymerization vessel, propylene was supplied at 30 kg/h and hydrogen was fed to a hydrogen concentration of 9.2 mel% in

SF-2185 : 105 the gas phase. Polymerization was carried out at a temperature of 68°C and a pressure of 3.4 MPa/G.

[0252]

The slurry obtained was delivered to a 500 L volume polymerization vessel equipped with a stirrer, and polymerization was further conducted therein. To the , polymerization vessel, propylene was supplied at 20 kg/h and hydrogen was fed to a hydrogen concentration of 7.5 mol% in the gas phase. Polymerization was carried out at a temperature of 68.5°C and a pressure of 3.3 MPa/G.

[0253]

The slurry obtained was delivered tec a 500 L volume polymerization vessel equipped with a stirrer, and polymerization was further conducted therein. To the polymerization vessel, propylene was supplied at 15 kg/h and hydrogen was fed to a hydrogen concentration of 3.2 mol% in the gas phase. Ethylene was fed such that the polymerization temperature was 60°C and the pressure was 3.1 MPa/G.

Diethylene glycol ethyl acetate was added in a molar amount 101 times that of the Ti component in the transition metal catalyst component.

[0254]

The slurry obtained was deactivated, gasified and subjected to gas-solid separation. The propylene polymer was

SF-2185 106 obtained at 78 kg/h. The propylene polymer obtained was introduced to a dryer and was vacuum dried at 80°C. [02551

The propylene polymer (A-7) obtained had a melt flow rate (MFR) (ASTM D-1238, measurement temperature 230°C, load 2.16 kg) of 120 ¢/10 min, a Dinse1 proportion of 94.00 wt%, a Ds proportion of 6.00 wt%, [Nsc1] of 2.00 dl/g, a weight percentage of ethylene-derived structural units in Deoy OF 27.7 wt%, and [Minser] of 0.90 dl/g. [C256] {Production of propylene polymer (A-c7)]

Polymerization was carried out in the same manner as in the production of the propylene polymer (A-4) except for the following.

[0257] (1) Main polymerization

A 1000 IL. volume polymerization vessel equipped with a stirrer was continuously charged with 140 kg/h of propylene, 1.4 g/h of the prepolymerized catalyst in terms of the transition metal catalyst component, 20.9 ml/h of triethylaluminum, and 2.6 ml/h of dicyclopentyldimethoxysilane. Hydrogen was supplied to a hydrogen concentration of 16.2 mol% in the gas phase.

Polymerization was carried out at a temperature of 63.5°C and

SF-2185 107 a pressure of 3.5 MPa/G.

[0258]

The slurry obtained was delivered to a 500 IL volume polymerization vessel equipped with a stirrer, and polymerization was further conducted therein. To the polymerization vessel, propylene was supplied at 30 kg/h and hydrogen was fed to a hydrogen concentration of 12.4 mol% in the gas phase. Polymerization was carried out at a temperature of 64.5°C and a pressure of 3.4 MPa/G.

[0259] “

The slurry obtained was delivered to a 500 1L volume polymerization vessel equipped with a stirrer, and : polymerization was further conducted therein. To the polymerization vessel, propylene was supplied at 20 kg/h and hydrogen was fed to a hydrogen concentration of 7.9 mol$% in the gas phase. Polymerization was carried out at a temperature of 67°C and a pressure of 3.3 MPa/G.

[0260]

The slurry obtained was delivered to a 500 L volume polymerization vessel equipped with a stirrer, and polymerization was further conducted therein. To the polymerization vessel, propylene was supplied at 15 kg/h and hydrogen to a hydrogen concentration of 4.8 mol% in the gas phase. Ethylene was fed such that the pclymerization

SF-2185 108 temperature was 60°C and the pressure was 3.2 MPa/G.

Diethylene glycol ethyl acetate was added in a molar amount 86 times that of the Ti component in the transition metal catalyst component.

[0261]

The slurry obtained was deactivated, gasified and subjected to gas—-solid separation. The propylene polymer was obtained at 75 kg/h. The propylene polymer obtained was : introduced to a dryer and was vacuum dried at 80°C.

[0262]

The propylene polymer (A-c7) cbtained had amelt flow rate (MFR) (ASTM D-1238, measurement temperature 230°C, load 2.16 kg) of 193 g/10 min, a Dinser proportion cf 93.60 wt%, a Dia proportion of 6.40 wt%, [Nso1] of 1.67 dl/q, a weight percentage of ethylene-derived structural units in Dg, of 28.3 wt%, and [Ninsoz] of 0.76 dl/g.

[0263] [Production of propylene polymer (A-c8}]

Polymerization was carried out in the same manner as in the production of the propylene polymer (A-4) except for the following.

[0264] (1) Main polymerization

A 1000 I. volume polymerization vessel equipped with a

SF-2185 109 stirrer was continuously charged with 140 kg/h of propylene, 0.7 g/h of the prepolymerized catalyst in terms of the transition metal catalyst component, 20.9 ml/h of triethylaluminum, and 1.4 ml/h of dicyclopentyldimethoxysilane. Hydrogen was supplied to a hydrogen concentration of 5.3 mol% in the gas phase.

Polymerization was carried out at a temperature of 72°C and a pressure of 3.4 MPa/G.

[0265]

The siurry obtained was delivered to a 500 L volume polymerization vessel equipped with a stirrer, and polymerization was further conducted therein. To the polymerization vessel, propylene was supplied at 30 kg/h and hydrogen was fed to a hydrogen concentration of 3.6 mol$% in the gas phase. Polymerization was carried out at a temperature of 71.5°C and a pressure of 3.3 MPa/G.

[0266]

The slurry obtained was delivered to a 500 L volume polymerization vessel equipped with a stirrer, and polymerization was further conducted therein. To the polymerization vessel, propylene was supplied at 20 kg/h and hydrogen was fed to a hydrogen concentration of 2.6 mol% in the gas phase. Polymerization was carried out ob o temperature of 71°C and a pressure of 3.2 MPa/G.

SF-2185 110

[0267]

The slurry obtained was delivered to a 500 L volume polymerization vessel equipped with a stirrer, and polymerization was further conducted therein. To the polymerization vessel, propylene was supplied at 15 kg/h and hydrogen was fed to a hydrogen concentration of 2.6 mol% in the gas phase. Ethylene was fed such that the polymerization remperature was 58°C and the pressure was 3.1 MPa/G.

Diethylene glycel ethyl acetate was added in a molar amount 68 times that of the Ti component in the transition metal catalyst component.

[0268]

The slurry obtained was deactivated, gasified and subjected to gas~solid separation. The propylene polymer was obtained at 78 kg/h. The propylene polymer obtained was introduced to a dryer and was vacuum dried at 80°C.

[6269]

The propylene polymer (A-cB8) obtained had amelt flow rate (MFR) (ASTM D-1238, measurement temperature 230°C, load 2.16 kg} of 31 g/10 min, a Dinsor proportion of 88.20 wt%, a Dge proportion of 11.80 wt%, [Msor] of 2.23 d1/g, a weight percentage of ethylene-derived structural units in Dg of 30.0 wt%, and [Minser] of 1.17 dl/g.

SF-2185 11% [Production of ethylene/a-olefin copolymer (B-1)] (Preparation of catalyst)

A thoroughly nitrogen-purged 300 L reactor was charged with 10.0 kg of silica dried at 600°C for 10 hours, and 154

IL of toluene. The silica was suspended, and the suspension was cooled to 0°C. Thereafter, 23.4 L of a toluene solution of methylaluminoxane (Al = 3.02 mol/L) was added dropwise to the suspension over a period of I hour. During the addition, the temperature of the system was kept at 0 to 5°C. The reaction was continuously performed at 0°C for another 30 minutes. The temperature was then increased to 95°C in 1.5 hours, and reaction was made at the temperature for 4 hours. The temperature was lowered to 60°C, and the supernatant was removed by decantation. The sclid obtained was washed two times with toluene and was resuspended in 100 L of toluene. The suspension was diluted to a volume of 160 L.

[0271]

To the resultant suspension, 20.0 L of a toluene solution of bis{l,3-n-butylmethylcyclopentadienyl) zirconium dichloride (Zr = 25.6 mmol/L) was added dropwise at 35°C over a period of 30 minutes, and the reaction was performed at 35°C for another 2 hours. The supernatant was removed, and the residue was washed two times with hexane, thereby obtaining a solid catalyst component (1) containing 3.2 mg of zirconium

SF-2185 112 per 1 g of the solid catalyst component.

[0272] (Preparation of prepolymerized catalyst)

A thoroughly nitrogen-purged 350 L reactor was charged with 7.0 kg of the solid catalyst component (1), and hexane.

The total volume was 285 I.. The system was cooled to 10°C, and ethylene was blown into the hexane at a flow rate of 8 N m*/h for 5 minutes. During the blowing, the temperature in the system was kept at 10 to 15°C. Thereafter, the ethylene feed was suspended, and 2.4 mol of diiscbutylaluminum hydride (DIBALH) and 1.2 kg of l-hexene were added. The system was tightly closed, and the ethylene feed was restarted at 8 Nm’/h.

After 15 minutes, the ethylene flow rate was lowered to 2 N m®*/h, and the pressure in the system became 0.08 MPa/G. During this procedure, the temperature in the system increased toc 35°C.

While controlling the system temperature in the range of 32 to 35°C, ethylene was supplied at 4 Nm®/h for 3.5 hours. During the supply, the pressure in the system was kept at 0.07 to 0.08

MPa/G. Subsequently, the system was purged with nitrogen, and the supernatant was removed. The residue was washed with hexane two times. As a result, a prepolymerized catalyst (2) was obtained in which 3 g of the polymer had been produced per 1 g of the solid catalyst component.

SF-2185 113 (Polymerization)

Ethylene and l-hexene were copolymerized using a continuous fluidized-bed gas-phase polymerization apparatus at a total pressure of 2.0 MPa/G, a polymerization temperature of 80°C, and a gas linear velocity of 0.7 m/sec.

[0274]

The polymerization was initiated by continuously supplying the prepolymerized catalyst (2) and TIBA at 4.1 g/h and 5 mmol/h, respectively. To maintain a constant gas composition during the polymerization, ethylene, l-hexene, hydrogen and nitrogen were continuously supplied (gas composition: 1-hexene/ethylene — 0.03, hydrogen/sthylene = 4.2 x 107%, ethylene concentration = 71%). The ethylene/l-hexene copolymer was obtained in a yield of 6.0 kg/h, and had a density of 913 kg/m’ and MFR of 3.8 g/10 min.

[0275]

The ethylene/l-hexene copolymer obtained will be also referred to as the ethylene/a-olefin copolymer (B-1).

[0276] : [Production of ethylene/a-oclefin copolymer (B-2)]

An ethylene/l-hexene copolymer was obtained in the same manner as in the production of the ethylene/o-olefin copolymer + (B-1), except that the gas composition in the production (polymerization) of the ethylene/a~olefin copolymer (B-1) was

SF-2185 114 changed to l~-hexene/ethylene = 0.02, hydrocgen/ethylene = 4.6 x 107%, and ethylene concentration = 70%. The ethylene/l-hexene copolymer was obtained ina yield of 5.8 kg/h, and had a density of 924 kg/m’ and MFR (ASTM D-123§, measurement temperature 190°C, load 2.16 kg) of 3.8 g/10 min.

[0277] :

The ethylene/l-hexene copolymer obtained will be also referred tc as the ethylene/a-olefin copolymer (B-=2).

[0278] [Production of ethylene/a-olefin copolymer (B-3)]

Ethylene and l-hexene were copolymerized using a continuous fluidized—-bed gas-phase polymerization apparatus at a total pressure of 2.0 MPa/G, a polymerization temperature of 70°C, and a gas linear velocity of 0.7 m/sec. [C279]

The polymerization was initiated by continuously supplying the prepolymerized catalyst (2) and TIBA at 4.1 g/h and 5 mmol/h, respectively. To maintain a constant gas composition during the polymerization, ethylene, 1-hexene, hydrogen and nitrogen were continuously supplied (gas composition: l-hexene/ethylene = 0.033, hydrogen/ethylene = 4.4 x 107%, ethylene concentration = 49.7%). The ethylene/l-hexene copolymer was obtained ina yieldof 6.0 kg/h, and had a density of 903 kg/m? and MFR (ASTM D-1238, measurement

SF-2185 115 temperature 190°C, load 2.16 kg) of 3.8 g/10 min.

[0280]

The ethylene/l-hexene copolymer obtained will be also referred to as the ethylene/a-olefin copolymer (B-3).

[0281] [Production of ethylene/a-olefin copolymer (B-4}]

An ethylene/l-hexene copolymer was obtained in the same manner as in the production of the ethylene/a-olefin copolymer (B~1), except that the gas composition in the production (polymerization) of the ethylene/a~olefin copolymer (B-1) was changed to l-hexene/ethylene = 0.0205, hydrogen/ethylene = 5.45 x 107%, and ethylene concentration = 56.4%. The ethylene/l-hexene copolymer was obtained ina yield of 5.8 kg/h, and had a density of 918 kg/m® and MFR (ASTM D-1238, measurement temperature 190°C, load 2.16 kg) of 3.8 g/10 min.

[0282]

The ethylene/l-hexene copolymer obtained will be also referred to as the ethylene/a-olefin copolymer (B-4).

[0283] [Example 1]

In a Henschel mixer, there were mixed by stirring 75 parts by weight of the propylene polymer (A-1), 25 parts by weight of the ethylene/a-olefin copolymer (B-1), 0.30 parts by weight of Millad NX800C (manufactured by Miliiken & Company) as a

SF-2185 116 nucleating agent, 0.10 parts by weight of [tris {2,4-di-t-butylphenyl) phosphite] as a phosphorous antioxidant additive, 0.09 parts by weight of calcium stearate as a neutralizer, and 0.07 parts by weight of erucamide as a > lubricant. The mixture was melt-kneaded using a twin-screw extruder (NR-36) manufactured by Nakatani Machinery Ltd. under the following conditions to give a strand. [02841 (Twin-gscrew extruder conditions)

Model: NR-36

Screw rotation: 250 rpm

Resin temperature: 200°C

The strand was cooled with water and cut with a pelletizer into pellets of the propylene resin composition. The pellets were tested as described later to determine the melt flow rate (MFR) (ASTM D-1238, measurement temperature 230°C, load 2.16 kg) of the propylene resin composition. The propylene resin composition obtained in Example 1 had a melt flow rate (MFR) (ASTM D-1238, measurement temperature 230°C, load 2.16 kg) of 57 g/10 min. The results are shown in Table 1.

[0285]

Separately, the pellets were injection molded using an electric injection molding machine with a clamping force of 110 tons (NEX110-12E manufactured by NISSEI PLASTIC INDUSTRIAL

SF-2185 117

CO., LTD.) at a cylinder temperature of 200°C and a mold temperature of 40°C to give an ISO test piece (Type A) for testing tensile elastic modulus. The test piece was used for the measurement of tensile elastic modulus.

[0286] :

Separately, the pellets were injection molded using an electric injection molding machine with a clamping force of 100 tons (AUTO SHOT T series model 100D manufactured by FANUC

LTD.) at a cylinder temperature of 200°C and a mold temperature of 40°C to give a test piece 129 mm in length, 119 mm in width and 1 mm in thickness. The plate test piece was used for the measurement of haze.

[0287]

Separately, the pellets were injection molded using an electric injection molding machine with a clamping force of 100 tons (AUTO SHOT T series model 100D manufactured by FANUC

LTD.) at a cylinder temperature of 200°C and a mold temperature of 40°C to give a test piece 129 mm in length, 119 mm in width and 2 mm in thickness. The plate test piece was used for high-rate impact testing.

[0288]

The tensile elastic modulus, the haze and the high-rate impact testing {hereinafter HRIT) were measured with respect to the test pieces prepared above. The results are set forth

SF-2185 118 in Table 1.

[0289]

Separately, the pellets of the prcpylene resin composition were molded into an article (for — observation).

In detail, the pellets of the propylene resin composition were injection molded using an electric injection molding machine with a clamping force of 100 tons (AUTO SHOT T series mcedel 100D manufactured by FANUC LTD.) at a cylinder temperature of 200°C, amold temperature of 40°C, a primary injection pressure of 1700 kg/cm?, an injection rate of 30 mm/sec, a primary dwell pressure of 350 kg/cm?, a primary dwell time of 4 sec, and a dwell rate of 4 mm/sec. The molded articie (for TEM observation) was 129 mm in length, 119 mm in width and 1 mm in thickness.

[0290] [Example 2]

The procedures in Example 1 were repeated, except that the propylene polymer (A-1) was replaced by the propylene polymer (A-2). The propylene resin composition obtained in

Example 2 had a melt flow rate (MFR) (ASTM D-1238, measurement temperature 230°C, load 2.16 kg) of 63 g/10 min. The results are shown in Table 1.

[0291] [Example 3}

SF-2385 119

In a Henschel mixer, there were mixed by stirring 80 parts by weight cof the propylene polymer (A-3), 20 parts by weight of the ethylene/a-olefin copolymer (B-1), 0.30 parts by weight of Millad NX8000 (manufactured by Milliken & Company) as a nucleating agent, 0.10 parts by weight of [tris (2,4-di~t-butylphenyl) phosphite] as a phosphorous antioxidant additive, 0.0% parts by weight of calcium stearate as a neutralizer, 0.07 parts by weight of erucamide as a lubricant, and 0.012 parts by weight of 2,5-~dimethyl-2,5~di(t-butylperoxy)hexane (trade name:

PERHEXA 25B manufactured by NOF CORPORATION} as an organic peroxide. The mixture was melt-kneaded using a twin-screw extruder (NR-36) manufactured by Nakatani Machinery Ltd. under the following conditions to give a strand.

[0292] (Twin-screw extruder conditions)

Model: NR-36

Screw rotation: 250 rpm

Resin temperature: 200°C

The strand was cooled with water and cut with a pelletizer into pellets of the propylene resin composition. The pellets were tested as described later to determine the melt flow rate (MFR) (ASTM D-1238, measurement temperature 230°C, load 2.16 kg} of the propylene resin composition. The propylene resin

SF-23i85 120 composition obtained in Example 3 had a melt flow rate (MFR) (ASTM D-1238, measurement temperature 230°C, load 2.16 kg) of 47 g/10 min. The results are shown in Table 1.

[0293]

Separately, the pellets were injection molded using an electric injection molding machine with a clamping force of 110 tons (NEX110-12FE manufactured by NISSEI PLASTIC INDUSTRIAL

CO., LTD.) at a cylinder temperature of 200°C and a mold temperature of 40°C to give an ISO test piece (Type 2) for testing tensile elastic modulus. The test piece was used for the measurement of tensile elastic medulus.

[0294]

Separately, the pellets were injection molded using an electric injection molding machine with a clamping force of 100 tons (AUTO SHOT T series model 100D manufactured by FANUC

LTD.) at a cylinder temperature of 200°C and a mold temperature of 40°C to give a test piece 129 mm in length, 119 mm in width and 1 mm in thickness. The plate test piece was used for the measurement of haze.

[0295]

Separately, the pellets were injection molded using an electric injection molding machine with a clamping force of 1C0 tons {AUTO SHOT T series model 100D manufactured by FANUC

LTD.) at a cylinder temperature of 200°C and a mold temperature

SE-2185 121 of 40°C to give a test piece 129 mm in length, 119 mm in width and 2 mm in thickness. The plate test piece was used for high-rate impact testing.

[0296]

The tensile elastic mcdulus, the haze and the high-rate impact testing (hereinafter HRIT) were measured with respect to the test pieces prepared above. The results are set forth in Table 1.

[0297] : [Example 4]

The procedures in Example 3 were repeated, except that the propylene polymer {(A-3) and the ethylene/a-oclefin copolymer (B-1) were used in amounts of 77 parts by weight and 23 parts by weight, respectively. The propylene resin composition obtained in Example 4 had a melt flow rate (MFR) (ASTM D-1238, measurement temperature 230°C, load 2.16 kg) of 52 g/10 min. The results are shown in Table 1.

[0298] [Example 5]

The procedures in Example 3 were repeated, except that the propylene polymer (A-3) and the ethylene/a-olefin copolymer (B-1) were weed in amounts of 75 parts by weight and parts by weight, respectively. The propylene resin composition obtained in Example 5 had a melt flow rate (MFR)

SF-2185 122 (ASTM D-1238, measurement temperature 230°C, load 2.16 kg) of 56 g/10 min. The results are shown in Table 1.

[0299]

The pellets of the propylene resin composition obtained in this example were molded into an article (for TEM observation). In detail, the pellets of the propylene resin composition were injection molded using an electric injection molding machine with a clamping force of 100 tons (AUTO SHOT

T series model 100D manufactured by FANUC LTD.) at a cylinder temperature of 200°C, a mold temperature of 40°C, a primary injection pressure of 1700 kg/cm?, an injection rate of 30 mm/sec, a primary dwell pressure of 350 kg/cm? a primary dwell time of 4 sec, and a dwell rate of 4 mm/sec. The molded article (for TEM observation) was 129% mm in length, 119 mm in width i5 and 1 mm in thickness.

[0300]

Separately, the pellets of the propylene resin composition were molded into a container as described below.

[0301]

The pellets of the propylene resin composition were injection molded using an electric injection molding machine with a clamping force of 100 tons (AUTO SHOT T series model 100D manufactured by FANUC LTD.) at a cylinder temperature of 250°C, amcld temperature of 20°C, a primary injection pressure

SF-2185 123 of 1700 kg/cm®, an injection rate of 70 mm/sec, primary and secondary dwell pressures of 900 and 830 kg/cm? respectively, primary and secondary dwell times of 3 sec and 3 sec respectively, and a dwell rate of 4 mm/sec. The injection-molded container had a height of 78.15 mm, a diameter of 90.21 mm and a side thickness of 0.5 mm.

[0302]

A side portion of the container was cut and tested by a haze testing method in accordance with JIS K 7136 using NDH2000 manufactured by NIPPON DENSHOKU INDUSTRIES CO., LTD., resulting in a haze value of approximately 8%. Separately, the : container was compression tested with tester model 205 manufactured by INTESCO Co., Ltd., at a testing rate of 300 mm/min and a testing temperature of 23°C. The compressive strength obtained was 556 N. The container was highly transparent and had rigidity, which is important in mold releasing.

[0303] [Example 6] 290 The procedures in Example 3 were repeated, except that the propylene polymer (A-3) and the ethylene/a-olefin copolymer (B-1) were used in amounts of 70 parts by weight and parts by weight, respectively. The propylene resin composition obtained in Example 6 had a melt flow rate (MFR)

SF-2185 124 (ASTM D-1238, measurement temperature 230°C, load 2.16 kg) of 44 g/10 min. The results are shown in Table 1.

[0304] [Example 7]

The procedures in Example 5 were repeated, except that the nucleating agent Millad NX8000 (manufactured by Milliken & Company) was replaced by nucleating agent ADK STAB NA-21 (manufactured by ADEKA CORPORATION) and that the amount of ADK

STAB NA-21 was 0.25 parts by weight. The propylene resin composition obtained in Example 7 had a melt flow rate (MFR) . (ASTM D-1238, measurement temperature 230°C, load 2.16 kg) of 48 g/10 min. The results are shown in Table 1.

[0305] [Comparative Example 1]

The procedures in Example 1 were repeated, except that the propyiene polymer (A~-1) was replaced by the propylene polymer (A-cl). The propylene resin composition obtained in

Comparative Example 1 had a melt flow rate (MFR) (ASTM D-1238, measurement temperature 230°C, load 2.16 kg) of 48 g/10 min.

The results are shown in Table 2. The propylene polymer (A-cl) used in this comparative example contained less Dinse1 and more

Dsor than specified in the requirement (Al) according to the claims of the present invention. As a result, the composition had poor rigidity (tensile elastic modulus).

SF-2185 125

[0306] [Comparative Example 2]

The procedures in Example 1 were repeated, except that the propylene polymer (A-1) was replaced by the propylene polymer (A-c2). The propylene resin composition obtained in

Comparative Example 2 had a melt flow rate (MFR) (ASTM D-1238, measurement temperature 230°C, load 2.16 kg) of 49 g/10 min.

The results are shown in Table 2. The propylene polymer (A-c2) used in this comparative example contained less Dipse:r and more

Dgor than specified in the requirement (Al) according to the claims of the present invention. As a result, the composition had poor rigidity (tensile elastic modulus) and transparency {haze}.

[0307] [Comparative Example 3]

The procedures in Example 1 were repeated, except that the propylene polymer (A-1) was replaced by the propvlene polymer (A-c3). The propylene resin composition obtained in

Comparative Example 3 had a melt flow rate (MFR) (ASTM D-1238, measurement temperature 230°C, load 2.16 kg) of 54 g/10 min.

The results are shown in Table 2. The propylene polymer (A-c3) used in this comparative exampie contained less Dipser and more

Dso1 Than specified in the requirement (Al) according to the claims of the present invention. As a result, the composition

SF-2185 126 had poor rigidity (tensile elastic modulus} and transparency (haze).

[0308] [Comparative Example 4]

The procedures in Example 1 were repeated, except that the propylene polymer (A-1l) was replaced by the propylene polymer (A-cd). The propylene resin composition obtained in

Comparative Example 4 had a melt fiow rate (MFR) (ASTM D-1238, measurement temperature 230°C, load 2.16 kg) of 61 g/10 min.

The results are shown in Table 2. The propylene polymer (A-cd) used in this comparative example contained less Dinse1 and more

Ds: than specified in the requirement (Al} according to the claims of the present invention. As a result, the composition had poor rigidity (tensile elastic modulus) and transparency (haze).

[0309] [Comparative Example 5]

The procedures in Example 1 were repeated, except that the propylene polymer {(A-1l) was replaced by the propylene polymer (A-cb5). The propylene resin composition obtained in

Comparative Example 5 had a melt flow rate {MFR} {ASTM D-1238, measurement temperature 230°C, load 2.16 kg) of 43 g/10 min.

The results are shown in Table 2. The propylene polymer (A-~cD) used in this comparative example had a smaller weight percentage

SF-2185 127 of ethylene-derived structural units in Ds, than specified in the requirement (A3) according to the claims cf the present invention. As a result, the compositicn had poor low-temperature impact resistance (HRIT (ductility)).

[0310] [Comparative Example 6]

The procedures in Example 3 were repeated, except that the propylene polymer (A-c6) and the ethylene/o-olefin copolymer (B-1) were used in amounts of 90 parts by weight and 10 parts by weight, respectively, and that no nucleating agents were used. The propylene resin composition obtained in

Comparative Example 6 had a melt flow rate (MFR) (ASTM D-1238, measurement temperature 230°C, load 2.16 kg) of 48 g/10 min.

The results are shown in Table 2. This comparative example involved 80 parts by weight of the propylene polymer (A-cb) and 10 parts by weight of the ethylene/a-olefin copolymer (B-1).

That is, the propylene polymer (A) was in excess and the ethylene/oa—olefin copolymer (B) was in short of the proportions of the propylene polymer (A) and the ethylene/a-olefin copolymer (B) specified in claim 1 of the present invention.

Further, the composition contained no nucleating agents. As a result, the composition had poor transparency (haze).

[06311] [Comparative Example 7]

SF-2185 128

The procedures in Comparative Example 6 were repeated, except that the propylene polymer (A-cb}) and the ethylene/a-olefin copolymer (B-1) were used in amounts of 70 parts by weight and 30 parts by weight, respectively. The propylene resin composition obtained in Comparative Example 7 had a melt flow rate (MFR) (ASTM D-1238, measurement temperature 230°C, load 2.16 kg) of 35 g/10 min. The results are shown in Table 2. This comparative example involved no nucleating agents. As a result, the composition had poor rigidity (tensile elastic modulus) and transparency (haze). oo [0312] [Comparative Example 8]

The procedures in Comparative Example 7 were repeated, except that the ethylene/a-olefin copolymer (B-1) was replaced by the ethylene/a-olefin copolymer (B-2). The propylene resin composition obtained in Comparative Example 8 had a melt flow rate (MFR) {ASTM D-1238, measurement temperature 230°C, load 2.16 kg) of 36 g/10 min. The results are shown in Table 2. The ethylene/oa-oclefin copolymer (B-2) used in this comparative example had a higher density than specified in the requirement {(B2) according to the claims of the present invention. Further, the composition contained no nucleating agents. As a result, the composition had poor rigidity (tensile elastic modulus) and transparency (haze).

SF-2185 129

[0313] [Comparative Example 9]

The procedures in Comparative Example 8 were repeated, except that nucleating agent Millad NX8000 {manufactured by

Milliken & Company) was used in an amount of 0.30 parts by weight.

The propylene resin composition obtained in Comparative

Example 9 had a melt flow rate (MFR) (ASTM D-1238, measurement temperature 230°C, load 2.16 kg) of 37 g/10 min. The results are shown in Table 2. The ethylene/a-clefin copolymer used in this comparative example had a higher density than specified : in the requirement (B2) according to the claims of the present invention. As a result, the composition had poor transparency (haze}.

[0314] [Comparative Example 10] :

The procedures in Example 5 were repeated, except that the single-site-catalyzed ethylene/a~olefin copolymer (B-1) was replaced by ULTZEX 15150J which is manufactured by Prime

Polymer Co., Ltd. (MFR 15 g/10 min (ASTM D-1238, measurement temperature 190°C, load 2.16 kg): density 915 kg/m?) and which is made not with a single-site catalyst but with a so-called

Ziegler—-Natta catalyst. The propylene resin composition obtained in Comparative Example 9 had a melt flow rate (MFR) (ASTM D-1238, measurement temperature 230°C, load 2.16 kg) of

SF-2185 130 65 g/10 min. The results are shown in Table 2. The ethylene/a~olefin copolymer used in this comparative example,

ULTZEX 15150J manufactured by Prime Polymer Co., Ltd., was a pelymer made with not a single-site catalyst but a so-called

Ziegler—-Natta catalyst. As a result, the composition had poor low-temperature impact resistance (HRIT (ductility)).

[0315] [Comparative Example 11]

The procedures in Comparative Example 10 were repeated, except that the nucleating agent Millad NX8000 {manufactured by Milliken & Company) was replaced by GEL ALL MD (manufactured by New Japan Chemical Ceo., Ltd.). The propylene resin composition obtained in Comparative Example 11 had a melt flow rate (MFR) (ASTM D-1238, measurement temperature 230°C, load 2.16 kg) of 65 g/10 min. The results are shown in Table 2. The ethylene/a~olefin copolymer used in this comparative example,

ULTZEX 15150J manufactured by Prime Polymer Co., Ltd., was a polymer made with not a single-site catalyst but a so-called

Ziegler-Natta catalyst. Thus, the requirement (Bl) according to the claims of the present invention was not satisfied. As a result, the composition had poor low-temperature impact resistance (HRIT (ductility)). Further, the composition had a strong odor because of the use of GEL ALL MD manufactured by New Japan Chemical Co., Ltd. as a nucleating agent.

SF-218B5 131

[6316] [Example 8]

The procedures in Example 1 were repeated, except that the propylene polymer (A-4) and the ethylene/a-olefin copolymer (B-1) were used in amounts of 73.5 parts by weight and 26.5 parts by weight, respectively. The propylene resin composition obtained in Example 8 had a melt flow rate (MFR) {ASTM D-1238, measurement temperature 230°C, load 2.16 kg) of 65 g/10 min. The results are shown in Table 3.

[0317] [Example 9]

The procedures in Example 1 were repeated, except that the propylene polymer (A-5) and the ethylene/a-olefin copolymer {(B-1) were used in amounts of 75 parts by weight and 25 parts by weight, respectively. The propylene resin composition obtained in Example 9 had a melt flow rate (MFR) (ASTM D-1238, measurement temperature 230°C, load 2.16 kg) of 62 g/10 min. The results are shown in Table 3. 10318] [Example 10]

The procedures in Example 1 were repeated, except that the propylene polymer (A-6) and the ethylene/a-olefin copolymer (B-1) were used in amounts of 73.5 parts by weight and 26.5 parts by weight, respectively. The propylene resin

SE-2185 132 composition obtained in Example 10 had a melt flow rate (MFR) (ASTM D-1238, measurement temperature 230°C, load 2.16 kg) of 55 g/10 min. The results are shown in Table 3.

[0319] [Example 11]

The procedures in Example 1 were repeated, except that the propylene polymer (A-3) and the ethylene/a-olefin copolymer (B-3) were used in amounts of 75 parts by weight and 25 parts by weight, respectively. The propylene resin composition obtained in Example 11 had a melt flow rate (MFR) (ASTM D-1238, measurement temperature 230°C, load 2.16 kg) of 52 g/10 min. The results are shown in Table 3.

[0320] [Example 12]

The procedures in Example 11 were repeated, except that the ethylene/a-olefin copolymer (B-4) was used. The propylene resin composition obtained in Example 12 had a melt flow rate (MFR) (ASTM D-1238, measurement temperature 230°C, load 2.16 kg) of 53 g/10 min. The results are shown in Table 3.

[0321] : [Example 13]

The procedures in Example 1 were repeated, except that the propylene polymer (A-7) and the ethylene/a-olefin } copolymer ({B-1l) were used in amounts of 73.5 parts by weight

SF-2185 133 and 26.5 parts by weight, respectively. The propylene resin composition obtained in Example 13 had a melt flow rate (MER) (ASTM D-1238, measurement temperature 230°C, load 2.16 kg) of 58 g/10 min. The results are shown in Table 3.

[0322] [Comparative Example 12]

The procedures in Example 1 were repeated, except that the propylene polymer (A-1) was replaced by the propylene polymer (A-c7). The propylene resin composition obtained in i0 Comparative Example 12 had a melt flow rate (MFR) (ASTM D-1238, measurement temperature 230°C, load 2.16 kg) of 90 g/10 min.

The results are shown in Table 4. The propylene polymer (A-c7) used in this comparative example had a higher melt flow rate than specified in the requirement (Al) according to the claims 15 of the present invention. As a result, the composition had poor transparency (haze).

[0323] [Comparative Example 13]

The procedures in Example 1 were repeated, except that 20 the propylene polymer (A-3) and the ethylene/a-olefin copolymer (B-1) were used in amounts of 90 parts by weight and parts by weight, respectively. The propylene resin composition obtained in Comparative Example 13 had a melt flow rate (MFR) (ASTM D-1238, measurement temperature 230°C, load

SF-2185 134 2.16 kg) of 68 g/10 min. The results are shown in Table 4. In this comparative example, the ethylene/a-olefin copolymer (B) was used in smaller parts by weight than specified in the claims of the present invention. As a result, the composition had poor low-temperature impact resistance (HRIT (ductility)) and transparency (haze).

[0324]

The pellets of the propylene resin composition obtained in this comparative example were molded into an article (for

TEM observation). In detail, the pellets of the propylene resin composition were injection molded using an electric injection molding machine with a clamping force of 100 tons (AUTO SHOT T series model 100D manufactured by FANUC LTD.) at a cylinder temperature of 200°C, a mold temperature of 40°C, a primary injection pressure of 1700 kg/cm®, an injection rate of 30 mm/sec, a primary dwell pressure of 350 kg/cm®, a primary dwell time of 4 sec, and a dwell rate of 4 mm/sec. The molded article (for TEM observaticn) was 129 mm in length, 119 mm in width and 1 mm in thickness.

[0325] [Comparative Example 14]

The procedures in Comparative Example 13 were repeated, except that the propylene polymer (A-3}) and the ethylene/a—-olefin copolymer (B-1) were used in amounts of 50

SF-2185 135 parts by weight and 50 parts by weight, respectively. The propylene resin composition obtained in Comparative Example 14 had a melt flow rate (MFR) (ASTM D-1238, measurement temperature 230°C, load 2.16 kg) of 28 g/10 min. The results are shown in Table 4. In this comparative example, the propylene polymer (A) and the ethylene/a-olefin copolymer (B) were used in partis by weight that were cutside the ranges specified in the claims of the present invention. As a result, the composition had poor rigidity (tensile elastic modulus).

[0326] [Comparative Example 15]

The procedures in Example 1 were repeated, except that 70 parts by weight of the propylene polymer (A-c8) was used and that 30 parts by weight of an ethylene/a-olefin copolymer (B-5) was used which was PETROTHENE 342 manufactured by TOSOH

CORPORATION (MFR 8 g/10 min (ASTM D-1238, measurement temperature 190°C, load 2.16 kg); density 919 kg/m’). The propylene resin composition obtained in Comparative Example 15 had a melt flow rate (MFR) (ASTM D-1238, measurement temperature 230°C, load 2.16 kg) of 18 g/10 min. The results are shown in Table 4. The propylene polymer {A-c8) used in this comparative example contained less Dinser and more Ds, than specified in the requirement (Al) acccrding to the claims of the present invention. As a result, the composition had poor

SF-2185 136 rigidity (tensile elastic modulus) and transparency (haze).

[0327] [Evaluation methods]

Properties of the propylene polymers (A}, the ethylene/a-olefin copolymers (B) and the propylene resin compositions were measured by the following methods. The results are shown in Tables 1 and 3 (Examples) and Tables 2 and 4 (Comparative Examples).

[0328] [Dinsor and Dsel

The proportions of Djgse1 and Dser in the propylene polymers (A) were determined by the following method.

[0329] 200 ml of n-decane was added to 5 g of a sample of the propylene polymer (A). The polymer was dissolved by heating at 145°C for 30 minutes to give a solution (1). Subseguently, the solution was cooled to room temperature of 25°C in approximately 2 hours and was allowed to stand at 25°C for 30 minutes, resulting in a solution (2) containing a precipitate {a) . The precipitate (a) was then separated from the solution (2) through a filter fabric having a mesh size of approximately 15 um. The precipitate (a) was dried, and the weight of the precipitate (a) was measured. The weight of the precipitate (a) was divided by the sample weight (5 g) to give a proportion

SF-2185 137 of the n-decane-insoluble component {Dinse1) . Separately, the sclution (2) separated from the precipitate (a) was added to an approximately 3-fold amount of acetone, and the component that had been dissolved in the n-decane was precipitated as a precipitate (B). The precipitate (Pp) was filtered through a glass filter (G2, mesh size: approximately 100 to 160 pum).

The precipitate (PB) was dried, and the weight thereof was measured. The weight of the precipitate () was divided by the sample weight (5 g) to give a proportion of the n-decane-soluble component (Dg). In Examples described hereinabove, the filtrate from the separation of the precipitate (B) was concentrated to dryness, but no residues were observed.

[0330] [Intrinsic viscosity [Mso1] of Dgor at 135°C in tetralin]

The intrinsic viscosity [Nso1] ©f Dse1 in the propylene polymers (A) at 135°C in tetralin was determined in the following manner.

[0331]

The sample used herein was the precipitate (Pf) obtained in the determination of the proportions of Diuser and Dgei- "Approximately 25 mg of the sample was dissolved in 25 ml of tetralin, and the specific viscosity Tsp was measured in an oil bath at 135°C. The tetralin solution was diluted by addition of 5 ml of tetralin solvent, and the specific viscosity nsp was

SF-2185 138 determined in the same manner. This dilution was repeated two more times. The concentration (C) was extrapolated to zerc concentration, and the value of m,,/C was obtained as the intrinsic viscosity [Mse1] ©f Dsor at 135°C in tetralin.

[0332] [Weight percentage of ethylene-derived structural units in

Dso1]

The weight percentage of the ethylene~derived structural units in Dgo1 in the propylene polymers (A) was calculated based on the results of C-NMR in the following manner.

[0333]

The sample used herein was the precipitate (B) obtained in the determination of the proportions of Djpse1 and Dge;. The precipitate (BP) as the sample was analyzed by **C~NMR under the following conditions.

[0334] 13C-NMR conditions

Measurement apparatus: nuclear magnetic resonance apparatus LA400 manufactured by JEOL 1td. 29 Measurement mode: BCM (bilevel complete decoupling)

Observation frequency: 100.4 MHz

Observation range: 17006.8 Hz

Pulse width: C nucleus 45° (7.8 psec)

Pulse repetition time: 5 sec

SF-2185 139

Sample tube: 5 mm diameter

Sample tube rotation speed: 12 Hz

Accumulation: 20000 scans

Measurement temperature: 125°C

Sclvents: 0.35 ml of 1,2,4-trichlorcbenzene/0.2 ml of deuterated benzene :

Sample amount: approximately 40 mg

From the spectrum obtained, the proportions ot monomer sequence distributions (triad (three units) distributions) were determined in accordance with Literature (1) below, and the molar fraction {(mcl%) of the ethylene-derived structural units (hereinafter E (mol%)) and the molar fraction (mol%) of the propylene-derived structural units (hereinafter P (mol%)) in Dge1 in the propylene polymer were calculated. The ethylene-derived structural units were converted to wt% based on the fractions E (mol%) and P (mol%)} according to the equation (Eg. 1) below, and thereby the weight percentage (wt%) of the ethylene-derived structural units (hereinafter BE (wt%)) in Dao: in the propylene polymer was calculated. 0335]

Literature (1): Kakugo, M.; Naito, Y.; Mizunuma, K.;

Miyatake, T., Carbon-13 NMR determination of monomer sequence distribution in ethylene-propylene copolymers prepared with delta-titanium trichloride~diethylaluminum chloride.

SF-2185 140

Macromolecules 1982, 15, (4), 1150-1152

E (wt) = FE (mol%) x 28 x 100/[P (mol%) x 42 + E (mol%) x 28] --- (Eg. 1) [Intrinsic viscosity [MNinso1] ©f Dinser at 135°C in tetralin]

The intrinsic viscosity [Ninse1] Of Dipnser in the propylene polymers (A) at 135°C in tetralin was determined in the following manner.

[0336]

The sample used herein was the precipitate {a) obtained in the determination of the proportions of Dipsor and Dgei.

Approximately 25 mg of the sample was dissolved in 25 ml of tetralin, and the specific viscosity ns, was measured in an oil bath at 135°C. The tetralin solution was diluted by addition of 5 ml of tetralin solvent, and the specific viscosity ns, was determined in the same manner. This dilution was repeated two more times. The concentration (C) was extrapolated to zero concentration, and the value of 1./C was obtained as the intrinsic viscosity [Minso1] ©f Dinser at 135°C in tetralin.

[0337]

Melt flow rate]

The melt flow rate of the propylene polymers (A) was measured in accordance with ASTM D-1238 (230°C, 2.16 kg load).

[0338]

The density of the ethylene/a-olefin copolymers (B) was

SF-2185 141 determined as described below.

[0339]

A strand that was cbtained in the measurement of the melt flow rate (ASTM D-1238) at 190°C under 2.16 kg lead of the ethylene/a-olefin copolymer (B) was heat treated at 120°C for 1 hour and was gradually cooled to room temperature in 1 hour, thereby preparing a sample. The sample was analyzed by a density gradient tube method to determine the density of the ethylene/a-olefin copolymer (B).

[0340]

The melt flow rate of the ethylene/o-olefin copolymers (B) was measured in accordance with ASTM D-1238 (measurement temperature 190°C, load 2.16 kg).

[0341]

The melt flow rate of the propylene resin compositions was measured in accordance with ASTM D-1238 (measurement temperature 230°C, load 2.16 kg).

[0342] [Tensile elastic modulus]

The test pieces for tensile elastic modulus measurement prepared in Examples and Comparative Examples were tested by a tensile elastic modulus testing method in accordance with

ISO 527-2. The tensile measurement temperature was 23°C, and the stress rate was 1 mm/min. The test pieces were Type A in

SF-2185 142 accordance with ISO 527-2 prepared by injection molding as described hereinabove. The tester was STROGRAPH V10-C manufactured by Toyo Seiki Seisaku-Sho Ltd. The tensile elastic modulus obtained was used as an indicator of rigidity.

In detail, a higher tensile elastic modulus indicated higher rigidity.

[0343]

Haze]

The plate test pieces for haze measurement prepared in

Examples and Comparative Examples were analyzed by a haze testing method in accordance with JIS K 7136 using NDH2000 manufactured by NIPPON DENSHOKU INDUSTRIES CO., LTD. The test pleces were prepared by injection mclding as described hereinabove, and were 129 mm in length, 119 mm in width and 1 mm in thickness. The haze cbtained was used as an indicator of transparency. In detail, a smaller value indicated higher transparency.

[0344] [Low-temperature impact resistance]

The plate test pieces for high-rate impact testing prepared in Examples and Comparative Examples were tested by a high-rate impact testing (HRIT) method in accordance with

ASTM (D 3763-02). The test pieces were prepared by injection molding as described hereinabove, and were 129 mm in length,

SF-2185 143 119 mm in width and 2 mm in thickness.

In detail, the test piece was conditioned at -20°C for 2 hours in a measurement apparatus manufactured by Shimadzu

Corporation (Shimadzu Servo Pulser high-rate impact tester

HTM-10KN equipped with thermostat) and thereafter a striking member (the top of a hemispherical member 1/2 inch in diameter) was caused to hit the center of the plate at a speed of 3 m/sec. :

The amount of energy which the test piece absorbed until fracture or penetration was measured. The plate was held with a clamp having a 3 inch diameter hole. In the tables, the term ductility indicates the amount of energy obtained by subtracting the energy required to reach the yield point from the total energy, and is an indicator of the level of ductile fracture. A higher value indicates more excellent low-temperature impact resistance.

[0345] . [Cdor]

To evaluate the odor of the propylene resin compositions, 10 g of the pellets of each composition were placed in a 100 ml conical flask, and the flask was sealed with a stopper. The pellets were heated in an oven at 100°C for 1 hour. Immediately after they were removed from the oven, the stopper was removed and the odor was evaluated by a sensory test method according to the following criteria.

SF-2185 : 144

[0346]

BAA --- No odor

BB --- Slight odor cc --- Odor [TEM observation]

The molded articles (for TEM observation) obtained in

Examples 1 and 5 and Comparative Example 13 were cut inte smaller pieces for the observation of cross section in the vicinity of the surface by TEM. The pieces were embedded in a resin for surface protection. Tocbtain contrast in the TEM observation, the resin-embedded pieces were sealed in glass bottles together with RuO4 crystal and were stained therewith for approximately 12 to 16 hours. Thereafter, the pieces were sliiced with an ultramicrotome (manufactured by Leica) at normal temperature into ultrathin pieces as TEM observation specimens having a thickness of about 50 to 120 nm. The ultrathin pieces (TEM observation specimens) were observed with a transmission electron microscope (TEM, H-7650 manufactured by Hitachi

High-Technologies Corporation, acceleration voltage: about 100 kv).

[0347]

In the TEM images obtained by TEM observation, the skin layer (a layer from the surface of the molded article (for TEM observation) to a depth of 2 to 5 um) and the core layer (a

SF-2185 145 layer from the surface of the molded article (for TEM observation) toc a depth of 50 to 60 pm) of the ultrathin pieces (the TEM observation specimens) were observed. :

[0348]

According to the TEM observation, the skin layers in

Examples 1 and 5 had a dark color phase with a width in the depth direction of not more than 0.4 pm.

[0349]

Further, the core layers (extending from the surface of the specimen to a depth of 50 to 60 um) in Examples 1 and 5 had a dark color phase with a width in the depth direction of not more than 0.7 pm.

[0350] [Table 1]

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Claims (10)

SF-2185 150 CLAIMS

1. A propylene resin composition comprising 60 to 80 parts by weight of a propylene polymer (A) satisfying the following requirements (Al) to (A5)}, 20 toc 40 parts by weight of an ethylene/a-olefin copolymer (B) satisfying the following requirements (Bl) to (B3) (wherein the total of the propylene polymer (A} and the ethylene/a-olefin copolymer (B) is 100 parts by weight), and 0.1 £0 0.4 parts by weight of a nucleating agent; (Al): the propylene polymer (A) contains 90.5 to 97.0 wt$% of a n-decane-insoluble component (Dipsoi) and 3.0 to 9.5 wt$ of a n-decane-soluble component (Dgo:) (wherein the total of Dinser and Dgo1 is 100 wt%); (A2) : the component Dg, has an intrinsic viscosity [Nse] of 1.0 to 2.5 dl/g as measured at 135°C in tetralin; (A3}: the component Dg, contains ethylene-derived structural units at 25 to 35 wt% based on 100 wt$% of the component Dsois (Ad): the component Diaser has an intrinsic viscosity [Ninso1] of 0.8 to 1.1 dl/g as measured at 135°C in fetralin; (AS): the propylene polymer (A) has a melt flow rate (MFR) (ASTM D-1238, measurement temperature 230°C, load 2.16 kg) of to 170 g/10 min;

SE-2185 1351 (Bl): the ethylene/a-olefin copolymer (B) is an ethylene/a-olefin copolymer made with a single-site catalyst; {B2): the ethylene/a-olefin copolymer (B) has a density of 900 to 919 kg/m’; (B3): the ethylene/a-olefin copolymer (B) has amelt flow rate (MFR) (ASTM D-1238, measurement temperature 190°C, load

2.16 kg) of 0.1 to 50 g/10 min.

2. The propylene resin composition according to claim 1, wherein the propylene polymer (A) satisfies the following requirement (A2'), and the ethylene/a-olefin copolymer (B) satisfies the following reguirement (B3'): (A2'): the component Dsoy has an intrinsic viscosity [Mso1] of 1.5 to 2.5 dl/g as measured at 135°C in tetralin: (B3'}: the ethylene/a-olefin copolymer (B) has a melt flow rate (MFR} (ASTM D-1238, measurement temperature 190°C, load 2.16 kg) of 1 to 10 g/10 min.

3. The propylene resin composition according to claim 1 or 2, which has a melt flow rate (MFR) (ASTM D-1238, measurement temperature 230°C, load 2.16 kg} of 20 tec 100 g/10 min.

4. The propylene resin composition according to any

SF-2185 152 one of claims 1 to 3, wherein the ethylene/a-olefin copolymer (B) has a melt flow rate (MFR) (ASTM D-1238, measurement temperature 190°C, load 2.16 kg) of 2.0 to 5.0 g/10 min.

5. The propylene resin composition according to any one of claims 1 to 4, wherein the propylene resin composition satisfies the following requirement (X1): (X1): pellets of the propylene resin composition are injection molded using an injection molding machine with a 16 clamping force of 100 tons, at a cylinder temperature of 200°C, a mold temperature of 40°C, a primary injection pressure of 1700 kg/cm?, an injection rate of 30 mm/sec, a primary dwell pressure of 350 kg/cm?, a primary dwell time of 4 sec, and a dwell rate of 4 mm/sec, thereby producing a shaped article 129 mm in length, 119 mm in width and 1 mm in thickness; the shaped article is cut into a small piece; the piece is embedded in a resin, and the resin-embedded piece is sealed in a glass bottle together with RuO4 crystal and is stained therewith; the piece is then sliced with an ultramicrotome at normal temperature; the resultant ultrathin piece is observed with TEM, and the TEM image obtained shows that the skin layer (a layer from the surface of the shaped article to a depth of 2 to. 5 um) has a dark color phase with a width in the depth direction of not more than 0.4 um.

SF-2185 153

6. The propylene resin composition according to any one of claims 1 to 5, which has a tensile elastic modulus of 1300 to 1800 MPa.

7. A shaped article formed from the propylene resin composition of any one of claims 1 to 6.

8. A container formed from the propylene resin 160 composition of any one of claims 1 to 6.

9. A food packaging container formed from the propylene resin composition of any one of claims 1 to 6.

10. A container obtained by injection molding or injection stretch blow molding the propylene resin composition of any one of claims 1 to 6.

il. A food packaging container obtained by injection molding or injection stretch blow molding the propylene resin composition of any one of claims 1 to 6.