JP2000327859A - Resin composition for film, film made therefrom, and film for heavy-duty packaging bag - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composition desirable for, especially, a heavy-duty packaging film by mixing an ethylene copolymer having specified physical properties with other ethylene (co)polymers in a specified ratio. SOLUTION: This composition comprises 90-20 wt.% copolymer having a density (d1) of 0.87-0.94, an MFR (MFR1) of 0.1-10, an Mw/Mn ratio of 1.5-3.5, and a compositional distribution parameter Cb of 1.08-2.00, and having a content X (wt.%) of o-dichlorobenzene solubles (25 deg.C) in the range: X<2.0 in the case when the relationships I hold between d1 and MFR1 or in the range satisfying relationships III in the case when the relationships II hold between them, and giving an elution temperature vs. eluate amount curve having a plurality of peaks when fractionated by continuous temperature-rising elutign fractionation and 10-80 wt.% (co)polymer obtained by polymerizing ethylene alone or copolymerizing ethylene with a 3-20C α-olefin in the presence of a catalyst containing a group IV transition metal compound and having a density of 0.88-0.97 and an MFR <MFR2) of 0.01-5 and/or (co)polymer having an Mw/Mn ratio of 1.5-5.0 and satisfying the relationships IV between MRF2 and η.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a film, particularly a film for heavy packaging bags used for transporting fertilizers and the like, and a polyethylene resin composition suitable for them.

[0002]

2. Description of the Related Art Polyethylene resins such as low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), and high-density polyethylene (HDPE) are well-balanced in mechanical properties and optical properties and are inexpensive. Therefore, it is generally used as a film for light packaging and heavy packaging such as resin bags such as confectionery bags and food packaging bags and fertilizer bags. Particularly in recent heavy packaging bag films, a high-dimensional balance of rigidity and impact resistance is strongly demanded in order to withstand further thinning for weight reduction. Generally, in order to improve rigidity, the degree of crystallinity of the film may be increased, and for that purpose, the amount of comonomer in the resin composition may be reduced to increase the density. On the other hand, in order to improve the impact resistance, it is sufficient to increase the number of tie molecules. For example, in the case of linear low density polyethylene (LLDPE), the inter-crystal content is increased by increasing the comonomer content or increasing the molecular weight. The number of Thai molecules should be increased. Therefore, improvement in rigidity and improvement in impact resistance must satisfy conflicting requirements, and it is extremely difficult to achieve both. Moreover, increasing the molecular weight is limited because it increases the melt viscosity and deteriorates the extrusion characteristics. Furthermore, conventional LLDPE using a Ziegler catalyst has a problem that, when the comonomer content is increased, a low molecular weight component is also increased, so-called sticky components are generated, blocking is caused, and slipperiness is deteriorated. In addition, a film for bags is required to have good low-temperature heat sealing characteristics with higher speed and higher strength.

[0003]

DISCLOSURE OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and in addition to satisfying a high level of balance between rigidity and impact resistance, has excellent extrusion characteristics, inflation moldability, and anti-blocking properties. It is an object of the present invention to provide a film having properties, slipperiness, sealing properties, heat resistance, and processability, particularly a film for heavy packaging bags and a resin composition therefor.

[0004]

Means for Solving the Problems As a result of diligent studies in line with the above-mentioned object, the present inventors have found that despite having a narrow molecular weight distribution, they have a relatively wide composition distribution, and have low molecular weight components and non-molecular weight components. The above object has been achieved by blending a novel ethylene copolymer having a low content of a crystalline portion with an ethylene (co) polymer having specific properties.

The resin composition for a film of the present invention comprises (A)
Ethylene copolymer and 90 to 20 wt%, the (B) has a 10 to 80 wt% of ethylene (co) polymer, and the density d ₁ <density d _2, MFR _1> MFR ₂ It is a feature. (A) Ethylene copolymer satisfying (a) to (f) (a) Density d ₁ 0.87 to 0.94 g / cm ³ (b) Melt flow rate (MFR ₁ ) 0.1 to 10 g / 10 min (C) Molecular weight distribution (Mw / Mn) 1.5 to 3.5 (d) Composition distribution parameter Cb 1.08 to 2.00 (e) Orthodichlorobenzene (ODC) at 25 ° C
B) The amount X (% by weight) of the soluble component, the density d ₁ and the MFR ₁ satisfy the following relationship. (B) When d ₁ -0.008 × logMFR ₁ ≧ 0.93 X <2.0 (b) When d ₁ -0.008 × logMFR ₁ <0.93 X <9.8 × 10 ³ × (0.9300-d ₁ + 0.008 × l
ogMFR ₁ ) ² +2.0 (f) There are a plurality of peaks in an elution temperature-elution amount curve by a continuous heating elution fractionation method (TREF). (B) Ethylene obtained by homopolymerizing ethylene or copolymerizing ethylene with an α-olefin having 3 to 20 carbon atoms in the presence of a catalyst containing at least a transition metal compound belonging to Group IV of the periodic table. (Co) polymer. (A) Density d ₂ 0.88 to 0.97 g / cm ³ (b) Melt flow rate (MFR ₂ ) 0.01 to 5 g / 10 min Here, (B) the ethylene (co) polymer further comprises the following ( It is desirable that the (C) ethylene (co) polymer satisfying the requirements (c) and (d) be used, or that they have both. (C) Molecular weight distribution (Mw / Mn) 1.5 to 5.0 (d) The relationship between MFR ₂ and intrinsic viscosity η (dl / g) satisfies the following relationship: log η ≦ −0.205 × log MFR ₂ +0 .218

It is preferable that d ₂ -d ₁ > 0.005 g / cm ³ . The ethylene copolymer (A) is an ethylene-α-olefin having 3 to 20 carbon atoms in the presence of a catalyst containing at least an organic cyclic compound having a conjugated double bond and a transition metal compound belonging to Group IV of the periodic table. And an ethylene copolymer obtained by copolymerizing the above. Further, the (B) ethylene (co) polymer or (C) ethylene (co) polymer is a catalyst containing at least an organic cyclic compound having a conjugated double bond and a transition metal compound belonging to Group IV of the periodic table. An ethylene (co) polymer obtained by homopolymerizing ethylene or copolymerizing ethylene with an α-olefin having 3 to 20 carbon atoms is desirable. Further, it is desirable to further contain an ethylene (co) polymer obtained by a high-pressure radical polymerization method. The film of the present invention comprises the above-described resin composition. The film for a heavy packaging bag of the present invention comprises the above-described resin composition.

[0007]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. [(A) Ethylene copolymer] The (A) ethylene copolymer of the present invention is a copolymer of ethylene and at least one selected from α-olefins having 3 to 20 carbon atoms. As the α-olefin having 3 to 20 carbon atoms, preferably 3 to 1
2, specifically propylene, 1-butene,
4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene and the like. The content of these α-olefins is usually 30 mol% in total.
It is desirable that the content be selected in the range of not more than 20 mol%.

The (A) of the ethylene copolymer (A) of the present invention
The density d ₁ is 0.87 to 0.94 g / cm ³ , preferably 0.88 to 0.94 g / cm ³ , and more preferably 0.90 to 0.94 g / cm ³ .
It is in the range of 0.93 g / cm ³ . The density d ₁ is 0.87 g /
If it is less than cm ³ , rigidity and heat resistance are inferior, and 0.94 g / cm ³
If it exceeds 300, transparency and impact resistance are not sufficient.

The (A) ethylene copolymer (B) of the present invention
MFR ₁ is 0.1 to 10 g / 10 min, preferably 0.5 to 5 g
g / 10 min. MFR ₁ is 10
If it exceeds g / 10 min, mechanical strength such as impact resistance and tensile strength will decrease.

The ethylene copolymer (A) of the present invention (c)
The method of calculating the molecular weight distribution Mw / Mn is to determine the weight average molecular weight (Mw) and the number average molecular weight (Mn) by gel permeation chromatography (GPC), and to determine the ratio Mw / Mn. Mw / Mn of the ethylene copolymer of the present invention is 1.5 to 3.5, preferably 1.8 to 3.5, and more preferably 2 to 3. When Mw / Mn is less than 1.5, the moldability is poor, and when it is 3.5 or more, the impact resistance is poor and the transparency is insufficient.

The ethylene copolymer (A) of the present invention (d)
The composition distribution parameter Cb is 1.08 to 2.00, preferably 1.10 to 1.80, and more preferably 1.12.
It is desirably in the range of ~ 1.70. If it is less than 1.08, the heat resistance is reduced, and if it exceeds 2.00, the transparency and impact resistance are reduced, and the molded product may be sticky and the heat shrinkage may be increased.

In the present invention, the method of measuring the composition distribution parameter Cb of the ethylene copolymer is as follows. Heat stabilizer is added to the sample, and the sample concentration is 0.2% by weight in ODCB.
Heat and dissolve at 135 ° C. so that The heated solution is transferred to a column filled with diatomaceous earth (Celite 545), filled and cooled to 25 ° C. at 0.1 ° C./min, and the sample is deposited on the celite surface. Next, O
While DCB is supplied at a constant flow rate, the column temperature is raised stepwise to 120 ° C. in steps of 5 ° C., and a solution in which the sample is dissolved is collected at each temperature. After cooling the solution, the sample is reprecipitated with methanol, filtered and dried to obtain samples at each elution temperature. The weight fraction and the degree of branching (the number of branches per 1000 carbon atoms) of the separated sample are measured. The degree of branching is determined by ¹³ C-NMR.

For each fraction collected at 30 ° C. to 90 ° C. by such a method, the following correction of the degree of branching is performed. First, the degree of branching measured with respect to the elution temperature is plotted, and the correlation is approximated to a straight line by the least squares method to create a calibration curve. The correlation coefficient of this approximation is large enough. The value obtained from this calibration curve is defined as the degree of branching of each fraction. Note that, for a fraction collected at an elution temperature of 95 ° C. or higher, this correction is not performed because a linear relationship is not always established between the elution temperature and the degree of branching.

[0014] Then, the weight fraction w _i of each fraction, the amount of change in the degree of branching b _i per the elution temperature 5 ° C. (b _i
Obtaining the relative concentration c _i is divided by -b _i-1), by plotting the relative concentration against the branching degree to obtain a composition distribution curve. This composition distribution curve is divided by a certain width, and the composition distribution parameter Cb is calculated from the following equation.

(Equation 1) Here, c _j and b _j are the relative density and branching degree of the j-th section, respectively. The composition distribution parameter Cb is 1.0 when the composition of the sample is uniform, and the value increases as the composition distribution spreads.

Many proposals have been made for a method of describing the composition distribution of the ethylene / α-olefin copolymer. For example, in Japanese Patent Application Laid-Open No. 60-88016, numerical processing is performed on the assumption that the cumulative weight fraction has a specific distribution (log normal distribution) with respect to the number of branches of each of the separated samples obtained by solvent separation of the sample. , The ratio between the weight average branching degree (Cw) and the number average branching degree (Cn). The accuracy of this approximation calculation decreases when the number of branches and the cumulative weight fraction of the sample deviate from the lognormal distribution, and when a commercially available LLDPE is measured, the correlation coefficient R2 is considerably low, and the accuracy of the value is not sufficient. This C
The definition and measurement method of w / Cn and Cb of the present invention are different.

The (A) ethylene copolymer of the present invention comprises:
(E) The ODCB-soluble content X at 25 ° C. indicates the proportion of the high branching degree component and the low molecular weight component contained in the ethylene copolymer, and causes a decrease in heat resistance and a stickiness on the molded product surface. Therefore, it is desirable that the number is small. OD
The amount of the CB-soluble component is affected by the α-olefin content and the average molecular weight of the entire copolymer, that is, the density d ₁ and MFR ₁ . Therefore, the amount X (% by weight) of the ODCB-soluble component is such that the relationship between the density d ₁ and the MFR ₁ is d ₁ −0.008 × lo.
When gMFR ₁ ≧ 0.93 is satisfied, it is desirably less than 2% by weight, preferably less than 1% by weight, and more preferably less than 0.5% by weight. When the relationship between d ₁ and MFR ₁ is d ₁ −0.008 × log MFR ₁ <0.93, X <9.8 × 10 ³ × (0.9300−d ₁ +0.000)
8 × logMFR ₁ ) ² +2.0 (Relational expression 1). More preferably, X <7.4.
× 10 ³ × (0.9300-d ₁ + 0.008 × logMF
R ₁ ) ² +1.0, more preferably X <5.6 × 10 ³ ×
(0.9300-d ₁ + 0.008 × log MFR ₁ ) ² +0.00.
It is desirably in the range of 5. Density d ₁ , MFR ₁ and O
The fact that the amount of the DCB-soluble component satisfies the above relationship indicates that the α-olefin contained in the whole copolymer is not ubiquitous.

The amount X of ODCB-soluble matter at 25 ° C. is measured by the following method. 0.5 g of the sample is added to 20 ml of ODCB and heated at 135 ° C. for 2 hours to completely dissolve the sample and then cooled to 25 ° C. After leaving this solution at 25 ° C. overnight, the filtrate is collected by filtering through a Teflon filter. The filtrate, which is a sample solution, is measured for the absorption peak intensity near the wave number of 2,925 cm ^-1 of asymmetric stretching vibration of methylene by an infrared spectrometer, and the sample concentration in the filtrate is calculated by a calibration curve created in advance. From this value, 2
Determine the ODCB solubles at 5 ° C.

The (A) ethylene copolymer of the present invention comprises:
(F) There must be a plurality of peaks in the elution temperature-elution amount curve obtained by the continuous heating elution fractionation method (TREF). Further, the peak on the high temperature side is from
It is particularly preferred that it is present between ° C. The presence of this peak increases the melting point and the crystallinity, thereby improving the heat resistance and rigidity of the molded article. FIG. 1 shows an elution temperature-elution amount curve of the copolymer of the present invention. FIG. 2 shows an elution temperature-elution amount curve of a copolymer with a so-called commercially available metallocene catalyst, and both are remarkably different.

The method for measuring TREF according to the present invention is as follows. A heat-resistant stabilizer is added to the sample, and the sample is heated and dissolved at 135 ° C. in ODCB so that the sample concentration becomes 0.05% by weight. After pouring 5 ml of the heated solution into a column filled with glass beads, the solution is cooled to 25 ° C. at a cooling rate of 0.1 ° C./min, and the sample is deposited on the surface of the glass beads. Next, the column temperature is raised at a constant rate of 50 ° C./hr while flowing ODCB through the column at a constant flow rate, and samples that can be dissolved in the solution at each temperature are sequentially eluted.
At this time, as for the concentration of the sample in the solvent, the absorption of the asymmetric stretching vibration of methylene at a wave number of 2925 cm ^-1 is continuously detected by an infrared detector. From this concentration, an elution temperature-elution amount curve can be obtained. TREF analysis is a very small sample,
Since the change in the elution rate with respect to the temperature change can be continuously analyzed, relatively fine peaks that cannot be detected by the fractionation method can be detected.

The ethylene copolymer (A) of the present invention is not particularly limited as long as it satisfies the above conditions (a) to (f). In the presence of a catalyst containing an organic cyclic compound and a transition metal compound of Group IV of the periodic table, ethylene and C 3-20
It is desirable to copolymerize the α-olefin of the formula (1). In addition,
Details of a preferred production method will be described later.

The ethylene copolymer (A) has a relatively wide composition distribution despite its narrow molecular weight distribution.
In addition, the content of the low molecular weight component and the amorphous portion is small, and in addition to improving flexibility, impact resistance, and sealing properties, it has anti-blocking properties and realizes good slip properties.

[(B) Ethylene (co) polymer] The (B) ethylene (co) polymer of the present invention comprises ethylene alone or at least one selected from ethylene and an α-olefin having 3 to 20 carbon atoms. Is a copolymer of The α-olefin having 3 to 20 carbon atoms is preferably 3 to 12 and specifically includes propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, -Decene, 1-dodecene and the like. The content of these α-olefins is desirably selected in a range of usually 30 mol% or less, preferably 20 mol% or less.

The (a) density d ₂ of the ethylene (co) polymer (B) of the present invention is 0.88 to 0.97 g / cm ³ , preferably 0.88 to 0.945 g / cm ³ , more preferably Is 0.
It is in the range of 90 to 0.935 g / cm ³ . Density d ₂ is 0.
If it is less than 88 g / cm ³ , rigidity and heat resistance are inferior, and 0.97 g
If it exceeds / cm ³ , transparency and impact resistance become insufficient.

The (B) MFR ₂ of the ethylene (co) polymer (B) of the present invention is 0.01 to 5 g / 10 min, preferably 0.1 to 5 g / 10 min.
It is desirable to be in the range of 1 to 3 g / 10 min. MFR ₂
Is less than 0.01 g / 10 min, the processability is reduced and the MFR ₂
Exceeds 5 g / 10 min, the mechanical strength such as impact resistance and tensile strength decreases.

The (c) molecular weight distribution Mw / Mn of the (B) ethylene (co) polymer of the present invention is preferably from 1.5 to 5.0, more preferably from 1.6 to 4.0. , 1.
More preferably, it is in the range of 8-3.5. Mw / Mn
If the value is less than 1.5, the molding processability tends to be poor, and if the value is 5.0 or more, the impact resistance is poor and the transparency tends to be insufficient. In the method of calculating the molecular weight distribution Mw / Mn of the ethylene (co) polymer of the present invention, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are determined by gel permeation chromatography (GPC).
Mn is determined.

[(C) Ethylene (co) polymer] The (C) ethylene (co) polymer of the present invention is the above-mentioned (a) and (b)
(B) an ethylene (co) polymer which satisfies the requirement of (c), which in addition to the requirement of (c) the molecular weight distribution Mw / Mn of 1.5 to 5.0, further satisfies the requirement of (d). is there. (D) The relationship between MFR ₂ and intrinsic viscosity η (dl / g) satisfies the following relationship. logη ≦ −0.205 × logMFR ₂ +0.218 (2) In this (C) ethylene (co) polymer, (d) M
The relationship between FR ₂ and intrinsic viscosity η is logη ≦ −0.205 × logM
FR ₂ +0.218, more preferably −0.1
33 × logMFR ₂ +0.067 <logη ≦ −0.205 × l
ogMFR ₂ +0.218, more preferably −
0.167 × logMFR ₂ +0.133 <logη ≦ −0.20
5 is a × logMFR ₂ +0.218. logη is -0.20
If the ratio is larger than 5 × logMFR ₂ +0.218, the melt tension is small, and especially the moldability is not sufficiently improved.
The effect of improving transparency is not sufficient.

The method for measuring the intrinsic viscosity η of the ethylene (co) polymer of the present invention is as follows. A heat stabilizer is added to the sample, and the sample is heated and dissolved in decalin at 135 ° C. so that the sample concentration becomes 1 g / l. Decalin to which the heat stabilizer has been added is also kept at 135 ° C. Each of these solutions is supplied to an improved Ubbelohde viscometer (maintained at 135 ° C.), for example, a capillary viscosity automatic measuring device (“ss” manufactured by Shibayama Scientific Instruments Co., Ltd.)
-290 s "). Then, the intrinsic viscosity η is measured by the following equation. η = ln (t / t ₀ ) × (1 / C) where t ₀ is the flow time of decalin (second), t is the flow time of the sample solution (second), and C is the sample concentration (sample per 100 ml of solution). (G). This (B) ethylene (co) polymer (or (C) ethylene (co) polymer)
Improves workability, rigidity and heat resistance.

The ethylene (co) polymer (B) (or (C) ethylene (co) polymer) of the present invention is polymerized in the presence of a catalyst containing at least a transition metal compound of Group IV of the periodic table, Moreover, it is necessary to satisfy the above conditions (a) to (b (or (d))). And preferably, an organic cyclic compound having at least a conjugated double bond and the periodic table
It is polymerized in the presence of a catalyst containing a Group IV transition metal compound. When the above-mentioned (A) ethylene copolymer and (B) ethylene (co) polymer (or (C) ethylene (co) polymer) are produced, specifically, the following components (a1) to Catalysts obtained by contacting (a4) with one another are desirable. (A1): the general formula ^{_{Me 1 R 1 p R 2 q}} (OR 3) r X 1 4-pqr
A transition metal compound of Group IV of the periodic table represented by
e ¹ represents zirconium, titanium, or hafnium; R ¹ and R ^{3 each} independently represent a hydrocarbon group having 1 to 24 carbon atoms; R ² represents a 2,4-pentanedionato ligand or a derivative thereof; or dibenzoylmethanato A ligand, a derivative such as a benzoylacetonate ligand, X ¹ represents a halogen atom,
p, q and r are respectively 0 ≦ p ≦ 4, 0 ≦ q ≦ 4, 0
≦ r ≦ 4, 0 ≦ p + q + r ≦ 4). (A2): a compound represented by the general formula Me ² R ⁴ m (OR ⁵ ) _n X ² _zmn (where Me ² is an element from Groups I to III of the periodic table,
R ⁴ and R ⁵ each represent a hydrocarbon group having 1 to 24 carbon atoms, X ²
Is a halogen atom or a hydrogen atom (however, when X ² is a hydrogen atom, Me ² is limited to a group III element of the periodic table)
, Z represents the number of Me ² , m and n are each 0
≦ m ≦ z, 0 ≦ n ≦ z, and an integer satisfying the range of 0 ≦ m + n ≦ z). (A3): an organic cyclic compound having a conjugated double bond. (A4): A catalyst obtained by bringing a modified organic aluminum oxy compound containing an Al-O-Al bond and / or a boron compound into contact with each other.

The general formula Me ¹ R ¹ _{p of the} catalyst component (a1)
In the formula of the transition metal compound belonging to Group IV of the periodic table represented by R ² _q (OR ³ ) _r X ¹⁴ _-pqr , Me ¹ represents zirconium, titanium, or hafnium. The type of these transition metals is not limited, and a plurality of transition metals can be used. However, it is particularly preferable that zirconium having excellent weather resistance of the copolymer is contained. R ¹ and R ³ each have 1 to 24 carbon atoms
Which preferably has 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, and specifically includes alkyl groups such as methyl, ethyl, propyl, isopropyl, and butyl; vinyl and allyl An alkenyl group such as a group; an aryl group such as a phenyl group, a tolyl group, a xylyl group, a mesityl group, an indenyl group, and a naphthyl group; a benzyl group, a trityl group, a phenethyl group, a styryl group, a benzhydryl group, a phenylbutyl group, and a neofyl group; And an aralkyl group. These may have branches. R
² is a 2,4-pentanedionato ligand or a derivative thereof,
Or a derivative such as a dibenzoylmethanato ligand or a benzoylacetonato ligand. X ¹ represents a halogen atom such as fluorine, iodine, chlorine and bromine;
And r are respectively 0 ≦ p ≦ 4, 0 ≦ q ≦ 4, 0 ≦ r ≦
4, 0 ≦ p + q + r ≦ 4.

Examples of the compound represented by the general formula of the catalyst component (a1) include tetramethyl zirconium, tetraethyl zirconium, tetrabenzyl zirconium,
Tetrapropoxyzirconium, tripropoxymonochlorozirconium, dipropoxydichlorozirconium, tetrabutoxyzirconium, tryptoxymonochlorozirconium, dibutoxydichlorozirconium,
Examples thereof include tetrabutoxytitanium and tetrabutoxyhafnium, and specific examples of the 2,4-pentanedionato ligand or a derivative thereof include tetra (2,4-
(Pentanedionato) zirconium, tri (2,4-pentanedionato) chloride zirconium, di (2,4-
Pentanedionato) diethoxide zirconium, di (2,4-pentanedionato) di-n-propoxide zirconium, di (2,4-pentanedionato) di-n
-Butoxide zirconium, di (2,4-pentanedionato) dibenzyl zirconium, di (2,4-pentanedionato) dineofylzirconium, tetra (dibenzoylmethanato) zirconium, di (dibenzoylmethanato) die Zirconium toxide, zirconium di (dibenzoylmethanato) di-n-propoxide, zirconium di (benzoylacetonate), zirconium di (benzoylacetonate) di-n-propoxide zirconium, di (benzoylacetonate) ) Di-n-
Butoxide zirconium and the like, and two or more of these may be used in combination.

The general formula Me ² R ⁴ _{m of the} catalyst component (a2)
(OR ⁵ ) _n X ^{2 In the} compound represented by _zmn , Me ²
Represents an element of Groups I to III of the periodic table, such as lithium, sodium, potassium, magnesium, calcium, zinc, boron, and aluminum. R ⁴ and R ⁵ are each a hydrocarbon group having 1 to 24 carbon atoms, preferably 1 to 1 carbon atoms.
2, more preferably 1 to 8, specifically alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group and butyl group; alkenyl groups such as vinyl group and allyl group; phenyl group, tolyl group, Aryl groups such as a xylyl group, a mesityl group, an indenyl group, and a naphthyl group; and aralkyl groups such as a benzyl group, a trityl group, a phenethyl group, a styryl group, a benzhydryl group, a phenylbutyl group, and a neofuyl group. These may have branches. X ² represents a halogen atom or a hydrogen atom such as fluorine, iodine, chlorine and bromine. However, when X ² is a hydrogen atom, Me ² is limited to a group III element of the periodic table exemplified by boron, aluminum and the like. Z represents the valence of Me ² , m and n are integers satisfying 0 ≦ m ≦ z and 0 ≦ n ≦ z, respectively, and 0 ≦ m + n ≦ z.

Examples of the compound represented by the general formula of the catalyst component (a2) include organic lithium compounds such as methyllithium and ethyllithium; dimethylmagnesium, diethylmagnesium, methylmagnesium chloride,
Organic magnesium compounds such as ethyl magnesium chloride; organic zinc compounds such as dimethyl zinc and diethyl zinc; organic boron compounds such as trimethyl boron and triethyl boron; trimethyl aluminum, triethyl aluminum, tripropyl aluminum, triisobutyl aluminum, trihexyl aluminum and trihexyl aluminum Decyl aluminum, diethyl aluminum chloride, ethyl aluminum dichloride, ethyl aluminum sesquichloride, diethyl aluminum ethoxide,
Derivatives such as organoaluminum compounds such as diethylaluminum hydride are exemplified.

Examples of the organic cyclic compound having a conjugated double bond of the catalyst component (a3) are as follows: 1) It has two or more, preferably two to four, more preferably two to three co-projected double bonds. A cyclic hydrocarbon compound having one or more carbocycles and a total carbon number of 4 to 24, preferably 4 to 12; 2) the cyclic hydrocarbon compound of the above 1) has 1 to 6 hydrocarbon groups ( Typically, a cyclic hydrocarbon compound partially substituted with an alkyl group or aralkyl group having 1 to 12 carbon atoms 3) 2 or more, preferably 2 to 4, more preferably 2 or more conjugated double bonds An organosilicon compound having a cyclic hydrocarbon group having 1 to 2 or more carbocycles having 3 to 3 carbon atoms and having a total carbon number of 4 to 24, preferably 4 to 12 4) the cyclic hydrocarbon group of the above 3) Hydrogen is partially from 1 to 6 hydrocarbon groups Organosilicon compounds having a substituted cyclic hydrocarbon group 5) Alkali metal salts (sodium or lithium salts) of the compounds shown in the above 1) to 4).

One of the cyclic hydrocarbon compounds suitable as the component (a3) is represented by the following chemical formula 1.

Embedded image [In the chemical formula 1, R ⁶ , R ⁷ , R ⁸ , R ⁹ , and R ^{10 each} independently represent hydrogen or a hydrocarbon group having 1 to 10 carbon atoms, and any two of the hydrocarbon groups are cyclically linked together. Hydrocarbon groups can be formed. The hydrocarbon group in Chemical Formula 1 includes an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a t-butyl group, a hexyl group, and an octyl group; a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. An alkoxy group;
Aryl groups such as a phenyl group; aryloxy groups such as a phenoxy group; and aralkyl groups such as a benzyl group. In addition, when any two of the hydrocarbon groups of Formula 1 form a cyclic hydrocarbon group together, the skeleton thereof includes cycloheptatriene, aryl, and a condensed ring thereof. Among the cyclic hydrocarbon compounds represented by the above Chemical Formula 1, preferred are cyclopentadiene, indene, azulene, etc., and those substituted with alkyl, aryl, aralkyl, alkoxy or aryloxy having 1 to 10 carbon atoms. And the like. Chemical formula 1
Is an alkylene group (the number of carbon atoms is usually 2 to 8, preferably 2 to 3) or an alkylidene group (the number of carbon atoms is usually 2 to 8, preferably 2 to 3)
Compounds bonded (crosslinked) via 3) are also preferably used.

The organosilicon compound having a cyclic hydrocarbon group can be represented by the following general formula. Here ^{_{A L SiR 11 M X 3 4L}} -M, A represents a cyclopentadienyl group, substituted cyclopentadienyl group, indenyl group, the cyclic hydrocarbon group exemplified by substituted indenyl group, R ¹¹ is methyl Alkyl group such as group, ethyl group, propyl group, isopropyl group, butyl group, pentyl group, hexyl group, octyl group; alkenyl group such as vinyl group, allyl group; methoxy group, ethoxy group, propoxy group, butoxy group, etc. An alkoxy group; an aryl group such as a phenyl group, a tolyl group, or a xylyl group; an aryloxy group such as a phenoxy group; an aralkyl group such as a benzyl group, a phenethyl group, a styryl group, or a neofuyl group; Preferably represents 1 to 12 hydrocarbon residues or hydrogen, wherein R ¹¹ is not only n-, but also iso-, s-, t-, neo-, etc. It includes various structural isomer groups. X
³ represents a halogen atom of fluorine, iodine, chlorine or bromine, and L and M are in the range of 0 <L ≦ 4, 0 ≦ M ≦ 3, and preferably 1 ≦ L + M ≦ 4.

Accordingly, the following compounds are included in the organic cyclic hydrocarbon compound usable as the component (a3). Cyclopentadiene, methylcyclopentadiene, ethylcyclopentadiene, t-butylcyclopentadiene, propylcyclopentadiene, isopropylcyclopentadiene, butylcyclopentadiene, isobutylcyclopentadiene, sec-butylcyclopentadiene, 1-methyl-3-ethylcyclopentadiene, 1-ethyl-3-methylcyclopentadiene, 1
-Methyl-3-propylcyclopentadiene, 1-propyl-3-methylcyclopentadiene, 2-ethyl-5
-Isopropylcyclopentadiene, 2-methyl-5
Phenylcyclopentadiene, 2-ethyl-3,5-dimethylcyclopentadiene, hexylcyclopentadiene, octylcyclopentadiene, 1,2-dimethylcyclopentadiene, 1,3-dimethylcyclopentadiene, 1,2,4-trimethylcyclopentadiene 1,2,
Substituted cyclopentadiene such as 3,4-tetramethylcyclopentadiene and pentamethylcyclopentadiene;
Indene, 2-methylindene, 4-methylindene,
Substituted indenes such as 4,7-dimethylindene, 4,5,6,7-tetrahydroindene, substituted cycloheptatrienes such as cycloheptatriene and methylcycloheptatriene, cyclooctatetraene, methylcyclooctatetraene and the like C 7 to C 24 cyclopolyene or substituted cyclopolyene such as substituted cyclooctatetraene, azulene, methylazulene, ethylazulene, fluorene, and substituted fluorene such as methylfluorene;

Dimethylsilylenebiscyclopentadiene, dimethylsilylenebisindene, dimethylsilylenebispropylcyclopentadiene, dimethylsilylenebisbutylcyclopentadiene, diphenylsilylenebiscyclopentadiene, diphenylsilylenebisindene, diphenylsilylenebispropylcyclopentadiene, diphenylsilylenebisbutyl Cyclopentadiene, monocyclopentadienylsilane, dicyclopentadienylsilane, tricyclopentadienylsilane, tetracyclopentadienylsilane, monocyclopentadienylmonomethylsilane, monocyclopentadienylmonoethylsilane, monocyclo Pentadienyldimethylsilane, monocyclopentadienyldiethylsilane, monocyclopentadienyltol Methylsilane, monocyclopentadienyltriethylsilane, monocyclopentadienyl monomethoxysilane, monocyclopentadienyl monoethoxysilane, monocyclopentadienyl monophenoxysilane, monocyclopentadienyl monomethylmonochlorosilane, monocyclopentadi Enyl monoethyl monochlorosilane, monocyclopentadienyl monomethyl dichlorosilane, monocyclopentadienyl monoethyl dichlorosilane, monocyclopentadienyl trichlorosilane, dicyclopentadienyl monomethyl silane,
Dicyclopentadienyl monoethylsilane, dicyclopentadienyldimethylsilane, dicyclopentadienyldiethylsilane, dicyclopentadienylmethylethylsilane, dicyclopentadienyldipropylsilane, dicyclopentadienylethylpropyl Silane, dicyclopentadienyldiphenylsilane, dicyclopentadienylphenylmethylsilane, dicyclopentadienylmethylchlorosilane, dicyclopentadienylethylchlorosilane, dicyclopentadienyldichlorosilane, dicyclopentadienylmonomethoxy Silane, dicyclopentadienyl monoethoxysilane, dicyclopentadienyl monomethoxy monochlorosilane, dicyclopentadienyl monoethoxy monochlorosilane, tricyclopentadienyl monomethyl Rushiran, tri cyclopentadienyl monoethyl silane, tri cyclopentadienyl monomethoxy silane, tri cyclopentadienyl mono silane, tri cyclopentadienyl monochlorosilane,
3-methylcyclopentadienylsilane, bis-3-methylcyclopentadienylsilane, 3-methylcyclopentadienylmethylsilane, 1,2-dimethylcyclopentadienylsilane, 1,3-dimethylcyclopentadienylsilane 1,1,4-trimethylcyclopentadienylsilane, 1,2,3,4-tetramethylcyclopentadienylsilane, pentamethylcyclopentadienylsilane,

Monoindenyl silane, diindenyl silane, triindenyl silane, tetraindenyl silane,
Monoindenyl monomethylsilane, monoindenyl monoethylsilane, monoindenyldimethylsilane, monoindenyldiethylsilane, monoindenyltrimethylsilane, monoindenyltriethylsilane, monoindenylmonomethoxysilane, monoindenylmonoethoxysilane , Monoindenyl monophenoxysilane, monoindenyl monomethyl monochlorosilane, monoindenyl monoethyl monochlorosilane, monoindenyl monomethyl dichlorosilane, monoindenyl monoethyl dichlorosilane, monoindenyl trichlorosilane, diindenyl monomethylsilane, Diindenylmonoethylsilane, diindenyldimethylsilane, diindenyldiethylsilane, diindenylmethylethylsilane, diindenyldipropylsilane, Indenyl ethylpropyl silane,
Diindenyldiphenylsilane, diindenylphenylmethylsilane, diindenylmethylchlorosilane, diindenylethylchlorosilane, diindenyldichlorosilane, diindenylmonomethoxysilane, diindenylmonoethoxysilane, diindenylmonomethoxy Monochlorosilane, diindenylmonoethoxymonochlorosilane, triindenylmonomethylsilane, triindenylmonoethylsilane, triindenylmonomethoxysilane, triindenylmonoethoxysilane, triindenylmonochlorosilane, 3-methylindenylsilane , Bis-3-methylindenylsilane, 3-methylindenylmethylsilane, 1,2-dimethylindenylsilane, 1,
Examples thereof include 3-dimethylindenylsilane, 1,2,4-trimethylindenylsilane, 1,2,3,4-tetramethylindenylsilane, and pentamethylindenylsilane.

Further, any one of the above-mentioned compounds may be an alkylene group (the carbon number of which is usually 2 to 8, preferably 2 to 8).
3) or an alkylidene group (the number of carbon atoms of which is usually 2 to 8,
Compounds linked via preferably 2-3) can also be used as component (a3) of the present invention, such as ethylene biscyclopentadiene, ethylene bispropylcyclopentadiene, ethylene bis Butylcyclopentadiene, isopropylidenebiscyclopentadiene, isopropylidenebisindene, isopropylidenebispropylcyclopentadiene, isopropylidenebisbutylcyclopentadiene,
Bisindenylethane, bis (4,5,6,7-tetrahydro-1-indenyl) ethane, 1,3-propanedienylbisindene, 1,3-propanedienylbis (4,5,6,7 , -Tetrahydro) indene, propylene bis (1-indene), isopropylidene (1-indenyl) cyclopentadiene, diphenylmethylene (9
-Fluorenyl) cyclopentadiene, isopropylidenecyclopentadienyl-1-fluorene and the like.

In order to produce the ethylene copolymer (A) of the present invention, the following (compound I) can be preferably selected from the above (a3) organic cyclic compounds having a conjugated double bond. (Compound I) Compound in which any two hydrocarbons represented by Chemical Formula 1 cooperate to form a cyclic hydrocarbon group Any two hydrocarbons represented by Chemical Formula 1 cooperate to form a cyclic hydrocarbon group Wherein the cyclic hydrocarbon group is substituted with a hydrocarbon group. Among R ^{6 to} R ¹⁰ represented by Chemical Formula 1, one compound is a hydrocarbon group and the other is hydrogen.

In order to produce (B) an ethylene (co) polymer (or (C) an ethylene (co) polymer), the following (a3) an organic cyclic compound having a conjugated double bond is required. (Compound II) can be preferably selected. (Compound II) A compound in which two or more of R ^{6 to} R ¹⁰ represented by Chemical Formula 1 are a hydrocarbon group and the others are hydrogen. The cyclic hydrocarbon compound represented by Chemical Formula 1 is bonded through an alkylene group or an alkylidene group. Bound compound

Catalyst component (a4) The modified organoaluminum oxy compound containing an Al-O-Al bond obtained by reacting an organoaluminum compound with water is usually reacted with an alkylaluminum compound and water to form an aluminoxane. A modified organoaluminum oxy compound is obtained, which usually contains 1 to 100, preferably 1 to 50 Al-O-Al bonds in the molecule. Also,
The modified organic aluminum oxy compound may be linear or cyclic.

The reaction between the organoaluminum and water is usually carried out in an inert hydrocarbon. As the inert hydrocarbon,
Aliphatic, alicyclic and aromatic hydrocarbons such as pentane, hexane, heptane, cyclohexane, benzene, toluene and xylene are preferred. The reaction ratio between water and the organoaluminum compound (water / Al molar ratio) is usually 0.25 / 1 to 1.2 /
1, and preferably 0.5 / 1 to 1/1.

The boron compound of the catalyst component (a4) includes, for example, triethylammonium tetra (pentafluorophenyl) borate, dimethylanilinium tetra (pentafluorophenyl) borate, butylammonium tetra (pentafluorophenyl) porate, N, N −
Dimethylanilinium tetra (pentafluorophenyl) borate, N, N-dimethylaniliniumtetra (3,5-difluorophenyl) borate and the like can be mentioned.

In the present invention, the catalyst component (a1)
The catalyst obtained by contacting (a4) with each other is converted into an inorganic carrier and / or a particulate polymer carrier (a
It can also be carried in 5) and used for the polymerization reaction. In the stage of preparing the catalyst of the present invention, the inorganic carrier of the component (a5) may be in any shape such as powder, granule, flake, foil, and fiber as long as the original shape is maintained. Although it does not matter, the maximum length of any shape is usually 5 to 200 μm, preferably 10 to 100 μm. Further, the inorganic carrier is preferably porous, and usually has a surface area of 50 to 100.
0 m ² / g, pore volume in the range of 0.05 to ³ cm ³ / g. As the inorganic carrier of the present invention, carbonaceous materials, metals,
Metal oxides, metal chlorides, metal carbonates or mixtures thereof can be used and are usually at 200-900 ° C.
And fired in air or in an inert gas such as nitrogen or argon.

Suitable metals that can be used for the inorganic carrier include iron, aluminum, nickel and the like. Examples of the metal oxide include single oxides and composite oxides of Groups I to VIII of the periodic table. Specifically, SiO ₂ , Al ₂ O ₃ , MgO, CaO, B ₂ O ₃ , Ti
O ₂ , ZrO ₂ , Fe ₂ O ₃ , SiO ₂ —Al ₂ O ₃ , Al ₂ O
_{3 -MgO, Al 2 O 3 -CaO} , Al 2 O 3 -MgO-C
_{aO, Al 2 O 3 -MgO-} SiO 2, Al 2 O 3 -Cu
_{O, Al 2 O 3 -Fe 2} O 3, Al 2 O 3 -NiO, SiO 2
—MgO and the like. Note that the above formulas expressed as oxides are not molecular formulas, but only compositions. That is, the structure and component ratio of the double oxide used in the present invention are not particularly limited. In addition, the metal oxide used in the present invention may adsorb a small amount of water, or may contain a small amount of impurities.

As the metal chloride, for example, an alkali metal or alkaline earth metal chloride is preferable, and specifically, MgCl ₂ , CaCl _{2 and the} like are particularly preferable. As the metal carbonate, a carbonate of an alkali metal or an alkaline earth metal is preferable, and specific examples include magnesium carbonate, calcium carbonate, barium carbonate and the like. Examples of the carbonaceous material include carbon black and activated carbon. Although any of the above inorganic carriers can be suitably used in the present invention, use of metal oxides such as silica and alumina is particularly preferable.

On the other hand, as the particulate polymer carrier, either a thermoplastic resin or a thermosetting resin can be used as long as it maintains a solid state without melting during the preparation of the catalyst and the polymerization reaction. The particle size is usually 5-2000μ
m, preferably in the range of 10 to 100 μm. The molecular weight of these polymer carriers is not particularly limited as long as the polymer can exist as a solid substance at the time of catalyst preparation and polymerization reaction.
It can be used arbitrarily from low molecular weight to ultra high molecular weight. Specifically, particulate ethylene polymer, ethylene (co) polymer, propylene polymer or copolymer,
Various polyolefins represented by poly 1-butene (preferably having 2 to 12 carbon atoms), polyesters, polyamides, poly (vinyl chloride), poly (meth) acrylate, polystyrene, polynorbornene, various natural polymers, and the like. Mixtures and the like can be mentioned.

The above-mentioned inorganic carrier and / or particulate polymer carrier can be used as they are. However, as a pretreatment, these carriers are preferably treated with an organic aluminum compound or a modified organic aluminum oxy compound containing an Al—O—Al bond. Can be used as the component (a5) after the contact treatment.

The process for producing (A) the ethylene copolymer and (B) the ethylene (co) polymer (or (C) the ethylene (co) polymer) according to the present invention includes a gas phase method, a slurry method, a solution method and the like. Although it is not particularly limited, such as a one-stage polymerization method and a multi-stage polymerization method, it is desirable to produce by a gas phase method from the viewpoint of a balance between physical properties and economy.

The mixing ratio of (A) the ethylene copolymer and (B) the ethylene (co) polymer (or (C) the ethylene (co) polymer) is such that (A) the ethylene copolymer is 90 to 20% by weight. , (B) the ethylene (co) polymer (or (C) the ethylene (co) polymer) is from 10 to 80% by weight. More preferably, (A) the ethylene copolymer is 85 to 30% by weight,
(B) Ethylene (co) polymer (or (C) ethylene (co) polymer) is 15 to 70% by weight. When the ethylene (co) polymers of (B) and (C) are used in combination, the weight ratio is preferably (B) 95 to 5: (C) 5 to 95, and (B) 70 to 30 :( C) The ratio of 30 to 70 is more preferable. (B) Ethylene (co) polymer (or (C)
Ethylene (co) polymer) is blended with (A) ethylene copolymer to maintain mechanical strength, increase melt tension,
It improves processability and transparency of molded products. (B (or C)) ethylene (co) polymer amount is 1
If it is less than 0% by weight, transparency and melt tension are not so much improved, while if it exceeds 80% by weight, heat resistance is undesirably reduced. (B (or (C))) ethylene (co)
The polymer may exhibit a nucleation effect in some cases.

In the resin composition of the present invention, the density d ₁ of the (A) ethylene copolymer must be lower than the density d _{2 of the} (B (or (C))) ethylene (co) polymer. Further, it is desirable that the difference between d ₂ and d ₁ is larger than 0.005 g / cm ³ . In the resin composition of the present invention, (A) the MFR _{1 of the} ethylene copolymer is (B)
(Or (C))) must be greater than the MFR _{2 of the} ethylene (co) polymer. By satisfying these requirements, the rigidity and impact resistance of the film are greatly improved, and the film is particularly suitable as a heavy packaging bag film.

Further, the resin composition of the present invention further contains an ethylene (co) polymer obtained by a high-pressure radical polymerization method such as low-density polyethylene, EVA, and ethylene / (meth) acrylate copolymer. It is desirable. By incorporating an ethylene (co) polymer by a high-pressure radical polymerization method, processability can be further improved. The content of the ethylene (co) polymer by the high-pressure radical polymerization method is 30 parts when the total amount of the (A) ethylene copolymer and the (B (or C)) ethylene (co) polymer is 100 parts by weight. It is preferably less than 5 parts by weight.
More preferably, it is 5 parts by weight.

The composition of the present invention may contain, if necessary, an antioxidant, a nucleating agent, a lubricant, an antistatic agent, a pigment, an antifogging agent as long as the properties of the present invention are not substantially impaired. Known additives such as an ultraviolet absorber, a flame retardant, and a dispersant can be added. Further, it can be used by blending with other thermoplastic resins, for example, polyolefins such as high-density polyethylene, low-density polyethylene, linear low-density polyethylene, and polypropylene, as long as the characteristics of the invention are not essentially impaired.

When the resin composition of the present invention is obtained by mixing, each polymer is mixed by various known methods, for example, a Henschel mixer, a V blender, a ribbon blender, a tumbler mixer, or the like. After melt-kneading with an extruder, a twin-screw extruder, a kneader, a Banbury mixer or the like, a method of granulating or pulverizing may be employed.

The resin composition for a film of the present invention has a relatively wide composition distribution in spite of a narrow molecular weight distribution, and has a low content of a low molecular weight component and an amorphous portion. By combining a polymer with an ethylene (co) polymer having specific properties, it exhibits high impact resistance while maintaining high rigidity, and has mechanical strength such as tensile strength and transparency. . In addition, low-temperature and low-pressure molding is possible, and it has excellent extrusion characteristics and exhibits high moldability. Also, it has good melt tension, and is excellent in low elution of resin components, heat seal strength, and heat resistance. And it is effective when used as a film or sheet. In order to form a film using the resin composition of the present invention, a well-known general method such as an inflation molding method can be applied.

[0057]

Next, the present invention will be described in more detail by way of examples, which should not be construed as limiting the invention thereto.

Various test methods are shown below. Density: Based on JIS K6760. Melt flow rate (MFR): based on JIS K6760. Static friction coefficient: Based on ASTM D1894. Elmendorf: Based on JIS P8116. Dart impact strength: based on ASTM D1709B. Tensile modulus: Based on JIS Z1702. Extrusion characteristics: △ as usual, ○ as improved,
Those which were particularly good were evaluated with ◎. Molding stability: Good stability during molding was evaluated as ○,
Those which were particularly good were evaluated with ◎.

[(A) Preparation of Ethylene Copolymer] [Preparation of Solid Catalyst] 60 ml of purified toluene was added to a catalyst preparation device equipped with an electromagnetic induction stirrer under nitrogen, and then 1 part of tetrapropoxyzirconium (Zr (OPr) ₄ ) was added. Then, while maintaining the system at 0 ° C., 3.0 g of triethylaluminum was added dropwise. After completion of the dropwise addition, the reaction system was kept at 80 ° C. and stirred for 8 hours. next,
A toluene solution of methylaluminoxane (A
280 ml (1 concentration 4.5 wt%) was added, and the mixture was stirred at room temperature for 1 hour. This is designated as solution a. Next, 100 g of silica (“Grade # 952” manufactured by Fuji Devison, surface area 300 m ² / g) previously calcined at 400 ° C. for 5 hours was added to another catalyst preparation device with an electromagnetic induction stirrer under nitrogen. The whole amount of the solution a was added and stirred at room temperature for 1 hour. Then, the solvent was removed by nitrogen blowing to obtain a solid catalyst powder having good fluidity. This is designated as catalyst b.

(Polymerization of Samples A1 and A2) Using a continuous fluidized bed gas phase polymerization apparatus, a polymerization temperature of 70 ° C. and a total pressure of 20 kg
Copolymerization of ethylene and 1-hexene was performed at f / cm ² G. Polymerization was carried out by continuously supplying the catalyst b, and polymerization was carried out while continuously supplying each gas in order to keep the gas composition in the system constant. Table 1 shows the physical properties of the produced copolymer.

[0061]

[Table 1]

[(B) Ethylene (co) polymer] As the (B) ethylene copolymer, an ethylene copolymer using a Ziegler catalyst having the physical properties shown in Table 2 was used.

[0063]

[Table 2]

[Preparation of (C) Ethylene (co) polymer] [Preparation of solid catalyst for polymerization of sample C] 60 ml of purified toluene was added to a catalyst preparation device equipped with an electromagnetic induction stirrer under nitrogen, and then tetrapropoxyzirconium (Zr ( OPr) ₄ )
1.3 g and 1,3-dimethylcyclopentadiene 2.
2 g was added, and while maintaining the system at 0 ° C., 3.0 g of triethylaluminum was added dropwise. After completion of the dropwise addition, the reaction system was
The mixture was kept at 0 ° C. and stirred for 8 hours. Next, a toluene solution of methylaluminoxane (Al concentration 4.5 w
(t%) 280 ml and stirred at room temperature for 1 hour. This is designated as solution c. Next, in a catalyst preparation device equipped with another electromagnetic induction stirrer under nitrogen, silica ("Grade # 952" manufactured by Fuji Devison Co., Ltd.,
After adding 100 g of the surface area (300 m ² / g), the whole amount of the solution c was added, followed by stirring at room temperature for 1 hour. Then, the solvent was removed by nitrogen blowing to obtain a solid catalyst powder having good fluidity. This is designated as catalyst d.

[Polymerization of Sample C] Using a continuous fluidized bed gas phase polymerization apparatus, a polymerization temperature of 70 ° C. and a total pressure of 20 kgf / cm
The copolymerization of ethylene and 1-hexene was carried out at ² G. The polymerization was carried out by continuously supplying the catalyst d, and the polymerization was carried out while continuously supplying each gas in order to keep the gas composition in the system constant. Table 3 shows the physical properties of the produced copolymer.

[0066]

[Table 3]

Each of the above-mentioned samples was kneaded at the compounding ratio shown in Table 4 to obtain a resin composition. A film was extruded using the obtained resin composition. For extrusion molding, a 55 mmφ extruder (100 mmφ die) was used.
hr, TUS: 8 m / min, thickness: 150 μm,
A film having a width of 315 mm (BUR: 2.0) was obtained.
The obtained film was measured for coefficient of static friction, Elmendorf (tear strength), dart impact strength, and tensile modulus. Extrusion characteristics and molding stability were evaluated.

[0068]

[Table 4]

As is evident from Table 4, the film of this example has good slipperiness, high strength, and high tensile modulus.

[0070]

According to the film made of the resin composition for a film of the present invention, the balance between rigidity and impact resistance is satisfied at a high level, and good extrusion properties, inflation moldability, anti-blocking properties, and slip are achieved. Properties, sealing properties,
It has heat resistance and processability, and is particularly excellent as a film for heavy packaging bags.

[Brief description of the drawings]

FIG. 1 shows the T of ethylene copolymer (A) in the present invention.
It is a graph which shows a REF curve.

FIG. 2 is a graph showing a TREF curve of a general metallocene copolymer.

Continued on the front page F term (reference)

Claims (7)

[Claims] 1. An ethylene copolymer of the following (A) 90 to 2
Has 0% by weight, and 10 to 80% by weight of (B) other ethylene (co) polymer and or (C) other ethylene (co) polymer, and a density d ₁ <density d _2, A resin composition for a film, wherein MFR ₁ > MFR ₂ . (A) (a) ~ ethylene which satisfies (f) (co) polymer (a) Density ^{_{d 1 0.87~0.94g / cm 3 (b}} ) a melt flow rate (MFR ₁₎ 0.1 to 10 g / 10 min (c) Molecular weight distribution (Mw / Mn) 1.5-3.5 (d) Composition distribution parameter Cb 1.08-2.00 (e) Orthodichlorobenzene (ODC) at 25 ° C.
B) The amount X (% by weight) of the soluble component, the density d ₁ and the MFR ₁ satisfy the following relationship. (B) When d ₁ -0.008 × logMFR ₁ ≧ 0.93 X <2.0 (b) When d ₁ -0.008 × logMFR ₁ <0.93 X <9.8 × 10 ³ × (0.9300-d ₁ + 0.008 × l
ogMFR ₁ ) ² +2.0 (f) There are a plurality of peaks in an elution temperature-elution amount curve by a continuous heating elution fractionation method (TREF). (B) Homopolymerization of ethylene or a copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms in the presence of a catalyst containing at least a transition metal compound of Group IV of the periodic table. Ethylene (co) polymer satisfying the requirements of (b). (A) density d ₂ 0.88 to 0.97 g / cm ³ (b) melt flow rate (MFR ₂ ) 0.01 to 5 g / 10 min (C) catalyst containing at least a transition metal compound of Group IV of the periodic table (A) to (d), which is a copolymer of ethylene or a copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms in the presence of (a) to (d). (A) density d ₂ 0.88 to 0.97 g / cm ³ (b) melt flow rate (MFR ₂ ) 0.01 to 5 g / 10 min (c) molecular weight distribution (Mw / Mn) 1.5 to 5.0 (D) The relationship between MFR ₂ and intrinsic viscosity η (dl / g) satisfies the following relationship: log η ≦ −0.205 × log MFR ₂ +0.218 2. The resin composition for a film according to claim _{1, wherein} d ₂ -d ₁ > 0.005 g / cm ³ . 3. The method according to claim 1, wherein the ethylene copolymer (A) is an ethylene cyclic compound having at least a conjugated double bond and a catalyst containing a transition metal compound belonging to Group IV of the periodic table. The resin composition for a film according to claim 1 or 2, which is an ethylene copolymer obtained by copolymerizing an α-olefin of No. 20 with an α-olefin. 4. The method according to claim 1, wherein the ethylene (co) polymer (B) and / or (C) comprises a catalyst containing at least an organic cyclic compound having a conjugated double bond and a transition metal compound belonging to Group IV of the periodic table. 4. An ethylene (co) polymer obtained by homopolymerizing ethylene or copolymerizing ethylene with an α-olefin having 3 to 20 carbon atoms, according to any one of claims 1 to 3, wherein Resin composition for film. 5. The resin composition for a film according to claim 1, further comprising an ethylene (co) polymer obtained by a high-pressure radical polymerization method. 6. A film comprising the resin composition for a film according to any one of claims 1 to 5. 7. A film for a heavy packaging bag, comprising the resin composition for a film according to any one of claims 1 to 5.