JP2000072824A - ETHYLENE.alpha-OLEFIN COPOLYMER, COMPOSITION OF THE SAME AND FILM USING THEM - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject copolymer having a broad distribution as to its composition comprising ethylene and α-olefin, good in tensile strength and shock resistance, having a heat sealability at low temperature and a high- temperature resistance, and useful for e.g. a packaging film. SOLUTION: This copolymer comprising ethylene and α-olefin has (A) 0.92 to 0.96 g/cm in density, (B) 0.01 to 30 g/10 min. in melt flow rate and (C) 1.5 to 5.0 in molecular weight distribution, and (D) the copolymer has a single peak in the elution temperature-amount of elution curve depending on the continuous temperature-rising elution fractionation method and the temperature difference T75-T25 and density (d) satisfy the equations I and II wherein T23 and T75 are temperatures, obtained from the integral elution curve of the above curve, at which 25% and 75% of the whole amount of elution are eluted, respectively, and (E) the polymer has 1 to 2 melting point peaks and the highest melting point Tm1 and density (d) satisfy the equation Tm1>=150×(d)-17.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an ethylene / α-olefin copolymer having 5 to 12 carbon atoms having excellent physical properties and processability, a composition thereof, and a film thereof. More specifically, injection molding of various containers, lids, containers, etc. by injection molding, various molded products such as various packaging films produced by T-die molding, blown film molding, etc. An object of the present invention is to provide a copolymer of ethylene and an α-olefin having 5 to 12 carbon atoms, a composition thereof, and a film thereof, which are suitable for coating a body or an electric wire, a cable, a steel pipe or the like.

[0002]

2. Description of the Related Art Linear low density polyethylene (LLDP)
E) is ethylene / ethylene obtained with a conventional Ziegler-type catalyst.
α-Olefin copolymer, which has higher strength and toughness than high-pressure low-density polyethylene (HPLDPE), and is used for various applications such as films, sheets, hollow molded articles, and injection molded articles. Further, in order to reduce the weight of these molded products, further enhancement of the strength of LLDPE is required.

In recent years, high-strength ethylene / α-olefin copolymers having a very narrow molecular weight distribution and composition distribution have been developed using metallocene catalysts. However, this conventional metallocene catalyst-based ethylene / α-olefin copolymer has some disadvantages. For example, since the composition distribution is very narrow and the changes in viscosity and strength with respect to temperature are very sharp, the applicable range of the temperature and extrusion conditions during molding is narrow, and the moldability is poor. Further, even if it is processed into a molded product, there are drawbacks such as poor heat resistance, a narrow temperature range in which a proper heat seal strength is exhibited, and poor heat seal characteristics. For example, when used in a film for retort packaging, during retort sterilization treatment at 121 ° C., heat resistance is required to such an extent that deformation or peeling of a heat-sealed portion does not occur. It is not appropriate to use film.

In general, the heat resistance is improved by increasing the density and increasing the high melting point component, but at the same time, the low melting point component is reduced, so that the heat sealing start temperature is increased, the transparency is reduced, and the elastic modulus is increased. However, there is a disadvantage that the flexibility is inevitably reduced. In order to solve this problem, a polyethylene resin based on a conventional Ziegler-type catalyst, which has excellent heat resistance, and a polyethylene resin based on a conventional metallocene catalyst, which has a low heat-sealing start temperature and excellent mechanical strength, are used. The method of mixing is described in Tokuhyo Hei 9-505090
No. is published in the official gazette.

However, polyethylene resins based on Ziegler type catalysts have drawbacks such as high heat-sealing starting temperature and poor mechanical strength, and polyethylene resins based on metallocene catalysts have poor heat resistance and moldability. Due to the drawbacks, simply mixing them would broaden the molecular weight distribution compared to conventional metallocene-based catalysts, which inevitably reduces mechanical strength. Is inferior in heat resistance and molding workability.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a mechanical strength superior to LLDPE by a Ziegler type catalyst,
It has optical properties, heat resistance, etc., and has the same low-temperature heat sealability and transparency as ethylene / α-olefin copolymers using a conventional metallocene catalyst, while maintaining transparency.
An object of the present invention is to provide an ethylene / α-olefin copolymer having better heat resistance, heat sealing properties and moldability than α-olefin copolymers, a composition thereof, and films thereof.

[0007]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies in view of the above-mentioned object, and have found that despite having a narrow molecular weight distribution, they have a relatively wide composition distribution, and yet have a high tensile strength and impact resistance. The present inventors have found an ethylene / α-olefin copolymer which is excellent and has both low-temperature heat sealability and high heat resistance, thereby achieving the above object.

That is, the ethylene of the present invention and C 5 -C 5
Copolymers with α-olefins of No. 12 include the following (A) to
It is characterized by satisfying the requirement of (E). (A) a density of 0.92 to 0.96 g / cm ³ (B) a melt flow rate (MFR) of 0.01 to 30
g / 10 min. (C) The molecular weight distribution (Mw / Mn) is 1.5 to 5.0. (D) One peak of the elution temperature-elution amount curve by the continuous heating elution fractionation method (TREF), and the elution temperature - the difference T ₇₅ -T ₂₅ and the density d of the temperature T ₇₅ to 75% of the total temperature T ₂₅ to 25% of the total determined from the integral elution curve of elution amount curve is eluted elutes the following ( The relationship of equation a),
And satisfying the following formula (formula b) (formula a) When d <0.950 g / cm ³ T ₇₅ −T ₂₅ ≧ −300 × d + 285 When d ≧ 0.950 g / cm ³ T ₇₅ −T ₂₅ ≧ 0 (Equation b) T ₇₅ −T ₂₅ ≦ −670 × d + 644 (E) It has one or two melting point peaks, and the highest melting point T _m1 and density d satisfy the relationship of the following (Equation c). Satisfy (Equation c) T _m1 ≧ 150 × d−17

Further, the ethylene and α having 5 to 12 carbon atoms are used.
-It is desirable that the copolymer with olefin further satisfies the following requirement (F). (F) Melt tension (MT) and melt flow rate (MFR) satisfy the relationship of the following (formula d). (Formula d) logMT ≦ −0.572 × logMFR +
0.3

Further, the ethylene and α having 5 to 12 carbon atoms.
-The copolymer with olefin, ethylene in the presence of a catalyst containing an organic cyclic compound having at least a conjugated double bond and a transition metal compound of Group IV of the periodic table, ethylene and 5-1 carbon atoms
Desirably obtained by copolymerizing α-olefin No. 2 with α-olefin.

Further, the ethylene and α having 5 to 12 carbon atoms.
The copolymer with the olefin has a halogen concentration of 10 pp
m or less.

Further, the ethylene / α-olefin copolymer composition of the present invention comprises a copolymer of ethylene and an α-olefin having 5 to 12 carbon atoms satisfying the following requirements (A) to (E): B) It is characterized by having 1 to 99% by weight and 1 to 99% by weight of another polyolefin (b). (A) a density of 0.92 to 0.96 g / cm ³ (B) a melt flow rate (MFR) of 0.01 to 30
g / 10 min. (C) The molecular weight distribution (Mw / Mn) is 1.5 to 5.0. (D) One peak of the elution temperature-elution amount curve by the continuous heating elution fractionation method (TREF), and the elution temperature - the difference T ₇₅ -T ₂₅ and the density d of the temperature T ₇₅ to 75% of the total temperature T ₂₅ to 25% of the total determined from the integral elution curve of elution amount curve is eluted elutes the following ( The relationship of equation a),
And satisfying the following formula (formula b) (formula a) When d <0.950 g / cm ³ T ₇₅ −T ₂₅ ≧ −300 × d + 285 When d ≧ 0.950 g / cm ³ T ₇₅ −T ₂₅ ≧ 0 (Equation b) T ₇₅ −T ₂₅ ≦ −670 × d + 644 (E) It has one or two melting point peaks, and the highest melting point T _m1 and density d satisfy the relationship of the following (Equation c). Satisfy (Equation c) T _m1 ≧ 150 × d−17

Further, the ethylene and α having 5 to 12 carbon atoms are used.
-The copolymer with olefin (a) further comprises the following (F)
It is desirable to satisfy the requirements of (F) Melt tension (MT) and melt flow rate (MFR) satisfy the relationship of the following (formula d). (Formula d) logMT ≦ −0.572 × logMFR +
0.3

Further, the ethylene and α having 5 to 12 carbon atoms.
A copolymer with an olefin (a) is obtained by reacting ethylene and α-C 5 to C 12 in the presence of a catalyst containing at least an organic cyclic compound having a conjugated double bond and a transition metal compound of Group IV of the periodic table. -It is desirable that it is obtained by copolymerizing with an olefin. The copolymer (a) of ethylene and an α-olefin having 5 to 12 carbon atoms preferably has a halogen concentration of 10 ppm or less.

The film of the present invention comprises a copolymer of any of the above-mentioned ethylene and an α-olefin having 5 to 12 carbon atoms or any of the above-mentioned ethylene / α-olefin copolymer compositions. It is characterized by the following.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The copolymer (a) of ethylene and an α-olefin having 5 to 12 carbon atoms (hereinafter referred to as an ethylene copolymer (a)) of the present invention satisfies the following requirements (A) to (E). I am satisfied. (A) a density of 0.92 to 0.96 g / cm ³ (B) a melt flow rate (MFR) of 0.01 to 30
g / 10 min. (C) The molecular weight distribution (Mw / Mn) is 1.5 to 5.0. (D) One peak of the elution temperature-elution amount curve by the continuous heating elution fractionation method (TREF), and the elution temperature - the difference T ₇₅ -T ₂₅ and the density d of the temperature T ₇₅ to 75% of the total temperature T ₂₅ to 25% of the total determined from the integral elution curve of elution amount curve is eluted elutes the following ( The relationship of equation a),
And satisfying the following formula (formula b) (formula a) When d <0.950 g / cm ³ T ₇₅ −T ₂₅ ≧ −300 × d + 285 When d ≧ 0.950 g / cm ³ T ₇₅ −T ₂₅ ≧ 0 (Equation b) T ₇₅ −T ₂₅ ≦ −670 × d + 644 (E) It has one or two melting point peaks, and the highest melting point T _m1 and density d satisfy the relationship of the following (Equation c). Satisfy (Equation c) T _m1 ≧ 150 × d−17

The α-olefin having 5 to 12 carbon atoms in the present invention is an α-olefin having 5 to 12 carbon atoms, preferably 5 to 10 carbon atoms.
Methyl-1-pentene, 1-hexene, 1-octene,
Examples thereof include 1-decene and 1-dodecene. The content of these α-olefins is usually 5 mol% in total.
It is desirable that the content be selected within the range of, preferably, 4 mol% or less.

(A) of the ethylene copolymer (a) of the present invention
Density, 0.92~0.96g / cm ^3, preferably in the range of 0.925~0.94g / cm ^3, more preferably 0.925~0.935g / cm ^3. If the density is less than 0.92 g / cm ³ , the rigidity and heat resistance are inferior. If it exceeds 0.96 g / cm ³ , the material is too hard and the mechanical strength such as tear strength and impact strength is low.

The ethylene copolymer (a) of the present invention has a melt flow rate (B) (hereinafter referred to as MFR) of 0.01 to 30 g / 10 min, preferably 0.05 to 25 g / min.
g / 10 minutes, more preferably 0.1 to 20 g / 10 minutes. If the MFR is less than 0.01 g / 10 min, the moldability will be poor, and if it exceeds 30 g / 10 min, the mechanical strength will be weak. Moreover, MFR is 0.01-30.
When the range is g / 10 minutes, the melt tension is in an appropriate range, and the moldability is further improved.

(C) of the ethylene copolymer (a) of the present invention
The molecular weight distribution (Mw / Mn) is in the range of 1.5 to 5.0, preferably 1.5 to 4.0, more preferably 1.5 to 3.0.
5, more preferably in the range of 1.8 to 3.0. If the Mw / Mn is less than 1.5, the moldability is poor, and5.
If it exceeds 0, the impact resistance is poor.

In general, the molecular weight distribution (Mw / Mn) of the ethylene copolymer (a) is determined by determining the weight average molecular weight (Mw) and the number average molecular weight (Mn) by gel permeation chromatography (GPC). (Mw / Mn)
Can be obtained by calculating

The ethylene copolymer (a) of the present invention is shown in FIG.
As shown in (D), continuous heating elution fractionation method (TREF)
And the temperature at which 25% of the total amount determined from the integrated elution curve of the elution temperature-elution amount curve elutes, ie, the elution temperature-
The temperature T ₂₅ at which the area obtained by integrating the elution amount curve becomes 25% of the total area, the temperature at which 75% of the total elutes,
That is, the difference T ₇₅ −T from the temperature T _{75 at} which the area obtained by integrating the elution temperature-elution amount curve becomes 75% of the total area.
₂₅ and density d satisfy the relationship of the following (formula a) and the relationship of the following (formula b). (Formula a) When d <0.950 g / cm ³ T ₇₅ −T ₂₅ ≧ −300 × d + 285 When d ≧ 0.950 g / cm ³ T ₇₅ −T ₂₅ ≧ 0 (Formula b) T ₇₅ −T ₂₅ When ≦ −670 × d + 644 T ₇₅ −T ₂₅ and the density d do not satisfy the relationship of the above (formula a), the heat seal strength and heat resistance are inferior, and when the relationship of the above (formula b) is not satisfied. In addition, the low-temperature heat sealability is poor.

The method for measuring TREF according to the present invention is as follows. The sample was treated with orthodichlorobenzene (O 2
DCB) so that the sample concentration becomes 0.1% by weight.
Heat and dissolve at 135 ° C. 5 ml of this sample solution is injected into a column filled with glass beads, 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 sample is sequentially eluted while the column temperature is raised at a constant rate of 50 ° C./hr while flowing ODCB through the column at a constant flow rate. At this time, the concentration of the sample eluted in the solvent is continuously detected by measuring the absorption of the asymmetric stretching vibration of methylene at a wave number of 2925 cm ^-1 with an infrared detector. From this value, the concentration of the ethylene / α-olefin copolymer in the solution was quantitatively analyzed,
Determine the relationship between elution temperature and elution rate. According to the TREF analysis, a change in the elution rate with respect to a temperature change can be continuously analyzed with a very small amount of sample, so that a relatively fine peak which cannot be detected by the fractionation method can be detected.

The ethylene copolymer of the present invention (a)
Has (E) one or two melting point peaks, and the highest melting point T _m1 and the density d satisfy the relationship of the following (formula c). (Formula c) T _m1 ≧ 150 × d−17 If the melting point T _m1 and the density d do not satisfy the relationship of the above (Formula c), the heat resistance will be poor.

Further, among the above ethylene copolymers (a), an ethylene copolymer (a) which further satisfies the following requirement (F) is preferable. (F) Melt tension (MT) and melt flow rate (MFR) satisfy the relationship of the following (formula d). (Formula d) logMT ≦ −0.572 × logMFR +
When the 0.3 MT and the MFR satisfy the relationship of the above (formula d), the moldability such as film molding is improved.

Although the ethylene copolymer (a) of the present invention has a relatively wide composition distribution despite its narrow molecular weight distribution, it has high mechanical strength such as tensile strength and impact strength, heat seal properties, It has excellent blocking properties and good heat resistance.

The ethylene copolymer (a) of the present invention comprises a conventional typical metallocene-based catalyst, that is, at least a ligand having a cyclopentadienyl skeleton and a transition metal compound belonging to Group IV of the periodic table. It has a wider molecular weight distribution than the ethylene copolymer obtained in the presence of one type of catalyst, and has a low-temperature heat-healing property than the low-density ethylene-α-olefin copolymer obtained with the Ziegler catalyst. It is clearly distinguished from an ethylene copolymer.

The ethylene copolymer (a) of the present invention is not particularly limited to a catalyst, a production method and the like as long as it satisfies the above-mentioned specific parameters, but is preferably an organic cyclic compound having at least a conjugated double bond. And ethylene and 5 carbon atoms in the presence of a catalyst containing a transition metal compound of Group IV of the Periodic Table.
It is desirable to be an ethylene copolymer obtained by copolymerizing the α-olefins of No. 1 to No. 12.

The ethylene copolymer (a) of the present invention is preferably polymerized with a catalyst obtained by mixing the following compounds a1 to a4. a1: Compound represented by the general formula Me ¹ R ¹ _p R ² _q (OR ³ ) _r X ¹⁴ _-pqr (where Me ¹ represents zirconium, titanium, or hafnium, and R ¹ and R ³ each represent a carbon number) 1 to
24 hydrocarbon groups, R ² is a 2,4-pentanedionato ligand or a derivative thereof, a benzoylmethanato ligand,
A benzoylacetonate ligand or a derivative thereof, X ¹ represents a halogen atom, p, q and r each represent 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 (In the formula, Me ² is an element in Groups I to III of the periodic table, R ⁴
And R ⁵ are each a hydrocarbon group having 1 to 24 carbon atoms, X
² represents 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 a valence of Me ² , and m and n represent A is an integer satisfying the ranges of 0 ≦ m ≦ z and 0 ≦ n ≦ z, and 0 ≦ m + n ≦ z. A3: Organic cyclic compound having a conjugated double bond a4: Al—O—Al bond Containing modified organoaluminum oxy compound and / or boron compound

The details will be described below. The above-mentioned catalyst component a1
In the formula of the compound represented by the general formula Me ¹ R ¹ _p R ² _q (OR ³ ) _r X ¹⁴ _-pqr , Me ¹ represents zirconium, titanium or hafnium, and the types of these transition metals are limited. It is not limited to this, and a plurality of them can be used, but it is particularly preferable that the copolymer contains zirconium having excellent weather resistance. R ¹ and R ³ are each a hydrocarbon group having 1 to 24 carbon atoms, preferably 1 to 12 carbon atoms, and more preferably 1 to 8 carbon atoms. Specifically, an alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group;
Alkenyl groups such as vinyl group and allyl group; phenyl group,
Aryl groups such as tolyl, xylyl, mesityl, indenyl and naphthyl; benzyl, trityl,
And aralkyl groups such as phenethyl group, styryl group, benzhydryl group, phenylbutyl group, and neofuyl group. These may have branches. R ² is 2,
It shows a 4-pentanedionato ligand or a derivative thereof, a benzoylmethanato ligand, a benzoylacetonato ligand or a derivative thereof. X ¹ represents a halogen atom such as fluorine, iodine, chlorine and bromine. p and q are respectively 0 ≦ p ≦ 4, 0 ≦ q ≦ 4, 0 ≦ r ≦ 4, 0 ≦ p + q
An integer satisfying the range of + r ≦ 4 is an integer.

Examples of the compound represented by the general formula of the above-mentioned catalyst component a1 include tetramethyl zirconium, tetraethyl zirconium, tetrabenzyl zirconium, tetrapropoxy zirconium, tripropoxy monochlorodiconium, tetraethoxy zirconium, tetrabutoxy zirconium, tetrabutoxy titanium , Tetrabutoxy hafnium and the like, and especially Z such as tetrapropoxy zirconium and tetrabutoxy zirconium.
r (OR) ₄ compounds are preferred, and two or more of these may be used in combination. Specific examples of the 2,4-pentanedionato ligand or derivative thereof, benzoylmethanato ligand, benzoylacetonato ligand or derivative thereof include tetra (2,4-pentanedionato) zirconium. , Tri (2,4-pentanedionato)
Zirconium chloride, di (2,4-pentanedionato) dichloride zirconium, (2,4-pentanedionato) trichloride 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 (dibenzoylmethanato), zirconium di (n-butoxide), zirconium diethoxide zirconium, di (benzoylacetonate) ) Di-n-propoxide zirconium, di (benzoylacetonate)
And di-n-butoxide zirconium.

The general formula Me ² R ⁴ _m (O
R ⁵ ) _n X ^{2 In} the formula of the compound represented by _zmn , Me ² represents a group I-III element of the periodic table, and lithium, sodium,
Potassium, magnesium, calcium, zinc, boron,
Aluminum and the like. 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 the ranges of 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; organic magnesium compounds such as dimethylmagnesium, diethylmagnesium, methylmagnesium chloride and ethylmagnesium chloride; Organic zinc compounds such as zinc and diethyl zinc; organic boron compounds such as trimethyl boron and triethyl boron; trimethyl aluminum, triethyl aluminum, tripropyl aluminum, triisobutyl aluminum, trihexyl aluminum, tridecyl aluminum, diethyl aluminum chloride, ethyl aluminum dichloride , Ethyl aluminum sesquichloride, diethyl aluminum ethoxide, diethyl aluminum Derivatives of organoaluminum compounds such as Idoraido the like.

The organic cyclic compound having a conjugated double bond of the catalyst component a3 has one or more rings having two or more, preferably 2 to 4, more preferably 2 to 3, conjugated double bonds. A cyclic hydrocarbon compound having 2 or more and having a total carbon number of 4 to 24, preferably 4 to 12; wherein the cyclic hydrocarbon compound partially has 1 to 6 hydrocarbon residues (typically, carbon A cyclic hydrocarbon compound substituted with an alkyl group or an aralkyl group of the formulas 1 to 12; two or more, preferably 2 to 4, more preferably 2 to 2, conjugated double bonds.
One or more rings having three rings and a total carbon number of 4
An organosilicon compound having a cyclic hydrocarbon group of from 24 to 24, preferably 4 to 12; said cyclic hydrocarbon group being partially substituted by 1 to 6 hydrocarbon residues or an alkali metal salt (sodium or lithium salt) Organosilicon compounds. Particularly preferably, those having a cyclopentadiene structure in any of the molecules are desirable.

The preferred compounds include cyclopentadiene, indene, azulene and their alkyl, aryl, aralkyl, alkoxy or aryloxy derivatives. Further, a compound obtained by bonding (crosslinking) these compounds via an alkylene group (the number of carbon atoms of which is usually 2 to 8, preferably 2 to 3) is also preferably used.

The organosilicon compound having a cyclic hydrocarbon group can be represented by the following general formula. A _L SiR _4-L wherein A represents the above-mentioned cyclic hydrogen group exemplified by a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, and a substituted indenyl group, and R represents a methyl group, an ethyl group, a propyl group. Alkyl groups such as methoxy, ethoxy, propoxy and butoxy groups; aryl groups such as phenyl groups; aryloxy groups such as phenoxy groups; aralkyl groups such as benzyl groups. And represents a hydrocarbon residue having 1 to 24 carbon atoms, preferably 1 to 12 carbon atoms or hydrogen, and L represents 1
≦ L ≦ 4, preferably 1 ≦ L ≦ 3.

Specific examples of the organic cyclic hydrocarbon compound of the component a3 include cyclopentadiene, methylcyclopentadiene, ethylcyclopentadiene, 1,3-dimethylcyclopentadiene, indene, 4-methyl-1-indene, and 4,7- C5-C24 cyclopolyene or substituted cyclopolyene such as dimethylindene, cycloheptatriene, methylcycloheptatriene, cyclooctatetraene, azulene, fluorene, methylfluorene, monocyclopentadienylsilane, biscyclopentadiene Examples include enylsilane, triscyclopentadienylsilane, monoindenylsilane, bisindenylsilane, and trisindenylsilane.

The modified organoaluminum oxy compound containing an Al—O—Al bond of the catalyst component a4 is obtained by reacting an alkylaluminum compound with water to obtain a modified organoaluminum oxy compound usually called aluminoxane. The molecule usually contains 1 to 100, preferably 1 to 50 Al-O-Al bonds. 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, preferably 0.5 / 1 to 1/1.

Examples of the boron compound include triethylaluminum tetra (pentafluorophenyl) borate (triethylammonium tetra (pentafluorophenyl)
Borate, dimethylanilinium tetra (pentafluorophenyl) borate (dimethylanilinium tetra (pentafluorophenyl) borate, butylammonium tetra (pentafluorophenyl) borate, N, N-
Dimethylanilinium tetra (pentafluorophenyl) borate, N, N-dimethylaniliniumtetra (3,5-difluorophenyl) borate and the like can be mentioned.

The above catalyst may be used by mixing and contacting a1 to a4, but it is preferable to use the catalyst by supporting it on an inorganic carrier and / or a particulate polymer carrier (a5). Examples of the inorganic carrier and / or the particulate polymer carrier (a5) include a carbonaceous material, a metal, a metal oxide, a metal chloride, a metal carbonate or a mixture thereof, a thermoplastic resin, and a thermosetting resin. Suitable metals that can be used for the inorganic carrier include iron, aluminum, nickel and the like.

Specifically, SiO ₂ , Al ₂ O ₃ , Mg
O, ZrO ₂ , TiO ₂ , B ₂ O ₃ , CaO, ZnO, B
aO, ThO ₂ or the like, or a mixture thereof,
SiO ₂ —Al ₂ O ₃ , SiO ₂ —V ₂ O ₅ , SiO ₂ —Ti
O ₂ , SiO ₂ -V ₂ O ₅ , SiO ₂ -MgO, SiO _2-
Cr ₂ O _{3 and the} like. Among these, those containing at least one component selected from the group consisting of SiO ₂ and Al ₂ O ₃ as a main component are preferable. Further, as the organic compound, any of a thermoplastic resin and a thermosetting resin can be used. Specifically, particulate polyolefin, polyester, polyamide, polyvinyl chloride, polymethyl (meth) acrylate, polystyrene, poly Examples include norbornene, various natural polymers, and mixtures thereof.

The above-mentioned inorganic carrier and / or particulate polymer carrier can be used as they are, but preferably, as a pretreatment, these carriers are converted into an organic aluminum compound or a modified organic aluminum compound containing an Al—O—Al bond. After the contact treatment, it can be used as the component a5.

The ethylene copolymer (a) of the present invention is produced by using a catalyst which does not contain halogen such as chlorine in the above-mentioned catalyst components, so that the halogen concentration is at most 10 ppm or less, preferably 5 ppm. Hereafter, it is more preferable that it is substantially not contained (ND: 2 ppm or less). By using such a halogen-free ethylene copolymer such as chlorine, it is not necessary to use an acid neutralizing agent as in the prior art, and the chemical stability and hygiene are excellent. It is possible to provide a film that is suitably used in the field of use and the like.

The process for producing the ethylene copolymer (a) of the present invention is carried out by a gas phase polymerization method, a slurry polymerization method, a solution polymerization method, etc., in the presence of the above-mentioned catalyst, in which substantially no solvent is present.
In a state where oxygen, water, etc. are substantially turned off, aliphatic hydrocarbons such as butane, pentane, hexane, and heptane; aromatic hydrocarbons such as benzene, toluene, and xylene; and alicyclic hydrocarbons such as cyclohexane and methylcyclohexane It is produced in the presence or absence of an inert hydrocarbon solvent exemplified as above. The polymerization conditions are not particularly limited, but the polymerization temperature is usually 15 to 350 ° C, preferably 20 to 200 ° C,
More preferably, the polymerization temperature is from 50 to 110 ° C., and the polymerization pressure is usually from normal pressure to 70 kg / cm ² G, preferably from normal pressure to 20 kg / cm ² G in the case of the low and medium pressure method, and is usually 1,500 kg / cm ^{2 in} the case of the high pressure method. G or less is desirable. The polymerization time is usually from 3 minutes to 10 hours, preferably from 5 minutes to 5 hours in the case of the low and medium pressure method.
Time is desirable. In the case of the high pressure method, usually 1 minute to 30 minutes
Minutes, preferably about 2 to 20 minutes. In addition, the polymerization is not only a one-stage polymerization method, but also a hydrogen concentration, a monomer concentration,
There is no particular limitation on a multi-stage polymerization method of two or more stages in which polymerization conditions such as polymerization pressure, polymerization temperature, and catalyst are different from each other.

The ethylene copolymer (a) of the present invention contains (un) saturated fatty acid amide, as long as its properties are not impaired.
Lubricants such as (un) saturated higher fatty acid metal salts; and antiblocking agents such as silica, calcium carbonate, talc, zeolite, magnesium carbonate, and alkylenebis (un) saturated higher fatty acid amides can be added. However,
Since the ethylene copolymer (a) of the present invention is very excellent in antiblocking properties, it is not always necessary to add these lubricants and antiblocking agents, and (un) saturated metal salts of (un) saturated higher fatty acids are used as lubricants. If not added, it is not necessary to add a neutralizing agent. Particularly in food and pharmaceutical applications, it is preferable that these lubricants, anti-blocking agents and neutralizing agents are not added from the viewpoint of hygiene.

Further, a phenolic antioxidant and / or a phosphorus antioxidant can be added to the ethylene copolymer (a) of the present invention as long as its properties are not impaired. Since the ethylene copolymer (a) of the invention can be formed at a lower temperature than conventional ones, it is not always necessary to add these antioxidants. Particularly in food and pharmaceutical applications, it is preferable not to add these antioxidants from the viewpoint of hygiene.

Further, the ethylene copolymer of the present invention (a)
May be mixed with other thermoplastic resins as long as the object of the present invention is not impaired.If necessary, an antistatic agent, a weathering agent, an ultraviolet absorber, an antifogging agent, an organic or inorganic Known additives such as a pigment, a dispersant, a nucleating agent, a flame retardant, a foaming agent, and a crosslinking agent can be added.

The ethylene copolymer (a) of the present invention can be made transparent and anti-blocking by being processed by ordinary air-cooled inflation molding, air-cooled two-stage cooling inflation molding, T-die film molding, water-cooled inflation molding and the like. Excellent film can be obtained. Since the ethylene copolymer (a) of the present invention has impact resistance, tear strength, transparency, low-temperature heat sealability, hot tack, heat resistance, etc., it can be used for standard bags, sugar bags, oil-based packaging. It is suitable for various packaging films such as bags and water packaging bags and agricultural materials. Further, the film made of the ethylene copolymer (a) of the present invention and a substrate such as nylon and polyester can be bonded together and used as a multilayer film. The film of the present invention is generally 10 to 2 due to its ease of handling.
It is selected in the range of 00 μm, preferably 30-100 μm.

As an example of the method for forming the film of the present invention,
Take-off speed 20-120 m / min, blow-up ratio 1.5
4 to 4 show a method for forming an inflation film for forming a blown film at a frost line of 100 to 700 mm.

The inflation molding generally comprises 12
At a temperature of 0 to 250 ° C., it is extruded through a circular die by an extruder, quenched by contacting with air blown from an air-cooled air ring, solidified, taken with a pinch roll, and wound around a frame. When additives such as antioxidants and stabilizers are not used,
It is desirable to perform low-temperature molding in a temperature range of 180 ° C. The molding conditions include a film take-up speed of 20 to 120 m.
/ Min, and the blow-up ratio is selected in the range of 1.5 to 4.0, preferably 1.7 to 3.0. When the blow-up ratio is less than 1.5, excellent strength and a balance between longitudinal and lateral strength cannot be exhibited. On the other hand, the blow-up ratio is 4.
If it exceeds 0, the vibration of the bubble increases during molding and molding stability is lost.

The height of the frost line during inflation molding is 100 mm to 700 mm, preferably 30 mm.
The range is 0 mm to 600 mm. If the frost line height is less than 100 mm, a large amount of cooling air is required, so that the vibration of bubbles during molding increases, and molding stability is lost. When the frost line height exceeds 700 mm, the bubbles are gradually cooled by a cooling air having a weak air volume, and thus there is a possibility that the strength cannot be exhibited.

Further, in the case of low-temperature molding, 120 to 180
° C, preferably 140-170 ° C, more preferably 15 ° C
It is desirable to mold in a temperature range of 0 to 160 ° C. At a molding temperature of 120 ° C. or lower, melt fracture and surging (extrusion fluctuation) occur. At 180 ° C. or higher, gels and fish eyes are generated mainly due to oxidative deterioration unless additives such as antioxidants and heat stabilizers are used.

The ethylene / α-olefin copolymer composition of the present invention comprises the ethylene copolymer (a) 1 to 99 of the present invention.
% By weight and 99 to 1% by weight of another polyolefin (b), preferably an ethylene copolymer (a).
5 to 99% by weight, and other polyolefin (b) 95 to 1
% By weight, more preferably an ethylene copolymer (a) 10
-99% by weight and 90-1% by weight of other polyolefin (b).

Other polyolefins (b) in the present invention
Is typically an ethylene / α-olefin copolymer different from the above ethylene copolymer (a), an ethylene (co) polymer obtained by a radical polymerization method, polypropylene (PP), α-olefin copolymer rubber (EPR, EPDM, etc.).

The ethylene / α-olefin copolymer different from the above-mentioned ethylene copolymer (a) does not satisfy the specific parameters specified for the above-mentioned ethylene copolymer (a) and is conventionally known. Or a Phillips catalyst (hereinafter referred to as a conventional catalyst including both) or an ethylene / α-olefin copolymer polymerized using a metallocene catalyst. It generally has a wider molecular weight distribution or composition distribution than the ethylene copolymer (a), and has a density of 0.86 to 0.96 g / cm.
^3. It is preferable that the MFR is in the range of 0.1 to 30 g / 10 min.
E), linear low density polyethylene (LLDPE), medium density polyethylene (MDPE), high density polyethylene (H
DPE).

The high density polyethylene (HDPE), medium density polyethylene (MDPE), and linear low density polyethylene (LLDPE) using the conventional catalysts have a density of 0.
91 to 0.97 g / cm ³ , preferably 0.91 to 0.
96 g / cm ³ , more preferably 0.91 to 0.94 g
/ Cm ³ and an MFR of 0.005 to 20 g /
It is selected within a range of 10 minutes, preferably 0.05 to 10 g / 10 minutes, and more preferably 0.08 to 10 g / 10 minutes. The melt tension is 0.3 to 40 g, preferably 0.4 to 35 g, more preferably 0.5 to 30 g. Mw / Mn is 2.5-13, preferably 3-8.

The above-mentioned conventional type of very low density polyethylene (VLDPE) has a density of 0.86 to 0.91 g /
less than cm ³ , preferably 0.88 to 0.905 g / cm
³ , MFR is selected in the range of 0.01 to 20 g / 10 min, preferably 0.1 to 10 g / 10 min. The very low-density polyethylene (VLDPE) has a polyethylene exhibiting an intermediate property between linear low-density polyethylene (LLDPE) and ethylene / α-olefin copolymer rubber (EPR, EPDM). Calorimetry (DS
C) a maximum peak temperature (Tm) of 60 ° C. or higher, preferably 100 ° C. or higher, and a boiling n-hexane insoluble content of 10
A specific ethylene / α-olefin copolymer having properties of not less than% by weight, which is polymerized using a catalyst comprising at least a solid catalyst component containing titanium and / or vanadium and an organoaluminum compound to form a linear low-molecular-weight copolymer. A resin having both a high crystalline portion represented by high density polyethylene (LLDPE) and an amorphous portion represented by ethylene / α-olefin copolymer rubber, and the mechanical strength,
Heat resistance and the like, rubbery elasticity and low-temperature impact resistance, which are the characteristics of the latter, coexist in a well-balanced manner.

The α-olefin of the ethylene / α-olefin copolymer produced by the conventional catalyst has a carbon number of 3
To 12, preferably 3 to 10, specifically propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene and the like. Can be Further, the content of these α-olefins is preferably selected in a range of usually 40 mol% or less in total.

Examples of the ethylene (co) polymer obtained by the radical polymerization method include low-density polyethylene (LDPE) by high-pressure radical polymerization method, ethylene / vinyl ester copolymer, ethylene and α, β-unsaturated carboxylic acid. Or a copolymer with a derivative thereof.

Low density polyethylene (LDPE) is made of MF
R is 0.05 to 20 g / 10 min, more preferably 0.1 to 20 g / 10 min.
The range is 1 to 10 g / 10 minutes. Within this range,
Melt tension is in an appropriate range, and moldability is improved. The density is 0.91 to 0.94 g / cm ³ ,
More preferably, it is in the range of 0.912 to 0.935 g / cm ³ . Within this range, the melt tension is in an appropriate range, and the moldability is improved. The melt tension is 1.5 to 25 g, preferably 3 to 20 g, more preferably 3 to 15 g. In addition, the molecular weight distribution Mw
/ Mn is 3.0 to 20, preferably 4.0 to 15. Melt tension is an elasticity item of the resin, and the moldability is good in the above range.

The ethylene / vinyl ester copolymer is
Copolymerization with vinyl ester monomers such as vinyl propionate, vinyl acetate, vinyl caproate, vinyl caprylate, vinyl laurate, vinyl stearate, and vinyl trifluoroacetate containing ethylene as a main component produced by the high-pressure radical polymerization method. It is a polymer. Among them, particularly preferred is vinyl acetate. Also,
50 to 99.5% by weight of ethylene, 0.5 of vinyl ester
-50% by weight, other copolymerizable unsaturated monomers 0-4
A copolymer consisting of 9.5% by weight is preferred. In particular, the content of the vinyl ester is 3 to 30% by weight, preferably 5 to 30%.
It is in the range of 25% by weight. The MFR of the ethylene / vinyl ester copolymer is in the range of 0.1 to 20 g / 10 min, more preferably 0.3 to 10 g / 10 min, and the melt tension is 2.0 to 25 g, preferably 3 to 20 g. It is.

Examples of the copolymer of ethylene and an α, β-unsaturated carboxylic acid or a derivative thereof include an ethylene / (meth) acrylic acid or an alkyl ester copolymer thereof. ,
Methacrylic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate, n-butyl methacrylate, cyclohexyl acrylate And cyclohexyl methacrylate, lauryl acrylate, lauryl methacrylate, stearyl acrylate, stearyl methacrylate, glycidyl acrylate, glycidyl methacrylate and the like. Of these, particularly preferred are alkyl esters of (meth) acrylic acid such as methyl and ethyl. In particular, the content of the (meth) acrylate is 3 to
It is in the range of 30% by weight, preferably 5 to 25% by weight.
The MFR of the copolymer of ethylene and α, β-unsaturated carboxylic acid or a derivative thereof is 0.1 to 20 g / 10 min, more preferably 0.3 to 10 g / 10 min, and the melt tension is 2.0. ２５25 g, preferably 3-20 g.

The polypropylene (PP) has an MFR of 0.1 to 50 g / 10 min, more preferably 0.1 to 2 g / min.
The range is 0 g / 10 minutes. Within this range, the melt tension is in an appropriate range, and the moldability is improved. Examples of the ethylene / α-olefin copolymer rubber include ethylene propylene rubber (EPR) and ethylene-propylene-diene terpolymer (EPDM).

The type of other polyolefin (b) to be blended in the ethylene / α-olefin copolymer composition of the present invention differs depending on the required properties and applications. For example, when high heat resistance is required, high-density polyethylene (HDPE) or linear low-density polyethylene (LLDPE) is selected. When transparency is required, it is preferable to use low density polyethylene (LDPE) or polypropylene (PP).

The ethylene / α-olefin copolymer composition of the present invention contains lubricants such as (un) saturated fatty acid amides and (un) saturated higher fatty acid metal salts as long as the properties thereof are not impaired; , Talc, zeolite, magnesium carbonate, alkylenebis (unsaturated) higher fatty acid amides and the like. However, since the ethylene copolymer (a) blended in the ethylene / α-olefin copolymer composition of the present invention is very excellent in antiblocking properties, these lubricants and antiblocking agents are always added. It is not necessary, and when a (un) saturated higher fatty acid metal salt is not added as a lubricant, it is not necessary to add a neutralizing agent. Particularly in food and pharmaceutical applications, it is preferable that these lubricants, anti-blocking agents and neutralizing agents are not added from the viewpoint of hygiene.

Further, a phenolic antioxidant and / or a phosphorus antioxidant can be added to the ethylene / α-olefin copolymer composition of the present invention as long as the properties are not impaired. However, the ethylene copolymer (a) blended in the ethylene / α-olefin copolymer composition of the present invention has a lower molding temperature than conventional ones. It is not necessary to add an antioxidant. Particularly in food and pharmaceutical applications, it is preferable not to add these antioxidants from the viewpoint of hygiene.

Further, the ethylene / α-olefin copolymer composition of the present invention may be mixed with another thermoplastic resin as long as the object of the present invention is not impaired. Known additives such as an inhibitor, a weathering agent, an ultraviolet absorber, an antifogging agent, an organic or inorganic pigment, a dispersant, a nucleating agent, a flame retardant, a foaming agent, and a crosslinking agent can be added.

The ethylene / α-olefin copolymer composition of the present invention is processed by ordinary air-cooled inflation molding, air-cooled two-stage cooling inflation molding, T-die film molding, water-cooled inflation molding, etc., to obtain transparency, A film having excellent blocking properties can be obtained. The ethylene copolymer (A) blended in the ethylene / α-olefin copolymer composition of the present invention has impact resistance,
Since it has tear strength, transparency, low-temperature heat sealing property, hot tack property, heat resistance, etc., the ethylene / α of the present invention
-The olefin copolymer composition is suitable for various packaging films such as standard bags, sugar bags, oily packaging bags, aqueous packaging bags, agricultural materials, and the like. Further, a film made of the ethylene / α-olefin copolymer composition of the present invention and a substrate such as nylon and polyester can be bonded together and used as a multilayer film. The film of the present invention generally has a thickness of 10 to 200 μm, preferably 3 μm, because of its ease of handling.
It is selected in the range of 0 to 100 μm.

[0070]

Next, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples.

The test method in this example is as follows. (Physical Properties of Ethylene Copolymer) [Density] Based on JIS K6760. [MFR] Based on JIS K6760. [Measurement of T _ml by DSC] A sheet having a thickness of 0.2 mm was formed by a hot press, a sample of about 5 mg was punched out, kept at 230 ° C for 10 minutes, cooled to 0 ° C at 2 ° C / min, and then again at 10 ° C / min.
The temperature was raised to 170 ° C. in minutes, and the temperature at the top of the highest temperature peak that appeared was defined as the highest peak temperature T _ml . [Mw / Mn] GPC (150C type manufactured by Waters)
And 135 ° C. ODCB was used as a solvent. The column used was GMH _HR- H (S) from Tosoh. [TREF] The column was maintained at 140 ° C., the sample was injected, the temperature was lowered at 4 ° C./hr to 25 ° C., and the polymer was deposited on the glass beads. The eluted polymer concentration was detected with an infrared detector. Solvent: ODCB, flow rate: 1 ml / min, heating rate: 5 ° C. /
Min, detector: infrared spectrometer (wavelength 2925 cm ^-1 ), column: 0.8 cmφ × 12 cmL (filled with glass beads), sample concentration: 1 mg / ml

[Melt Tension] The stress when the melted polymer was stretched at a constant speed was determined by measuring with a strain gauge. The measurement sample was granulated into pellets and measured using an MT measuring device manufactured by Toyo Seiki Seisaku-sho. The orifice used has a hole diameter of 2.
09mmφ, length 8mm, measurement condition is resin temperature 1
90 ° C., extrusion speed 20 mm / min, winding speed 15 m / min. [Chlorine concentration] It was measured by a fluorescent X-ray method. When chlorine of 10 ppm or more was detected, this was taken as an analysis value.
When it was less than 10 ppm, it was measured with a TOX-100 type chlorine / sulfur analyzer manufactured by Dia Instruments Co., Ltd., and when it was 2 ppm or less, it was regarded as ND and was not substantially contained.

(Evaluation of Film Performance) [Film Impact] This was performed using a film impact tester manufactured by Toyo Seiki. The impact head spherical surface was 1/2 "φ. [Haze (degree of haze)] conformed to ASTM D 1003-61. [Clarity] TM-1 manufactured by Murakami Color Research Laboratory
Using a D-type transparency measuring device, a light beam was made to enter the film perpendicularly, and the ratio of the light beam that passed through the film to the incident step was expressed as a percentage. This clarity measurement was performed only on the blown film.

[Low-temperature heat-sealing property] Using a heat-sealing tester manufactured by Tester Sangyo Co., Ltd., pressure of 2 kg / cm ² , seal bar width of 1 mm,
Heat sealing was performed for a sealing time of 1 second. 15 seals
Cut out into strips with a width of mm and 300mm with a tensile tester
The peeling test was performed on the sealed portion at a rate of / min. The temperature at which the peel strength of the test piece at this time was 500 g was represented by a value obtained by interpolation. The lower the temperature, the better the low-temperature heat sealability. [High-temperature retort resistance] A container was prepared by heat-sealing one end of an inflation film, filled with distilled water and heat-sealed at the other end.
(21 ° C.) for 20 minutes under high-pressure steam sterilization. The mouth opening and the cloudiness of the film were visually observed. Those that became cloudy were opened with a triangle, and those that were extremely cloudy were evaluated as x.

(Examples 1 to 5) [Preparation of solid catalyst] In a catalyst preparation device equipped with an electromagnetic induction stirrer, 1000 ml of toluene purified under nitrogen, 22 g of tetraethoxyzirconium (Zr (OEt) ₄ ) and 74 g of indene were added. Was added, and 100 g of tripropylaluminum was added dropwise over 100 minutes while maintaining the temperature at 90 ° C.
Thereafter, the reaction was carried out at the same temperature for 2 hours. After cooling to 40 ° C., a toluene solution of methylalumoxane (concentration: 2.5 m
(mol / ml) and stirred for 2 hours.
Next, silica (manufactured by Grace, # 952, surface area 300 m ² / g) 2 previously calcined at 450 ° C. for 5 hours 2
After stirring at room temperature for 1 hour, nitrogen blowing and drying under reduced pressure were performed at 40 ° C. to obtain a solid catalyst having good fluidity.

[Gas Phase Polymerization] Copolymerization of ethylene and 1-hexene was carried out at a polymerization temperature of 80 ° C. and a total pressure of 20 kgf / cm ² G using a continuous fluidized bed gas phase polymerization apparatus. The solid catalyst was continuously supplied, and ethylene, 1-hexene and hydrogen were supplied so as to maintain a predetermined molar ratio to carry out polymerization, thereby obtaining various ethylene copolymers. Each physical property of the obtained ethylene copolymer was measured using the test methods described above. Table 1 shows the results.

[Cast film molding] The polymerized copolymer powder was granulated and then extruded using a T-die molding machine (65 mmφ extruder, 650 mm single-layer coat hanger die, lip gap 1 mm) at a molding temperature of 230 ° C. 40k
g / hr, take-off speed 25 m / min, chill roll temperature 45
A film having a thickness of 50 μm was formed at a temperature of ° C. The above-mentioned evaluation was performed about the obtained film. Table 1 shows the results.

[0078]

[Table 1]

Comparative Example 1 Using a catalyst comprising titanium tetrachloride and triethylaluminum, ethylene and 1-hexene were copolymerized by a gas phase method to obtain a linear low-density polyethylene. In the same manner as in Examples 1 to 5, measurement of physical properties of linear low-density polyethylene, production and evaluation of a film were performed. Table 2 shows the results.

(Comparative Examples 2 to 4) A linear low-density polyethylene obtained by copolymerizing ethylene and 4-methyl-1-pentene by a solution method using a catalyst comprising titanium tetrachloride and diethylaluminum chloride was obtained. Was. In the same manner as in Examples 1 to 5, measurement of physical properties of linear low-density polyethylene, production and evaluation of a film were performed. Table 2 shows the results.

Comparative Example 5 Commercially available linear low-density polyethylene (brand name: Affinity HF1) using a metallocene catalyst
030, manufactured by Dow Chemical Co., Ltd.). In the same manner as in Examples 1 to 5, measurement of physical properties of linear low-density polyethylene, production and evaluation of a film were performed. Table 2 shows the results.

[0082]

[Table 2]

As can be seen from Examples 1 to 5, the copolymers of the present invention have a good balance of physical properties and are halogen-free, whereas Comparative Example 1 has a high chlorine concentration and poor film impact. is there. In Comparative Examples 2 to 4, although the film balance is relatively good, heat resistance is inferior and deformation during retort processing is observed. Comparative Example 5 also has poor heat resistance,
Deformation during retort processing is observed.

(Examples 6 to 10) [Inflation film molding] The ethylene copolymer (a) obtained by the gas phase polymerization method of Examples 1 to 5 and the other polyolefin (b) obtained by a commercial high pressure method Density polyethylene (brand: J-LEX LD F31N,
Prepared by Nippon Polyolefin Co., Ltd.
After mixing for 5 minutes using a Henschel mixer at the mixing ratio shown in Table 1, the mixture was kneaded with a 40 mmφ extruder and pelletized to obtain an ethylene / α-olefin copolymer composition. Using the obtained ethylene / α-olefin copolymer composition, 50
mmφ LLDPE film dedicated molding machine 100m in diameter
Attach a die with mφ, lip gap 2mm, blow ratio 1.9, take-off speed 20m / min, molding temperature 200
A film having a thickness of 30 µm was formed under the forming conditions of ° C. Each evaluation was performed about the obtained film. Table 3 shows the results.

[0085]

[Table 3]

(Example 11) Another polyolefin (b)
Examples 6 to 10 except that a commercially available linear low-density polyethylene (brand name: J-LEX LL A807F, manufactured by Nippon Polyolefin Co., Ltd.) using a Ziegler catalyst was used.
Performed similarly to 10. Table 4 shows the results.

(Examples 12 and 13) As another polyolefin (b), a commercially available high-density polyethylene (brand name: J-LEX HD F5002) using a Ziegler catalyst
M, manufactured by Nippon Polyolefin Co., Ltd.). Table 4 shows the results.

(Example 14) Another polyolefin (b)
Commercially available random polypropylene (brand: J-Aroma PF731S, Nippon Polyolefin Co., Ltd.)
Ex.) Was used in the same manner as in Examples 6 to 10. Table 4 shows the results.

[0089]

[Table 4]

(Comparative Examples 6 to 8) Ethylene copolymer (a)
Instead of Ziegler-based catalyst, a commercially available linear low-density polyethylene (brand name: J-LEX LL A820F,
Example 6 except that Nippon Polyolefin Co., Ltd.) was used.
Performed in a similar manner to Table 5 shows the results. Film impact and low-temperature heat sealability were poor. (Comparative Example 9) Examples 6 to 10 except that a commercially available linear low-density polyethylene (brand name: J-LEX LL BF3350, manufactured by Nippon Polyolefin Co., Ltd.) using a Ziegler catalyst was used instead of the ethylene copolymer (a). Performed similarly to 10. Table 5 shows the results. Film impact and low-temperature heat sealability were poor.

Comparative Example 10 Example 6 was repeated except that a commercially available linear low-density polyethylene (brand name: Affinity HF1030, manufactured by Dow Chemical Co., Ltd.) using a metallocene catalyst was used in place of the ethylene copolymer (a). Performed in a similar manner to Table 5 shows the results. Low temperature heat sealability,
Heat resistance was inferior.

(Comparative Example 11) The procedure was performed except that a commercially available linear low-density polyethylene (brand name: J-LEX LL A820F, manufactured by Nippon Polyolefin Co., Ltd.) was used instead of the ethylene copolymer (a) using a Ziegler catalyst. Example 11
The same was done. Table 6 shows the results. The low-temperature heat sealability was poor.

Comparative Example 12 Other Polyolefin (b)
Was carried out in the same manner as in Comparative Example 11 except that was not blended. Table 7 shows the results. Film impact and low-temperature heat sealability were poor.

(Comparative Examples 13 and 14) A commercially available linear low-density polyethylene (brand name: J-LEX LL A82) using a Ziegler catalyst instead of the ethylene copolymer (a)
0F, manufactured by Nippon Polyolefin Co., Ltd.), except that the mixing ratio was changed. Table 6 shows the results. Optical properties (haze, clarity), film impact, and low-temperature heat sealability were poor.

(Comparative Example 15) The procedure was carried out except that a commercially available linear low-density polyethylene (brand name: JALEX LL A820F, manufactured by Nippon Polyolefin Co., Ltd.) was used instead of the ethylene copolymer (a) using a Ziegler catalyst. Example 14
The same was done. Table 6 shows the results. Film impact and low-temperature heat sealability were poor.

[0096]

[Table 5]

[0097]

[Table 6]

[0098]

As described above, the copolymer of ethylene and α-olefin having 5 to 12 carbon atoms according to the present invention satisfies the above-mentioned specific requirements, and thus is a Ziegler type copolymer. It has better mechanical strength, optical properties, heat resistance, etc. than LLDPE by the catalyst, and has the same low-temperature heat sealability and transparency as the ethylene / α-olefin copolymer by the conventional metallocene catalyst. It has better heat resistance, heat sealing properties and moldability than ethylene / α-olefin copolymers.

Further, the ethylene and α having 5 to 12 carbon atoms are used.
-When the melt flow rate (MFR) and the melt tension (MT) of the copolymer with the olefin satisfy specific requirements, the mechanical strength and the moldability are more excellent. In addition, the ethylene and α having 5 to 12 carbon atoms
The copolymer with olefin is ethylene and 5-1 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 of Group IV of the periodic table.
When it is obtained by copolymerizing α-olefin No. 2 with α-olefin of No. 2, the mechanical strength, heat resistance, moldability and the like are further excellent. In addition, when the halogen concentration of the copolymer of ethylene and an α-olefin having 5 to 12 carbon atoms is 10 ppm or less, chemical stability and hygiene are excellent, and particularly, food packaging materials and medical applications are used. Can be provided.

Further, in the ethylene / α-olefin copolymer composition of the present invention, the copolymer (a) of ethylene and an α-olefin having 5 to 12 carbon atoms contained in the above-mentioned specific Which has better mechanical strength, optical properties, heat resistance, etc. than the composition containing LLDPE by Ziegler type catalyst, and ethylene / α-olefin by conventional metallocene catalyst. Low-temperature heat-sealing properties equivalent to the composition blended with the copolymer,
While having transparency, it has better heat resistance, heat sealing properties, and moldability than the composition containing the ethylene / α-olefin copolymer.

Further, the above ethylene and α having 5 to 12 carbon atoms
-When the melt flow rate (MFR) and the melt tension (MT) of the copolymer (a) with olefin satisfy specific requirements, the mechanical strength and the moldability are more excellent. Further, the ethylene and α- having 5 to 12 carbon atoms.
The copolymer with an olefin (a) is obtained by reacting ethylene and a carbon atom having 5 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 of Group IV of the periodic table.
In the case where it is obtained by copolymerizing an α-olefin of (1) to (12), mechanical strength, heat resistance, moldability and the like are further excellent. Further, when the halogen concentration of the copolymer (a) of ethylene and an α-olefin having 5 to 12 carbon atoms is 10 ppm or less, chemical stability and hygiene are excellent, and especially food packaging materials and medical use Etc. can be provided.

Since the film of the present invention is composed of the ethylene / α-olefin copolymer of the present invention or a composition thereof, the film has excellent mechanical strength, heat resistance, heat sealing properties, moldability and the like. Become.

Such ethylene and α having 5 to 12 carbon atoms
A copolymer with an olefin (a), and ethylene / α
-The olefin copolymer composition is particularly suitable as a film for various packaging films, a raw material for lamination, etc., produced by a T-die molding method, an inflation film molding method or the like. Further, containers for mayonnaise, tubular containers for wasabi, etc., thin-walled containers for interior such as cardboard, hollow molded articles such as containers for liquid detergents, stoppers, caps, lids for containers,
It is also suitable for applications such as injection molded articles such as ski shoes, covering electric wires and cables, and covering steel pipes. Further, the copolymer of ethylene and an α-olefin having 5 to 12 carbon atoms of the present invention, and an ethylene / α-olefin copolymer composition can be prepared by dry lamination, coextrusion, extrusion lamination, and various multilayer films. Alternatively, it can be used as a laminated sheet.

[Brief description of the drawings]

FIG. 1 is a TREF of the ethylene copolymer (a) of the present invention.
It is a graph which shows an example of a curve.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Kazuyuki Sakamoto 2-3-2, Yakko, Kawasaki-ku, Kawasaki-shi, Kanagawa Japan F-term (reference) 4F071 AA15 AA20X AA21X AA31X AF06Y AF14 AF15 AF23 AF43Y BC01 4J002 BB03X BB05W BB05X BB12X BB15X 4J100 AA02P AA03Q AA04Q AA15Q AA16Q AA17Q AA19Q AA21Q CA04 DA04 DA11 DA24 DA36 DA40 DA43 FA10

Claims (10)

[Claims] 1. A copolymer of ethylene and an α-olefin having 5 to 12 carbon atoms, wherein the copolymer satisfies the following requirements (A) to (E): Coalescing. (A) a density of 0.92 to 0.96 g / cm ³ (B) a melt flow rate (MFR) of 0.01 to 30
g / 10 min. (C) The molecular weight distribution (Mw / Mn) is 1.5 to 5.0. (D) One peak of the elution temperature-elution amount curve by the continuous heating elution fractionation method (TREF), and the elution temperature - the difference T ₇₅ -T ₂₅ and the density d of the temperature T ₇₅ to 75% of the total temperature T ₂₅ to 25% of the total determined from the integral elution curve of elution amount curve is eluted elutes the following ( The relationship of equation a),
And satisfying the following formula (formula b) (formula a) When d <0.950 g / cm ³ T ₇₅ −T ₂₅ ≧ −300 × d + 285 When d ≧ 0.950 g / cm ³ T ₇₅ −T ₂₅ ≧ 0 (Equation b) T ₇₅ −T ₂₅ ≦ −670 × d + 644 (E) It has one or two melting point peaks, and the highest melting point T _m1 and density d satisfy the relationship of the following (Equation c). Satisfy (Equation c) T _m1 ≧ 150 × d−17 2. The ethylene / α-olefin copolymer according to claim 1, further satisfying the following requirement (F). (F) Melt tension (MT) and melt flow rate (MFR) satisfy the relationship of the following (formula d) (formula d) logMT ≦ −0.572 × logMFR +
0.3 3. Copolymerizing ethylene with an α-olefin having 5 to 12 carbon atoms in the presence of a catalyst containing at least an organic cyclic compound having at least a conjugated double bond and a transition metal compound belonging to Group IV of the periodic table. The ethylene / α-olefin copolymer according to claim 1 or 2, wherein the ethylene / α-olefin copolymer is obtained by the above method. 4. The ethylene / α-olefin copolymer according to claim 1, wherein the halogen concentration is 10 ppm or less. 5. The ethylene of any one of claims 1 to 4,
A film comprising an α-olefin copolymer. 6. A copolymer of ethylene and an α-olefin having 5 to 12 carbon atoms (a) satisfying the following requirements (A) to (E): 1 to 99% by weight, and another polyolefin (b) 9
9 to 1% by weight of ethylene · α
-An olefin copolymer composition. (A) a density of 0.92 to 0.96 g / cm ³ (B) a melt flow rate (MFR) of 0.01 to 30
g / 10 min. (C) The molecular weight distribution (Mw / Mn) is 1.5 to 5.0. (D) One peak of the elution temperature-elution amount curve by the continuous heating elution fractionation method (TREF), and The difference T ₇₅ -T ₂₅ and the density d between the temperature T _{25 at} which 25% of the total elutes and the temperature T _{75 at} which 75% of the total elutes, obtained from the integrated elution curve of the elution temperature-elution amount curve, are as follows: The relationship of equation a),
And satisfying the following formula (formula b) (formula a) When d <0.950 g / cm ³ T ₇₅ −T ₂₅ ≧ −300 × d + 285 When d ≧ 0.950 g / cm ³ T ₇₅ −T ₂₅ ≧ 0 (Equation b) T ₇₅ −T ₂₅ ≦ −670 × d + 644 (E) It has one or two melting point peaks, and the highest melting point T _m1 and density d satisfy the relationship of the following (Equation c). Satisfy (Equation c) T _m1 ≧ 150 × d−17 7. The ethylene / α according to claim 6, wherein the copolymer (a) of ethylene and an α-olefin having 5 to 12 carbon atoms further satisfies the following requirement (F). -An olefin copolymer composition. (F) Melt tension (MT) and melt flow rate (MFR) satisfy the relationship of the following (formula d). (Formula d) logMT ≦ −0.572 × logMFR +
0.3 8. The copolymer (a) of ethylene and an α-olefin having 5 to 12 carbon atoms includes at least an organic cyclic compound having a conjugated double bond and a transition metal compound belonging to Group IV of the periodic table. In the presence of a catalyst, ethylene and C5-C5
The ethylene / α-olefin copolymer composition according to claim 6 or 7, which is obtained by copolymerizing the α-olefin of No. 12 with the α-olefin. 9. A copolymer of ethylene and an α-olefin having 5 to 12 carbon atoms (a) having a halogen concentration of 10 p
9. The ethylene / α-olefin copolymer composition according to any one of claims 6 to 8, wherein the composition is not more than pm. 10. A film comprising the ethylene / α-olefin copolymer composition according to any one of claims 6 to 9.