JP2006312753A - Ethylene copolymer composition and use thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an ethylene-based copolymer composition having excellent transparency, mechanical strength and moldability. <P>SOLUTION: The ethylene-based copolymer composition comprises (B) a copolymer of ethylene and a 6-8C α-olefin, whose density, MFR, Mw/Mn are in specific ranges and decane-soluble part and density, Tm and density, MT and MFR, and activation energy, C number of α-olefin in the copolymer and α-olefin content, satisfy each specific relation, (C) a copolymer of ethylene and a 6-8C α-olefin, whose density and MFR are in specific ranges and decane-soluble part and density, Tm and density, and MT and MFR, satisfy each specific relation, and (E) a low density polyethylene of high pressure radical polymerization method, whose MFR is in a specific range and Mw/Mn and MFR satisfy a specific relation, wherein, the ratio of MFR of (C) to MFR of (B) satisfies a specific relation. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

The present invention relates to an ethylene copolymer composition and use thereof.
Moreover, this invention relates to the use of the said ethylene-type copolymer composition.

  Ethylene copolymers are molded by various molding methods and are used for various purposes. The ethylene-based copolymer has different required characteristics depending on the molding method and application. For example, when an inflation film is to be molded at a high speed, there is no bubble swaying or tearing, and in order to stably perform high speed molding, the ethylene-based copolymer has a melt tension (melting tension) for its molecular weight. You must choose the bigger one. Similar properties are necessary to prevent sagging or tearing in hollow molding or to minimize width drop in T-die molding.

Incidentally, a method for improving the mold tension by improving the melt tension (melting tension) or expansion ratio (die swell ratio) of an ethylene polymer obtained by using a Ziegler type catalyst, particularly a titanium-based catalyst, is disclosed in JP-A-56-56. No. 90810 or JP-A-60-106806 (Patent Documents 1 and 2). However, ethylene polymers obtained using a titanium-based catalyst, particularly low-density ethylene copolymers, have a wide composition distribution and may contain components that cause stickiness when formed into a molded body such as a film. It has been desired to further reduce the components that cause many stickiness.

  Among ethylene polymers produced using Ziegler-type catalysts, ethylene polymers obtained using chromium-based catalysts have a relatively high melt tension, but further thermal stability has been desired. .

Some ethylene copolymers obtained from olefin polymerization catalysts containing transition metal metallocene compounds have high melt tension and good thermal stability, and are expected to meet the above requirements. . However, in an ethylene-based copolymer obtained with a metallocene catalyst, generally, melt tension (MT) and flow activation energy (E _a ) are in a proportional relationship.

As described above, a polymer having a large melt tension is excellent in bubble stability and thus has good moldability. However, the flow activation energy (E _a ) is high, which means that the temperature dependence of the molding conditions is large. For this reason, unless the molding conditions are controlled very strictly and uniformly, unevenness occurs in the obtained molded body. For example, in the case of a film, transparency may be lowered.

On the other hand, if the flow activation energy (E _a ) is low, the occurrence of unevenness in the molded body can be prevented, but the melt tension is low, the bubbles become unstable, and the moldability is poor.
JP 56-90810 A JP-A-60-106806

The present invention has been made in view of the situation as described above, and can produce a film, a molded article, and the like excellent in transparency and mechanical strength, and is excellent in moldability. The purpose is to provide the use of this ethylene copolymer.

Ethylene copolymer composition (A)
(A) a copolymer of ethylene and an α-olefin having 6 to 8 carbon atoms,
(Ai) The melt tension (MT) and melt flow rate (MFR) at 190 ° C.
9.0 × MFR ^-0.65 >MT> 2.2 × MFR ^-0.84
Satisfy the relationship indicated by
(A-ii) Flow activation energy ((E _a ) × 10 ⁻⁴ J / molK) determined from the time-temperature superposition shift factor of the flow curve and the carbon atom of the α-olefin in the copolymer Number (C
) And the α-olefin content (x mol%) in the copolymer,
(0.039Ln (C-2) +0.0096) × x + 2.87 <E _a × 10 ^-4 ≦ (0.039Ln (C-2) +0.1660) × x + 2.87
Satisfy the relationship indicated by
(A-iii) When the copolymer is blown to produce a film having a thickness of 30 μm, an haze (Haze) of the film satisfies the following relationship:
When the fluidity index (FI) and melt flow rate (MFR) defined by the shear rate when the shear stress at 190 ° C. reaches 2.4 × 10 ⁶ dyne / cm ² is FI ≧ 100 × MFR α -When the number of carbon atoms (C) of the olefin is 6,
Haze <0.45 / (1-d) × log (3 × MT ^1.4 ) × (C-3) ^0.1
When the α-olefin has 7 or 8 carbon atoms (C),
Haze <0.50 / (1-d) × log (3 × MT ^1.4 )
When the fluidity index (FI) defined by the shear rate when the shear stress at 190 ° C. reaches 2.4 × 10 ⁶ dyne / cm ² and the melt flow rate (MFR) are FI <100 × MFR α -When the number of carbon atoms (C) of the olefin is 6,
Haze <0.25 / (1-d) × log (3 × MT ^1.4 ) × (C-3) ^0.1
When the α-olefin has 7 or 8 carbon atoms (C),
Haze <0.50 / (1-d) × log (3 × MT ^1.4 )
(However, d represents density (g / cm ³ ), and MT represents melt tension (g).)
(E)
(Ei) The melt flow rate measured at 190 ° C. and a 2.16 kg load is in the range of 0.1 to 50 g / 10 min.
(E-ii) The molecular weight distribution measured by gel permeation chromatography (Mw / Mn: Mw = weight average molecular weight, Mn = number average molecular weight) and melt flow rate (MFR) are 7.5 × log (MFR) − 1.2 ≦ Mw / Mn ≦ 7.5 × log (MFR) +12.5
The high-pressure radical process low-density polyethylene that satisfies the relationship shown in FIG.

The ethylene / α-olefin copolymer (A) is, for example,
(a) an organoaluminum oxy compound;
(bI) at least one transition metal compound selected from transition metal compounds represented by the following general formula (I);
ML ¹ _X (I)
(In the formula, M is a transition metal atom selected from Group 4 of the periodic table, L ¹ is a ligand coordinated to transition metal atom M, and at least two of these ligands L ¹ are A substituted cyclopentadienyl group having at least one group selected from hydrocarbon groups having 3 to 10 carbon atoms, and the ligand L ¹ other than the substituted cyclopentadienyl group has 1 to 1 carbon atoms 12 hydrocarbon groups, alkoxy groups, aryloxy groups, trialkylsilyl groups, halogen atoms or hydrogen atoms, and X is the valence of the transition metal M.)
(b-II) at least one transition metal compound selected from transition metal compounds represented by the following general formula (II);
ML ² _X (II)
(In the formula, M is a transition metal atom selected from Group 4 of the periodic table, L ² is a ligand coordinated to the transition metal atom M, and at least two of these ligands L ² are , A methylcyclopentadienyl group or an ethylcyclopentadienyl group, and the ligand L ² other than the methylcyclopentadienyl group or the ethylcyclopentadienyl group is a hydrocarbon group having 1 to 12 carbon atoms, An alkoxy group, an aryloxy group, a trialkylsilyl group, a halogen atom or a hydrogen atom, and X is the valence of the transition metal atom M.)
It is obtained by copolymerizing ethylene and an α-olefin having 6 to 8 carbon atoms in the presence of an olefin polymerization catalyst.

In the catalyst, the (a) organoaluminum oxy compound, (bI) transition metal compound and (b-II) transition metal compound are:
(c) It is preferably supported on a carrier.

The ethylene copolymer composition (A ′) according to the present invention is:
(B) a copolymer of ethylene and an α-olefin having 6 to 8 carbon atoms,
(Bi) the density is in the range of 0.880 to 0.970 g / cm ³ ;
(B-ii) The melt flow rate (MFR) at 190 ° C. and a 2.16 kg load is in the range of 0.02 to 200 g / 10 min.
(B-iii) The decane-soluble component amount ratio (W) and density (d) at room temperature,
When MFR ≦ 10g / 10min,
W <80 × exp (-100 (d-0.88)) + 0.1
When MFR> 10g / 10min,
W <80 × (MFR-9) ^0.26 × exp (-100 (d-0.88)) + 0.1
Satisfy the relationship indicated by
(B-iv) The temperature (Tm) and density (d) at the maximum peak position of the endothermic curve measured by a differential scanning calorimeter (DSC) are Tm <400 × d−248.
Satisfy the relationship indicated by
(B-v) Melt tension (MT) and melt flow rate (MFR) at 190 ° C.
9.0 × MFR ^-0.65 >MT> 2.2 × MFR ^-0.84
Satisfy the relationship indicated by
(B-vi) Flow activation energy ((E _a ) × 10 ^-4 J / molK) obtained from shift factor of time-temperature superposition of flow curve and carbon atom of α-olefin in copolymer The relationship between the number (C) and the α-olefin content (x mol%) in the copolymer is
(0.039Ln (C-2) +0.0096) × x + 2.87 <E _a × 10 ^-4 ≦ (0.039Ln (C-2) +0.1660) × x + 2.87
Satisfy the relationship indicated by
(B-vii) Ratio of weight average molecular weight (Mw) and number average molecular weight (Mn) determined by GPC (Mw /
Mn)
2.2 <Mw / Mn <3.5
An ethylene / α-olefin copolymer represented by
(C) a copolymer of ethylene and an α-olefin having 6 to 8 carbon atoms,
(C-i) the density is in the range of 0.880 to 0.970 g / cm ³ ;
(C-ii) The melt flow rate (MFR) at 190 ° C. and a 2.16 kg load is in the range of 0.02 to 200 g / 10 minutes,
(C-iii) The amount of decane-soluble component at room temperature (W) and the density (d)
When MFR ≦ 10g / 10min,
W <80 × exp (-100 (d-0.88)) + 0.1
When MFR> 10g / 10min,
W <80 × (MFR-9) ^0.26 × exp (-100 (d-0.88)) + 0.1
Satisfy the relationship indicated by
(C-iv) The temperature (Tm) and density (d) at the maximum peak position of the endothermic curve measured by a differential scanning calorimeter (DSC) are Tm <400 × d−248.
Satisfy the relationship indicated by
(Cv) The melt tension (MT) at 190 ° C. and the melt flow rate (MFR)
MT ≦ 2.2 × MFR ^-0.84
An ethylene / α-olefin copolymer represented by
(E)
(Ei) The melt flow rate measured at 190 ° C. and a 2.16 kg load is in the range of 0.1 to 50 g / 10 min.
(E-ii) The molecular weight distribution measured by gel permeation chromatography (Mw / Mn: Mw = weight average molecular weight, Mn = number average molecular weight) and melt flow rate (MFR) are 7.5 × log (MFR) − 1.2 ≦ Mw / Mn ≦ 7.5 × log (MFR) +12.5
A high-pressure radical process low-density polyethylene that satisfies the relationship represented by
A composition comprising
The ratio of the melt flow rate (MFR (C)) of (C) to the melt flow rate (MFR (B)) of (B) is 1 <(MFR (C)) / (MFR (B)) ≦ 20
It is.

The composition comprising the ethylene / α-olefin copolymer (B) and the ethylene / α-olefin copolymer (C) is substantially the same as the ethylene / α-olefin copolymer (A). Have the same composition and utility.

In the ethylene copolymer composition (A ′), the ethylene / α-olefin copolymers (B) and (C) are both ethylene / hexene-1 copolymers, and the ethylene / α-olefin copolymer. A composition comprising the polymers (B) and (C),
(A′-i) The melt tension (MT) and melt flow rate (MFR) at 190 ° C.
9.0 × MFR ^-0.65 >MT> 2.2 × MFR ^-0.84
Satisfy the relationship indicated by
(A'-ii) Flow activation energy ((E _a ) × 10 ^-4 J / molK) obtained from the shift factor of time-temperature superposition of the flow curve, and copolymers (B) and (C) The relationship between the number of carbon atoms (C) in hexene-1 and the total content (x mol%) of hexene-1 in copolymers (B) and (C),
(0.039Ln (C-2) +0.0096) × x + 2.87 <E _a × 10 ^-4 ≦ (0.039Ln (C-2) +0.1660) × x + 2.87
Satisfy the relationship indicated by
(A′-iii) When the composition is blown to produce a film having a thickness of 30 μm, the haze of the film preferably satisfies the following relationship.

When the fluidity index (FI) and melt flow rate (MFR) defined by the shear rate when the shear stress at 190 ° C. reaches 2.4 × 10 ⁶ dyne / cm ² are FI ≧ 100 × MFR
Haze <0.45 / (1-d) × log (3 × MT ^1.4 ) × (C-3) ^0.1
When the fluidity index (FI) defined by the shear rate when the shear stress at 190 ° C. reaches 2.4 × 10 ⁶ dyne / cm ² and the melt flow rate (MFR) are FI <100 × MFR
Haze <0.25 / (1-d) × log (3 × MT ^1.4 ) × (C-3) ^0.1
(Where d is density (g / cm ³ ), MT is melt tension (g), and C is the number of carbon atoms of hexene-1, that is, “6”).

Furthermore, in the ethylene-based copolymer composition (A ′), the composition comprising the ethylene / α-olefin copolymers (B) and (C) is any of the above (A′-i) to (A′-iii). In addition to the requirements of (A′-iv), the ratio of the weight average molecular weight (Mw) and the number average molecular weight (Mn) determined by GPC (Mw /
Mn)
2.0 ≦ Mw / Mn ≦ 2.5
It is preferable to satisfy.

The ethylene-based copolymer composition (A) or the ethylene-based copolymer composition (A ′) further includes
(D)
(a) an organoaluminum oxy compound;
(b-III) ethylene and an α-olefin having 3 to 20 carbon atoms in the presence of an olefin polymerization catalyst comprising a transition metal compound of Group 4 of the periodic table containing a ligand having a cyclopentadienyl skeleton; Obtained by copolymerizing
(D-i) the density is in the range of 0.850 to 0.980 g / cm ³ ,
(D-ii) An ethylene / α-olefin copolymer having an intrinsic viscosity [η] measured in decalin at 135 ° C. in the range of 0.4 to 8 dl / g is blended. Composition (A) composed of polymer (A) and high-pressure radical method low-density polyethylene (E) and ethylene / α-olefin copolymer (D) (ethylene-based copolymer composition (A ″)) ), An ethylene copolymer composition (A ′) and an ethylene / α-olefin copolymer (D) (ethylene copolymer composition (A ′ ″)).

  However, the ethylene / α-olefin copolymer (A) and the ethylene / α-olefin copolymer (D) are not the same, and the ethylene / α-olefin copolymers (B) and (C) It is not the same as the α-olefin copolymer (D).

  Single-layer films or sheets according to the present invention, multilayer films or sheets, injection-molded bodies, extrusion-molded bodies, fibers, foam-molded bodies, sheaths for electric wires, and the like are ethylene copolymer compositions as described above. Formed from.

  The ethylene copolymer composition according to the present invention is itself excellent in moldability and can produce a film excellent in transparency and mechanical strength.

Hereinafter, the ethylene copolymer composition according to the present invention and its application will be described.
In the present invention, the term “polymerization” may be used to mean not only homopolymerization but also copolymerization, and the term “polymer” includes not only homopolymers but also copolymers. May be used with the intention.

First, an ethylene / α-olefin copolymer (A), an ethylene / α-olefin copolymer (B), an ethylene / α-olefin copolymer (B) forming the ethylene copolymer composition according to the present invention ( C) and the high-pressure radical process low-density polyethylene (E) will be described.

Ethylene / α-olefin copolymer (A)
The ethylene / α-olefin copolymer (A) is a random copolymer of ethylene and an α-olefin having 6 to 8 carbon atoms. As the α-olefin having 6 to 8 carbon atoms used for copolymerization with ethylene, a linear α-olefin having no branch is preferable, specifically,
Examples thereof include 1-hexene, 1-heptene and 1-octene, and hexene-1 is particularly preferably used.

The ethylene / α-olefin copolymer (A) has the following properties (Ai) to (A-iii).
( ^Ai ) Melt tension [MT (g)] and melt flow rate [MFR (g / 10 min)] are 9.0 × MFR ^−0.65 >MT> 2.2 × MFR ^−0.84
Preferably 9.0 × MFR ^−0.65 >MT> 2.3 × MFR ^−0.84
More preferably 8.5 × MFR ^−0.65 >MT> 2.5 × MFR ^−0.84
The relationship indicated by is satisfied.

An ethylene / α-olefin copolymer having such characteristics is melt tension (M
Since T) is high, the moldability is good.
MFR is measured under conditions of 190 ° C. and 2.16 kg load according to ASTM D1238-65T.

The melt tension (MT) is determined by measuring the stress when the molten polymer is stretched at a constant speed. That is, the produced polymer powder is melted by a conventional method and pelletized to obtain a measurement sample. Using an MT measuring instrument manufactured by Toyo Seiki Seisakusho, the resin temperature is 190 ° C., the extrusion speed is 15 mm / min, and the winding speed is 10 to 20 m / min. , Nozzle diameter 2.09mm
The measurement was performed under the conditions of φ and nozzle length 8 mm. At the time of pelletization, 0.05% by weight of tri (2,4-di-t-butylphenyl) phosphate as a secondary antioxidant is added to the ethylene / α-olefin copolymer in advance as a heat stabilizer. 0.1% by weight of n-octadecyl-3- (4′-hydroxy-3 ′, 5′-di-t-butylphenyl) propionate was mixed with 0.05% by weight of calcium stearate as a hydrochloric acid absorbent.
(A-ii) Flow activation energy ((E _a ) × 10 ^-4 J / molK) determined from the time-temperature superposition shift factor of the flow curve and the carbon atom of the α-olefin in the copolymer The relationship between the number (C) and the α-olefin content (x mol%) in the copolymer is
(0.039Ln (C-2) +0.0096) × x + 2.87 <E _a × 10 ^-4 ≦ (0.039Ln (C-2) +0.1660) × x + 2.87
Preferably,
(0.039Ln (C-2) +0.0096) × x + 2.87 <E _a × 10 ^-4 ≦ (0.039Ln (C-2) +0.1500) × x + 2.87
More preferably,
(0.039Ln (C-2) +0.0096) × x + 2.87 <E _a × 10 ^-4 ≦ (0.039Ln (C-2) +0.1300) × x + 2.87
The relationship indicated by is satisfied.

In order to improve the film moldability, it is necessary to improve the melt tension, and it is known that introduction of long chain branching is effective for that purpose. E _a of the ethylene / α-olefin copolymer having no long chain branching is represented by E _a × 10 ⁻⁴ = (0.039Ln (C-2) +0.0096) × x + 2.87. If a long chain branch is present, E _a becomes large. Therefore, if E _a × 10 ⁻⁴ > (0.039Ln (C-2) +0.0096) × x + 2.87, it is estimated that a long chain branch exists, Film formability and transparency are improved. On the other hand, when E _a × 10 ⁻⁴ > (0.039Ln (C-2) +0.1660) × x + 2.87, although the moldability is excellent, film strength and film transparency are deteriorated, which is not preferable.

The measurement of the flow activation energy (E _a ) is, for example, as described in “Polymer Experimental Studies Vol. Page) ”, the viscoelastic frequency dependence is measured, and the activation energy (E _a ) of the flow is determined from the shift factor of the time-temperature superposition. When the graph of storage elastic modulus (vertical axis) vs angular velocity (horizontal axis) measured at a certain reference temperature is fixed and the data measured at another measurement temperature is moved in parallel to the horizontal axis, the reference temperature data and Overlap (thermorheological simplicity). The amount of log (aT) by which the data at each measurement temperature is shifted so that it can be overlaid with the reference temperature data is plotted against the linear gradient obtained by plotting the log (aT) against the reciprocal 1 / T of the measurement temperature (absolute temperature). Multiplying by 303R (R is a gas constant), the activation energy is obtained as a constant independent of temperature.

Specifically, _Ea is measured as follows.
Using a rheometer RDS-II manufactured by Rheometrics, the angular velocity (ω (rad / second)) dispersion of the storage elastic modulus (G ′ (dyne / cm ² )) was measured. The sample holder was a 25 mmφ parallel plate, and the sample thickness was about 2 mm. The measurement temperatures were 130, 170, 200, and 230 ° C., and G ′ was measured in the range of 0.04 ≦ ω ≦ 400 at each temperature. In the case of measuring at 130 ° C., in order to completely melt the crystal, the temperature was raised to 150 ° C. and then set to 130 ° C., and then measured. The amount of strain was appropriately selected in the range of 2 to 25% so that the torque in the measurement range could be detected and the torque was not exceeded. After the measurement, flow curves under four temperature conditions were superimposed with 130 ° C. as the reference temperature, and E _a was obtained from the Arrhenius type plot of the shift factor. The calculation was performed using analysis software RHIOS attached to RDS-II.
(A-iii) When a film having a thickness of 30 μm is produced from the ethylene / α-olefin copolymer by inflation molding, the haze of the film satisfies the following relationship.

When the fluidity index (FI) and melt flow rate (MFR) defined by the shear rate when the shear stress at 190 ° C. reaches 2.4 × 10 ⁶ dyne / cm ² is FI ≧ 100 × MFR α -When the number of carbon atoms (C) of the olefin is 6,
Haze <0.45 / (1-d) × log (3 × MT ^1.4 ) × (C-3) ^0.1
When the α-olefin has 7 or 8 carbon atoms (C),
Haze <0.50 / (1-d) × log (3 × MT ^1.4 )
When the fluidity index (FI) defined by the shear rate when the shear stress at 190 ° C. reaches 2.4 × 10 ⁶ dyne / cm ² and the melt flow rate (MFR) are FI <100 × MFR α -When the number of carbon atoms (C) of the olefin is 6,
Haze <0.25 / (1-d) × log (3 × MT ^1.4 ) × (C-3) ^0.1
When the α-olefin has 7 or 8 carbon atoms (C),
Haze <0.50 / (1-d) × log (3 × MT ^1.4 )
(Where d is the density (g / cm ³ ) and MT is the melt tension (g)).

An ethylene / α-olefin copolymer satisfying such requirements is excellent in moldability and transparency of the resulting film.
The flow index (FI) is determined by extruding the resin from the capillary while changing the shear rate and measuring the stress at that time. That is, using the same sample as the MT measurement, using a capillary flow characteristic tester manufactured by Toyo Seiki Seisakusho, the resin temperature is 190 ° C., and the shear stress range is about 5 × 10 ^{4 to} 3 × 10 ⁶ dyne / cm ² . Measured.

In addition, it changes by changing the diameter of a nozzle as follows by MFR (g / 10min) of resin to measure.
0.5 mm when MFR> 20
1.0 mm when 20 ≧ MFR> 3
2.0 mm when 3 ≧ MFR> 0.8
3.0mm when 0.8 ≧ MFR
The density (d) is the melt flow rate (MF) at 2.16 kg load at 190 ° C.
R) The strand obtained at the time of measurement is heat-treated at 120 ° C. for 1 hour, slowly cooled to room temperature over 1 hour, and then measured with a density gradient tube.

In addition to the above requirements, the ethylene / α-olefin copolymer (A) preferably satisfies the following requirements.
In the ethylene / α-olefin copolymer (A), the structural unit derived from ethylene is 50 to 100% by weight, preferably 55 to 99% by weight, more preferably 65 to 98% by weight, and most preferably 70 to 96%. The structural unit present in an amount of% by weight and derived from an α-olefin having 6 to 8 carbon atoms is 0 to 50% by weight, preferably 1 to 45% by weight, more preferably 2 to 35% by weight, particularly preferably. It is desirable to be present in an amount of 4-30% by weight.

The composition of the ethylene / α-olefin copolymer is usually about 200 m in a 10 mmφ sample tube.
¹³ C-NMR of a sample prepared by uniformly dissolving 1 g of the copolymer in 1 ml of hexachlorobutadiene.
The spectrum is determined by measurement under measurement conditions of a measurement temperature of 120 ° C., a measurement frequency of 25.05 MHz, a spectrum width of 1500 Hz, a pulse repetition time of 4.2 sec., And a pulse width of 6 μsec.

The density (d) of the ethylene / α-olefin copolymer (A) is 0.880 to 0.970 g / cm ³ , preferably 0.880 to 0.960 g / cm ³ , and more preferably 0.890 to 0. It is desirable that it is in the range of 0.935 g / cm ³ , most preferably 0.905 to 0.930 g / cm ³ .

The melt flow rate (MFR) of the ethylene / α-olefin copolymer (A) is from 0.02 to
It is desirable to be in the range of 200 g / 10 min, preferably 0.05 to 50 g / 10 min, more preferably 0.1 to 10 g / 10 min.

The fraction of the n-decane soluble component [W (% by weight)] and the density [d (g / cm ³ )] at 23 ° C. of the ethylene / α-olefin copolymer (A) is MFR ≦ 10 g / 10 min. When,
W <80 × exp (-100 (d-0.88)) + 0.1
Preferably W <60 × exp (-100 (d-0.88)) + 0.1
More preferably, W <40 × exp (-100 (d-0.88)) + 0.1
When MFR> 10g / 10min W <80 × (MFR-9) ^0.26 × exp (-100 (d-0.88)) + 0.1
It is desirable to satisfy the relationship indicated by.

The amount of n-decane soluble component of ethylene / α-olefin copolymer (the smaller the amount of soluble component, the narrower the composition distribution) was measured by adding about 3 g of copolymer to 450 ml of n-decane at 145 ° C. After dissolution, the solution is cooled to 23 ° C., the n-decane insoluble part is removed by filtration, and the n-decane soluble part is recovered from the filtrate.

The temperature [Tm (° C.)] and the density [d (g / cm ³ )] of the endothermic curve of the ethylene / α-olefin copolymer (A) measured by a differential scanning calorimeter (DSC)
Tm <400 × d-248
Preferably Tm <450 × d-296
More preferably, Tm <500 × d-343
Particularly preferably, Tm <550 × d-392
It is desirable to satisfy the relationship indicated by.

The temperature (Tm) at the maximum peak position of the endothermic curve measured with a differential scanning calorimeter (DSC) is about 5 mg of a sample packed in an aluminum pan, heated to 200 ° C. at 10 ° C./min, and then at 200 ° C. for 5 minutes. After holding, the temperature is lowered to room temperature at 10 ° C./min and then obtained from an endothermic curve when the temperature is raised at 10 ° C./min. The measurement uses a DSC-7 type apparatus manufactured by PerkinElmer.

  The relationship between the temperature (Tm) and the density (d) at the maximum peak position of the endothermic curve measured by a differential scanning calorimeter (DSC), the n-decane soluble component amount fraction (W) and the density (d) It can be said that an ethylene / α-olefin copolymer having a relationship as described above has a narrow composition distribution.

The ethylene / α-olefin copolymer (A) as described above can be used in combination of two or more.
The ethylene / α-olefin copolymer (A) is, for example,
(a) an organoaluminum oxy compound;
(bI) at least one transition metal compound selected from the transition metal compounds represented by the general formula (I);
(b-II) ethylene and carbon atoms in the presence of an olefin polymerization catalyst (Cat-1) formed from at least one transition metal compound selected from the transition metal compounds represented by the general formula (II) It can be obtained by copolymerizing an α-olefin of formula 6-8.

In the above, (a) an organoaluminum oxy compound, (bI) at least one transition metal compound selected from the transition metal compounds represented by the general formula (I), and (b-II) represented by the general formula (II). At least one transition metal compound selected from the above transition metal compounds may be supported on (c) a support (hereinafter, such a supported catalyst may be abbreviated as Cat-2).
.

Next, each catalyst component forming the olefin polymerization catalysts (Cat-1) and (Cat-2) will be described.
(a) Organoaluminum Oxy Compound The organoaluminum oxy compound (a) (hereinafter sometimes referred to as “component (a)”) may be a conventionally known benzene-soluble aluminoxane. It may be a benzene-insoluble organoaluminum oxy compound as disclosed in Japanese Patent No. 276807.

The aluminoxane as described above can be produced, for example, by the following method, and is usually obtained as a hydrocarbon solution.
(1) Compounds containing adsorbed water or salts containing water of crystallization, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, and cerium chloride hydrate A method in which an organoaluminum compound such as trialkylaluminum is added to and reacted with a suspension of the above hydrocarbon medium.

  (2) A method of allowing water, ice or water vapor to act directly on an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether or tetrahydrofuran.

  (3) A method in which an organotin oxide such as dimethyltin oxide or dibutyltin oxide is reacted with an organoaluminum compound such as trialkylaluminum in a medium such as decane, benzene, or toluene.

  In addition, this aluminoxane may contain a small amount of organometallic components. Further, after removing the solvent or the unreacted organoaluminum compound by distillation from the recovered solution of the above aluminoxane, it may be redissolved in the solvent.

Specific examples of organoaluminum compounds used in the production of aluminoxane include trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, trisec-butylaluminum, tritert- Trialkylaluminum such as butylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum; tricycloalkylaluminum such as tricyclohexylaluminum, tricyclooctylaluminum; dimethylaluminum chloride, diethylaluminum chloride, diethylaluminum bromide , Dialkylaluminum such as diisobutylaluminum chloride Umuharaido diethyl aluminum hydride, dialkylaluminum hydride such as diisobutylaluminum hydride; dimethyl aluminum methoxide, dialkylaluminum alkoxides such as diethylaluminum ethoxide; and dialkylaluminum Ally Loki Sid such as diethyl aluminum phenoxide and the like.

Of these, trialkylaluminum and tricycloalkylaluminum are particularly preferred. Further, as the organoaluminum compound represented by the following general formula _{(i-C 4 H 9)} x Al y (C 5 H 10) z
(X, y, z are positive numbers and z ≧ 2x)
Isoprenylaluminum represented by the formula can also be used.

  The above organoaluminum compounds are used alone or in combination. Solvents used in the production of aluminoxane include aromatic hydrocarbons such as benzene, toluene, xylene, cumene, and cymene, and aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane, and octadecane; Cycloaliphatic hydrocarbons such as cyclopentane, cyclohexane, cyclooctane, and methylcyclopentane; petroleum fractions such as gasoline, kerosene, and light oil or halides of the above aromatic hydrocarbons, aliphatic hydrocarbons, and alicyclic hydrocarbons ( Examples thereof include hydrocarbon solvents such as chlorinated products and brominated products. In addition, ethers such as ethyl ether and tetrahydrofuran can also be used. Of these solvents, aromatic hydrocarbons are particularly preferred.

  The benzene-insoluble organoaluminum oxy compound has an Al component dissolved in benzene at 60 ° C. of 10% or less, preferably 5% or less, particularly preferably 2% or less in terms of Al atom, and is insoluble or difficult to benzene. It is soluble.

The solubility of such an organoaluminum oxy compound in benzene is determined by suspending the organoaluminum oxy compound corresponding to 100 milligrams of Al in 100 ml of benzene, mixing at 60 ° C. for 6 hours with stirring, and then attaching a jacket. Using a G-5 glass filter, hot filtration was performed at 60 ° C., and the solid portion separated on the filter was washed four times with 50 ml of benzene at 60 ° C., and the Al atoms present in the total filtrate were removed. It is determined by measuring the abundance (x mmol) (x%).

(bI) Transition metal compound and (b-II) Transition metal compound Transition metal compound (bI) is a transition metal compound represented by the following general formula (I), and transition metal compound (b-II) is It is a transition metal compound represented by the formula (II).

ML ¹ _X (I)
(In the formula, M is a transition metal atom selected from Group 4 of the periodic table, L ¹ is a ligand coordinated to transition metal atom M, and at least two of these ligands L ¹ are A substituted cyclopentadienyl group having at least one group selected from hydrocarbon groups having 3 to 10 carbon atoms, and the ligand L ¹ other than the substituted cyclopentadienyl group has 1 to 1 carbon atoms 12 hydrocarbon groups, alkoxy groups, aryloxy groups, trialkylsilyl groups, halogen atoms or hydrogen atoms, and X is the valence of the transition metal atom M.)
ML ² _X (II)
(In the formula, M is a transition metal atom selected from Group 4 of the periodic table, L ² is a ligand coordinated to the transition metal atom M, and at least two of these ligands L ² are , A methylcyclopentadienyl group or an ethylcyclopentadienyl group, and the ligand L ² other than the methylcyclopentadienyl group or the ethylcyclopentadienyl group is a hydrocarbon group having 1 to 12 carbon atoms, An alkoxy group, an aryloxy group, a trialkylsilyl group, a halogen atom or a hydrogen atom, and X is the valence of the transition metal atom M.)
Hereinafter, the transition metal compound represented by the general formula (I) or (II) will be described more specifically.

  In the above general formula (I), M is a transition metal atom selected from Group 4 of the periodic table, specifically zirconium, titanium or hafnium, preferably zirconium.

L ¹ is a ligand coordinated to the transition metal atom M, and at least two of the ligands L ¹ are at least one substitution selected from hydrocarbon groups having 3 to 10 carbon atoms. A substituted cyclopentadienyl group having a group. These ligands L ¹ may be the same or different.

  The substituted cyclopentadienyl group may have two or more substituents, and the two or more substituents may be the same or different. When the substituted cyclopentadienyl group has two or more substituents, at least one substituent may be a hydrocarbon group having 3 to 10 carbon atoms, and the other substituents are methyl group, ethyl group Or a hydrocarbon group having 3 to 10 carbon atoms.

  Specific examples of the hydrocarbon group having 3 to 10 carbon atoms include an alkyl group, a cycloalkyl group, an aryl group, and an aralkyl group. More specifically, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, pentyl group, hexyl group, octyl group, 2-ethylhexyl group, decyl group, etc. Examples include alkyl groups; cycloalkyl groups such as cyclopentyl group and cyclohexyl group; aryl groups such as phenyl group and tolyl group; and aralkyl groups such as benzyl group and neophyll group.

  Of these, an alkyl group is preferable, and an n-propyl group and an n-butyl group are particularly preferable. In the present invention, the substituted cyclopentadienyl group coordinated to the transition metal is preferably a disubstituted cyclopentadienyl group, particularly preferably a 1,3-substituted cyclopentadienyl group.

In the general formula (I), the ligand L ¹ other than the substituted cyclopentadienyl group coordinated to the transition metal atom M is a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a trioxy group, An alkylsilyl group, a halogen atom or a hydrogen atom;

  Examples of the hydrocarbon group having 1 to 12 carbon atoms include an alkyl group, a cycloalkyl group, an aryl group, and an aralkyl group. More specifically, a methyl group, an ethyl group, an n-propyl group, Alkyl groups such as isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, pentyl group, hexyl group, octyl group, 2-ethylhexyl group, decyl group; cyclopentyl group such as cyclopentyl group and cyclohexyl group Examples include alkyl groups; aryl groups such as phenyl groups and tolyl groups; and aralkyl groups such as benzyl groups and neophyll groups.

Examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group, a t-butoxy group, a pentoxy group, a hexoxy group, and an octoxy group. be able to.

Examples of the aryloxy group include a phenoxy group.
Examples of the trialkylsilyl group include a trimethylsilyl group, a triethylsilyl group, and a triphenylsilyl group.

Halogen atoms are fluorine, chlorine, bromine and iodine.
Examples of the transition metal compound represented by the general formula (I) include bis (n-propylcyclopentadienyl) zirconium dichloride, bis (n-butylcyclopentadienyl) zirconium dichloride, bis (n-hexylcyclopenta). Dienyl) zirconium dichloride, bis (methyl-n-propylcyclopentadienyl) zirconium dichloride, bis (
Methyl-n-butylcyclopentadienyl) zirconium dichloride, bis (dimethyl-n-butylcyclopentadienyl) zirconium dichloride, bis (n-butylcyclopentadienyl) zirconium dibromide, bis (n-butylcyclopentadi) Enyl) zirconium methoxychloride, bis (n-butylcyclopentadienyl) zirconium ethoxychloride, bis (n-butylcyclopentadienyl) zirconium butoxychloride, bis (n-butylcyclopentadienyl) zirconium diethoxide, bis (N-Butylcyclopentadienyl) zirconium methyl chloride, bis (n-butylcyclopentadienyl) zirconium dimethyl, bis (n-butylcyclopentadienyl) zirconium benzyl chloride, bis (n-butylcyclopentadienyl) Benzalkonium dibenzyl, bis (n- butylcyclopentadienyl) zirconium phenyl chloride, and bis (n- butylcyclopentadienyl) zirconium hydride chloride.

In the above examples, the disubstituted product of the cyclopentadienyl ring includes 1,2- and 1,3-substituted products, and the trisubstituted product includes 1,2,3- and 1,2,4-substituted products. Including.
In the present invention, a transition metal compound in which zirconium metal is replaced with titanium metal or hafnium metal in the above-described zirconium compound can be used.

Among these transition metal compounds represented by the general formula (I), bis (n-propylcyclopentadienyl) zirconium dichloride, bis (n-butylcyclopentadienyl) zirconium dichloride, bis (1-methyl-3 -n-propylcyclopentadienyl) zirconium dichloride and bis (1-methyl-3-n-butylcyclopentadienyl) zirconium dichloride are particularly preferred.

In the above general formula (II), M is a transition metal atom selected from Group 4 of the periodic table, specifically zirconium, titanium or hafnium, preferably zirconium.
L ² is a ligand coordinated to the transition metal atom M, and at least two of these ligands L ² are a methylcyclopentadienyl group or an ethylcyclopentadienyl group, and each is the same. It may or may not be.

In the general formula (II), a ligand L ² other than a methylcyclopentadienyl group or an ethylcyclopentadienyl group coordinated to the transition metal atom M is L ¹ in the general formula (I). It is the same C1-C12 hydrocarbon group, alkoxy group, aryloxy group, trialkylsilyl group, halogen atom or hydrogen atom.

Examples of the transition metal compound represented by the general formula (II) include bis (methylcyclopentadienyl) zirconium dichloride, bis (ethylcyclopentadienyl) zirconium dichloride, and bis (methylcyclopentadienyl) zirconium dibromide. , Bis (ethylcyclopentadienyl) zirconium dibromide, bis (methylcyclopentadienyl) zirconium methoxychloride, bis (ethylcyclopentadienyl) zirconium methoxychloride, bis (methylcyclopentadienyl) zirconium ethoxychloride, bis (Ethylcyclopentadienyl) zirconium ethoxy chloride, bis (methylcyclopentadienyl) zirconium diethoxide, bis (ethylcyclopentadienyl) zirconium diethoxide, Sus (methylcyclopentadienyl) zirconium methyl chloride, bis (ethylcyclopentadienyl) zirconium methyl chloride, bis (methylcyclopentadienyl) zirconium dimethyl, bis (ethylcyclopentadienyl) zirconium dimethyl, bis (methylcyclo Pentadienyl) zirconium benzyl chloride, bis (ethylcyclopentadienyl) zirconium benzyl chloride, bis (methylcyclopentadienyl) zirconium dibenzyl, bis (ethylcyclopentadienyl) zirconium dibenzyl, bis (methylcyclopentadi) Enyl) zirconium phenyl chloride, bis (ethylcyclopentadienyl) zirconium phenyl chloride, bis (methylcyclopentadienyl) zirconium hydride Examples include chloride and bis (ethylcyclopentadienyl) zirconium hydride chloride.

In the present invention, a transition metal compound in which zirconium metal is replaced with titanium metal or hafnium metal in the above-described zirconium compound can be used.
Of these transition metal compounds represented by the general formula (II), bis (methylcyclopentadienyl) zirconium dichloride and bis (ethylcyclopentadienyl) zirconium dichloride are particularly preferable.

  At least one transition metal compound selected from the transition metal compounds represented by the general formula (I) as the transition metal compound and at least one transition selected from the transition metal compounds represented by the general formula (II) A metal compound is used in combination. As a combination method, under the same polymerization conditions, an MFR (MFR (I)) of an olefin polymer obtained from a catalyst component containing only the transition metal compound represented by the general formula (I) as a transition metal compound component, and The ratio of the olefin polymer obtained from the catalyst component containing only the transition metal compound represented by the general formula (II) as the transition metal compound component to the MFR (MFR (II)) is MFR (I) / MFR (II ) ≦ 20 is preferable.

  Specifically, a combination of bis (1,3-n-butylmethylcyclopentadienyl) zirconium dichloride and bis (methylcyclopentadienyl) zirconium dichloride, bis (1,3-n-propylmethylcyclopentadiene) A combination of enyl) zirconium dichloride and bis (methylcyclopentadienyl) zirconium dichloride and a combination of bis (n-butylcyclopentadienyl) zirconium dichloride and bis (methylcyclopentadienyl) zirconium dichloride are preferred.

At least one transition metal compound (bI) selected from the transition metal compounds represented by the general formula (I) and at least one transition metal selected from the transition metal compounds represented by the general formula (II) Compound (b-II) is a molar ratio (bI / b-II) of 99/1 to 40/60, preferably 95/5 to 45/55, more preferably 90/10 to 50/50, most preferably Is preferably used in such an amount as to be in the range of 85/15 to 55/45.

Hereinafter, at least one selected from the transition metal compound (bI) represented by the general formula (I), and at least one selected from the transition metal compound (b-II) represented by the general formula (II): The transition metal compound catalyst component containing may be described as “component (b)”.

The olefin polymerization catalyst (Cat-1) is formed from the organoaluminum oxy compound (a), the transition metal compound (bI), and the transition metal compound (b-II). ) Can carry the organoaluminum oxy compound (a), transition metal compound (bI), and transition metal compound (b-II) as a catalyst (Cat-2).

(c) Carrier used as necessary (c) The carrier is an inorganic or organic compound having a particle size of 10
A granular or fine particle solid having a particle size of ˜300 μm, preferably 20 to 200 μm is used. Among these, as the inorganic compound, a porous oxide is preferable, and specifically, SiO ₂ , Al ₂
O ₃ , MgO, ZrO ₂ , TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, ThO ₂ etc. or a mixture containing these, for example, SiO ₂ —MgO, SiO ₂ —Al ₂ O ₃ , SiO ₂ —TiO ₂ ,
Examples thereof include SiO ₂ —V ₂ O ₅ , SiO ₂ —Cr ₂ O ₃ , SiO ₂ —TiO ₂ —MgO.

Of these, those containing as a main component at least one component selected from the group consisting of SiO ₂ and Al ₂ O ₃ are preferred.
The inorganic oxide includes a small amount of Na ₂ CO ₃ , K ₂ CO ₃ , CaCO ₃ , MgCO ₃ , Na ₂ SO ₄ , Al ₂ (SO ₄ ) ₃ , BaSO ₄ , KNO ₃ , Mg (NO ₃ ). ₂ , Al (NO ₃ ) ₃ , Na ₂ O, K ₂ O, Li ₂ O and other carbonates, sulfates, nitrates and oxide components may be contained.

Such (c) carrier has different properties depending on the type and production method, but the carrier preferably used has a specific surface area of 50 to 1000 m ² / g, preferably 100 to 700 m ² / g, and a pore volume of 0. It is desirable to be from ^{3 to} 2.5 cm ³ / g. The carrier is used after being calcined at 100 to 1000 ° C., preferably 150 to 700 ° C., if necessary.

In such a carrier (c), the amount of adsorbed water is desirably less than 1.0% by weight, preferably less than 0.5% by weight, and the surface hydroxyl group is not less than 1.0% by weight, preferably 1.5 to 4%. 0.0% by weight,
Particularly preferably, the content is 2.0 to 3.5% by weight.

Here, the amount of adsorbed water (% by weight) and the amount of surface hydroxyl groups (% by weight) of the carrier (c) are determined as follows.
[Amount of adsorbed water]
The amount of adsorbed water is the percentage of the weight loss when dried at 200 ° C. under normal pressure and nitrogen flow for 4 hours with respect to the weight before drying.

[Surface hydroxyl group content]
The weight of the support obtained by drying for 4 hours at 200 ° C. under normal pressure and nitrogen flow is X (g), and the surface hydroxyl group obtained by calcining the support for 20 hours at 1000 ° C. disappears. The weight of the fired product is Y (g) and is calculated according to the following formula.

Surface hydroxyl group content (% by weight) = {(XY) / X} × 100
Furthermore, examples of the carrier (c) that can be used in the present invention include granular or particulate solids of organic compounds having a particle size in the range of 10 to 300 μm. These organic compounds include (co) polymers made mainly of α-olefins having 2 to 14 carbon atoms such as ethylene, propylene, 1-butene and 4-methyl-1-pentene, vinylcyclohexane and styrene. Examples thereof include a polymer or a copolymer produced by using as a main component.

Furthermore, the following organoaluminum compound (d) can be used as necessary as a component for forming the olefin polymerization catalysts (Cat-1) and (Cat-2).
(d) Organoaluminum compound (d) Organoaluminum compound (hereinafter sometimes referred to as “component (d)”) used as necessary, for example, organoaluminum represented by the following general formula (i) A compound can be illustrated.

R ¹ _n AlX _3-n (i)
(In the formula, R ¹ is a hydrocarbon group having 1 to 12 carbon atoms, X is a halogen atom or a hydrogen atom, and n is 1 to 3).
In the general formula (i), R ¹ is a hydrocarbon group having 1 to 12 carbon atoms, such as an alkyl group, a cycloalkyl group, or an aryl group. Specifically, a methyl group, an ethyl group, or an n-propyl group. Isopropyl group, isobutyl group, pentyl group, hexyl group, octyl group, cyclopentyl group, cyclohexyl group, phenyl group, tolyl group and the like.

Specific examples of the (d) organoaluminum compound include the following compounds.
Trialkylaluminum such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trioctylaluminum, tri-2-ethylhexylaluminum; alkenylaluminum such as isoprenylaluminum; dimethylaluminum chloride, diethylaluminum chloride, diisopropylaluminum chloride, diisobutyl Dialkylaluminum halides such as aluminum chloride and dimethylaluminum bromide; alkylaluminum sesquichlorides such as methylaluminum sesquichloride, ethylaluminum sesquichloride, isopropylaluminum sesquichloride, butylaluminum sesquichloride and ethylaluminum sesquibromide; Aluminum dichloride, ethyl aluminum dichloride, isopropyl aluminum dichloride, alkyl aluminum dihalides such as ethyl aluminum dibromide; diethylaluminum hydride, and alkyl aluminum hydride such as diisobutyl aluminum hydride.

Further, as the (d) organoaluminum compound, a compound represented by the following general formula (ii) can also be used.
R ¹ _n AlY _3-n (ii)
(In the formula, R ¹ is the same as above, and Y is —OR ² group, —OSiR ³ ₃ group, —OAlR ⁴ ₂ group, —NR ⁵ ₂ group, —SiR ⁶ ₃ group or —N (R ⁷ ). a AlR ⁸ ₂ group, n is ^{1~2, R 2, R 3,} R 4 and R ⁸ are a methyl group, an ethyl group, an isopropyl group, an isobutyl group, a cyclohexyl group, a phenyl group, R ⁵ Are a hydrogen atom, a methyl group, an ethyl group, an isopropyl group, a phenyl group, a trimethylsilyl group, etc., and R ⁶ and R ⁷ are a methyl group, an ethyl group, etc.) Includes the following compounds.
(1) Compounds represented by R ¹ _n Al (OR ² ) _3-n , such as dimethylaluminum methoxide, diethylaluminum ethoxide, diisobutylaluminum methoxide,
(2) Compounds represented by R ¹ _n Al (OSiR ³ ₃ ) _3-n , such as Et ₂ Al (OSiMe ₃ ), (iso-Bu) ₂ Al (OSiMe ₃ ), (iso-Bu) ₂ Al ( OSiEt ₃ ) etc .;
(3) a compound represented by R ¹ _n Al (OAlR ⁴ ₂ ) _3-n , such as Et ₂ AlOAlEt ₂ , (iso-Bu) ₂ AlOAl (iso-Bu) ₂ ;
(4) Compounds represented by R ¹ _n Al (NR ⁵ ₂ ) _3-n , for example, Me ₂ AlNEt ₂ , Et ₂ AlNHMe, Me ₂ AlNHEt, Et ₂ AlN (SiMe ₃ ) ₂ , (iso-Bu) ₂ AlN (SiMe ₃ ) ₂ etc .;
(5) a compound represented by R ¹ _n Al (SiR ⁶ ₃ ) _3-n , such as (iso-Bu) ₂ AlSiMe ₃ ;
(6) R ¹ _n Al (N (R ⁷ ) AlR ⁸ ₂ ) _3-n , for example, Et ₂ AlN (Me) AlEt ₂ , (iso-Bu) ₂ AlN (Et) Al (iso- Bu) ₂ etc.

Among the organoaluminum compounds represented by the general formulas (i) and (ii), the general formula R
Compounds represented by ¹ ₃ Al, R ¹ _n Al (OR ² ) _{3 -n} , R ¹ _n Al (OAlR ⁴ ₂ ) _{3 -n} are preferred, and in particular, R ¹ is an isoalkyl group and n = 2 Is preferred.

The olefin polymerization catalyst (Cat-1) is formed from the above components (a) and (b) and, if necessary, the component (d). The olefin polymerization catalyst (Cat-2) (Solid catalyst (Cat-2))
Is a solid catalyst (component) in which component (a) and component (b) as described above are supported on a carrier (c),
It is formed from component (d) as required.

  The olefin polymerization catalyst (Cat-1) can be prepared by mixing and contacting each catalyst component inside or outside the polymerization vessel. However, after the component (a) is a solid component, the component (b) Can be mixed and contacted to form a solid catalyst, or the component (a) and the component (b) can be mixed and contacted in advance to form a solid catalyst, and then the solid catalyst can be added to the polymerization system. .

The olefin polymerization catalyst (Cat-1) can be formed by mixing and contacting the component (a), the component (b) and, if necessary, the component (d) in an inert hydrocarbon solvent. The contact order of each component is arbitrarily selected, but when component (a) and component (b) are mixed and contacted, component (b) is preferably added to the suspension of component (a). In addition, it is preferable that the component (b) is premixed with two or more transition metal compounds (components (bI) and (b-II)) forming the component (b) and then mixed with other components. .

  Specific examples of the inert hydrocarbon solvent used for the preparation of the olefin polymerization catalyst (Cat-1) include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; And alicyclic hydrocarbons such as pentane, cyclohexane, and methylcyclopentane; aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene, and dichloromethane; and mixtures thereof. .

When mixing component (a) and component (b), and optionally component (d), the concentration of component (a) is about 0.1 to 5 mol in terms of aluminum in component (a). / Liter (solvent), preferably in the range of 0.3 to 3 mol / liter (solvent). The atomic ratio (Al / transition metal) between aluminum (Al) in component (a) and the transition metal in component (b) is usually 10 to 500, preferably 20 to 200. The atomic ratio (Al-d / Al-a) of the aluminum atom (Al-d) in the component (d) and the aluminum atom (Al-a) in the component (a), which is used as necessary, is usually 0. 02-3
The range is preferably from 0.05 to 1.5. The mixing temperature when the component (a) and the component (b) and, if necessary, the component (d) are mixed and contacted is usually −50 to 150 ° C., preferably −20 to 120 ° C.
The contact time is 1 minute to 50 hours, preferably 10 minutes to 25 hours.

The olefin polymerization catalyst (Cat-1) prepared as described above has a component (b) of 5 × 10 ^{−6 to} 5 × 10 ⁻⁴ mol in terms of transition metal atom per 1 g of the catalyst, preferably It is contained in an amount of 10 ^{−5 to} 2 × 10 ⁻⁴ mol, and component (a) and component (d) are 10 ⁻² in terms of aluminum atoms
It is desirable that it is contained in an amount of ˜2.5 × 10 ⁻² mol, preferably 1.5 × 10 ⁻² to 2 × 10 ⁻² mol.

The solid catalyst (Cat-2) comprises the above components (a) and (b), and optionally component (d),
It can be prepared by supporting the carrier (c).
The order of contacting the component (a), the component (b), the carrier (c) and the component (d) when preparing the solid catalyst (Cat-2) is arbitrarily selected, but preferably the component (a) and the carrier mixed contact with (c) and then component (b)
Are mixed and contacted, and if necessary, the component (d) is mixed and contacted. In addition, it is preferable that the component (b) is preliminarily mixed with two or more transition metal compounds forming the component (b), the components (bI) and (b-II)), and then mixed and contacted with other components. .

  The contact of the component (a), the component (b), the support (c) and the component (d) can be performed in an inert hydrocarbon solvent, and is specifically exemplified as an inert hydrocarbon solvent used for preparing a catalyst. Examples thereof include an inert hydrocarbon solvent used in the preparation of the olefin polymerization catalyst (Cat-1) described above.

When the component (a), the component (b) and the carrier (c) are mixed and contacted as necessary, the component (d) is usually converted into a transition metal atom per gram of the carrier (c). It is used in an amount of 5 × 10 ^{−6 to} 5 × 10 ⁻⁴ mol, preferably 10 ⁻⁵ to 2 × 10 ⁻⁴ mol, and the concentration of component (b) is about 10 ⁻⁴ to 2 × 1.
The range is 0 ^-2 mol / liter (solvent), preferably 2 x 10 ^-4 to 10 ^-2 mol / liter (solvent). The atomic ratio (Al / transition metal) between aluminum (Al) in component (a) and the transition metal in component (b) is usually 10 to 500, preferably 20 to 200. The atomic ratio (Al-d / Al-a) of the aluminum atom (Al-d) in the component (d) and the aluminum atom (Al-a) in the component (a), which is used as necessary, is usually 0. It is in the range of 02 to 3, preferably 0.05 to 1.5. The mixing temperature when the component (a), the component (b) and the carrier (c) and, if necessary, the component (d) are mixed and contacted is usually −50 to 150 ° C., preferably −20 to 120 ° C., The contact time is 1 minute to 50 hours, preferably 10 minutes to 25 hours.

The solid catalyst (Cat-2) prepared as described above has a component (b) of 5 × 10 ^{−6 to} 5 × 10 ⁻⁴ mol in terms of transition metal atom per 1 g of the support (c), preferably It is supported in an amount of 10 ^{−5 to} 2 × 10 ⁻⁴ mol, and component (a) and component (d) per 1 g of carrier (c) are converted to aluminum atoms and 1
It is desirable that the catalyst is supported in an amount of 0 ^{−3 to} 5 × 10 ⁻² mol, preferably 2 × 10 ⁻³ to 2 × 10 ⁻² mol.

The olefin polymerization catalyst (Cat-2) as described above may be a prepolymerization catalyst in which an olefin is prepolymerized.
The prepolymerization catalyst can be prepared by introducing an olefin into an inert hydrocarbon solvent and performing prepolymerization in the presence of the component (a), the component (b) and the carrier (c). The solid catalyst component (Cat-2) is preferably formed from the component (a), the component (b) and the carrier (c). In this case, in addition to the solid catalyst component (Cat-2), component (a) and / or component (d) may be further added.

  As the prepolymerization catalyst, an olefin may be introduced into the suspension prepared from the above-mentioned solid catalyst (Cat-2) (solid catalyst component), and the solid produced after preparing the solid catalyst (Cat-2). The catalyst (Cat-2) may be separated from the suspension, and then the solid catalyst (Cat-2) may be suspended again with an inert hydrocarbon, and the olefin may be introduced thereto.

In preparing the prepolymerization catalyst, the component (b) is usually 10 ⁻⁶ to 2 × 10 ⁻² mol / liter (solvent) in terms of the transition metal atom in the component (b), preferably It is used in an amount of 5 × 10 ⁻⁵ to 10 ⁻² mol / liter (solvent), and the component (b) is usually 5 × 10 ^{−6 to} 5 × 10 in terms of transition metal atom per 1 g of the carrier (c). It is used in an amount of ⁻⁴ mol, preferably 10 ⁻⁵ to 2 × 10 ⁻⁴ mol. The atomic ratio (Al / transition metal) of aluminum in component (a) to transition metal in component (b) is usually 10 to 500, preferably 20 to 200. The atomic ratio (Al-d / Al-a) of the aluminum atom (Al-d) in the component (d) and the aluminum atom (Al-a) in the component (a), which is used as necessary, is usually 0. It is in the range of 02 to 3, preferably 0.05 to 1.5.

The solid catalyst component is usually in an amount of 10 ⁻⁶ to 2 × 10 ⁻² mol / liter (solvent), preferably 5 × 10 ⁻⁵ to 10 ⁻² mol / liter (solvent) as a transition metal in the transition metal compound. Used.

The prepolymerization temperature is -20 to 80 ° C, preferably 0 to 60 ° C, and the prepolymerization time is 0.5 to 100 hours, preferably about 1 to 50 hours.
Examples of the olefin used in the prepolymerization include ethylene and an α-olefin having 3 to 20 carbon atoms, such as propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-hexene, Examples include octene, 1-decene, 1-dodecene, 1-tetradecene and the like. Among these, ethylene or a combination of ethylene and an α-olefin used for polymerization is particularly preferable.

The prepolymerization catalyst is prepared, for example, as follows. That is, the support is suspended with an inert hydrocarbon. Next, an organoaluminum oxy compound (component (a)) is added to the suspension and allowed to react for a predetermined time. The supernatant is then removed and the resulting solid component is resuspended with inert hydrocarbons. A transition metal compound (component (b)) is added to the system and reacted for a predetermined time, and then the supernatant is removed to obtain a solid catalyst component. Subsequently, the prepolymerized catalyst is obtained by adding the solid catalyst component obtained above to the inert hydrocarbon containing the organoaluminum compound (component (d)) and introducing the olefin therein.

  In the prepolymerization, the olefin polymer to be produced is desirably in an amount of 0.1 to 500 g, preferably 0.2 to 300 g, more preferably 0.5 to 200 g, per 1 g of the carrier (c).

In the prepolymerization catalyst, the component (b) per gram of the carrier (c) is about 5 × 10 ^{−6 to} 5 × 10 ⁻⁴ mol, preferably 10 ⁻⁵ to 2 × 10 ⁻⁴ in terms of transition metal atoms. The aluminum atom (Al) in the component (a) and the component (d) is supported in a molar amount, and the molar ratio (Al / M) to the transition metal atom (M) in the component (b) is 5 to 200. It is desirable that it is supported in an amount in the range of 10 to 150.

The prepolymerization can be performed either batchwise or continuously, and can be performed under reduced pressure, normal pressure, or increased pressure. In the prepolymerization, the intrinsic viscosity [η] measured in decalin at least 135 ° C. in the presence of hydrogen is in the range of 0.2 to 7 dl / g,
It is desirable to produce a prepolymer that is preferably 0.5-5 dl / g.

The copolymerization of ethylene and α-olefin is carried out in the gas phase or slurry liquid phase in the presence of the olefin polymerization catalyst as described above, preferably in the gas phase. In slurry polymerization, an inert hydrocarbon may be used as a solvent, or olefin itself may be used as a solvent.

  Specific examples of the inert hydrocarbon solvent used in the slurry polymerization include aliphatic hydrocarbons such as propane, butane, isobutane, pentane, hexane, octane, decane, dodecane, hexadecane, and octadecane; cyclopentane, methylcyclopentane, Examples thereof include alicyclic hydrocarbons such as cyclohexane and cyclooctane; aromatic hydrocarbons such as benzene, toluene and xylene; petroleum fractions such as gasoline, kerosene and light oil. Of these inert hydrocarbon media, aliphatic hydrocarbons, alicyclic hydrocarbons, petroleum fractions and the like are preferable.

When the slurry polymerization method or the gas phase polymerization method is used, the catalyst as described above is usually 10 ⁻⁸ to 10 ⁻³ mol / liter, preferably 10 ⁻ as the transition metal atom concentration in the polymerization reaction system. It is preferably used in an amount of ⁷ to 10 ^-4 mol / liter.

In the olefin polymerization catalyst formed from the component (a) and the component (b), and if necessary, the component (d), a transition with the aluminum atom (Al) in the component (d) used as necessary The atomic ratio (Al / M) with the transition metal atom (M) in the metal compound (b) is in the range of 5 to 300, preferably 10 to 200, more preferably 15 to 150.

In the olefin polymerization catalyst formed from the component (a), the component (b) and the support (c), and optionally the component (d), an organoaluminum oxy compound (component) supported on the support during the polymerization In addition to (a)), an unsupported organoaluminum oxy compound may be used. In this case, the atomic ratio (Al / M) of the aluminum atom (Al) in the unsupported organoaluminum oxy compound and the transition metal atom (M) in the transition metal compound (b) is:
It is in the range of 5-300, preferably 10-200, more preferably 15-150. The component (d) used as necessary may be supported on the carrier (c) or may be added during the polymerization. Furthermore, the component (d) is supported on the carrier (c) and may be added during the polymerization. At this time, the component (d) supported on the carrier and the component (d) added in the polymerization may be the same or different. The atomic ratio (Al / M) of the aluminum atom (Al) in the component (d) used as necessary and the transition metal atom (M) in the transition metal compound (b) is 5 to 300, preferably The range is 10 to 200, more preferably 15 to 150.

  When carrying out the slurry polymerization method, the polymerization temperature is usually in the range of −50 to 100 ° C., preferably 0 to 90 ° C. When carrying out the gas phase polymerization method, the polymerization temperature is usually from 0 to 120 degreeC, Preferably it is the range of 20-100 degreeC.

The polymerization pressure is usually from atmospheric pressure 100 kg / cm ^2, and preferably a pressurized condition of to 50 kg / cm ^2, the polymerization is a batch, semi-continuous, be carried out by any of the methods of continuous it can.

  Furthermore, the polymerization can be performed in two or more stages having different reaction conditions. The olefin polymerization catalyst may contain other components useful for olefin polymerization in addition to the above components.

Examples of olefins that can be polymerized by such an olefin polymerization catalyst include ethylene and α-olefins having 6 to 8 carbon atoms, for example, propylene, 1-butene, 1-pentene, 4-methyl-1- Α-olefins such as pentene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene; cyclic olefins having 3 to 20 carbon atoms such as cyclopentene, cycloheptene, norbornene, 5 -Methyl-2-norbornene, tetracyclododecene, 2-methyl 1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene . Furthermore, styrene, vinylcyclohexane, diene, etc. can also be used.

In the ethylene / α-olefin copolymer obtained by the olefin polymerization method, the structural unit derived from ethylene is 50 to 100% by weight, preferably 55 to 99% by weight, more preferably 65 to 98% by weight, Most preferably, it is present in an amount of 70 to 96% by weight, and the structural unit derived from an α-olefin having 6 to 8 carbon atoms is 0 to 50% by weight, preferably 1 to 4%.
It is desirable to be present in an amount of 5 wt%, more preferably 2 to 35 wt%, most preferably 4 to 30 wt%.

The ethylene / α-olefin copolymer thus obtained is preferably the above-described (A-i).
A film having characteristics as shown in (A-iii), excellent moldability, and excellent transparency and mechanical strength can be produced.
Ethylene / α-olefin copolymer (B)
The ethylene / α-olefin copolymer (B) is a random copolymer of ethylene and an α-olefin having 6 to 8 carbon atoms. Examples of the α-olefin having 6 to 8 carbon atoms are the same as those described above.

In the ethylene / α-olefin copolymer (B), the structural unit derived from ethylene is 50 to 100% by weight, preferably 55 to 99% by weight, more preferably 65 to 98% by weight, and most preferably 70 to 96%. The structural unit present in an amount of% by weight and derived from an α-olefin having 6 to 8 carbon atoms is 0 to 50% by weight, preferably 1 to 45% by weight, more preferably 2 to 35% by weight, particularly preferably. It is desirable to be present in an amount of 4-30% by weight.

The ethylene / α-olefin copolymer (B) preferably has the following characteristics (Bi) to (B-vii), and the following (Bi) to (B-viii) It is particularly preferable to have the characteristics shown in FIG.

(Bi) The density (d) is 0.880 to 0.970 g / cm ³ , preferably 0.880 to 0.960 g / cm ³ , more preferably 0.890 to 0.935 g / cm ³ , Preferably 0.90
It is in the range of 5 to 0.930 g / cm ³ .

(B-ii) The melt flow rate (MFR) is in the range of 0.02 to 200 g / 10 minutes, preferably 0.05 to 50 g / 10 minutes, more preferably 0.1 to 10 g / 10 minutes.
(B-iii) When the n-decane soluble component fraction [W (wt%)] and density [d (g / cm ³ )] at 23 ° C. are MFR ≦ 10 g / 10 min,
W <80 × exp (-100 (d-0.88)) + 0.1
Preferably W <60 × exp (-100 (d-0.88)) + 0.1
More preferably, W <40 × exp (-100 (d-0.88)) + 0.1
When MFR> 10g / 10min W <80 × (MFR-9) ^0.26 × exp (-100 (d-0.88)) + 0.1
The relationship indicated by is satisfied.

(B-iv) The temperature [Tm (° C.)] and the density [d (g / cm ³ )] of the maximum peak position of the endothermic curve measured by a differential scanning calorimeter (DSC).
Tm <400 × d-248
Preferably Tm <450 × d-296
More preferably, Tm <500 × d-343
Particularly preferably, Tm <550 × d-392
The relationship indicated by is satisfied.

  The relationship between the temperature (Tm) and the density (d) at the maximum peak position of the endothermic curve measured by a differential scanning calorimeter (DSC), the n-decane soluble component amount fraction (W) and the density (d) It can be said that the ethylene / α-olefin copolymer (B) having a relationship as described above has a narrow composition distribution.

( ^Bv ) Melt tension [MT (g)] and melt flow rate [MFR (g / 10 min)] are 9.0 × MFR ^−0.65 >MT> 2.2 × MFR ^−0.84
Preferably 9.0 × MFR ^−0.65 >MT> 2.3 × MFR ^−0.84
More preferably 8.5 × MFR ^−0.65 >MT> 2.5 × MFR ^−0.84
The relationship indicated by is satisfied.

An ethylene / α-olefin copolymer having such characteristics is melt tension (M
Since T) is high, the moldability is good.
(B-vi) Flow activation energy ((E _a ) × 10 ^-4 J / molK) obtained from shift factor of time-temperature superposition of flow curve and carbon atom of α-olefin in copolymer The relationship between the number (C) and the α-olefin content (x mol%) in the copolymer is
(0.039Ln (C-2) +0.0096) × x + 2.87 <E _a × 10 ^-4 ≦ (0.039Ln (C-2) +0.1660) × x + 2.87
Preferably,
(0.039Ln (C-2) +0.0096) × x + 2.87 <E _a × 10 ^-4 ≦ (0.039Ln (C-2) +0.1500) × x + 2.87
More preferably,
(0.039Ln (C-2) +0.0096) × x + 2.87 <E _a × 10 ^-4 ≦ (0.039Ln (C-2) +0.1300) × x + 2.87
The relationship indicated by is satisfied.

(B-vii) Molecular weight distribution measured by GPC (Mw / Mn, where Mw: weight average molecular weight,
Mn: number average molecular weight) is 2.2 <Mw / Mn <3.5
Preferably 2.4 <Mw / Mn <3.0
It is in the range.

The molecular weight distribution (Mw / Mn) was measured as follows using GPC-150C manufactured by Millipore.
The separation column is TSK GNH HT, the column size is 72 mm in diameter and 600 mm in length, the column temperature is 140 ° C., the mobile phase is o-dichlorobenzene (Wako Pure Chemical Industries) and BHT ( (Takeda Pharmaceutical) using 0.025% by weight, moving at 1.0 ml / min, the sample concentration is 0.1% by weight, the sample injection volume is 500 microliters,
A differential refractometer was used as a detector. Standard polystyrenes were manufactured by Tosoh Corporation for molecular weights of Mw <1000 and Mw> 4 × 10 ⁶ , and pressure chemicals were used for 1000 <Mw <4 × 10 ⁶ .

(B-viii) The number of unsaturated bonds present in the molecule is 0.5 or less per 1000 carbon atoms and less than 1 per polymer molecule.
The unsaturated bond was quantified using ¹³ C-NMR, a signal attributed to other than the double bond, ie, a signal in the range of 10 to 50 ppm, and a signal attributed to the double bond, ie, in the range of 105 to 150 ppm. The area intensity of the signal is determined from the integral curve and determined from the ratio.

The ethylene / α-olefin copolymer (B) is prepared in the presence of an olefin polymerization catalyst containing, for example, (a) an organoaluminum oxy compound and (b-II) a transition metal compound represented by the general formula (II). It is obtained by copolymerizing ethylene and an α-olefin having 6 to 8 carbon atoms. The (a) organoaluminum oxy compound and the (b-II) transition metal compound are the same as those described in the method for producing the ethylene / α-olefin copolymer (A). And as before,
Carrier (c), organoaluminum compound (d) may be used, and prepolymerization may be performed. The amount of each component used, prepolymerization conditions, and main polymerization conditions are the same as in the production of the ethylene / α-olefin copolymer (A).
Ethylene / α-olefin copolymer (C)
The ethylene / α-olefin copolymer (C) is a random copolymer with an α-olefin having 6 to 8 carbon atoms. Examples of the α-olefin having 6 to 8 carbon atoms are the same as those described above.

The ethylene / α-olefin copolymer (C) has 50 to 1 structural units derived from ethylene.
A structural unit derived from an α-olefin having 6 to 8 carbon atoms, present in an amount of 00 wt%, preferably 55 to 99 wt%, more preferably 65 to 98 wt%, and most preferably 70 to 96 wt%. Is preferably present in an amount of 0 to 50% by weight, preferably 1 to 45% by weight, more preferably 2 to 35% by weight, particularly preferably 4 to 30% by weight.

The ethylene / α-olefin copolymer (C) preferably has the following properties (Ci) to (Cv), and the following (Ci) to (C-vi) It is particularly preferable to have the characteristics as shown.

(C-i) The density (d) is 0.880 to 0.970 g / cm ³ , preferably 0.880 to 0.960 g / cm ³ , more preferably 0.890 to 0.935 g / cm ³ , Preferably 0.90
It is in the range of 5 to 0.930 g / cm ³ .

(C-ii) The melt flow rate (MFR) is in the range of 0.02 to 200 g / 10 minutes, preferably 0.05 to 50 g / 10 minutes, more preferably 0.1 to 10 g / 10 minutes.
(C-iii) When the n-decane soluble component fraction [W (wt%)] and density [d (g / cm ³ )] at 23 ° C. are MFR ≦ 10 g / 10 min,
W <80 × exp (-100 (d-0.88)) + 0.1
Preferably W <60 × exp (-100 (d-0.88)) + 0.1
More preferably, W <40 × exp (-100 (d-0.88)) + 0.1
When MFR> 10g / 10min W <80 × (MFR-9) ^0.26 × exp (-100 (d-0.88)) + 0.1
The relationship indicated by is satisfied.

(C-iv) The temperature [Tm (° C.)] and the density [d (g / cm ³ )] of the maximum peak position of the endothermic curve measured by a differential scanning calorimeter (DSC).
Tm <400 × d-248
Preferably Tm <450 × d-296
More preferably, Tm <500 × d-343
Particularly preferably, Tm <550 × d-392
The relationship indicated by is satisfied.

  The relationship between the temperature (Tm) and the density (d) at the maximum peak position of the endothermic curve measured by a differential scanning calorimeter (DSC), the n-decane soluble component amount fraction (W) and the density (d) It can be said that an ethylene / α-olefin copolymer having a relationship as described above has a narrow composition distribution.

(C-v) Melt tension [MT (g)] and melt flow rate [MFR (g / 10 minutes)] MT ≦ 2.2 × MFR ^−0.84
Satisfies the relationship.

(C-vi) The number of unsaturated bonds present in the molecule is 0.5 or less per 1000 carbon atoms and less than 1 per polymer molecule.
Such an ethylene / α-olefin copolymer (C) includes, for example, the presence of an olefin polymerization catalyst containing (a) an organoaluminum oxy compound and (bI) a transition metal compound represented by the general formula (I). It is obtained by copolymerizing ethylene and an olefin having 6 to 8 carbon atoms below. The (a) organoaluminum oxy compound and (bI) transition metal compound are the same as those described in the process for producing the ethylene / α-olefin copolymer (A). In the same manner as described above, the carrier (c) and the organoaluminum compound (d) may be used, and prepolymerization may be performed. The amount of each component used, prepolymerization conditions, and main polymerization conditions are the same as in the production of the ethylene / α-olefin copolymer (A).

(E) High Pressure Radical Method Low Density Polyethylene High Pressure Radical Method Low Density Polyethylene is a highly branched polyethylene having a long chain branch produced by so-called high pressure radical polymerization, and has a load of 190 ° C. and 2.16 kg according to ASTM D1238-65T. It is desirable that the MFR measured under the conditions is in the range of 0.1 to 50 g / 10 minutes, preferably 0.2 to 10 g / 10 minutes, more preferably 0.2 to 8 g / 10 minutes.

This high-pressure radical method low-density polyethylene has an index of molecular weight distribution (Mw / Mn: where Mw = weight average molecular weight, Mn = number average molecular weight) and melt flow rate (MFR) measured using gel permeation chromatography (GPC). And 7.5 × log (MFR) −1.2 ≦ Mw / Mn ≦ 7.5 × log (MFR) +12.5
Preferably 7.5 × log (MFR) −0.5 ≦ Mw / Mn ≦ 7.5 × log (MFR) +12.0
More preferably 7.5 × log (MFR) ≦ Mw / Mn ≦ 7.5 × log (MFR) +12.0
The relationship indicated by is satisfied.

The method for measuring the molecular weight distribution of the high-pressure radical method low-density polyethylene is the same as described above.
The high-pressure radical process low-density polyethylene desirably has a density in the range of 0.910 to 0.930 g / cm ³ .

The density is measured with a density gradient tube after heat-treating the strand obtained at the melt flow rate measurement at 190 ° C. under a load of 2.16 kg at 120 ° C. for 1 hour and gradually cooling to room temperature over 1 hour.

Further, the high-pressure radical method low-density polyethylene uses a swell ratio representing the degree of long-chain branching, that is, a capillary type flow characteristic tester, and has a diameter (D) of 2.0 mm and a length of 15 mm under a condition of 190 ° C. It is desirable that the ratio (Ds / D) of the diameter (Ds) of the strand extruded at an extrusion speed of 10 mm / min to the nozzle inner diameter D is 1.3 or more.

Note that the high-pressure radical method low-density polyethylene may be a copolymer with other α-olefin, vinyl acetate, acrylate ester and other polymerizable monomers as long as the object of the present invention is not impaired. Good.
Ethylene-based copolymer composition The ethylene-based copolymer composition (A) according to the present invention includes an ethylene / α-olefin copolymer (A) as described above, a high-pressure radical method low-density polyethylene (E), and Consists of.

The composition ratio of the ethylene copolymer composition (A) comprising the ethylene / α-olefin copolymer (A) and the high-pressure radical process low-density polyethylene (E) is not particularly limited. The α-olefin copolymer (A) is usually 99 to 60% by weight, preferably 99 to 80% by weight,
More preferably, it is contained in a proportion of 99 to 90% by weight, and the high-pressure radical method low-density polyethylene (E) is usually 1 to 40% by weight, preferably 1 to 20% by weight, more preferably 1 to 10% by weight.
It is desirable to be included in the ratio.

Such an ethylene-based copolymer composition (A) can be produced by using a known method, and for example, can be produced by the following method.
(1) A method of mechanically blending an ethylene / α-olefin copolymer (A), a high-pressure radical process low-density polyethylene (E), and other components added as required, using an extruder, a kneader or the like.
(2) Ethylene / α-olefin copolymer (A), high-pressure radical process low-density polyethylene (E), and other components to be added as required are used as appropriate good solvents (eg, hexane, heptane, decane, cyclohexane, benzene) , Hydrocarbon solvents such as toluene and xylene), and then the solvent is removed.
(3) After preparing a solution in which an ethylene / α-olefin copolymer (A) and a high-pressure radical method low-density polyethylene (E) and other components added as desired are separately dissolved in an appropriate good solvent, they are mixed. And then removing the solvent.
(4) A method of combining the methods (1) to (3) above.

  The ethylene copolymer composition (A ′) according to another embodiment of the present invention includes the ethylene / α-olefin copolymer (B), the ethylene / α-olefin copolymer (C), and a high-pressure radical. The method consists of low density polyethylene (E).

An ethylene-based copolymer composition (A ′) comprising an ethylene / α-olefin copolymer (B), an ethylene / α-olefin copolymer (C), and a high-pressure radical process low-density polyethylene (E) is The composition ratio is not particularly limited, but the ethylene / α-olefin copolymers (B) and (C) are in a total amount, usually 99 to 60% by weight, preferably 99 to 80% by weight, more preferably 99 to 99%. 90% by weight, (E) high pressure radical low density polyethylene is usually 1-40% by weight
, Preferably 1 to 20% by weight, more preferably 1 to 10% by weight.

  Further, the ethylene / α-olefin copolymer (B) and (C) has a total amount of the (B) and (C) of 100% by weight, and the ethylene / α-olefin copolymer (B) is 1 to It is contained in an amount of 90% by weight, preferably 2 to 80% by weight, and the ethylene / α-olefin copolymer (C) is 10 to 99% by weight, preferably 20 to 98% by weight.

Such an ethylene-based copolymer composition (A ′) can be produced by using a known method, and for example, can be produced by the following method.
(1) The ethylene / α-olefin copolymers (B) and (C), the high-pressure radical process low-density polyethylene (E), and other components added as required are mechanically used using an extruder, a kneader, or the like. How to blend into.
(2) Ethylene / α-olefin copolymers (B) and (C), high-pressure radical process low-density polyethylene (E), and other components to be added as required are mixed with a suitable good solvent (eg, hexane,
In a solvent such as heptane, decane, cyclohexane, benzene, toluene and xylene, and then the solvent is removed.
(3) Solutions in which the ethylene / α-olefin copolymers (B) and (C), the high-pressure radical process low-density polyethylene (E), and other components added as required are separately dissolved in a suitable good solvent. Is prepared, mixed, and then the solvent is removed.
(4) A method of combining the methods (1) to (3) above.

Further, in the present invention, a composition (F) is formed from the ethylene / α-olefin copolymers (B) and (C), and then from the composition (F) and the high-pressure radical process low-density polyethylene (E). The ethylene copolymer composition (A ′) can also be produced by a known method as described above.

The composition (F) comprising the ethylene / α-olefin copolymer (B) and the ethylene / α-olefin copolymer (C) is a melt flow rate of the ethylene / α-olefin copolymer (B). (M
FR (B)) and melt flow rate of ethylene / α-olefin copolymer (C) (MFR (C))
The ratio with
1 <(MFR (C)) / (MFR (B)) ≦ 20
It is preferable that

Particularly in the present invention, both the ethylene / α-olefin copolymers (B) and (C) are desirably ethylene / hexene-1 copolymers. In this case, the composition (F) comprising the ethylene / α-olefin copolymer (B) and (C) is preferably substantially the same as the ethylene / α-olefin copolymer (A) as shown below. The same usefulness is expected. (A'-i) Melt tension [MT (g)] and melt flow rate [MFR (g / 10 min)
] 9.0 × MFR ^-0.65 >MT> 2.2 × MFR ^-0.84
Preferably 9.0 × MFR ^−0.65 >MT> 2.3 × MFR ^−0.84
More preferably 8.5 × MFR ^−0.65 >MT> 2.5 × MFR ^−0.84
The relationship indicated by is satisfied.

Since the composition (F) having such characteristics has a high melt tension (MT), the moldability is good.
(A'-ii) Flow activation energy ((E _a ) × 10 ^-4 J / molK) obtained from the shift factor of time-temperature superposition of the flow curve, and copolymers (B) and (C) The relationship between the number of carbon atoms (C) in hexene-1 and the total content (x mol%) of hexene-1 in copolymers (B) and (C),
(0.039Ln (C-2) +0.0096) × x + 2.87 <E _a × 10 ^-4 ≦ (0.039Ln (C-2) +0.1660) × x + 2.87
Preferably,
(0.039Ln (C-2) +0.0096) × x + 2.87 <E _a × 10 ^-4 ≦ (0.039Ln (C-2) +0.1500) × x + 2.87
More preferably,
(0.039Ln (C-2) +0.0096) × x + 2.87 <E _a × 10 ^-4 ≦ (0.039Ln (C-2) +0.1300) × x + 2.87
The relationship indicated by is satisfied.
(A′-iii) When a film having a thickness of 30 μm is produced by inflation molding of the composition (F), the haze of the film satisfies the following relationship.

When the fluidity index (FI) and melt flow rate (MFR) defined by the shear rate when the shear stress at 190 ° C. reaches 2.4 × 10 ⁶ dyne / cm ² are FI ≧ 100 × MFR
Haze <0.45 / (1-d) × log (3 × MT ^1.4 ) × (C-3) ^0.1
When the fluidity index (FI) defined by the shear rate when the shear stress at 190 ° C. reaches 2.4 × 10 ⁶ dyne / cm ² and the melt flow rate (MFR) are FI <100 × MFR
Haze <0.25 / (1-d) × log (3 × MT ^1.4 ) × (C-3) ^0.1
(Where d is density (g / cm ³ ), MT is melt tension (g), and C is the number of carbon atoms of hexene-1, that is, “6”).

The composition (F) comprising the ethylene / α-olefin copolymers (B) and (C) satisfying such requirements is excellent in moldability and transparency of the resulting film.
In addition to the above requirements, the composition (F) comprising the ethylene / α-olefin copolymers (B) and (C) preferably satisfies the following requirements.
(A'-iv) Molecular weight distribution measured by GPC (Mw / Mn, where Mw: weight average molecular weight, M
n: number average molecular weight) is 2.0 ≦ Mw / Mn ≦ 2.5.
Preferably 2.0 ≦ Mw / Mn ≦ 2.4
It is in the range.

Furthermore, in the composition (F), the structural unit derived from ethylene is in an amount of 50 to 100% by weight, preferably 55 to 99% by weight, more preferably 65 to 98% by weight, most preferably 70 to 96% by weight. The structural unit derived from an α-olefin having 6 to 8 carbon atoms, preferably hexene-1, is 0 to 50% by weight, preferably 1 to 45% by weight, more preferably 2 to 35% by weight, in particular. Preferably it is present in an amount of 4-30% by weight.

The density (d) of the composition (F) is 0.880 to 0.970 g / cm ³ , preferably 0.880 to 0.960 g / cm ³ , more preferably 0.890 to 0.935 g / cm ³ , Most preferably, it is in the range of 0.905 to 0.930 g / cm ³ .

  The melt flow rate (MFR) of the composition (F) is in the range of 0.05 to 200 g / 10 minutes, preferably 0.08 to 50 g / 10 minutes, more preferably 0.1 to 10 g / 10 minutes. Is desirable.

N-decane soluble component fraction [W (wt%)] and density [d (g) of composition (F) at 23 ° C.
/ Cm ³ )] and MFR ≦ 10 g / 10 min,
W <80 × exp (-100 (d-0.88)) + 0.1
Preferably W <60 × exp (-100 (d-0.88)) + 0.1
More preferably, W <40 × exp (-100 (d-0.88)) + 0.1
When MFR> 10g / 10min W <80 × (MFR-9) ^0.26 × exp (-100 (d-0.88)) + 0.1
It is desirable to satisfy the relationship indicated by.

The temperature [Tm (° C.)] and the density [d (g / cm ³ )] of the maximum peak position of the endothermic curve measured by the differential scanning calorimeter (DSC) of the composition (F)
Tm <400 × d-248
Preferably Tm <450 × d-296
More preferably, Tm <500 × d-343
Particularly preferably, Tm <550 × d-392
It is desirable to satisfy the relationship indicated by.

  The relationship between the temperature (Tm) and the density (d) at the maximum peak position of the endothermic curve measured by a differential scanning calorimeter (DSC), the n-decane soluble component amount fraction (W) and the density (d) It can be said that the composition (F) having a relationship as described above has a narrow composition distribution.

The composition (F) comprising the ethylene / α-olefin copolymer (B) and the ethylene / α-olefin copolymer (C) can be produced using a known method, for example, It can manufacture by the method of.

  (1) The ethylene / α-olefin copolymer (B), the ethylene / α-olefin copolymer (C), and other components added as required are mechanically used using a tumbler, an extruder, a kneader or the like. Blending or melt mixing.

(2) The ethylene / α-olefin copolymer (B), the ethylene / α-olefin copolymer (C), and other components added as required are mixed with a suitable good solvent (eg, hexane, heptane, decane, A hydrocarbon solvent such as cyclohexane, benzene, toluene and xylene), and then the solvent is removed.

  (3) Prepare solutions in which ethylene / α-olefin copolymer (B), ethylene / α-olefin copolymer (C), and other components added as required are separately dissolved in an appropriate good solvent. And then mixing and then removing the solvent.

(4) A method of combining the methods (1) to (3) above.
As described above, both the ethylene copolymer composition (A) and the ethylene copolymer composition (A ′) according to the present invention are excellent in moldability, excellent in transparency and mechanical strength. In addition to other polymers, preferably in combination with an ethylene / α-olefin copolymer, for example, an ethylene copolymer composition (A) and another ethylene / α-olefin copolymer (Ethylene copolymer composition (A '')), ethylene copolymer composition (A ') and other ethylene / α-olefin copolymers (ethylene copolymer) It can be used as a composition (A ′ ″)). As such other ethylene / α-olefin copolymer, an ethylene / α-olefin copolymer (D) described below is particularly preferably used.

The ethylene / α-olefin copolymer (D) used in the present invention is a random copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms. Examples of the α-olefin having 3 to 20 carbon atoms used for copolymerization with ethylene include propylene, 1-butene, 1-pentene, 1-
Examples include hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicocene.

In the ethylene / α-olefin copolymer (D), the structural unit derived from ethylene is 50 to 100% by weight, preferably 55 to 99% by weight, more preferably 65 to 98% by weight, and most preferably 70 to 96%. The constituent unit present in an amount of% by weight and derived from an α-olefin having 3 to 20 carbon atoms is 0 to 50% by weight, preferably 1 to 45% by weight, more preferably 2 to 35% by weight, most preferably It is desirable to be present in an amount of 4-30% by weight.

Such an ethylene / α-olefin copolymer (D) preferably has the following properties (D-i) and (D-ii). It is more preferable to have the characteristics as shown in D-iv).
(D-i) Density (d) is 0.850 to 0.980 g / cm ³ , preferably 0.910 to 0.960 g / cm ³ , more preferably 0.915 to 0.955 g / cm ³ , most Preferably 0.920
It is in the range of ˜0.950 g / cm ³ .
(D-ii) Intrinsic viscosity [η] measured in decalin at 135 ° C. is 0.4 to 8 dl / g, preferably 0.4 to 1.25 dl / g, more preferably 0.5 to 1.23 dl / g. It is in the range of g.
(D-iii) The temperature (Tm (° C.)) and density (d (g / cm ³ )) of the maximum peak position in the endothermic curve measured by a differential scanning calorimeter (DSC)
Tm <400 × d−250
Preferably Tm <450 × d-297
More preferably, Tm <500 × d-344
Particularly preferably, Tm <550 × d−391
It is desirable to satisfy the relationship indicated by.
(D-iv) When the n-decane soluble component fraction (W (% by weight)) and the density (d (g / cm ³ )) at room temperature are MFR ≦ 10 g / 10 minutes,
W <80 × exp (-100 (d-0.88)) + 0.1
Preferably W <60 × exp (-100 (d-0.88)) + 0.1
More preferably, W <40 × exp (-100 (d-0.88)) + 0.1
When MFR> 10g / 10min W <80 × (MFR-9) ^0.26 × exp (-100 (d-0.88)) + 0.1
The relationship indicated by is satisfied.

  Thus, the relationship between the temperature (Tm) and the density (d) at the maximum peak position in the endothermic curve measured by the differential scanning calorimeter (DSC), the n-decane soluble component fraction (W) and the density ( It can be said that the ethylene / α-olefin copolymer (D) having the above relationship with d) has a narrow composition distribution.

  However, the ethylene / α-olefin copolymer (A) and the ethylene / α-olefin copolymer (D) are not the same, and the ethylene / α-olefin copolymers (B) and (C) It is not the same as the α-olefin copolymer (D). Specifically, the ethylene / α-olefin copolymer (D) and the ethylene / α-olefin copolymers (A) to (C) can be distinguished in the following characteristics.

In other words, the ethylene / α-olefin copolymer (D) must satisfy the requirements for defining the copolymer (A) (A-
It is a copolymer that does not satisfy at least one of the requirements i) to (A-iii).
The ethylene / α-olefin copolymer (D) is a copolymer that does not satisfy at least one of the requirements (B-iii) to (B-vii) for defining the copolymer (B).

Further, the ethylene / α-olefin copolymer (D) is a copolymer that does not satisfy at least one of the requirements (C-iii) to (Cv) that define the copolymer (C).
Further, the ethylene / α-olefin copolymer (D) preferably has a lower intrinsic viscosity [η] measured in decalin at 135 ° C. and a lower density than the ethylene / α-olefin copolymer. This is one aspect. Further, the ethylene / α-olefin copolymer (D) has a lower intrinsic viscosity [η] measured in decalin at 135 ° C. than the ethylene / α-olefin copolymers (B) and (C), and One having a low density is also a preferred embodiment.

Such an ethylene / α-olefin copolymer (D) is, for example, an olefin polymerization catalyst containing (a) an organoaluminum oxy compound and (b-III) a transition metal compound represented by the following general formula (III) It is obtained by copolymerizing ethylene and an olefin having 3 to 20 carbon atoms in the presence of. (a) The organoaluminum oxy compound is the same as that described in the process for producing the ethylene / α-olefin copolymer (A). In the same manner as described above, the carrier (c) and the organoaluminum compound (d) may be used, and prepolymerization may be performed. The amount of each component used, prepolymerization conditions, and main polymerization conditions are the same as in the production of the ethylene / α-olefin copolymer (A).

Hereinafter, the transition metal compound (b-III) will be described.
(b-III) Transition metal compounds Transition of Group 4 of the periodic table containing ligands having (b-III) cyclopentadienyl skeleton used in the production of ethylene / α-olefin copolymer (D) Metal compound (hereinafter “component (b-III)”
May be described. ) Is not particularly limited as long as it is a Group 4 transition metal compound containing a ligand having a cyclopentadienyl skeleton, but is preferably a transition metal compound represented by the following general formula (III).

ML ³ _x (III)
In the formula, M is a transition metal atom selected from Group 4 of the periodic table, specifically zirconium, titanium or hafnium, preferably zirconium.

X is the valence of the transition metal.
L ³ is a ligand coordinated to the transition metal atom M, at least one L ³ is a ligand having a cyclopentadienyl skeleton, and as a ligand having a cyclopentadienyl skeleton, For example, cyclopentadienyl group, methylcyclopentadienyl group, dimethylcyclopentadienyl group, trimethylcyclopentadienyl group, tetramethylcyclopentadienyl group, pentamethylcyclopentadienyl group, ethylcyclopentadienyl group Alkyl substituted cyclohexane such as methylethylcyclopentadienyl group, propylcyclopentadienyl group, methylpropylcyclopentadienyl group, butylcyclopentadienyl group, methylbutylcyclopentadienyl group, hexylcyclopentadienyl group Pentadienyl group or indenyl group, 4,5,6,7-tetrahi Roindeniru group, and the like can be exemplified fluorenyl group. These groups may be substituted with a halogen atom, a trialkylsilyl group or the like.

Among these ligands having a cyclopentadienyl skeleton, an alkyl-substituted cyclopentadienyl group is particularly preferable.
The compound represented by the general formula (III) is a ligand having a cyclopentadienyl skeleton 2
When two or more are included, the ligands having two cyclopentadienyl skeletons are alkylene groups such as ethylene and propylene, substituted alkylene groups such as isopropylidene and diphenylmethylene, silylene groups or dimethylsilylene groups, It may be bonded via a substituted silylene group such as a diphenylsilylene group or a methylphenylsilylene group.

In the general formula (III), L ³ other than the ligand having a cyclopentadienyl skeleton is used.
Is the same hydrocarbon group having 1 to 12 carbon atoms, alkoxy group, aryloxy group, trialkylsilyl group, halogen atom, hydrogen atom, or SO ₃ as L ¹ in the general formula (I).
R group (wherein R is a hydrocarbon group having 1 to 8 carbon atoms which may have a substituent such as halogen). Examples of the ligand represented by SO ₃ R include a p-toluenesulfonate group, a methanesulfonate group, a trifluoromethanesulfonate group, and the like.

The transition metal compound represented by the general formula (III) is more specifically represented by the following general formula (III ′) when the valence of the transition metal is 4, for example.
R ² _k R ³ _l R ⁴ _m R ⁵ _n M (III ′)
(Wherein M is the transition metal atom, R ² is a group (ligand) having a cyclopentadienyl skeleton, and R ³ , R ⁴ and R ⁵ are groups having a cyclopentadienyl skeleton, An alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, a trialkylsilyl group, a SO ₃ R group, a halogen atom or a hydrogen atom, k is an integer of 1 or more, and k + 1 + m + n = 4 is there.)
In the present invention, a metallocene compound in which one of R ³ , R ⁴ and R ⁵ is a group (ligand) having a cyclopentadienyl skeleton, for example, R ² and R ³ are cyclopentadienyl. A metallocene compound which is a group having a skeleton (ligand) is preferably used. These groups having a cyclopentadienyl skeleton include alkylene groups such as ethylene and propylene, substituted alkylene groups such as isopropylidene and diphenylmethylene, silylene groups or substituted silylene groups such as dimethylsilylene, diphenylsilylene and methylphenylsilylene groups. May be connected via each other. In this case, other ligands (for example, R ⁴ and R ⁵ ) are groups having a cyclopentadienyl skeleton, alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, alkoxy groups, aryloxy groups, trialkylsilyl groups. , SO ₃ R, a halogen atom or a hydrogen atom.

Examples of the transition metal compound represented by the general formula (III) include bis (indenyl) zirconium dichloride, bis (indenyl) zirconium dibromide, bis (indenyl) zirconium bis (p-toluenesulfonate), bis (4 , 5,6,7-Tetrahydroindenyl) zirconium dichloride, bis (fluorenyl) zirconium dichloride, ethylenebis (indenyl) zirconium dichloride, ethylenebis (indenyl) zirconium dibromide, ethylenebis (indenyl) dimethylzirconium, ethylenebis (indenyl) ) Diphenylzirconium, ethylenebis (indenyl) methylzirconium monochloride, ethylenebis (indenyl) zirconium bis (methanesulfonate), ethylenebis (indenyl) zirconium bis ( p-toluenesulfonato), ethylenebis (indenyl) zirconium bis (trifluoromethanesulfonato), ethylenebis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, isopropylidene (cyclopentadienyl-fluorenyl) zirconium Dichloride, isopropylidene (cyclopentadienyl-methylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (cyclopentadienyl) zirconium dichloride, dimethylsilylenebis (methylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (dimethylcyclo) Pentadienyl) zirconium dichloride, dimethylsilylenebis (trimethylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (indenyl) di Konium dichloride, dimethylsilylene bis (indenyl) zirconium bis (trifluoromethanesulfonate), dimethylsilylene bis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl-fluorenyl) zirconium dichloride , Diphenylsilylenebis (indenyl) zirconium dichloride, methylphenylsilylenebis (indenyl) zirconium dichloride, bis (cyclopentadienyl) zirconium dichloride, bis (cyclopentadienyl) zirconium dibromide, bis (cyclopentadienyl) methylzirconium Monochloride, bis (cyclopentadienyl) ethylzirconium monochloride, bis (cyclopentadienyl) cyclohexylzirconium monochloride Lido, bis (cyclopentadienyl) phenylzirconium monochloride, bis (cyclopentadienyl) benzylzirconium monochloride, bis (cyclopentadienyl) zirconium monochloride monohydride, bis (cyclopentadienyl) methylzirconium monohydride Bis (cyclopentadienyl) dimethylzirconium, bis (cyclopentadienyl) diphenylzirconium, bis (cyclopentadienyl) dibenzylzirconium, bis (cyclopentadienyl) zirconium methoxychloride, bis (cyclopentadienyl) Zirconium ethoxy chloride, bis (cyclopentadienyl) zirconium bis (methanesulfonate), bis (cyclopentadienyl) zirconium bis (p-toluenesulfonate) Bis (cyclopentadienyl) zirconium bis (trifluoromethanesulfonate), bis (methylcyclopentadienyl) zirconium dichloride, bis (dimethylcyclopentadienyl) zirconium dichloride, bis (dimethylcyclopentadienyl) zirconium ethoxy chloride Bis (dimethylcyclopentadienyl) zirconium bis (trifluoromethanesulfonate), bis (ethylcyclopentadienyl) zirconium dichloride, bis (methylethylcyclopentadienyl) zirconium dichloride, bis (propylcyclopentadienyl) zirconium Dichloride, bis (methylpropylcyclopentadienyl) zirconium dichloride, bis (butylcyclopentadienyl) zirconium dichloride, bis (meth Rubutylcyclopentadienyl) zirconium dichloride, bis (methylbutylcyclopentadienyl) zirconium bis (methanesulfonate), bis (trimethylcyclopentadienyl) zirconium dichloride, bis (tetramethylcyclopentadienyl) zirconium dichloride, Examples include bis (pentamethylcyclopentadienyl) zirconium dichloride, bis (hexylcyclopentadienyl) zirconium dichloride, bis (trimethylsilylcyclopentadienyl) zirconium dichloride, and the like.

  In the above examples, the disubstituted product of the cyclopentadienyl ring includes 1,2- and 1,3-substituted products, and the trisubstituted product includes 1,2,3- and 1,2,4-substituted products. . Alkyl groups such as propyl and butyl include isomers such as n-, i-, sec- and tert-.

In addition, in the zirconium compound as described above, a compound in which zirconium is replaced with titanium or hafnium can be used.
The transition metal compound represented by the general formula (III) includes the transition metal compound (bI) represented by the general formula (I) and the transition metal compound (b-II) represented by the general formula (II). ) Is included.

In the presence of the olefin polymerization catalyst, the ethylene / α-olefin copolymer (D) comprises ethylene and an α-olefin having 3 to 20 carbon atoms, and the resulting copolymer has a density of 0.850. It can be produced by copolymerizing to 0.980 g / cm ³ .

The ethylene / α-olefin copolymer (D) is preferably 99 to 60% by weight with respect to 100 parts by weight of the above-mentioned ethylene copolymer composition (A) or ethylene copolymer composition (A ′). Parts, more preferably 95-60 parts by weight.

The composition of the ethylene / α-olefin copolymer (D) and the above-mentioned ethylene copolymer composition (A) or ethylene copolymer composition (A ′) is obtained by the known method already described. It can be manufactured using.

The molded body according to the present invention is formed from the ethylene copolymer composition (A), (A ′), (A ″) or (A ″ ′) as described above.
Molded products include single-layer films, multilayer films, injection-molded products, extrusion-molded products, fibers, foams, and sheaths for electric wires. More specifically, agricultural films (single-layer, multi-layer), water shielding Sheet, multilayer film, packaging film (multilayer film, stretch film, high-load packaging film), multilayer barrier film, laminated film sealant, heavy packaging film, grain bag, fluid packaging pouch, batch packaging package, bag Examples include in-box interior containers, medical containers, heat-resistant containers, fibers, foamed molded products, gaskets, extruded products, pipes, various injection molded products, and sheaths for electric wires.

The molded product formed from the ethylene-based copolymer composition (A), (A ′), (A ″) or (A ′ ″) will be described in more detail below.
Agricultural film (single layer):
The agricultural film is composed of the ethylene copolymer composition (A), (A '), (A'') or (A'''), and, if necessary, a conventionally known antioxidant, UV absorber. Additives, lubricants, slip agents, anti-blocking agents, drop agents, antistatic agents, colorants, carbon black, medium density polyethylene, ethylene / vinyl acetate copolymer, ethylene / α-olefin copolymer rubber, etc. Consists of.

The agricultural film according to the present invention has a thickness of 3 to 30 μm, preferably 7 to 20 μm.
The agricultural film is prepared from the ethylene-based copolymer composition (A), (A ′), (A ″) or (A ′ ″) by, for example, film formation by an inflation method or a T-die method. be able to. Film formation by the inflation method is performed by extruding the composition (A), (A ′), (A ″) or (A ′ ″) through a slit die and expanding it by a predetermined air flow.

  Such agricultural films have excellent adhesion to the soil, that is, flexibility, as well as various properties such as weather resistance, tensile properties, tearing properties, impact resistance, and rigidity, and are mainly required to increase the soil temperature. As a multi-film, it is effectively used for outdoor cultivation, tunnel cultivation, house semi-forcing cultivation, no-post cultivation for processing, Hayabori cultivation and the like.

Agricultural multilayer film:
The agricultural multilayer film according to the present invention is a three-layer laminated film composed of an outer layer, an intermediate layer, and an inner layer.
(Outer layer)
The outer layer constituting the agricultural multilayer film according to the present invention is composed of the ethylene copolymer composition (A), (A ′), (A ″) or (A ′ ″), an inorganic compound, and if necessary. And a composition containing a weather resistance stabilizer and an antifogging agent.

  The outer layer made of this composition (A), (A '), (A' ') or (A' '') has a very small decrease in light transmittance over time, so that the agricultural layer having such an outer layer is used. The multilayer film can be spread over a long period of time.

Furthermore, when the composition (A), (A ′), (A ″) or (A ′ ″) is used, the outer layer of the multilayer film can be thinned, and the weight of the multilayer film can be reduced. be able to.
(Inorganic compounds)
Inorganic compounds used for forming the outer layer of the multilayer film are inorganic oxides, inorganic hydroxides, hydrotalcites and the like containing at least one atom of Mg, Ca, Al, and Si that are effective as heat insulating agents.

Specifically, inorganic oxides such as SiO ₂ , Al ₂ O ₃ , MgO, CaO; inorganic hydroxides such as Al (OH) ₃ , Mg (OH) ₂ , Ca (OH) ₂ ;
Formula M ²⁺ _1-x Al _x (OH) ₂ (A ⁿ⁻ ) _{x / n} · mH ₂ O
[ ^Wherein M ²⁺ is a divalent metal ion of Mg, Ca or Zn,
A ^n- is ^{Cl -, Br -, I -} , NO 3 2-, ClO 4-, SO 4 2-, CO 2 2-, SiO 3 2-, HP
Anions such as O ₄ ²⁻ , HBO ₃ ²⁻ , PO ₄ ²⁻ ,
x is a numerical value satisfying the condition of 0 <x <0.5,
m is a numerical value satisfying the condition of 0 ≦ m ≦ 2]
And hydrotalcites such as a fired product thereof. Among these, hydrotalcites are preferable, and a fired product of an inorganic composite compound represented by the above formula is particularly preferable.

The above inorganic compounds can be used alone or in combination of two or more.
The average particle size of the inorganic compound is 10 μm or less, preferably 5 μm or less, more preferably 3 μm or less.

When the average particle size of the inorganic compound is within the above range, a multilayer film with good transparency can be obtained.
In the present invention, the inorganic compound is used in an amount of 1 to 20 parts by weight, preferably 1 to 18 parts per 100 parts by weight of the composition (A), (A ′), (A ″) or (A ′ ″). Part by weight, more preferably 2 to 15 parts by weight is used.

When an inorganic compound is used in the above ratio when forming the outer layer of the multilayer film, a multilayer film excellent in heat retention can be obtained.
(Weather resistance stabilizer)
Weather stabilizers used as needed when forming the outer layer of a multilayer film are broadly divided into ultraviolet absorbers and light stabilizers, but light stabilizers are more effective for agricultural films and are weather resistant. Great improvement in sex.

As the light stabilizer, conventionally known light stabilizers can be used, and among them, hindered amine light stabilizers (HALS; Hindered Amine Light Stabilizers) are preferably used.
As the hindered amine stabilizer, specifically, the following compounds are used.
(1) bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate,
(2) Dimethyl succinate-1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate,
(3) tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate,
(4) 2,2,6,6-tetramethyl-4-piperidinylbenzoate,
(5) bis- (1,2,6,6-tetramethyl-4-piperidinyl) -2- (3,5-di-t-butyl-4-hydroxybenzyl) -2-n-butylmalonate,
(6) Bis (N-methyl-2,2,6,6-tetramethyl-4-piperidinyl) sebacate,
(7) 1,1 ′-(1,2-ethanediyl) bis (3,3,5,5-tetramethylpiperazinone),
(8) (Mixed 2,2,6,6-tetramethyl-4-piperidyl / tridecyl) -1,2,3,4-butanetetracarboxylate,
(9) (Mixed 1,2,2,6,6-pentamethyl-4-piperidyl / tridecyl) -1,2,3,4-butanetetracarboxylate,
(10) Mixed {2,2,6,6-tetramethyl-4-piperidyl / β, β, β ', β'-tetramethyl-3-9- [2,4,8,10-tetraoxaspiro (5,5) undecane] diethyl} -1,2,3,4-butanetetracarboxylate,
(11) Mixed {1,2,2,6,6-pentamethyl-4-piperidyl / β, β, β ', β'-tetramethyl-3-9- [2,4,8,10-tetraoxa Spiro (5,5) undecane] diethyl} -1,2,3,4-tan tetracarboxylate,
(12) N, N′-bis (3-aminopropyl) ethylenediamine-2-4-bis [N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino] -6 -Chloro-1,3,5-triazine condensate,
(13) a condensate of N, N′-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 1,2-dibromoethane,
(14) [N- (2,2,6,6-tetramethyl-4-piperidyl) -2-methyl-2- (2,2,6,6-tetramethyl-4-piperidyl) imino] propionamide, etc. .

These hindered amine light stabilizers can be used alone or in combination of two or more.
Such a light stabilizer is 0.005 to 5 parts by weight, preferably 0.5 to 100 parts by weight of the composition (A), (A ′), (A ″) or (A ′ ″). 005 to 2 parts by weight, more preferably 0.01 to 1
Used in parts by weight.

Specifically, as an ultraviolet absorber,
Salicylic acid ultraviolet absorbers such as phenyl salicylate, p-tert-butylphenyl salicylate, p-octylphenyl salicylate;
2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2, Benzophenone ultraviolet absorbers such as 2'-dihydroxy-4,4'-dimethoxybenzophenone and 2-hydroxy-4-methoxy-5-sulfobenzophenone;
2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-5'-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'- Di-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5 Benzotriazole-based absorbents such as '-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3', 5'-di-tert-amylphenyl) benzotriazole;
Examples thereof include cyanoacrylate ultraviolet absorbers such as 2-ethylhexyl-2-cyano-3,3′-diphenyl acrylate and ethyl-2-cyano-3,3′-diphenyl acrylate.

The UV absorber is 0.0% with respect to 100 parts by weight of the composition (A), (A ′), (A ″) or (A ′ ″).
It is used in a ratio of 05 to 5 parts by weight, preferably 0.005 to 2 parts by weight, and more preferably 0.01 to 1 part by weight.
(Other ingredients)
In the above composition (A), (A ′), (A ″) or (A ′ ″), conventionally known additives such as an antifogging agent, an antistatic agent, and a heat stabilizer are added according to the present invention. It can mix | blend in the range which does not impair the objective.

As the antifogging agent, an antifogging agent mainly composed of a partially esterified product composed of a polyhydric alcohol and a higher fatty acid having 12 to 24 carbon atoms (including a hydroxy fatty acid) is preferably used. (Middle layer)
The intermediate layer constituting the agricultural multilayer film according to the present invention comprises an ethylene / vinyl acetate copolymer, an inorganic compound and, if necessary, an ethylene / α-olefin copolymer (A-1), a weather resistance stabilizer, an antifogging agent. It is formed from the composition containing an agent.
(Ethylene / vinyl acetate copolymer)
The ethylene / vinyl acetate copolymer used in the present invention has a vinyl acetate content of 2.0-3.
It is in the range of 0% by weight, preferably 3.0-25% by weight, more preferably 5.0-20% by weight.

When an intermediate layer is formed from this ethylene / vinyl acetate copolymer, a multilayer film having excellent heat retention can be obtained. Here, “heat retention” means the temperature inside the house, tunnel, etc. (air temperature and ground temperature) by absorbing and reflecting radiation emitted at night from the ground that has absorbed solar heat during the day and increased in temperature. The ability to hold
(Inorganic compounds)
The inorganic compound used for forming the intermediate layer of the multilayer film is the same as the inorganic compound used for forming the outer layer described above.

  In the present invention, the inorganic compound is used in an amount of 1 to 20 parts by weight, preferably 100 parts by weight of the total amount of the ethylene / vinyl acetate copolymer and the ethylene / α-olefin copolymer (A-1) described later, 1 to 18 parts by weight, more preferably 2 to 15 parts by weight. However, since the component (A-1) is an optional component, it may be 0 part by weight.

When an inorganic compound is used in the above ratio when forming the intermediate layer of the multilayer film, a multilayer film having better heat retention can be obtained.
(Ethylene / α-olefin copolymer (A-1))
The ethylene / α-olefin copolymer (A-1) used as necessary in forming the intermediate layer of the multilayer film has a density of 0.925 g / of the ethylene / α-olefin copolymer (A) described above. It is an ethylene / α-olefin copolymer of cm ³ or less, preferably 0.880 to 0.920 g / cm ³ .

In the present invention, the weight ratio [(A-1) / (C)] of the ethylene / α-olefin copolymer (A-1) to the ethylene / vinyl acetate copolymer (C) is 99/1 to 1/99, preferably 9
It is in the range of 0/10 to 10/90, more preferably 80/20 to 20/80.

When the intermediate layer of the multilayer film is formed, the intermediate layer can be thinned by using the ethylene / α-olefin copolymer (A-1) in the above weight ratio with respect to the ethylene / vinyl acetate copolymer. .
(Weather resistance stabilizer)
The weathering stabilizer used as necessary when forming the intermediate layer of the multilayer film is the ultraviolet absorber and the light stabilizer used when forming the outer layer described above.

  The light stabilizer is 0.005 to 5 parts by weight, preferably 0.005 to 100 parts by weight of the total amount of the ethylene / α-olefin copolymer (A-1) and the ethylene / vinyl acetate copolymer. 2 parts by weight, more preferably 0.01 to 1 part by weight is used. However, since the component (A-1) is an optional component, it may be 0 part by weight.

The ultraviolet absorber is 0.005 to 5 parts by weight, preferably 0.005 to 100 parts by weight of the total amount of the ethylene / α-olefin copolymer (A-1) and the ethylene / vinyl acetate copolymer. It is used in an amount of 2 parts by weight, more preferably 0.01 to 1 part by weight. However, since component (A-1) is an optional component, it may be 0 parts by weight.
(Other ingredients)
Addition of conventionally known additives such as an antifogging agent, an antifogging agent, an antistatic agent and a heat stabilizer to the ethylene / vinyl acetate copolymer for forming the intermediate layer within a range not impairing the object of the present invention. Can do.

  As the antifogging agent, an antifogging agent mainly composed of a partially esterified product composed of the above-described polyhydric alcohol and a higher fatty acid having 12 to 24 carbon atoms (including a hydroxy fatty acid) is preferably used.

The antifogging agent is 0.05 to 5 parts by weight, preferably 0.1 to 100 parts by weight of the total amount of the ethylene / α-olefin copolymer (A-1) and the ethylene / vinyl acetate copolymer. -4 parts by weight, more preferably 0.5-3 parts by weight. However, since component (A-1) is an optional component, it may be 0 parts by weight.
(Inner layer)
The inner layer constituting the agricultural multilayer film according to the present invention is formed from the composition (A), (A ′), (A ″) or (A ′ ″). The composition (A), (A ′), (A ″) or (A ′ ″) can be blended with an inorganic compound, a weather resistance stabilizer and an antifogging agent.

In the present invention, the inorganic compound is in a ratio of 1 to 3 parts by weight with respect to 100 parts by weight of the total amount of the composition (A), (A ′), (A ″) or (A ′ ″). Used.
When the inorganic compound (B) is used in the above ratio when forming the inner layer of the multilayer film, a multilayer film excellent in heat retention can be obtained.
(Weather resistance stabilizer)
The weathering stabilizer used as necessary when forming the inner layer of the multilayer film is the above-described ultraviolet absorber and light stabilizer.

The light stabilizer is 0.005 with respect to 100 parts by weight of the composition (A), (A ′), (A ″) or (A ′ ″).
It is used in an amount of ˜5 parts by weight, preferably 0.005 to 2 parts by weight, more preferably 0.01 to 1 part by weight.

The UV absorber is 0.0% with respect to 100 parts by weight of the composition (A), (A ′), (A ″) or (A ′ ″).
It is used in an amount of 05 to 5 parts by weight, preferably 0.005 to 2 parts by weight, more preferably 0.01 to 1 part by weight.
(Other ingredients)
Addition of conventionally known antifogging agents, antistatic agents, heat stabilizers, etc. to the composition (A), (A '), (A'') or (A''') used for forming the inner layer of the multilayer film An agent can be mix | blended in the range which does not impair the objective of this invention.

  As the antifogging agent, an antifogging agent mainly composed of a partially esterified product composed of the above-described polyhydric alcohol and a higher fatty acid having 12 to 24 carbon atoms (including a hydroxy fatty acid) is preferably used.

The antifogging agent is used in an amount of 0.05 with respect to 100 parts by weight of the composition (A), (A ′), (A ″) or (A ′ ″).
-5 parts by weight, preferably 0.1-3 parts by weight, more preferably 0.5-2 parts by weight.
(Multilayer film)
The agricultural multilayer film according to the present invention comprising the outer layer, the intermediate layer and the inner layer as described above has a thickness of the outer layer of usually 3 to 100 μm, preferably 10 to 80 μm, more preferably 20 to 70 μm. The layer thickness is 10 to 150 μm, preferably 20 to 120 μm, more preferably 30 to 100 μm, and the inner layer thickness is 3 to 100 μm, preferably 10 to 80 μm, more preferably 20 to 70 μm, And the thickness of these whole layers is 30-200 micrometers, Preferably it is 50-180 micrometers, More preferably, it exists in the range of 70-150 micrometers.

The multilayer film for agriculture according to the present invention has the following physical properties and characteristics.
(I) Elmendorf tear strength is 90 kg / cm or more in the MD direction, preferably 100 kg / cm or more, and 90 kg / cm or more, preferably 100 kg / cm or more in the TD direction.
(Ii) The dart impact strength at a thickness of 100 μm is 900 g or more, preferably 1,000 g or more.
(Iii) The tensile strength at break is 350 kg / cm ² or more in the MD direction, preferably 370 kg / cm ² or more, and 350 kg / cm ² or more in the TD direction, preferably 370 kg / cm ^2.
That's it.
(Iv) The initial light transmittance at a thickness of 100 μm is 90% or more, preferably 92% or more, and the light transmittance after 120 days of outdoor exposure is 85% or more, preferably 87% or more.

  The Elmendle tear strength is determined by conducting a tear strength test in the MD direction and the TD direction of the multilayer film in accordance with JIS Z 1702. The dirt impact strength is obtained by conducting an impact test in accordance with JIS Z 1707 (dirt tip diameter: 38 mm). The tensile strength at break is in accordance with JIS K 6781, and a tensile test is performed with a constant crosshead moving speed type tensile tester (Instron) in the MD direction and TD direction of the multilayer film under the following conditions. This is the value obtained.

The 50 μm thick agricultural multilayer film according to the present invention has a gloss of usually 60% or more and a haze of usually 15% or less.
The gloss of the film was measured at an incident angle of 60 ° C. according to ASTM D523. Moreover, the haze of the film was measured according to ASTM D 1003-61.
(Preparation of multilayer film)
The agricultural multilayer film according to the present invention as described above is prepared by mixing the polyethylene resin used in each layer of the multilayer film and the components such as the above-mentioned additives, and melt-mixing them with a Banbury mixer or a roll mill. It can be prepared by laminating an outer layer, an intermediate layer and an inner layer by an extrusion inflation method or a coextrusion T-die method.

Such a multilayer film for agriculture is excellent in heat retention, dust resistance and toughness, and can be spread over agricultural and horticultural facilities such as houses and tunnels and used for cultivation of useful crops for a long time.
Impermeable sheet:
The water shielding sheet is composed of the ethylene copolymer composition (A), (A ′), (A ″) or (A ′ ″), and optionally carbon black, a heat stabilizer, a weather stabilizer. , Pigments, fillers (excluding carbon black), lubricants, antistatic agents, flame retardants, foaming agents, and other known additives. The water-impervious sheet is combined with other base material, reinforcing material, drainage material, etc., and the layer made of the composition (A), (A '), (A'') or (A''') is an inner layer or an outer layer. It may be a multilayer body.

The water-impervious sheet has an elongation at tearing (JIS A 6008, crepe method, speed 200 mm / min) at a thickness of 1.5 mm of 80% or more, and an elongation at the time of piercing at a thickness of 1.5 mm is 5 mm or more. The peel strength (JIS K 6328, speed 50 mm / min) at the fused part when heat-sealed at a set temperature of 500 ° C. and a seal speed of 5 m / min using a field-use heat sealer is 10 kg / 20 mm or more It is preferable that

  Since the water-impervious sheet may hit an object with unevenness, particularly a pointed object, the elongation at tearing and the elongation at the time of piercing are important factors for maintaining the performance of the water-impervious sheet.

In addition, a hot air sheet welding machine 10E type manufactured by Leister is used as a heat sealer for use on site. In the peel test, two sheets were fused at a set temperature of 500 ° C. and a speed of 5 m / min using a hot air sheet welding machine 10E manufactured by Leister, and the condition was adjusted at 23 ° C. for 48 hours or more. In accordance with JIS K 6328, a peel strength test was performed at a speed of 50 mm / min, the peel strength was measured, and used as an index of the fusion property. For the piercing test, an Instron universal testing machine is used, the water shielding sheet is fixed to a jig with a diameter of 5 cm, and a needle having a flat tip with a diameter of 0.7 mm is pierced at a speed of 50 mm / min. The strength was measured, and the breaking strength / sheet thickness (kg / mm) and elongation at break were determined.

The water shielding sheet according to the present invention can be heat-sealed easily and with high strength by a heat sealer that is actually used in the field, which is extremely preferable in practice.
Such a water-impervious sheet is excellent in mechanical strength such as tensile strength, tear strength, elongation at tearing, piercing strength, and elongation at piercing, flexibility and fusion property.

Multilayer film:
The multilayer film is formed of a base film layer and a layer composed of the ethylene copolymer composition (A), (A ′), (A ″) or (A ′ ″).

The material for forming the base film is not particularly limited as long as it has film forming ability, and any polymer, paper, aluminum foil, cellophane, or the like can be used. Examples of such polymers include high density polyethylene, medium and low density polyethylene, ethylene / vinyl acetate copolymer, ethylene / acrylic acid ester copolymer, ionomer, polypropylene, poly-1-butene, and poly-4. Olefin polymers such as 2-methyl-1-pentene,
Vinyl polymers such as polyvinyl chloride, polyvinylidene chloride, polystyrene, polyacrylate, and polyacrylonitrile, and polyamides such as nylon 6, nylon 66, nylon 10, nylon 11, nylon 12, nylon 610, and polymetaxylylene adipamide Examples thereof include polyesters such as polymers, polyethylene terephthalate, polyethylene terephthalate / isophthalate, polybutylene terephthalate, polyvinyl alcohols, ethylene / vinyl alcohol copolymers, and polycarbonate polymers.

Moreover, when a base film consists of a polymer, this polymer film may be non-oriented and may be extended | stretched uniaxially or biaxially.
These substrates can be appropriately selected depending on the use of the multilayer film. For example, in the case of a composite film for packaging, the substrate can be appropriately selected depending on the article to be packaged. For example, if the package is a food that is easily corroded, a resin having excellent transparency, rigidity, gas permeation resistance, such as polyamide, polyvinylidene chloride, ethylene / vinyl alcohol copolymer, polyvinyl alcohol, polyester, etc. Can be used. When the package is a confectionery or fiber wrapping, it is preferable to use polypropylene having good transparency, rigidity and water permeation resistance.

  When the ethylene-based copolymer composition (A), (A ′), (A ″) or (A ′ ″) is extrusion coated on the substrate as described above, the composition is directly applied to the substrate. Article (A), (A '), (A' ') or (A' '') may be extrusion coated, and the substrate and composition (A), (A '), (A' ') Alternatively, in order to increase the adhesive force with (A '' '), a known method, for example, an organic titanium-based, polyethyleneimine-based, isocyanate-based anchor coating agent, or an adhesive polyolefin, The composition (A), (A ′), (A ″) or (A ″ ′) may be extrusion-coated after providing the undercoat resin layer of any high-pressure polyethylene.

  Also, extrude to ensure adhesion between the substrate and the resin in contact with the substrate (base resin or composition (A), (A '), (A' ') or (A' '')) It is also possible to forcibly oxidize the surface of the film by spraying ozone onto the molten resin film.

  Such multi-layer films include various packaging bags such as liquid soups, pickles, konjac, water paste packaging bags, miso, jammed paste paste packaging bags, sugar, flour, sprinkled powder packaging bags, pharmaceutical tablets, etc. It is suitable for use in granule packaging bags, and plays a role as a sealant layer in such applications.

Multilayer film for packaging:
The packaging multilayer film is composed of a film having at least a three-layer structure of an outer layer, one or more intermediate layers, and an inner layer. The resin composition used for the outer layer and the inner layer is different from the resin composition constituting the intermediate layer.

  The outer layer and the inner layer are formed from the ethylene copolymer composition (A), (A ′), (A ″) or (A ′ ″). The compositions (A), (A ′), (A ″) or (A ′ ″) forming the outer layer and the inner layer may be the same or different from each other.

  The intermediate layer is arbitrarily selected from the resin composition used as a material for the base film, but it is a 1-butene-based (co) polymer and, if necessary, ethylene / propylene 1-butene random copolymer What is formed from the resin or resin composition which consists of coalescence is preferable.

The 1-butene-based (co) polymer is a 1-butene homopolymer or a 1-butene / propylene copolymer having a 1-butene content of 75 to 85 mol% and a propylene content of 15 to 25 mol%.
This 1-butene-based (co) polymer has an MFR of 0.1 to 5 g / 10 min, preferably 0.5 to 2 g / 10 min, and a density of 0.890 to 0.925 g / cm ³ , preferably Is in the range of 0.895 to 0.920 g / cm ³ . This 1-butene-based (co) polymer can be produced using a normal Ziegler-Natta catalyst.

  In the present invention, the 1-butene-based (co) polymer is 40 to 100% by weight based on 100% by weight of the total amount of the 1-butene-based (co) polymer and the ethylene / propylene 1-butene random copolymer. , Preferably 50 to 90% by weight, more preferably 55 to 95% by weight.

The ethylene / propylene 1-butene random copolymer desirably has a propylene content in the range of 50 to 98 mol%, preferably 70 to 97 mol%.
The ethylene / propylene 1-butene random copolymer has an MFR of 0.1 to 100 g / 10 min, preferably 1 to 30 g / 10 min, and a density of 0.890 to 0.910 g / cm ³ .

This ethylene / propylene 1-butene random copolymer can be produced using a normal Ziegler-Natta catalyst.
In the present invention, the ethylene / propylene 1-butene random copolymer is used in an amount of 0 to 60% with respect to 100% by weight of the total amount of the 1-butene-based (co) polymer and the ethylene / propylene 1-butene random copolymer. %, Preferably 10 to 50% by weight, more preferably 5 to 45% by weight.

  When the ratio of the 1-butene-based (co) polymer and the ethylene / propylene 1-butene random copolymer falls within the range of the above blending ratio, a multilayer film excellent in cutability by an automatic packaging machine can be obtained.

  In the present invention, in the same manner as the resin or resin composition constituting the outer layer and the inner layer, the 1-butene-based (co) polymer and ethylene propylene 1-butene are contained in the resin or resin composition constituting the intermediate layer. In addition to the random copolymer, various stabilizers, compounding agents, fillers, and the like can be added as long as the object of the present invention is not impaired. In particular, anti-fogging agents, antistatic agents, etc. can be added to improve the appearance of the contents, and UV inhibitors, etc. can be added to protect the contents, and antioxidants and lubricants are added. You can also

The intermediate layer may be composed of one or more layers in which a 1-butene-based (co) polymer and an ethylene / propylene 1-butene random copolymer are blended in an amount within the above range.
The multilayer film for packaging according to the present invention is usually formed to a thickness of 10 to 20 μm, and the intermediate layer is adjusted to a thickness of 1 to 5 μm, and the outer layer and the inner layer are adjusted to a thickness of 2 to 8 μm. Depending on the application, it is possible to form another resin layer further outside the inner layer and / or the outer layer.

  The multilayer film for packaging is prepared by mixing the components forming each layer using various blenders, and then using a normal molding method, that is, an inflation film molding machine equipped with a plurality of die lips in an extruder, or T-die molding. Manufactured by supplying to a machine.

The packaging multilayer film preferably has a ratio of the Elmendorf tear strength in the longitudinal direction and the transverse direction (lateral direction / longitudinal direction) of 9.1 or less, and in this case, it can be used as an excellent packaging film. In particular, when the film is applied to an automatic packaging machine, it is cut by a knife that runs in the lateral direction of the film. Therefore, whether the cutting property is good or bad can be evaluated by the ratio of the Elmendorf tear strength in the longitudinal direction and the transverse direction. This Elmendorf tear strength ratio is 9.
If it is 1 or less, it is judged that the cutting ability by the automatic packaging machine is good.

The multilayer film for packaging according to the present invention has an Elmendorf tear strength ratio of 9.1 or less, can be easily cut by an automatic packaging machine, and can be continuously packaged at high speed. In addition, Elmendorf tear strength is measured by the method based on JISZ-1702.

Moreover, the multilayer film for packaging according to the present invention is excellent in transparency and has a haze value of usually 2.0% or less.
Furthermore, the multilayer film for packaging according to the present invention is excellent in finger pressing restoration property, has an initial restoration rate of 70% or more, and a residual strain of 5.5 mm or less.

Furthermore, the multilayer film for packaging according to the present invention is excellent in low-temperature sealing property, and the sealing strength of the film heat-sealed at 90 ° C. is 100 kg / cm ² or more.
Such a multilayer film for packaging is excellent in mechanical strength characteristics, transparency and low-temperature heat-sealing properties, and after packaging, for example, even if it is pushed to the contents side with a finger, the restorability of the film afterwards is good. Suitable for packaging of goods and daily necessities.

Stretch packaging film:
The stretch packaging film has the ethylene-based copolymer composition (A), (A ′), (A ″) or (A ′ ″) and, if necessary, other resin components such as a density. 0.880 to 0.895 g / cm ³ of ethylene / propylene random copolymer, density of 0.880 to 0.895 g / cm ³ of ethylene / butene random copolymer, density of 0.910 to 0.924 g / It is formed from a high pressure process ethylene / vinyl acetate random copolymer of cm ³ .

Such other resin component is used in an amount of 0 to 40 parts by weight with respect to 100 parts by weight of the composition (A), (A ′), (A ″) or (A ′ ″). .
In the present invention, the composition (A), (A ′), (A ″) or (A ′ ″), or the composition (A), (A ′), (A ″) or (A ''') And other resin components include various additives such as slip agents, anti-blocking agents, anti-fogging agents, anti-static agents, and anti-ultraviolet agents to protect the contents. Can be blended as long as the object of the present invention is not impaired.

As the slip agent, for example, higher fatty acid amides such as oleic acid amide, stearic acid amide and erucic acid amide are preferably used.
As the anti-blocking agent, inorganic substances such as silica and talc are preferably used.

As the antistatic agent, for example, glycerin fatty acid esters and sorbitol fatty acid esters are preferably used.
The film comprising the composition (A), (A ′), (A ″) or (A ′ ″) has the necessary moderate tackiness (stickiness), but is more tacky. If necessary, liquid polybutadiene, polyisobutylene or the like may be blended with the linear low density polyethylene in an amount of about 2 to 10% by weight.

The film for stretch packaging according to the present invention contains a film made of the composition (A), (A ′), (A ″) or (A ′ ″) as described above.
The film for stretch packaging according to the present invention has a thickness of usually 10 to 50 μm. The film for stretch packaging may have a single layer structure or a multilayer structure.

The film for stretch packaging having a single layer structure can be produced by a usual film forming method such as an inflation method or a T-die method.
The stretch packaging film having a multilayer structure can be produced by a conventionally known molding method, for example, an inflation film molding machine provided with a plurality of die lips in an extruder, or a molding apparatus such as a T-die molding machine.

The film for stretch packaging has a tensile stress at break in the longitudinal direction (JIS Z1702) of 400 kg / cm ² or more and an elongation at break in the longitudinal direction (JIS Z1702) of 500.
%, Impact strength (ASTM D3420) is 2500 kg · cm / cm or more, longitudinal tear strength (JIS Z1720) is 50 kg / cm or more, and adhesive strength (2
0 kg, 50 ° C. × 1 day) is 3 to 25 g / cm, the force after 300% stretching and 1 hour has passed is preferably 150 to 300 g / 15 mm, and the maximum stretching limit is preferably 300% or more. .

  The stretch packaging film according to the present invention has a higher elongation at break than conventional low density polyethylene or ethylene / vinyl acetate copolymer films and can be stretched by 300 to 600%. Suitable for stretch packaging of objects (two or more objects having different shapes).

In addition, the stretch packaging film according to the present invention has less stress applied after packaging than a conventional low density polyethylene or ethylene / vinyl acetate copolymer film, and does not deform the package. The film strength is high and the film appearance is good.

  The film for stretch packaging according to the present invention may be a film composed of one composition (A), (A ′), (A ″) or (A ′ ″), or this composition. A film having a multilayer structure having one or two or more film layers in addition to the film layer comprising the product (A), (A ′), (A ″) or (A ′ ″) may be used.

  A multi-layer stretch packaging film, for example, a multi-layer film having a non-adhesive surface and an adhesive surface shared on a stretch packaging film is a composition (A), (A '), (A' ') or (A' ' The film layer of ') is used as an intermediate layer, and on one surface of the intermediate layer, a film layer made of high-density linear low-density polyethylene as a non-adhesive layer is 5 to 30% based on the total thickness of the stretch packaging film. In addition to the composition (A), (A '), (A' ') or (A' '') as an adhesive layer on the other surface, liquid polyisobutylene, liquid polybutadiene The film layer which consists of a composition which mix | blended 2-10 weight% etc. can be obtained by methods, such as forming so that it may become a thickness of about 5-30% with respect to the total thickness of the film for stretch packaging.

  Such a stretch packaging film is capable of high stretching and has an appropriate tackiness. After the packaging, an excessive stress is not applied to the packaged article, it has excellent strength characteristics and appearance after packaging, and is excessively applied to the film. It is excellent in productivity, packaging, and handling properties.

Packaging film:
A packaging film is an improved packaging or wrapping film, and more particularly a shrink, envelope, which exhibits improved transparency, toughness, extrusion processability and irradiation crosslinking efficiency. (Skin), stretch, hot tack
And vacuum wrap film. These films comprise at least one layer of at least one ethylene-based copolymer composition (A), (A ′), (A ″) or (A ′ ″), and 2 It may be axially oriented, multi-layered and / or configured to have barrier properties.

The ethylene-based copolymer composition (A), (A '), (A'') or (A''') has a degree of not interfering with the improved film properties found by the applicants, Additives such as antioxidants (eg hindered phenols (eg Irganox ™ 1010 manufactured by Chiba Geigy Corp.), phosphites (eg Irgafos ™ 168)), cling (cling ) Additives (eg polyisobutylene (PIB) etc.), PEPQ ™ (Sandoz Chemical trademark, the main material of which is considered to be biphenylphosphonite), pigments, colorants, fillers etc. it can. The manufactured film can also include additives that improve its antiblocking and coefficient of friction characteristics, including but not limited to untreated and treated silicon dioxide. , Talc, calcium carbonate and clay, and primary and secondary fatty acid amides, silicone coatings and the like. It is also possible to add other additives which improve the anti-fogging properties exhibited by this film, as described, for example, in US Pat. No. 4,486,552 (Niemann). In addition, it is possible to improve the antistatic property of the film, which enables packaging of sensitive items such as quaternary ammonium compounds alone or with EAA or other functional polymers. It is also possible to add in combination.

The ethylene copolymer composition (A), (A ′), (A ″) or (A ′ ″) used in the production of the olefin film for packaging and wrapping of the present invention has a structure to be used. Whether it is a single layer or a multilayer structure, it can be used as the only polymer component of this film. By blending other polymers together with this ethylene copolymer composition (A), (A '), (A'') or (A'''), film processability, film strength, Heat sealability or adhesion can be improved. For packaging and wrapping produced by appropriately blending this ethylene copolymer composition (A), (A '), (A'') or (A''') with other polymer components The film maintains improved performance and, in certain cases, provides an improved combination of properties. Several materials suitable for blending together with the ethylene copolymer composition (A), (A '), (A'') or (A''') are not limited to these. For example high pressure low density polyethylene (LDPE), ethylene / vinyl acetate copolymer (EVA), ethylene / carboxylic acid copolymers and their ionomers, polybutylene (PB) and α-olefin polymers such as high density polyethylene, medium density These include polyethylene, polypropylene, ethylene / propylene interpolymers, linear low density polyethylene (LLDPE) and very low density polyethylene, and graft modified polymers and blends thereof, such as density, Variations in MWD and / or comonomer combinations, such as Smith US Pat. No. 5,032,463 (Incorporated herein by reference) and the like are also included. However, the ethylene copolymer composition (A), (A ′), (A ″) or (A ′ ″) is preferably at least 50% of the blend composition, more preferably It constitutes at least 80% of this blend composition. However, in the case of a multi-layer film structure, it is highly preferred that the outer film layer (also referred to in the art as “skin layer” or “surface layer”) and sealant layer are the ethylene-based copolymer It consists essentially of the composition (A), (A ′), (A ″) or (A ′ ″).

  The oriented and unoriented film structures of the present invention can be manufactured using conventional simple hot blown bubble, cast extrusion or extrusion coating techniques, and more particularly in the case of oriented films such as " It can be manufactured using "tenter framing" or "double bubble" or "trapped bubble" methods.

Although the technique and the present specification use “stretched” and “oriented” in an interchangeable manner, the orientation is actually a tenter frame that pushes the edge of the film, for example, internal air pressure against the tube This is a result of the film being stretched.

A simple hot blown bubble film method is, for example, “The encyclopedia of Chemical
Technology ", Kirk-Othmer), 3rd edition, John Wiley & Sons, New York) 1981, 16, 416-417 and 18, 191-192. Suitable for producing biaxially oriented films, such as the “double bubble” method described in US Pat. No. 3,456,044 (Pahlke), as well as producing biaxially stretched or oriented films Other suitable methods are US Pat. No. 4,865,902 (Golike et al.), US Pat. No. 4,352,849 (Mueller), US Pat. No. 4,820,557 (Warren), US Pat. No. 4,927,708 (Herran et al.), US Pat. No. 4,963,419. No. (Lustig et al.) And US Pat. No. 4,952,451 (Mueller).

As described by Pahlke in U.S. Pat. No. 3,456,044, and as a comparison of simple bubble methods, performing “double bubble” or “trapped bubble” film processing results in film orientation in both the machine and lateral directions. The orientation can increase significantly. This increase in orientation results in a higher free shrinkage value when the film is subsequently heated. Also, Pahlke in U.S. Pat.No. 3,456,044 and Lustig et al. In U.S. Pat.No. 5,059,481 produce low density polyethylene and ultra-low density polyethylene materials in a simple bubble process, which are machine direction and cross direction, respectively. Show inferior shrinkage characteristics, for example, the free shrinkage is about 3 percent worse in both directions. However, in contrast to known film materials, in particular, in contrast to the film materials disclosed by Lustig et al. In U.S. Patent No. 5,059,481, U.S. Patent No. 4,976,898 and U.S. Patent No. 4,863,796, and in the United States In contrast to the film material disclosed by Smith in Patent No. 5,032,463, the ethylene-based copolymer composition (A), (A ′), (A ″) or (A ″) of the present invention. ') Shows a significantly improved shrinkage in both the machine and transverse directions in a simple bubble method. In addition, a simple bubble method is used with a high blow-up ratio, eg, a blow-up ratio equal to or greater than 2.5: 1, or more preferably disclosed by Pahlke in US Pat. No. 3,456,044. And the ethylene copolymer composition (A), (A '), (A'') or (using the `` double bubble''method disclosed by Lustig et al. In U.S. Pat.No. 4,976,898. When A ′ ″) is produced, good shrinkage can be achieved in the machine direction and in the transverse direction, from which the resulting film is suitable for shrink wrap packaging purposes.

Using the equation: BUR = bubble diameter ÷ die diameter, calculate the Blow-Up Ratio, abbreviated as “BUR” herein.
The olefin film for packaging and wrapping of the present invention may be a single layer or a multilayer film. In an embodiment where the film structure is a single layer, the single layer comprises at least one ethylene-based copolymer composition (A), (A ′), (A ″) or (A ′ ″). It may contain at least 10% by weight, preferably at least 30% by weight, and at least one ethylene-based copolymer composition (A), (A ′), (A ″) or (A ′ ″). ) May be included up to 100% by weight.

The ethylene copolymer composition (A), (A '), (A'') or (A''') used for the purpose of constituting this monolayer depends on the properties desired for this film. In an embodiment in which two or more ethylene copolymer compositions (A), (A ′), (A ″) or (A ′ ″) are used in the film configuration, both processing and use conditions are These polymers are selected based in part on their compatibility with each other. Similarly, in this monolayer configuration, one or more ethylene copolymer compositions (A), (A ′), (A ″) or (A ′ ″) and one or more ordinary copolymer compositions Ethylene polymers such as conventional homogeneously branched linear ethylene / α prepared as described in US Pat. No. 3,645,992, for example.
Olefin copolymers, or blends with conventional heterogeneously branched ethylene / α-olefin copolymers made by the Ziegler method as described in US Pat. No. 4,076,698). Make these choices based in part on the compatibility exhibited by this class for this ethylene copolymer composition (A), (A '), (A'') or (A''') .

Depending on the various properties that these single layers exhibit, any of these single layers can be used in any of its diverse five packaging methods, but as a matter of practice, as a single layer film, Best suited for use in stretch overlap and envelope packaging methods. As required for stretch wrapping, the ethylene copolymer composition (A), (A ') of the present invention.
, (A ″) or (A ′ ″) monolayer films exhibit surprisingly good oxygen permeability.

The permeation of oxygen occurs when individual sections of red meat are stretched and wrapped (ie, the food company / butcher actually cuts the first meat for individual sales purposes to produce smaller sections, “Instore ( In-store) “for packaged meats” is particularly beneficial, and the permeation of oxygen makes it possible to “add” the desired red glow to fresh red meat. Films that are effective in packaging individual red meat slices will typically exhibit minimal shrinkage and good stretchability. The film is preferably oxygen permeable and allows the consumer to inspect the meat without permanently deforming the film and making the meat unattractive. Good elastic recovery. Pak-Wing Steve Chum and Nicole F. Whiteman submitted the title “Method of Packaging Fo” dated 28 April 1993.
A co-pending US application entitled “od Products” discloses a method of packaging foods containing such individual red meat portions. However, even if shrinkage is not used in the current technology, a film used when packaging individual red meat portions can be manufactured as a heat-shrinkable film.

  One particularly desirable monolayer suitable for use in the stretch overlap method is an ethylene-based copolymer composition (A), (A ′), (A ″) or (A ′ ″) and ethylene / α , Β-unsaturated carbonyl copolymers such as EVA, EAA) ethylene / methacrylic acid / (EMAA), and their alkali metal salts (ionomers), esters and other derivatives.

For co-extruded or laminated multilayer film structures (eg, 3 and 5 layer film structures), the ethylene copolymer compositions (A), (A ′), (A ″) described herein. Alternatively, (A ′ ″) can be used as the core layer, outer surface layer, intermediate layer and / or inner sealant layer of the structure. In particular, in the hot tack film of the present invention, at least one of the ethylene-based copolymer compositions (A), (A ′), (A ″) or (A ′ ″) described herein is used. The film structure is used as at least one heat-sealable outer layer. This heat-sealable outer layer may coextrude with other layer (s), or the heat-sealable outer layer may be laminated to another layer (s) in a second operation, for example As described in “Packaging Foods With Plastics” (1991) by Wilmer A. Jenkins and James P. Harrington, or “Society
of Plastics Engineers RETEC Proceedings ", June 15-17 (1981), pages 211-229, WJ Schrenk and CRFinch," Coextrusion For Barrier Packaging ".

For multilayer film structures, the ethylene copolymer compositions (A) generally described herein
, (A ′), (A ″) or (A ′ ″) make up at least 10 percent of the total multilayer film structure. Other layers of the multilayer structure include, but are not limited to, a barrier layer and / or a tie layer and / or a structural layer. In these layers, various materials can be used, some of which may be used as two or more layers in the same film structure. Some of these materials include foil, nylon, ethylene / vinyl alcohol (EVOH) copolymers, polyvinylidene chloride (PVDC), polyethylene terephthalate (PET), oriented polypropylene (OPP), ethylene / vinyl acetate (EVA) copolymers. , Ethylene / acrylic acid (EAA) copolymers, ethylene / methacrylic acid (EMAA) copolymers, ULDPE, LLDPE) HDPE, MDPE, LMDPE, LDPE, ionomers, graft modified polymers (eg maleic anhydride grafting) Polyethylene) and paper. Generally, this multilayer film structure contains 2 to 7 layers.

The multilayer film structure in one embodiment disclosed herein includes at least three layers (eg, “A / B / A” structures, etc.), wherein each outer layer is at least one ethylene-based copolymer. The polymer composition (A), (A ′), (A ″) or (A ′ ″) and at least one core layer or hidden layer is a low Density polyethylene (LDPE). Such multilayer film structures exhibit surprisingly good optical properties while maintaining good overall film strength properties. In general, the ratio of layers provided in the film structure is such that the core layer is a major part of the film structure in the sense of a percentage of the total structure. This core layer must be at least 33 percent of the total film structure (eg, in a three-layer film structure, each “A” outer layer constitutes 33% by weight of the total film structure, while LDPE The core layer ("B" layer) comprises 33% by weight of the total film structure). In a three-layer film structure, the LDPE core layer preferably comprises at least 70 percent of the total film structure. Also, additional hidden layers may be incorporated into the film structure as long as the optical properties are not deteriorated. For example, made of ethylene / vinyl acetate copolymers, ethylene acrylic acid copolymers or anhydride graft modified polyethylenes, such as using bonding or interlayers, or eg vinylidene chloride / vinyl chloride copolymers or ethylene vinyl A barrier layer made of alcohol copolymers or the like can be used. In a more preferred three-layer film structure, each “A” outer layer has at least one ethylene-based copolymer composition (A), (A ′), (A ″) or (A ′ ″). In an amount of 15% by weight of the total film structure and the “B” core layer contains LDPE in an amount of 70% by weight of the total film structure. Orienting and / or irradiating (in any order) this multi-layer film structure can result in a multi-layer shrink film structure or a jacket package that exhibits controlled linear tearability. . LDPEs suitable for multilayer film structures exhibiting improved optical transparency disclosed herein generally have a density of 0.915 g / cm ³ to 0.935 g / cm ³ , 0.1 g / 10 min to 10 g. A melt index of / 10 minutes and a melt tension of at least 1 gram. To improve optical transparency, this or ethylene copolymer composition (A), (A ′), (A ″) or (A ′ ″) is generally from 0.85 g / cm ³ 0.9
Density of 6 g / cm ³ , preferably 0.9 g / cm ³ to 0.92 g / cm ³ , 0.2 g / 10 min to 10 g / 10 min, preferably 0.5 g / 10 min to 2 g / 10 min The melt index (I2) is shown.

  These multilayer film structures are also included in the film in the ethylene-based copolymer composition (A), (A ′), (A ″) or (A ′ ″) (of the film structure described below). When used alone or in combination with other oxygen permeable film layers such as ethylene / vinyl acetate (EVA) and / or ethylene / acrylic acid (EAA), Can exhibit oxygen permeability. Of particular interest are, for example, (A) / EAA / (A), (A) / VLDPE / (A) and LLDPE / (A) / LLDPE film structures, which are conventional PVC such as PVC A variety of fresh foods, such as retail cut red meat, fish, poultry, vegetables, fruits, cheese, etc., as well as film substitutes, as well as destined for retail display and the introduction of environmental oxygen It is well suited to stretch and wrap other food products that can benefit or need to breathe properly. Preferably, these films are produced as non-shrinkable films that exhibit good oxygen permeability, stretchability, elastic recovery and heat sealability (eg, do not have a biaxial orientation induced by double bubble processing) This allows wholesalers and retailers to make them available in any of the usual forms, such as stock rolls, as well as in normal packaging equipment.

  In another aspect, these multilayer film structures are oxygen barrier films (eg, SARAN ™, a film made from polyvinylidene chloride polymer manufactured by Dow Chemical Company, or Kurray of America, Inc. Eval Company of America, an EVAL ™ resin that is an ethylene / vinyl alcohol copolymer manufactured by Kuraray Ltd. Oxygen barrier properties are important in film applications, such as when wrapping sections (ie, large meat sections that are transported to a special store for further cutting for consumption by a particular consumer). As described by Davis et al. In the issue, the oxygen bar should be removed so that the first section of the package can be removed upon arrival at the butcher / food company. The layer can also be designed to be “peelable”, and the peelable structure or design is particularly suitable for “case-ready” vacuum envelope packages on individual parts. Effective, which eliminates the need to repackage in an oxygen permeable package for the purpose of providing a bright red color.

The ethylene-based copolymer composition (A), (A ′), (A ″) or (A ″) described herein may also be used by any known method, such as an extrusion thermoforming method. The film structure produced from ') may be pre-shaped with respect to the shape and contour of the product to be packaged. The benefits of using a pre-formed film structure can be given to each individual, such as increasing stretchability, reducing film thickness at a given stretch requirement, shortening heat-up and cycle times, etc. It is possible to supplement or avoid the packaging operation items.

The thickness of these single or multilayer film structures can vary. However, the thickness of both monolayer and multilayer film structures described herein is typically from 0.1 mil (2.5 micrometers) to 50 mils (1270 micrometers), preferably 0.5. 4 mils (1
0 micrometer) to 15 mil (381 micrometer), in particular 0.6 mil (15 micrometer) to 4 mil (102 micrometers).

Film structures made from the ethylene-based copolymer compositions (A), (A ′), (A ″) or (A ′ ″) described herein are surprisingly comparative. It exhibits irradiation crosslinking that is more efficient than conventional Ziegler polymerized linear ethylene / α-olefin polymers. As one aspect of the present invention, film structures with differentially or selectively cross-linked film layers can be produced by using the irradiation efficiency advantage exhibited by these unique polymers. . Specific film layers comprising this ethylene-based copolymer composition (A), (A ′), (A ″) or (A ′ ″) in order to take advantage of the additional advantages of such discoveries The material may be a pro-rad agents such as triallyl cyanurate as described by Warren in US Pat. No. 4,957,790 and / or a cross-linking inhibitor which is an antioxidant, such as in US Pat. Can be formulated with butylated hydroxytoluene as described by Evert et al.

Moreover, also when it is going to raise the shrinkage temperature range and heat sealing range of these film structures, the bridge | crosslinking by irradiation is effective. For example, US Pat. No. 5,089,321 discloses a multilayer film structure comprising at least one heat-sealable outer layer and at least one core layer that exhibits good radiation crosslinking performance. Among the irradiation crosslinking techniques, beta irradiation with an electron beam source and gamma irradiation with a radioactive element such as cobalt 60 are the most common methods that cause crosslinking of film materials.

  In the irradiation crosslinking method, a thermoplastic film is produced by the blown film method, and then the polymer film is crosslinked by exposure to an irradiation source (beta or gamma) with an irradiation dose ranging up to 20 Mrad. Whenever an oriented film is desired, for example in the case of shrinkage and jacket wrapping, irradiation crosslinking can be induced before or after the final film orientation is performed, however, preferably the final film Irradiation cross-linking is induced before orientation. When producing heat-shrinkable films or film for envelope packaging by a method that irradiates pellets or films before final film orientation, these films must exhibit consistently higher shrinkage tension. Package bending and paperboard curvature tend to be higher, and conversely, orientation prior to irradiation will result in lower shrinkage tension of the resulting film. Unlike the shrinkage tension, the free shrink property exhibited by the ethylene-based copolymer composition (A), (A '), (A' ') or (A' '') of the present invention is that the irradiation is the final film orientation. It is essentially unaffected whether done before or after.

Illumination techniques effective for processing the film structures described herein include techniques known to those skilled in the art. Preferably, this irradiation is accomplished using an electron beam (beta) irradiator at a dose level of 0.5 Mrad to 20 Mrad. Shrinkable film structures made from the ethylene copolymer compositions (A), (A ′), (A ″) or (A ′ ″) as described herein are also the result of this irradiation treatment. Is expected to exhibit improved physical properties due to the lower degree of chain scission that occurs as

The hot tack film of the present invention exhibits utility in bag-n-box and foam-fill-seal operations as an oriented or unoriented monolayer or multilayer structure. An example of using the film of the present invention in a foam-fill-seal operation is described in Wilmer AJ enkins and James P. Harrington, “Packaging Foods With Plastics” (1991), pages 32-83. "Packaging Machinery Operations: No. 8, Form-Fill-Sealing, A Self-Instructional Course" (April 1982) by CGDavis of Packaging Machinery Manufacturers Institute; "The Wiley Encyclopedia of Packaging Technology" by M. Bakker (Editor) John Wiley & Sons (1986) (334, pp. 364-369); and S. Sacharow and ALBrody “Packaging: An Introduction”, Harcourt Brace Java® novich Publications, Inc. (1987) (332-). Packages can also be produced using vertical or horizontal foam / fill / seal packaging and thermofoam / fill / seal packaging as described in page 326). A particularly effective device for foam / fill / seal operations is the Hayssen Ultima Super CMB. Vertical foam / fill / seal machine, which is used to package typical products such as food, drugs and hardware. . Other manufacturers of devices that perform pouch thermoforming and evacuation include Cryovac and Koch.

High load packaging film:
The high-load packaging film is a film comprising the ethylene-based copolymer composition (A), (A ′), (A ″) or (A ′ ″), and the thickness of the film is at least about 1 .25 mil (31 microns) and this has a film density in the range of 0.923 to 0.95 grams / cubic centimeter (g / cc) and is typically used in industry today It exhibits a tear strength or impact resistance that is at least 30 percent higher than conventional polyethylene films. This film can be used in heavy-duty packaging and transportation applications and also in hot-fill packaging applications.

  In this specification, the term “medium modulus” is used to refer to a novel film, meaning that the calculated film density is in the range of 0.923 to 0.95 g / cc. In this specification, the term “calculated film density” is used to mean the film density as calculated from the known weight of the constituent polymers or layers and the measured density after annealing.

As used herein, the term “thick” is used to refer to a novel film, with the purpose of meaning a film thickness of about 1.25 mils (31 microns) or greater.
The term "variable stalk extrusion" refers to the distance between the film annular die and the stalk height, the bubble expansion point, from 0 inches (0 centimeters) to 144 inches (366 centimeters) or more during blown film production. That can be changed. This term encompasses both the well-known pocket blown film extrusion process and the stalk blown film extrusion process. As used herein, the term “high-stoke extrusion” in the normal sense means that the distance between the film ring die and the air ring is equal to or greater than 30 inches (76 centimeters). "Processing" is used.

  As used herein, the term “hot filling” refers to performing a packaging or product filling operation at a product temperature of 45 ° C. or higher. As used herein, the term “high load” generally refers to packaging industrial items in large quantities or having a single package weight of 10 pounds (4.5 kilograms) or more.

The tear resistance exhibited by the film of the present invention is measured according to ASTM D1922 and reported in grams. The tear resistance is measured in both the machine direction (MD) and the transverse direction (CD). In this specification, the term “tear strength” is used to represent the average between the MD tear resistance value and the CD tear resistance value, which is also reported in grams. The impact resistance exhibited by the film of the present invention is determined by ASTM.
Measure according to D1709. If there is a relationship where the performance value increases as the thickness increases, it can be accurately measured by increasing or decreasing the tear and impact results proportionally based on the actual measured film thickness (micrometers). Normalize to 3 mils, however, normalization calculations are performed and reported in this way only when the thickness variation is within 10 percent, i.e., the measured thickness is in the range of 2.7 to 3.3 mils. It's only within.

The calculated film density of the medium modulus film of the present invention is from 0.923 g / cc to 0.95 g / cc, particularly from 0.926 g / cc to 0.948 / cc, more particularly from 0.93 g / cc to 0.945 / cc. It is in the range of cc.

The film thickness is generally greater than about 1.25 mils, particularly in the range of 1.5 mils to 8.75 mils, more particularly in the range of 2 mils to 8 mils.
The tear strength or impact resistance exhibited by the new film is at least 30 percent higher than the tear strength or impact resistance exhibited by comparable prior art polyethylene films having approximately the same film density, melt index and film thickness.

  This novel film can be conveniently formed into a bag and is useful for use in hot-fill packaging applications in addition to high-load packaging and transportation applications, in which films exhibit a good balance of properties, i.e. tearing, There is a need for films that have good impact and dimensional stability, high strength, and moderate modulus.

This new film can be produced by variable-stalk blown extrusion. The production of films by blown film extrusion is well known. See, for example, Dowd, US Pat. No. 4,632,801, which describes a typical blown film extrusion process. In a typical method, the polymer is introduced into a screw extruder, the polymer is melted therein and advanced forward under pressure in the extruder. The molten polymer is extruded through an annular die for film to produce a molten tube. The tube is then inflated by supplying air into the annular die, creating “bubbles” having the desired diameter. Air is trapped in the bubble by the annular die and nip rollers located downstream of the die, and then the bubble is crushed to produce a lay flat film. The final thickness of the film is adjusted by extrusion rate, bubble diameter and nip speed, and these can be adjusted by variables such as screw speed, haul-off rate and winding speed. Increasing the extrusion rate with a constant bubble diameter and nip speed results in a thicker final film thickness.

Typical blown extrusion methods can generally be categorized as “Stoke” or “Pocket” extrusion. In the case of Stoke extrusion, bubble bulging and expansion occurs well above the annular die and the adjustment is made. An air ring (this will keep the tube approximately the same diameter as the annular die for film) until the molten tube swells at a height of at least 5 inches above the annular die. Usually has a single lip structure) and supplies an air flow outside the tube parallel to the machine direction. It is also possible to cool the inside of the bubble for the purpose of ensuring the optimum stability of the bubble during manufacture, and it is also possible to use a bubble stabilizing means on the inside.

  The use of Stoke extrusion can improve molecular relaxation, thus reducing the tendency to over-orientation in one direction, thereby enabling balanced film properties to be obtained. Are known. Increasing the stalk, i.e., the height of the inflated portion, generally improves the transverse (CD) characteristics, thereby improving the average film characteristics. High molecular weight polyethylene compositions such as high molecular weight high density polyethylene (HMW-HDPE) and high molecular weight low density polyethylene (HMW-LDPE), which have sufficient melt strength to ensure sufficient bubble stability ), A stalk extrusion process, particularly a high stalk extrusion process, is very useful.

  In the case of pocket extrusion, air is supplied by an air ring located immediately adjacent to the annular die so that the bubbles coming out of the die immediately expand and expand. This air ring is typically a double lip shape in order to guarantee the stability exhibited by the bubble after it is added. Pocket extrusion is more widely used than Stoke extrusion, and is generally a polyethylene composition with lower molecular weight and lower melt strength, such as linear low density polyethylene (LLDPE) and ultra low density polyethylene (ULDPE). It is suitable for such cases.

  Both monolayer and multilayer films can be produced by stalk and pocket extrusion, and the films of the present invention can be single layer structures or multilayer structures. The multilayer film can be produced by any technique known in the art, including, for example, coextrusion, lamination, or a combination of both. However, the preferred thick medium modulus polyethylene film of the present invention is a single layer film structure.

  In the ethylene copolymer composition (A), (A ′), (A ″) or (A ′ ″) used in the production of the film of the present invention, additives such as antioxidants and phosphites , Cling, additives, Standostab PEPQ ™ (supplied by Sandoz), pigments, colorants and fillers, etc. The improved tear and impact resistance disclosed by the Applicants, such additives and materials It is also possible to contain it in such a degree that does not interfere. Additives that generally do not require but also improve antiblocking and coefficient of friction characteristics, including but not limited to untreated and treated silicon dioxide, talc, calcium carbonate and In addition to clay, primary, secondary, and substituted fatty acid amides are included), release agents, silicon coating materials, and the like can also be included in the film of the present invention. Further, for the purpose of improving the antistatic property exhibited by the film of the present invention and enabling high-load packaging of, for example, an electron-sensitive product, another additive such as a quaternary ammonium compound is used alone. Alternatively, it can be added in combination with ethylene-acrylic acid (EAA) copolymers or other functional polymers.

  Advantageously, because the strength properties of the new film are improved, the diluent polymer is added to the recycled and scrap materials in the film composition used in the production of the new film, and the prior art polyethylene film composition. Can be mixed or compounded in amounts greater than would typically be possible when using the product, and this new film is further desired when trying to be used successfully in heavy duty packaging and shipping applications. May provide or retain performance characteristics. Suitable diluent materials include, for example, elastomers, rubbers and anhydride modified polyethylenes (eg, LLDPE and HDPE grafted with polybutylene and maleic anhydride) as well as high pressure polyethylenes such as low density polyethylene (LDPE) And the like, ethylene / acrylic acid (EAA) interpolymers, ethylene / vinyl acetate (EVA) interpolymers, ethylene / methacrylate (EMA) interpolymers, and the like, and combinations thereof.

Stretched adhesive film:
The present invention is a multilayer film comprising at least two layers, having substantial tack on one side, and suitable for use as a stretch wrap material. The novel multilayer film comprises: at least one ethylene copolymer composition (A), (A ′), (A ″) having a density of at least about 0.90 g / cc or about 0.90 g / cc. Or from a backside layer consisting of (A '''), a surface layer consisting of at least one film-forming olefin polymer composition having a density of about 0.90 g / cc, and optionally at least one high-strength ethylene polymer composition. At least one core or structural layer.

The surface layer shows significantly less tack than the back layer. The core or structural layer can be varied to meet specific film strength requirements.
According to the present invention, films made with single-sided tack are particularly useful for stretch wrapping, stretch bundling and tension winding operations to wrap or hold small or large articles. The single-sided adhesive film of the present invention is provided without the need for adhesive additives or functional polymers.

  Advantages of the present invention include reduction or elimination of die lip swell, accumulation and transfer of low molecular weight materials. This means that cleaning and holding times during film production and lapping operations are reduced. Problems with adhesion to adjacent articles and packaging and surface retention of contamination, dust or debris are also reduced.

  Another aspect of the present invention provides single-sided adhesive films consisting of polymers with similar rheology and monomer chemistry, thereby providing improved melt viscosity consistent with coextrusion and good polymer compatibility for recycling. To make it easier.

  Another aspect of the present invention is to provide a single-sided adhesive film in which high tack does not decrease when the film is under stretch conditions and the film exhibits significant stretch and unstretch tack.

It has been discovered that the amount of tack is related to the density of the polymer or blend combination forming the back and top layers of the film, with the tack improving as the back layer polymer density decreases. The back layer of the present invention has a back layer density of 0.90 g / cc or less, preferably in the range of 0.85 g / cc to 0.89 g / cc, and most preferably in the range of 0.86 g / cc to 0.88 g / cc.
When in the cc range, it shows substantial adhesion to the surface layer. The density of the surface layer of the present invention is 0.9.
It is 0 g / cc or more, preferably in the range of 0.91 g / cc to 0.96 g / cc, more preferably in the range of 0.93 g / cc to 0.95 g / cc. A surface layer in a more preferred density range of 0.93 g / cc to 0.95 g / cc gives a single-sided adhesive film with equal stretch and non-stretch adhesion.

The density of the core layer or structural layer contained in the multilayer film of the present invention can be varied to match the total film strength requirements depending on the final application.
The ethylene polymer having a density of 0.90 g / cc or less than 0.90 g / cc constituting the back layer of the present invention is a homogeneously branched very low density polyethylene (VLDPE), said ethylene copolymer composition (A), (A ′), (A ″) or (A ′ ″), and blend combinations thereof. Preferably, the back layer consists of the composition (A), (A ′), (A ″) or (A ′ ″).

Film forming olefin polymer compositions having a density greater than 0.90 g / cc constituting the surface layer of the present invention include propylene and ethylene polymers such as polypropylene, ethylene propylene copolymer, low density polyethylene (LDPE), medium density polyethylene (MDPE). ), High density polyethylene (HDPE), composition (A), (A ′), (A ″) or (A ′ ″), heterogeneous and uniform branched linear low density polyethylene (LLDPE), heterogeneous And homogeneously branched very low density polyethylene (VLDPE), and blends thereof. Preferably, the surface layer consists of polypropylene, for example polypropylene in a blend combination with MDPE or HDPEMDPE alone and is preferred for its ability to provide equal stretch and non-stretch adhesion.

  The ethylene polymer constituting the core or structural layer of the present invention is low density polyethylene (LDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), composition (A), (A ′), (A ″) Or (A ′ ″), including heterogeneous and homogeneously branched linear low density polyethylene (LLDPE), heterogeneous and homogeneously branched very low density polyethylene (VLDPE).

Heterogeneous branched VLDPE and LLDPE are well known to those skilled in the art of linear polyethylene technology. They are produced using Ziegler-Natta solutions, slurry or gas phase polymerization processes, and coordination metal catalysts as described in Anderson et al. US Pat. No. 4,076,698. These Ziegler-type linear polyethylenes are not uniformly branched and they have a low melt tension. Also, these polymers are low density and do not exhibit substantial amorphousness. Because they inherently have a substantial high density (crystalline) polymer portion. At densities below 0.90 g / cc, these materials are very difficult to produce using conventional Ziegler-Natta catalysts and are also very difficult to pelletize. The pellets are sticky and tend to clump together.

Uniformly branched VLDPE and LLDPE are also well known among those skilled in the art of linear polyethylene technology. See, for example, the disclosure of Elston US Pat. No. 3,645,992. They are produced in solution, slurry or gas phase processes using zirconium and vanadium catalyst systems. Ewen et al., In US Pat. No. 4,937,299, describe a production process using a metallocene catalyst. This second class of linear polyethylene is a homogeneous branched polymer, but like Ziegler type non-uniform linear polyethylene, they have low melt tension. Commercial examples of these polymers are sold by Mitsui Chemicals under the trade name “TAFMER” and by Exxon Chemical under the trade name “EXACT”.

  The ethylene polymer composition used for the back layer, the film-forming olefin polymer composition used for the surface layer, and the high-strength ethylene polymer composition used for the core or structural layer of the present invention are ethylene homopolymerization or ethylene Is an ethylene polymer produced by the interpolymerization of and a small amount of various monomers.

  Additives such as adhesive additives, adhesives (eg PIB), slip and anti-blocking agents, antioxidants (eg Irganox 1010 or Irganox 1076 supplied by hindered phenols such as Ciba Geigy), phosphites (eg by Ciba Geigy) Irgafos 168), stand stub PEPQ (supplied by Sands), pigments, colorants, fillers, and processing aids are not necessary to achieve the desired results of the present invention, but are disclosed herein. It can also be included in the wrap material. However, the additives should be formulated to the extent that they do not interfere with or interfere with the substantial tack and non-tackiness found in the present invention.

  The multilayer film of the present invention comprises a film lamination and / or coextrusion technique from two or more film layers comprising A / B and A / B / C structures, and blown or cast films known in the art. It can be manufactured by an extrusion device. However, the preferred structure is an A / B / C structure produced by coextrusion technology, more preferably by cast coextrusion technology.

  Suitable blown film methods are described, for example, in The Encyclopedia of Chemical Technology, Kirk-Othmer, 3rd edition, John Wylie and Sons, New York, 1981, Vol. 16, pp. 416-417 and Vol. 18, pp.191-192. A suitable cast extrusion method is described, for example, in Modern Plastics, Mid-October 1989, Encyclopedia Issue, Vol. 66, No. 11, pages 256-257. Suitable coextrusion techniques and requirements are described by Tom I Butler in Film Extrusion Manual: Process, Materials, Properties, “Coextrusion”, Ch. 4, pp. 31-80, TAPPI Press, (Atlanta, Ga. 1992). It is described in.

The melt index of each polymer layer of the multilayer film of the present invention is in the range of 0.4 to 20 g / 10 min, preferably in the range of 0.5 to 12 g / 10 min, more preferably 0.8 to 6 g / 1.
It is in the range of 0 minutes.

The total film thickness of the multilayer film of the present invention is 0.4 to 20 mils (10 microns to 508).
In the range of 0.6 to 10 mils (15 microns to 254 microns), more preferably in the range of 0.8 to 5 mils (20 microns to 127 microns).

  The layer ratio of the A / B multilayer film of the present invention is larger than the A / B layer of 2:98, preferably in the range of 5:95 to 35:65, more preferably in the range of 10:90 to 25:75. is there. The layer ratio of the multilayer film of two or more layers is such that the back layer and the surface layer of the film are kept at the same thickness, and the ratio of the core or structural layer is in the range of 60 to 98% by weight, preferably in the range of 65 to 95% by weight. The layer ratio is more preferably in the range of 70 to 90% by weight.

Multilayer barrier film:
The multilayer barrier film is an oxygen and moisture impermeable multilayer barrier film and also includes ostomy bags, laminates for transdermal delivery of drugs, and heat sealable bags. Includes products made from multilayer barrier films.

According to one aspect of the invention, at least 1.0 lb per inch of film width,
An oxygen and moisture impermeable multilayer barrier film having a heat seal strength of preferably greater than 1.5 lb is provided. “Oxygen impermeability” means that the film is 90 cc / m ² / H · at
It means having an oxygen permeability of not more than m. “Moisture impermeable” means that the film has a water vapor permeability of 5 gm / m ² / H or less.

  In one aspect, the film includes a barrier layer having at least one heat-sealable skin layer thereon. The barrier layer includes any suitable barrier layer material that provides the desired oxygen and moisture impermeability that is compatible with, for example, a heat-sealable skin layer (single layer or multiple layers). A preferred barrier material is a copolymer of vinylidene chloride and vinyl chloride or methyl methacrylate. When the barrier layer comprises a copolymer of vinylidene chloride and vinyl chloride or methyl methacrylate, the barrier layer optionally comprises 0-6% by weight of a copolymer of ethylene and vinyl acetate, more preferably 4-6% as a processing aid. It can also be included.

In one aspect of the invention, the barrier layer is coextruded with at least one heat-sealable skin layer. In order to provide the desired flexibility, the heat-sealable skin layer preferably has a 2% secant modulus of less than 15,000 psi in both the machine direction (MD) and the transverse direction (TD). The heat-sealable skin layer includes the ethylene-based copolymer composition (A), (A ′), (A ″) or (A ′ ″). In order to aid the processing of the film, the skin layer (single layer or multiple layers) contains 0 to 10% by weight of a copolymer of ethylene and vinyl acetate, more preferably 0.5 to 5% as a processing aid. Can do. Further, the skin layer can optionally include a slip agent / anti-stick agent. It may be desirable to coextrude an adhesive tie layer of a copolymer of ethylene and vinyl acetate between the skin layer and the barrier layer to improve the adhesion of those layers.

In a preferred embodiment of the invention, a barrier layer is coextruded between two heat-sealable skin layers. In that case, the skin layer is 70% by volume (thickness) of the film and the barrier layer is 30% by volume (thickness) of the film. This structure can be used to make a reusable ostomy bag or pouch. The barrier layer and skin layer (single layer or multiple layers) can be made separately and then laminated together using a suitable adhesive polymer, liquid adhesive, or hot melt adhesive. The multilayer barrier film of the present invention is 65 ° at 0.45 Hz.
Bend at an angle of less than 85 dB, preferably 6 at 0.45 Hz.
When bent at an angle of 5 °, it exhibits less than 83 dB noise, and most preferably, when bent at an angle of 65 ° at 0.45 Hz, it exhibits less than 81 dB.

In another aspect of the invention, an additional layer can be added to the barrier layer to create a system for transdermal delivery of the drug. Preferably, the system includes a backing layer of a barrier film that acts as a barrier to the drug system. The adhesive containing the active agent is preferably attached to one surface of the film. Adjacent to the adhesive is a modified release membrane adapted to contact the patient's skin and to release the drug in a controlled manner.

  In another form of this embodiment, the backing layer creates a reservoir containing the active agent having a controlled release membrane that conceals the reservoir opening to regulate the diffusion of the drug into the patient's skin. be able to. Peripheral or all adhesives can be used to adhere the transdermal delivery system to the patient's skin. Preferably, a release liner is placed over the adhesive and film to protect the structure prior to use.

  Accordingly, it is a feature of the present invention to provide an oxygen and moisture impermeable multilayer barrier film that can be manufactured using a coextrusion method or a lamination method. Furthermore, characteristics of the present invention include odor barrier properties, flexibility, and low noise properties. In addition, a heat sealable surface is provided for use in making bags and pouches.

In one embodiment, the multilayer barrier film of the present invention can be manufactured using standard extrusion techniques such as, for example, feedblock coextrusion, multi-manifold die coextrusion, or a combination of the two. The volume (thickness) of each independent layer can be adjusted when extruding. Therefore, the total thickness of the multilayer structure can be adjusted. Alternatively, the independent layers can be made separately and laminated together using a suitable adhesive bond layer.

The polymers present in the film are not intentionally stretched or stretched other than as a natural result of their manufacture to protect their low noise properties. For example, films produced by the blow process are machine direction (MD) and transverse direction (TD)
Both have essentially some orientation and the cast film remains unstretched in the transverse direction. In general, the smaller the orientation introduced into the film, the smaller the noise. The multilayer barrier film of the present invention exhibits a noise of less than 85 dB when bent at a 65 ° angle at 0.45 Hz, preferably 65 at 0.45 Hz.
When bent at an angle of °, it exhibits a noise of less than 83 dB and most preferably 0.45 Hz
When bent at an angle of 65 °, noise of less than 81 dB is exhibited.

Further, in order to provide the desired flexibility, the heat-sealable skin layer preferably has a 2% secant modulus of less than 15,000 psi in both the machine direction (MD) and the transverse direction (TD). The 2% secant modulus is a measure of the stiffness or flexibility of the film. We have found that the lower the 2% secant modulus value for a heat-sealable skin layer, the softer the resulting film. In general, it is desirable that the 2% secant modulus of the film be as low as possible and still be processable by conventional equipment. For the entire multilayer film, the 2% secant modulus is preferably 30,000 psi or less. The resulting multilayer film has low oxygen and vapor permeability, and also has odor barrier properties, flexibility, and low noise properties required in sculptural applications.

Oxygen and moisture impermeable multilayer barrier films are copolymers of vinyl chloride (15-20 wt%) and vinylidene chloride (80-85 wt%) or vinylidene chloride (93-94 wt%) and methyl methacrylate (6-7 A barrier layer which can consist of a copolymer with Suitable barrier materials include, for example, Saran® 469 and Saran MA, commercially available from Dow Chemical Company. When the saran barrier layer material is used, the barrier layer may contain 0 to 6% by weight, more preferably 4 to 6% by weight, of a copolymer of ethylene and vinyl acetate as a processing aid. A suitable set of ethylene / vinyl acetate copolymer compositions are those commercially available from EI du Pont de Nemours &; Co., Inc. under the trademark Elvax®.

  Preferably, the barrier layer is coextruded with two heat-sealable skin layers comprising the ethylene copolymer composition (A), (A ′), (A ″) or (A ′ ″). Or between the two layers.

The barrier film is reused by folding the film and then heat sealing the ethylene copolymer composition (A), (A '), (A'') or (A''') skin layers together It can be used to make possible ostomy bags or pouches. Preferably, the bag has an oxygen permeability of less than 90 cc / m ² / H · atm (1.8 cc / 100 in ² / H · atm). The barrier film has a total thickness of 35-100 micrometers, and the barrier layer constitutes 10-30% of the total thickness of the film. The skin layer (and adhesive layer, if necessary) typically constitutes 70-90% of the total thickness of the film.

  The multilayer barrier film of the present invention can also be made by a lamination technique using a suitable adhesive. For example, the barrier layer and skin layer (single layer or multiple layers) can be made separately and then laminated together using an adhesive polymer, liquid adhesive, or hot melt adhesive. Suitable adhesive polymers for bonding the barrier and skin layers include, but are not limited to, vinyl acetate, ethyl acrylate, ethyl methacrylate, methyl acrylic acid, acrylic acid, and carbon monoxide. And ethylenically unsaturated copolymers. Other acids include ionomers of ethylene and methylacrylic acid or acrylic acid, and grafted anhydride copolymers. Suitable liquid or hot melt adhesives include, but are not limited to, those based on copolymers of urethane, copolyester, and amide acrylate.

The five-layer oxygen and moisture impermeable barrier film includes a barrier layer made of a suitable barrier material as previously discussed. Preferably, the barrier layer is coextruded with the two outer heat-sealable skin layers, sandwiching an adhesive layer between the two outer heat-sealable skin layers. The heat-sealable skin layer in this five-layer embodiment is a substantially linear copolymer of ethylene and α-olefin as described in published PCT application No. PCT / US92 / 08812, or, Uniformly branched linear polyolefin resins such as toughmer resins can be included. Suitable adhesives include copolymers of ethylene and vinyl acetate that improve the mutual adhesion of the barrier and skin layers.

  In its simplest form in another aspect of the invention where an additional layer is included with the barrier film to make a system for transdermal delivery of the drug, the barrier layer and skin layer of the film comprise the drug system. Work as a backing film that is a barrier against The barrier film further includes an adhesive layer comprising an active agent formulated in a matrix adhered to one side of the film. The adhesive selected should be compatible with the active agent and permeable to the active agent. Many active agents can be administered to patients in this manner, including, for example, estrogen, nitroglycerin, nicotine, and scopolamine. Theoretically, almost any drug can be administered in this manner.

  There is a modified release membrane on the adhesive layer adapted to contact the patient's skin and release the drug in a controlled manner. Additional adhesive layers that can be applied around the membrane or over the entire surface of the membrane can also be present to secure the transdermal delivery system to the patient's skin. The adhesive used in the practice of this aspect of the invention should be a medical adhesive such as a silicone adhesive, an acrylic acid adhesive or a vinyl acetate adhesive. In general, in this embodiment, the system is sealed in the package or secured to the second barrier film and they are removed prior to use.

  6 illustrates another form of a transdermal drug delivery system according to the present invention. The barrier layer and skin layer form a barrier film that is molded into a reservoir for containing the active agent therein. The opening to the reservoir is concealed with a controlled release membrane. An adhesive that can be applied to the periphery of the membrane or over the entire area of the membrane serves to secure the system to the patient's skin layer. Also, the adhesive selected should be compatible with the active agent and permeable with respect to the agent. Preferably, a release liner or the like conceals and protects the adhesive and film prior to use.

  A typical reusable ostomy bag including an opening made from a multilayer barrier film can be made by folding the edges of the multilayer film and heat sealing the edges. Preferably, the film is folded and sealed so that the inner surface of the bag or pouch is provided by a single heat-sealable skin layer. The barrier film of the present invention provides the desired flexibility and quietness for ostomy applications, as well as waterproof and odor barrier and oxygen barrier properties. As will be appreciated by those skilled in the art, the barrier film of the present invention may find use in other packaging applications where moisture and oxygen barrier properties are required.

Laminated film sealant:
The laminated film sealant can be formed by the air-cooled inflation method using the ethylene copolymer composition (A), (A ′), (A ″) or (A ′ ″).

  The sealant for laminated film according to the present invention has a dart impact strength of 100 kg / cm or more, preferably 150 kg / cm or more. This film has a complete sealing temperature of 130 ° C. or lower, preferably 110 to 130 ° C.

Moreover, the sealant for laminated films according to the present invention usually has a blocking strength of 1.5 kg.
The tensile Young's modulus is usually 3500 kg / cm ² or more.
The thickness of the sealant for laminated film according to the present invention is in the range of 10 to 150 μm, preferably 10 to 60 μm.

A laminated film can be obtained by laminating the above-described laminated film sealant according to the present invention on a substrate.
As the base material, a thin film body made of any material capable of forming a film-like form can be used. Examples of such a thin film include a polymer film or sheet, cloth, paper, metal foil, and cellophane.

Such a laminated film sealant is excellent in low-temperature heat sealability, hot tackiness, impact resistance, blocking resistance, and openability.
Heavy packaging film:
The film for heavy packaging has a Young's modulus measured according to JIS K 6781 of 4000 kg / cm ² or more, and a dart impact strength measured according to ASTM D 1709 A method is 5
The film thickness is usually from 30 to 200 μm.

  The heavy packaging film can be produced by using the ethylene copolymer composition (A), (A ′), (A ″) or (A ′ ″) by an inflation method or a T-die method. For example, it can be laminated with a polyester or polyamide film to form a multilayer film.

  Such a heavy packaging film is excellent in mechanical strength, transparency, and smoothness of the film surface, and is suitable for packaging food, office supplies, furniture, toys, electrical equipment, mechanical parts and the like. It can also be used as a heavy packaging bag in cold regions.

Grain bag:
The grain bag of the present invention comprises a film of the above-mentioned ethylene copolymer composition (A), (A '), (A'') or (A'''), and is composed of two superposed films. Three directions are closed. This may be done in any way as long as an opening is formed at one end and a bottom is formed at the other end. For example, one film may be folded in two and closed on both sides, or two synthetic resin films may be stacked and closed in three directions, or inflation One of the cylindrical (tube-shaped) films formed by the method may be closed and the other may be the opening.

When closing one direction of the film, for example, it is preferable to weld the films, but as long as the contents can be closed in a state where the contents can be sealed when the films are closed, any method can be used. May be used.
(Extended end)
The extension end portion serves as a base for attaching a binding string described below, and serves as a winding margin when closing the opening of the grain bag of the present invention.

This extended end may be formed by overlapping the film so that the extended end is formed when a bag is formed, and a separate film may be attached to one end of the open end of the bag-like film. May be.
(Tie string)
The tie strap is for closing the opening of the grain bag. Any kind of material may be used for the binding string, but the same material as the film is preferable in terms of improving convenience when recycling the grain bag of the present invention.
(Seal for string)
The string seal portion is provided to mount the tied string on the extended end portion. This string seal portion is formed by bending a part of the extended end portion toward the opening end portion side of the other film, and folding it so as to tie it inside and contain the string. Then, for example, the tied ends may be simply inserted by sealing the folded extended ends. Alternatively, the binding string may be prevented from moving by sealing the binding string together with the extended ends. However, for example, an adhesive may be applied to the inside of the string seal portion to bond the string and the string seal portion so that the string does not move.
(gap)
The gap is provided between the string seal portion and the opening end of the other film. Providing this gap is preferable in that the opening is easy to open when the grain bag is used, and that it becomes a winding margin when the grain bag is wound and closed. The width of this gap is 5 to 100 mm, more preferably 10 to 30 mm.
(Additional components of the present invention)
The grain bag according to the present invention is composed of the above-described essential constituent elements, but it is established even when the constituent elements described below are added.
(Flap part)
The grain bag of the present invention may be provided with a flap portion extending from the string seal portion toward the opening end and having a predetermined width so as to cover the opening. In this case, since the flap part stops the contents in the vicinity of the opening, it is preferable in that the stored grain is not easily spilled even when the grain bag is arranged horizontally.

  In addition, the width | variety of a flap part is more than the width | variety of the said space | gap at least, and is 30-150 mm, More preferably, it is 50-100 mm. (Folded part) A pleated part having a V-shaped cross section formed by folding one end of the synthetic resin film inward may be provided on the bottom part. This is preferable because the bottom of the bag becomes flat when the grain is put inside the grain bag, and the bag stands stably.

At this time, if each corner on the bottom side of the grain bag is subjected to a diagonal seal that draws a hypotenuse of an isosceles triangle whose two sides are approximately the same as the width of each pleat, the bottom width Is preferable in that it is constant regardless of the grain capacity.
(Vent hole)
It is preferable that the film is provided with a plurality of vent holes along both sides of the grain bag because the state of the stored grain can be appropriately maintained. A plurality of the air holes may be formed along at least one of the opening end portion and the bottom end portion of the film. Moreover, each ventilation hole may be provided in a rectangular shape integrally with the film.

Note that the vent hole may be provided in only one of the two films, or may be provided in both films.
Moreover, since the grain bag accommodates the polymer and is frequently moved, it is required to have excellent impact resistance and tear resistance.

The grain bag according to the present invention is formed of a film obtained by molding the composition (A), (A ′), (A ″) or (A ′ ″) by, for example, an inflation method. Therefore, it is possible to make the grain bag thinner than conventional polyethylene. A film formed from this composition (A), (A ′), (A ″) or (A ′ ″) by an air-cooled inflation method has (i) a tensile Young's modulus of 4,000 kg / cm ² or more. Yes, and (ii) a dirt impact strength of 55 kg / cm or more is suitable for use as a grain bag.

Furthermore, the gloss of the film is preferably 50% or more, and the grain bag preferably has a thickness of 30 to 200 μm.
In addition, this film has excellent low-temperature characteristics such as low-temperature bag drop strength characteristics that can be used for grain bags even in cold regions below freezing point. Is possible.

  According to the grain bag of the present invention, first, an opening provided at the other end of the grain bag is opened, and an appropriate amount of grain is put through the opening. Next, the extension end portion is appropriately wound several times toward the opening end side of the other film. Finally, the opening is closed by tying the tie straps together. Therefore, the method of using the grain bag is the same as the method of using the conventional paper grain bag, and it is changed to the working practice of the producer or trader who is working with the conventional grain bag. Never come.

Moreover, since the bag for cereals of the present invention is made of a synthetic resin bag, it can be manufactured at a lower cost than a conventional paper cereal bag. In addition, each above component can be combined arbitrarily as much as possible.
(Production method for grain bags)
Next, the grain bag manufacturing method of the present invention is configured as follows. That is, in the extended end portion, the extended end forming step of providing an extended end in which the end of one of the two films extends in the opening direction from the open end of the other film, A string supplying step of supplying a tied string along a width direction of the bag body at a predetermined distance from the opening end of the other film, and including the tied string in the extended end portion The folding step of folding the other film to the opening end side of the other film, and the extending end portion folded and reversed, the binding string is included, and the opening end of the other film A sealing process is provided in which a gap is left between the two and welded together.

  Here, the three directions of the two laminated synthetic resin films are closed, and the grain bag with the bottom formed at one end and the opening formed at the other is formed by two independent films. It may be formed by sealing three sides, or it may be formed by folding one film into two sheets and sealing in two directions, but when using a film formed in a cylindrical shape in advance, such as an inflation film, Further, since the two directions are closed, the manufacturing process becomes easy.

Furthermore, a bottom folding process may be provided in which the bottom is folded inward to form a fold having a V-shaped cross section. Moreover, you may provide the punching process which provides a some ventilation hole along the both sides of the film of the said other end.
Furthermore, you may provide the 2nd perforation process which forms a some ventilation hole along at least any one of the said opening edge part and bottom side edge part of said other film.

Flowable material packaging pouch:
The flowable material packaging pouch is a pouch used in consumer packaging useful for packaging a flowable material (for example, a liquid such as milk), and the ethylene copolymer composition (A), (A '), (A ") or a specific film structure containing (A''').

  In the present invention, a flowable material is formed using a single-layer film structure of a polymer seal layer which is an ethylene-based copolymer composition (A), (A ′), (A ″) or (A ′ ″). A pouch of the present invention for packaging is produced.

  In general, the ethylene copolymer composition (A), (A ′), (A ″) or (A ′ ″) is used alone in the sealing layer of this film or film structure. However, it is also possible to blend the ethylene copolymer composition (A), (A '), (A' ') or (A' '') with other polymers used as a heat seal layer. is there. Generally, the ethylene-based copolymer composition (A), (A ′), (A ″) or (A ′ ″) is 10% to 100% by weight of the film structure.

In addition, additives known to those skilled in the art, such as antioxidants, phosphites, cling additives, Sandoz, are supplied to the polymer from which the pouches of the present invention are produced. Standostab PEPQ ™, anti-blocking additive, slip additive, UV stabilizer, pigment,
It is also possible to add processing aids and the like.

The film and film structure disclosed in the present specification include an ethylene copolymer composition (A).
, (A ′), (A ″) or (A ′ ″) may be a single layer or multilayer film structure provided that it is used as at least one layer, preferably a sealing layer. The thickness of this seal layer is at least about 0.1 mil (2.5 microns) and more, preferably 0.2 mils (5 microns) to 10 mils (254 microns), more preferably 0.4 mils. (10 microns) to 5
It may be a mill (127 microns).

A surprising feature of the film structure for pouches of the present invention is the wide heat sealing range of the film. The heat sealing range of the film structure can generally be 50 ° C to 160 ° C, preferably 75 ° C to 130 ° C. It has been found that the seal layer of the present invention has a wider heat seal range than prior art polyethylene films made from non-uniformly branched ethylene polymers even at about the same density. To increase the flexibility in the heat sealing method for producing a pouch from a film structure, it is important to widen the heat sealing range. The melting point range of the composition (A), (A ′), (A ″) or (A ′ ″) used in the manufacture of the film structure having the heat seal range specified above is generally 50 ° C. To 130 ° C, preferably 55 ° C to 115 ° C.

Another unexpected feature of the film structure for pouches of the present invention is that the film exhibits heat seal strength at low temperatures. In general, the film structure of the present invention is about 0.3 at a seal bar temperature of about 110 ° C. when using the DTC Hot Tack Strength Method as defined herein below. At least about 1 N / inch (3
9.4 N / m) of hot tack strength, or 0 at a seal bar temperature of about 110 ° C. when using the DTC Heat Seal Strength Method as defined herein below. Achieve a heat seal strength of at least 11 bf / inch (175 N / m) within .4 seconds. The film structure of the present invention is also at least about 1 N / inch (39.4 N).
Hot tack or heat seal initiation temperature of less than about 110 ° C. with a force of / m). It has been found that seals made using the seal layer of the present invention exhibit higher strength at lower sealing temperatures than seals where higher density prior art polyethylene is used. It is important to provide a high heat seal strength at a low temperature in order to be able to operate a normal packaging device, such as a vertically formed filling and sealing machine, at high speeds to produce a leak-free pouch.

  When the ethylene-based copolymer composition (A), (A ′), (A ″) or (A ′ ″) is used in the seal layer of the film structure for a pouch of the present invention, the pouch of the present invention is particularly useful. When compared to pouches manufactured using linear low density polyethylene, linear ultra low density polyethylene, high pressure low density polyethylene, or combinations thereof, (1) a pouch capable of high-speed processing with a molding, filling and sealing machine is obtained. (2) It is considered that a pouch package with little leakage is obtained.

In one embodiment of the present invention, a pouch is manufactured from a tubular form film structure and has a transversely heat sealed end. This film structure
(I) 10 to 100% by weight of at least one layer comprising an ethylene-based copolymer composition (A), (A ′), (A ″) or (A ′ ″), and (II) heterogeneous A film layer comprising from 0 to 90% by weight of at least one polymer selected from the group consisting of linear ethylene / C3-C18 alpha-olefin copolymers branched to high pressure low density polyethylene and ethylene-vinyl acetate copolymers. It has at least one layer.

This (II) heterogeneously branched linear ethylene / C3 -C18 α-olefin copolymer is generally a linear low density polyethylene (eg, polyethylene produced using a Ziegler catalyst). This linear low density polyethylene is often further classified into subsets, which are designated as very low density polyethylene (VLDPE) or very low density polyethylene (ULDPE). As used herein, VLDPE and ULDPE are interchangeable terms and those skilled in the art generally use them in this manner. The density of the linear low density polyethylene (II) is generally in the range of 0.87 g / cm ³ to 0.94 g / cm ³ , preferably 0.87 g / cm ³ to 0.915 g / cm ³ . This (II) heterogeneously branched linear low density ethylene / C3-C18 α-olefin copolymer preferably exhibits a melt index of 0.1 to 10 g / 10 min.

This high pressure low density polyethylene of (II) preferably exhibits a density of 0.916 to 0.93 g / cm ³ and a melt index of 0.1 to 10 g / 10 min.
Preferably, the ethylene: vinyl acetate copolymer of this (II) ethylene: vinyl acetate weight ratio is from 2.2: 1 to 24: 1, indicating a melt index of 0.2 to 10 g / 10 min.

Another aspect of the present invention provides:
(A) at least one composition (A), (A ′), (A ″) or (A ′) exhibiting a density of 0.915 g / cm ³ or less and a melt index of 10.0 g / 10 minutes or less. '') From 10 to 100% by weight and (b) the group consisting of heterogeneously branched linear ethylene / C3-C18 alpha-olefin copolymers, high pressure low density polyethylene and ethylene-vinyl acetate (EVA) copolymers Pouches made from blends in which at least one polymer selected from 0 to 90% by weight is included.

This (II) heterogeneously branched linear ethylene / C3 -C18 α-olefin copolymer is generally a linear low density polyethylene (eg, polyethylene produced using a Ziegler catalyst). This linear low density polyethylene includes very low density polyethylene (VLDPE) and very low density polyethylene (ULDPE), as described above. The density of the linear low density polyethylene (II) is generally in the range of 0.87 g / cm ³ to 0.94 g / cm ³ , preferably 0.87 g / cm ³ to 0.915 g / cm ³ . This (II) heterogeneously branched linear low density ethylene / C3-C18 α-olefin copolymer preferably exhibits a melt index of 0.1 to 10 g / 10 min.

The high pressure low density polyethylene of (b) preferably exhibits a density of 0.916 to 0.93 g / cm ³ and a melt index of 0.1 to 10 g / 10 min.
Preferably, the ethylene: vinyl acetate copolymer of this (b) has an ethylene: vinyl acetate weight ratio of 2.2: 1 to 24: 1, which exhibits a melt index of 0.2 to 10 g / 10 min.

The pouch film structure of the present invention also includes a multilayer or composite film structure, and preferably the polymer seal layer included in the structure is the inner layer of the pouch.
As those skilled in the art will appreciate, the multi-layer film structure for pouches of the present invention can include a variety of film layer combinations as long as the seal layer forms part of the final film structure. The multilayer film structure for pouches of the present invention may be a coextruded film, a coated film or a laminated film. The film structure may also be a barrier film such as polyester, nylon, ethylene-vinyl alcohol copolymer (EVOH), polyvinylidene chloride (PVDC), such as Saran ™ (The Dow Chemical Company). The seal layer is included in combination with a metal-coated film and the like. Depending on the final use of this pouch, the choice of other materials or materials to be used in combination with the present seal layer film will be greatly influenced. The pouch described herein refers to a sealing layer that is used at least inside the pouch.

  In one embodiment of the film structure for a pouch of the present invention, the sealing layer of the ethylene-based copolymer composition (A), (A ′), (A ″) or (A ′ ″) and at least one Include polymer outer layer. The polymer outer layer is preferably a polyethylene film layer, more preferably “linear low density polyethylene” (“LLDPE”) and / or “linear ultra low density polyethylene” (“ULDPE”) herein below. ) And / or non-uniformly branched linear polyethylene, referred to as “very low density polyethylene” (“VLDPE”). An example of a commercially available LLDPE is DOWLEX ™ 2045 (trademark of The Dow Chemical Company and is commercially available from this company). An example of a commercially available ULDPE is ATTANE ™ 4201 (trademark of The Dow Chemical Company and is commercially available from this company).

LLDPEs useful herein (including both VLDPE and ULDPE) are ethylene and small amounts of alpha-olefins having 3 to 18 carbon atoms, preferably alpha-olefins having 4 to 10 carbon atoms. Heterogeneously branched linear copolymers made from (eg 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene and 1-decene, etc.). Generally, a Ziegler catalyst is used to produce this heterogeneously branched LLDPE (eg, using the method described in US Pat. No. 4,076,698 (Anderson et al.)).

The density of LLDPE for the outer layer is generally at least 0.87 g / cm ³ , more preferably 0.9.
From a 0.93 g / cm ^3, melt index is generally 10 g / 10 min 0.1, and preferably from 2 g / 10 min 0.5.

The thickness of the outer layer can be any thickness as long as the seal layer has a minimum thickness of 0.1 mil (2.5 microns).
Another embodiment of the pouch film structure of the present invention includes a polymer layer sandwiched between two polymer seal layers 31.

  Yet another embodiment of the pouch film structure of the present invention includes at least one polymer core layer between at least one polymer outer layer and at least one polymer seal layer. The polymer layer may be the same LLDPE film layer as the outer layer, or preferably a different LLDPE, more preferably an LLDPE having a higher density than the outer layer. The thickness of the core layer can be any thickness as long as the seal layer has a minimum thickness of 0.1 mil (2.5 microns).

Yet another embodiment of the pouch film structure of the present invention may be a structure comprising a sealing layer and another polyethylene film layer referred to hereinbelow as “high pressure low density polyethylene” (“LDPE”). Good. In general, this LDPE layer has a density of 0.916 to 0.930 g / cm ³ and exhibits a melt index of 0.1 to 10 g / 10 min. The thickness of this LDPE layer is
It can be any thickness as long as the sealing layer has a minimum thickness of 0.1 mil (2.5 microns).

  Yet another aspect of the pouch film structure of the present invention is that the weight ratio of sealing layer to ethylene: vinyl acetate is from 2.2: 1 to 24: 1 and has a melt index of from 0.2 to 20 g / 10 min. It may be a structure including the EVA copolymer layer shown. The thickness of the EVA layer can be any thickness as long as the seal layer has a minimum thickness of 0.1 mil (2.5 microns).

The thickness of the film structure used in making the pouches of the present invention ranges from 0.5 mil (12.7 microns) to 10 mils (254 microns), preferably from 1 mil (25.4 microns) to 5 mils (12
7 microns).

  The design of the pouch film structure of the present invention is flexible. Different LLDPEs (eg, VLDPE and ULDPE) can be used in the outer and core layers for the purpose of optimizing certain film properties, such as film stiffness. In this way, the film can be optimized to suit a particular application, such as a vertical form fill seal machine.

The polyethylene film structure used in the manufacture of the pouch of the present invention is manufactured using either a blown tube extrusion method or a cast extrusion method, which are well known in the art. . This blown tube extrusion method is described, for example, in Modern Plastics Mid-October 1989 Encylopedia Issue, Volume 66, Number 11, pp. 264-266. Cast extrusion method is Modern Plastics Mid-O
ctober 1989 Encylopedia Issue, 66, Number 11, 256-257.

  The pouch aspect of the present invention is a hermetically sealed container filled with “flowable material”. “Flowable material” means a material that can flow under gravity or be pumpable, but the term “flowable material” does not include gaseous materials. Non-carbonated liquids (eg milk, water, fruit juice, wine etc.) and carbonated liquids (eg soda, beer, water etc.); emulsions (eg ice cream mix, soft margarine etc.); pastes (eg meat Pastes, peanut butter, etc .; preserved products (eg jam, pie filling, marmalade, etc.); jelly; dough; minced meat (eg sausage meat); powder (eg gelatin powder, detergent etc.); granular solids (eg nuts, sugar, etc.) , Grains, etc.); and similar materials. The pouches of the present invention are particularly useful for use in packaging liquids (such as milk). The flowable material may also include oily liquids such as cooking oil or motor oil.

  When the film structure for pouches of the present invention is manufactured, the film structure is cut so as to have a width desired for use in a normal pouch manufacturing machine. The pouch embodiment of the present invention is manufactured using a so-called form-fill-seal machine well known in the art. The pouch embodiment of the present invention includes a pouch that is a tubular member having a longitudinal wrap seal and a lateral seal so that a “pillow-shaped” pouch is produced when a flowable material is packed in the pouch.

  The pouch embodiment of the present invention also has a fin seal around the three sides of the tubular member, i.e., a top seal and a longitudinal side seal, and is filled with a flowable material in a cross-section. The bottom of the tubular member has a member that is substantially concave or “ball-shaped” so that a bottom portion that is substantially semi-circular or “bow-shaped” in the longitudinal direction occurs when viewed at There is a pouch that is a tubular member. This pouch is a so-called “Enviro-Pak” pouch known in the art.

The pouch made in accordance with the present invention is preferably a pouch made on a so-called vertical form fill seal (VFFS) machine well known in the art. Examples of commercially available VFFS machines include VFFS machines made by Hayssen or Prepac. VFFS machines are described in the following literature: FCLewis “Form-Fill-Seal”, Packaging Encylopedia, page 180, 1980.

In the VFFS packaging method, a sheet of plastic film structure as described herein is fed to a VFFS machine and the sheet is formed into a continuous tube in its tube forming section. By sealing the longitudinal edges of the film together--fold the plastic film and seal the film with an inner / outer seal, or fin seal the plastic film with an inner / inner seal By doing so, the tubular member is produced. The sealing bar is then used to seal the tube laterally at one end that will become the bottom of the “pouch” and the “pouch” is filled with a stuffing material, such as milk. The resulting pouch is then separated from the tube by sealing the upper end of the pouch with a sealing bar and either burning through the plastic film or cutting the film. Pouch manufacturing methods using this VFFS machine are generally described in US Pat. Nos. 4,503,102 and 4,521,437.

  The capacity of the pouch of the present invention can be varied. The pouch can generally contain 5 to 10 liters of flowable material, preferably 10 to 8 liters, more preferably 1 to 5 liters.

When the ethylene-based copolymer composition (A), (A '), (A ") or (A''') seal layer is used in a two-layer or three-layer coextruded film product, a pouch is formed using the VFFS. Can be produced at a higher speed and a film structure is obtained which reduces the leakage of the pouch thus produced.

It is also possible to print on the pouch of the present invention using techniques known in the art, for example corona treatment prior to printing.
The pouch of the present invention provides excellent performance results when tested in the 5 foot (1.52 m) drop test--the test defined herein. The percentage of breakage the pouch exhibits under this 5 foot drop test is preferably no more than 40 percent, more preferably no more than 20 percent, especially no more than 10 percent.

  The use of this pouch in packaging consumer liquids, such as milk, provides advantages over previously used containers: glass bottles, paper cartons, high density polyethylene jugs, and the like. Containers used before that consume large amounts of natural sources in their production, require space to a significant degree in landfills, require storage space to a large degree, and control the temperature of the product for energy. (Due to the heat transfer characteristics of the container).

  Manufacturing the pouch of the present invention with a thin film and using it in liquid packaging provides a number of advantages over containers used in the past. In the case of this pouch, (1) low consumption of natural sources, (2) small space required for landfill, (3) reusable, (4) easy processing, (5) required Small storage space, (6) low energy use for storage (heat transfer characteristics of the package), (7) safe incineration, and (8) reusable (eg empty Can be used in other applications such as freezer bags, sandwich bags and general purpose storage bags).

Batch inclusion package:
Batch inclusion packages are made from the ethylene copolymer composition (A), (A ′), (A ″) or (A ′ ″) or a composition containing any of these. This is a batch inclusion package. This package is made from a film and used to protect it by including powders, pellets and flowable material, where the entire package (ie film and contents) is protected during the production of a product. For example, the package can be placed in an extruder / mixer at the same time as the product contained therein.

The ethylene-based copolymer composition (A), (A ′), (A ″) or (A ′ ″) used in the film of this batch inclusion package is preferably used as only one polymer component. . However, blending and / or multi-layer extrusion and / or multi-layer lamination of other polymers together with the ethylene copolymer composition (A), (A ′), (A ″) or (A ′ ″) By doing so, the processability, film hardness, film barrier properties, film strength, film melting properties or other desired film properties of the film may be modified. The ethylene-based copolymer composition (A), (A ′)
, (A ″) or (A ′ ″) and other polymer components made with a suitable blend of polymer components will still maintain improved performance. Some useful polymer blend components include, for example, ethylene / vinyl acetate copolymer (EVA), ethylene / vinyl alcohol copolymer (EVOH), polybutylene (PB), linear with a density of 0.941 to 0.965 g / cm ³ . High density polyethylene (HDPE) and linear low density polyethylene (LLDPE) produced with a conventional Ziegler catalyst having a density of 0.87 to 0.94 g / cm ³ are included. Preferably, the ethylene copolymer composition (A), (A ′), (A ″) or (A ′ ″) is at least about 50 percent of the blend composition, more preferably It constitutes at least about 80 percent of the blend composition. However, very preferably, the inner layer consists essentially of at least one said ethylene-based copolymer composition (A), (A ′), (A ″) or (A ′ ″). .

In addition, the ethylene-based copolymer composition (A), (A ′), (A ″) or (A ′ ″), other additives, to the extent that they do not interfere with the function of this batch inclusion package, For example, plasticizers, antioxidants, phosphites, cling additives, heat stabilizers, light stabilizers (eg Cyasorb ™ UV 531 benzophenone manufactured by Cyanamid and Chiba Geigy Corp. Tinubin ™ 622 hindered amine light stabilizers), pigments (eg titanium dioxide, calcium carbonate, carbon black etc.), processing aids (eg polyethylene glycol, fluoropolymers, fluoroelastomers, waxes etc.), flame retardants (For example, Amgard ™ CPC 102, a phosphorus-based flame retardant manufactured by Albright and Wilson Americas),
Lubricants (eg, waxes, stearates, mineral oils, etc.), slip agents (eg, erucamide, oleamide, etc.), anti-blocking additives (eg, talc, silicon dioxide, etc.), crosslinking agents (eg, peroxides (eg, DuPont) Booster (TM) etc.)),
Anti-fogging agents (eg Atmer ™ 100 sorbitan ester manufactured by ICI), impact modifiers (eg Paxon ™ Pax Plus, a rubber-modified film resin manufactured by Allied Corp.) , Antistatic agents (such as Armostat 410, an ethoxylated tertiary amine manufactured by Akzo Chemical, Inc.), fillers (such as talc, calcium carbonate, clay, fumed silicas, etc.) Is possible. This list of additives is merely exemplary and is not intended to be exhaustive or limiting.

Films and film structures having the novel properties described herein can be manufactured using conventional hot blown film or cast film manufacturing techniques. It is also possible to use a biaxial orientation method such as a tenter frame or double bubble method in cooperation with this normal manufacturing technique. Conventional hot blown film methods are described, for example, in “The Encyclopedia of Chemical Technology”, Kirk-Othmer, 3rd edition, John Wiley & Sons, New York, 1981, 16, 416-417 and 18, 191-192. It is described in. Biaxially oriented film manufacturing methods, such as the “double bubble” method as described in US Pat. No. 3,456,044 (Pahlke), as well as US Pat. No. 4,865,920 (Golike et al.), US Pat. No. 4,352,849 (Mueller), US Pat. No. 4,820,557 (Warren), US Pat. No. 4,927,708 (Herran et al.),
The novel films and film structures described herein can also be produced using methods such as those described in US Pat. No. 4,963,419 (Lustig et al.) And US Pat. No. 4,952,451 (Mueller). it can. It is also possible to produce this film and film structure as described in tenter frame technology, such as technology used in polypropylene orientation.

The film may be a single layer or a multilayer film, but the ethylene-based copolymer composition (A), (A ′), at least one layer of the film structure, preferably the inner layer, At least one of (A ″) or (A ′ ″) is used. This inner layer is the layer adjacent to the material to be included in the package. "Society of Plastics Engineers RETEC Proceedings", June 15-17 (1981), "Coextrusion For Barrier Packaging" on pages 211-229, WJ Schrenk
And, as described by CRFinch, the inner layer may be coextruded with another layer (s) or the inner layer may be laminated to another layer (s) in a secondary operation. Tubular film (ie blown film technology) or flat die (ie cast film) as described by KROsborn and WAJenkins in “Plastic Films, Technology and Packaging Applications” (Technnomic Publishing Co., Inc. (1992)). Can be used to produce a single layer film, and optionally the film can be added to another layer of packaging material or it can be extruded and laminated to produce a multilayer structure. It may be subjected to a post-extrusion step. Even if this film is a coextruded product of two or more layers (also described by Osborn and Jenkins), depending on other physical requirements for the final packaging film,
This film may be further laminated to additional layers of packaging material. In addition, D. Dumbleton's "Laminations Vs. Coextrusion" (Converting Magazine (September 1992)) discusses the contrast between coextrusion and lamination. It is also possible to subject the monolayer and coextruded films to other post-extrusion techniques such as biaxial orientation.

  Extrusion coating is yet another technique for producing multilayer packaging materials. Like cast film, extrusion coating is a flat die technique. Film layers can be extrusion coated onto a substrate in the form of either a single layer or a coextruded extrudate.

  In the case of a polymer blend and / or a multilayer film structure, generally an all-multilayer film structure is obtained with the ethylene copolymer composition (A), (A ′), (A ″) or (A ′ ″). At least one layer, preferably the inner layer. Other layers of the multilayer structure include, but are not limited to, barrier layers and / or tie layers and / or structural layers. A variety of materials can be used for such layers, some of which can be used as two or more layers in the same film structure. Some of these materials include ethylene / vinyl alcohol (EVOH) copolymers, polyvinylidene chloride (PVDC), polyethylene terephthalate (PET), oriented polypropylene (OPP), high density polyethylene (HDPE), ethylene / vinyl acetate. (EVA) copolymers, ethylene / acrylic acid (EAA) copolymers, ethylene / methacrylic acid (EMAA) copolymers, LLDPE, HDPE, LDPE, nylon, adhesive graft polymers (eg, polyethylene grafted with maleic anhydride) ) And paper. The multilayer film structure typically includes 2 to 7 layers.

Single layer film or multilayer film structures typically have a thickness of 0.2 mil (5 microns) to 15 mils (381 microns) (total thickness), preferably 1 mil (25.4 microns) to 5 mils ( 127 microns). For coextrusion (or multi-layer extrusion), the inner layer containing this substantially linear ethylene / α-olefin polymer is typically from 0.2 mil (5 microns) to 15 mils (381 microns). Preferably from 1 mil (25.4 microns) to 5 mils (127 microns).

Films and film structures made from the ethylene-based copolymer composition (A), (A ′), (A ″) or (A ′ ″) can be used as bags, liners or Process into packaging material. For example, a tub liner can be used to blend various materials sequentially, where the contents and liner are transferred from one tab to another and further blended with other ingredients. , And optionally send to a powerful mixer. In another example, an additive used in rubber manufacture may be packaged in a bag, and the entire bag containing its contents is added to the process without being opened during rubber manufacture. Techniques for using and manufacturing such batch-containing bags include U.S. Pat.No. 4,394,473, U.S. Pat.No. 5,120,787, U.S. Pat.No. 4,248,348,
It is well known in the industry as described in all of European Patent Application 0 270902 and Canadian Patent 2,053,051.

Numerous advantages are obtained when the ethylene-based copolymer composition (A), (A ′), (A ″) or (A ′ ″) is used in batch inclusion bags and films. The ethylene-based copolymer composition (A), (A ′), (A ″) or (A ′ ″) exhibits excellent processability with respect to the production of blown films and is also a conventional Ziegler catalyst. It has a lower melting point and softening range compared to polyethylene produced by Further, since the ethylene copolymer composition (A), (A ′), (A ″) or (A ′ ″) is made of carbon and hydrogen atoms, ethylene / acrylic acid or ethylene / In contrast to using batch inclusion films and bags made from methacrylic acid copolymers (as described in EP 0 270 902), or ethylene / vinyl acetate copolymers ( Compared to films and bags made from such as described in US Pat. No. 5,120,787 and US Pat. No. 4,248,348, the ethylene copolymer compositions (A), (A ′), (A ′ ') Or (A''') is compatible with various elastomer additives particularly useful in the rubber industry.

  The material (s) placed in this batch containing bag (or packaging material, dressing or liner) is a material that exhibits free flow (i.e. this material (s) flows easily under its own weight under gravity). There may be, or they may be materials that do not exhibit free flow (ie, this material (s) does not flow under its own weight under gravity). This material (s) varies, but typically includes materials that do not exhibit free flow, such as unvulcanized rubber, uncrosslinked elastomers, and tars.

  Typical materials showing free flow include clay, silicate, calcium carbonate, cadmium diethyldithiocarbamate, tetramethylthiuram disulfide, benzothiazyl disulfide, substituted thioesters and amine type antioxidants, aniline anti-ozone derivatives, diamines And / or thiourea curing agents selected from sulfur, sulfur-providing compounds and peroxides, UV agents selected from substituted benzotriazoles and substituted benzophenones, iron oxides, titanium dioxide and organic dyes Reinforcing pigments selected from color pigments, carbon black, zinc oxide and hydrated silicon compounds, processing aids such as silicon dioxide, pumice, stearates and rubber processing oils, cross-linked elastomers, materials for unvulcanized rubber compounds , Ground tire, herbicide, sterilization Bi agents, and the like chlorinated polyethylene (CPE). Free flow materials that are effectively included within the packages of the present invention include solids in addition to liquids.

In the rubber industry, typically small amounts of rubber processing oil (eg, 0.5 to 10 weight percent)
In use, this is mixed with at least one other compounding material. The materials listed above are not intended to be all-inclusive of, but limited to, the materials that can be packaged using the novel package of the present invention.

  The packages of the present invention relate to compounding materials that are encased or wrapped and also relate to mixtures thereof with additives such as rubber processing oils. In the case of unvulcanized rubber, in general, a film is attached around the rubber, and in the case of a wrapping form, the rubber is tightly wrapped with the film, and then the film is heated and sealed against itself. Adhering under normal tension to complete the package. In forming the package, it is desirable to heat seal the film, but this is not necessary.

  Products made from this batch inclusion package vary according to the type of material to be included in this package. Some products include asphalt animal feed and wire. For example, packaging of ground tires in asphalt manufacturing, packaging of titanium dioxide in animal feed manufacturing, and packaging of CPE in wire film manufacturing, using the batch inclusion package of the present invention, and including the specific materials listed above therein . Other products include various rubbers (eg, by packaging rubber or rubber additives in the batch-containing films described herein). It is also possible to produce energy by packaging waste material (such as heavy tar effluent or waste plastic) and placing the entire package in an incinerator. It is also possible to form other useful products, such as garbage bags or park benches, by packaging and reusing waste plastic and other materials.

Inner container for back-in box:
The inner container for bag-in-box is formed of a film made of the ethylene copolymer composition (A), (A ′), (A ″) or (A ′ ″).

The thickness of the film forming the bag-in-box interior container varies depending on the specific contents or manufacturing method, but is usually 30 to 1000 μm, preferably 50 to 700 μm.

The wall of the interior container for bag-in-box according to the present invention is:
(I) the blocking force is less than 1.0 g / cm,
(Ii) 20 after the number of repeated twists in the gelboflex tester reaches 2000 times.
The number of pinholes in an area of 5cm x 28.0cm is 2 or less,
(Iii) The film preferably has a bending resistance of 90,000 times or more measured according to JIS P-8115. Further, a film having a neck-in at the time of molding of 20 cm or less on one side is preferable.

  The bag-in-box interior container may be formed of a single-layer film composed of the ethylene copolymer composition (A), (A ′), (A ″) or (A ′ ″), Films composed of (A), (A '), (A ") or (A' '') and other resins (nylon, ethylene / vinyl alcohol copolymer, polyvinyl alcohol (EVOH), adhesive resin, etc.) ) May be formed from a so-called multilayer film.

  The bag-in-box interior container has, for example, a substantially cubic shape as a whole, and a lid is attached to the upper end portion of the inner container, and when this cube is cut obliquely, it is thick at a position corresponding to the peripheral portion. There is a thick heat seal part. The bag-in-box interior container is formed so that one container half can be folded and inserted so as to overlap the other container half.

  An interior container for a bag-in-box is filled with a liquid or the like and stored or transported in a hard outer container such as a cardboard box. An empty container has one container half attached to the other container half. Stored or transported in a shape inserted and folded so as to overlap the body.

As described above, when the bag-in-box interior container is folded, inflated into a cube shape, or filled with the content liquid and transported, various forces are applied to the corner of the bag-in-box interior container. Therefore, pinholes are likely to be generated due to severe stress more than that of a general flat bag. Therefore, the interior container is required to have high performance such as pinhole resistance, bending resistance, and blocking resistance.
The bag-in-box interior container according to the present invention satisfies the required physical properties as described above.

The interior container for bag-in-box can be manufactured, for example, by the following method.
(I) Using a mold having such a shape that two molten resins are extruded into a sheet shape by a T-die arranged in parallel in the length direction, and the peripheral portions of the opposing surfaces of the container can be joined. Vacuum forming method.
(Ii) A method in which a resin melted in a cylindrical shape is extruded from a circular die (parison extrusion), and hollow molding is performed using a mold similar to the above.
(Iii) A method of stacking two or more resin films and heat-sealing four sides to form a bag (in this case, the film is the composition (A), (A ′), (A ″) or (A ''') Or a film made of the composition (A), (A'), (A '') or (A ''') and another resin (nylon, A so-called multilayer film obtained by laminating films made of ethylene / vinyl alcohol copolymer resin (EVOH), polyvinyl alcohol, adhesive resin, etc.) may also be used.

Such a bag-in-box is excellent in thermal stability, blocking resistance, pinhole resistance and flex resistance, and is excellent in economic efficiency, so it can be used for liquor, vinegar, photographic developer, bleach,
Widely used as a container for storing various liquids such as a bactericide solution.

Medical container:
The medical container is a bag made of a multilayer film, a bag made of a single layer film, a bottle made of a single layer, or the like. It is formed from an object (A), (A ′), (A ″) or (A ′ ″).

  The medical container can be produced by a water-cooled or air-cooled inflation method, a T-die method, a dry lamination method, an extrusion lamination method, a hollow molding method, or the like. As a method for molding a medical bag, an inflation method and a coextrusion T-die method are preferable from the viewpoint of hygiene and economy, and a hollow molding method is preferable as a method for molding a medical bottle.

The thickness of the medical container is usually in the range of 0.05 to 1.00 mm, preferably 0.1 to 0.7 mm, and more preferably 0.15 to 0.3 mm. If the thickness of the container is 0.05mm or more,
It has good impact resistance and does not cause any practical problems.

Such medical containers do not lose transparency even when sterilized, have excellent heat resistance, and do not cause wrinkles or deformation.
Heat-resistant container:
The heat-resistant container is a bag made of a multilayer film, a bag made of a single layer film, a multilayer bottle, a single layer bottle, etc., and at least one layer of the multilayer film, a single layer film, at least one layer of the multilayer bottle, The ethylene-based copolymer composition (A), (A ′), (A ″) or (A ′ ″) is formed.

  When the heat-resistant container is a multilayer, there are no particular restrictions on layers other than the composition (A), (A ′), (A ″) or (A ′ ″), and polypropylene, nylon, polyester, polyvinyl Alcohol or the like may be used.

The heat-resistant container can be produced by a water-cooled or air-cooled inflation method, a T-die method, a dry lamination method, an extrusion lamination method, a hollow molding method, or the like.
When the heat-resistant container is in the form of a bag, the inflation method and the co-extrusion T-die method are preferable from the viewpoint of hygiene and economy, and when the heat-resistant container is in the shape of a bottle, the hollow molding method is preferable. .

The thickness of the heat-resistant container is in the range of 0.05 to 1.00 mm, preferably 0.1 to 0.7 mm, and more preferably 0.15 to 0.3 mm. If the thickness of the container is 0.05 mm or more, the impact resistance is good and there is no practical problem.

The heat-resistant container of the present invention has a haze (ASTM D-1003-61) of 3 after heat sterilization.
0% or less, preferably 20 to 0%.
Moreover, the heat deformation start temperature of the heat-resistant container is 115 ° C. or higher, and the thickness of the retort food container is usually in the range of 0.05 to 1.00 mm.

  The thermal deformation start temperature is measured as follows. That is, a sample of a bag or bottle made of a molded film is sterilized with hot water at a sterilization temperature × 30 minutes using a small heat and high pressure steam sterilizer manufactured by Alps RK-4016, and the sample taken out from the sterilizer is visually observed. And evaluate the change. Starting from a sterilization temperature of 110 ° C., the sterilization temperature is increased by 1 ° C. after each sterilization. This operation is repeated, and when the sample taken out from the sterilizer is deformed for the first time, the sterilization temperature is set as the deformation start temperature.

Such heat-resistant containers, such as retort food containers, do not lose transparency even when sterilized, and are excellent in heat resistance and impact resistance.
Elastic fiber:
The elastic fiber is a fiber in which the fiber exhibits a recovery rate of at least 50% at 100% strain, and the ethylene-based copolymer composition (A), (A ′), (A ″) or (A ′ ″). Consists of.

Fiber is typically classified according to the diameter it has. Monofilament fibers are generally defined as having an individual fiber diameter of greater than about 15 denier per filament, usually greater than about 30 denier. Fine denier fibers are generally applied to fibers having a diameter of less than about 15 denier per filament. Microdenier fibers are generally defined as fibers having a diameter of less than 100 microns. Fibers can also be classified in the way they are manufactured, for example, as monofilaments, continuous wound fine filaments, staples or shortcut fibers, spun bond and melt blown fibers. Can be divided.

The melt index in the case of the ethylene copolymer composition (A), (A ′), (A ″) or (A ′ ″) used in the production of the elastic fiber used herein is a monofilament (generally, For fibers greater than 15 denier / filament) is generally from 0.01 g / 10 min to 1000 g / 10 min, preferably from 0.1 g / 10 min to 5 g / 10 min, and small denier fibers (generally 15 denier in diameter) / Fibers equal to or less than the filament) is preferably 5 g / 10 min to 250 g / 10 min.

The ethylene-based copolymer composition (A), (A ′), (A ″) or (A ′ ″) used in the production of this elastic fiber also contains improved fibers and Additives such as antioxidants, phosphites, cling additives, antiblock additives and pigments may also be included to the extent that they do not interfere with the dough properties.

A variety of homofil fibers can be produced using this ethylene copolymer composition (A), (A ′), (A ″) or (A ′ ″). Homofil fiber is a single region (domain)
And has no other distinct polymer regions (as do bicomponent fibers). Such homofil fibers include staple fibers, spunbond fibers or meltblown fibers (eg, US Pat. No. 4,340,563 (Appel et al.), US Pat. No. 4,663,220 (Wisneski et al.), US Pat. No. 4,668,566 (Braun) or US Pat. 4,322,027 (Reba)) and gel spun fibers (eg, the system disclosed in US Pat. No. 4,413,110 (Kavesh et al.)). Staple fibers can be melt spun (ie, they can be extruded directly to the final fiber diameter without additional stretching) or they can be melt spun to yield fibers with large diameters. After that, the desired diameter can be obtained by heat drawing or cold drawing using a normal fiber drawing technique. The novel elastic staple fibers disclosed herein can also be used as binding fibers, particularly where the novel elastic fibers have a lower melting point than the matrix fibers surrounding them. In bonding fiber applications, typically, the bonding fiber is blended with other matrix fibers and then the entire structure is heated, where the bonding fiber melts and surrounds it. Connect the existing matrix fibers. Typical matrix fibers that would benefit from using this new elastic fiber include, but are not limited to, poly (ethylene terephthalate) fiber, cotton fiber, nylon fiber, polypropylene fiber, and other non-uniformly distributed fibers. Branched polyethylene fibers as well as linear polyethylene homopolymer fibers are included. Depending on the end use application, the diameter of this matrix fiber can be varied.

  Surprisingly, the recovery rate exhibited by melt spun fibers made from this ethylene copolymer composition (A), (A '), (A' ') or (A' '') The recovery rate is approximately the same as that of a fiber that has been melt-spun so that it is twice or three times the diameter of the spun fiber and then cold drawn to the same diameter. Since elasticity here is not the result of an orientation that would be ineffective upon heat treatment, a product is obtained that has the ability to maintain its elastic performance upon subsequent thermal exposure.

  In the case of the novel elastic fiber disclosed herein, the ethylene-based copolymer composition (A), (A ′), (A ″) or The melt index of (A '' ') can be varied widely. As a result, the strength and shrinkage force of the fiber and the fabric can be changed independently of the elasticity thereof, so that the flexibility regarding the design of the fabric and the final product can be further increased. For example, changing the melt index of the polymer rather than the fiber diameter can change the shrink force of this fiber (lower melt index results in higher shrink force) and thus the elasticity / requirement required for the fabric. It is possible to better optimize the “hand” (ie, feel) of the fabric while maintaining strength performance.

  It is also possible to produce bicomponent fibers using this ethylene copolymer composition (A), (A ′), (A ″) or (A ′ ″). At least a part of the bicomponent fiber is made into the ethylene copolymer composition (A), (A ′), (A ″) or (A ″ ′). For example, in the case of a shell / core bicomponent fiber (ie, a fiber in which the shell concentrically surrounds the core), the ethylene copolymer composition (A), (A ′), (A ″) or (A ″ ′) can be present in either the shell or the core. Also, different ethylene copolymer compositions (A), (A '), (A' ') or (A' '') can be used independently as a shell and a core in the same fiber, In this case, preferably both components are elastic and in this case in particular the melting point of the shell component is lower than the melting point of the core component. Other types of bicomponent fibers are also within the scope of the present invention, including side-by-side fibers (eg, fibers having individual polymer regions, where the ethylene And a structure such as (a), (A ′), (A ″) or (A ′ ″) constitute at least a part of the fiber surface).

  The shape of this fiber is not limited. For example, typical fibers have a circular cross-sectional shape, but sometimes the fibers have a different shape, such as a trilobal shape or a flat (ie, “ribbon” -like) shape. The elastic fiber disclosed in the present specification is not limited by the fiber shape.

Fiber diameter can be measured and reported in a variety of ways. Generally, the fiber diameter is measured in denier per fiber. Denier is a fabric term defined as the number of grams of fiber per 9000 meters of fiber length. Monofilaments are generally applied to extruded strands with a denier per filament of 15 or more, usually 30 or more. Small denier fibers are generally applied to fibers having a denier of about 15 or less. Microdenier (also known as microfiber) is generally applied to fibers having a diameter of about 100 micrometers or less. In the case of the novel elastic fiber disclosed herein, the diameter can be varied widely with little effect on the elasticity of the fiber. However, the denier of this fiber can be adjusted to suit the function of the finished product, and is preferably 0.5 to 30 denier / filament for meltblown and 1 to 30 denier / filament for spunbond. And in the case of continuous wound filaments will be 1 to 20,000 denier / filament.

Fabrics made from the new fibers include both woven and non-woven fabrics. Nonwoven fabrics including spunlaced (or hydraulic entangled) fabrics such as those disclosed in US Pat. No. 3,485,706 (Evans) and US Pat. No. 4,939,016 (Radwanski et al.) Can be produced in a variety of ways. By fuzzing staple fibers and thermally bonding them, by spunbonding continuous fibers in a single continuous operation, or the resulting web after meltblown fiber Can be made by calendering or by heat bonding to produce a dough. Such various nonwoven fabric manufacturing techniques are well known to those skilled in the art, and the present disclosure is not limited to any particular method. Other structures made from the above fibers are also encompassed within the scope of the present invention, including, for example, blends of the new fibers with other fibers such as poly (ethylene terephthalate) (PET) or cotton. Etc. are included.

The term “consisting essentially of” as used in the claims herein refers to the ethylene-based copolymer composition (A), (A ′), (A ″) or It means that (A ″ ′) can contain additional materials that do not substantially affect the elasticity of this fiber or fabric. Such effective non-limiting additive materials include pigments, antioxidants, stabilizers, surfactants [eg, US Pat. No. 4,486,552 (Niemann), US Pat. No. 4,578,414 (Sawyer et al.) Or US Pat. No. 4,835,194. (As disclosed in Bright et al.).

Articles of manufacture that can be manufactured using the novel elastic fibers and fabrics disclosed herein include composite fabric products (eg, diapers, etc.) that are desired to have a portion that exhibits elasticity. For example, elastic parts such as a waistband part of a diaper for preventing a diaper from slipping and a leg band part for preventing a leak are desired (as shown in US Pat. No. 4,381,781 (Sciaraffa)). ). This elastic part often helps to make the shape fitting and / or fastening system better for a good combination of comfort and reliability. Structures that combine elasticity and breathability can also be produced using the novel elastic fibers and fabrics disclosed herein.

The novel elastic fibers and fabrics disclosed herein are also US Pat. No. 2,957,512 (Wade).
Can be used in various structures as described in 1. For example, the layer 50 (ie, the elastic component) of the structure described in this US Pat. No. '512 (particularly here the non-elastic material is flattened, pleated and creped. Etc.) to produce a structure exhibiting elasticity) can be replaced with this new elastic fiber and fabric. The novel elastic fibers and / or fabric can be attached to non-elastic fibers, fabrics or other structures by melt bonding or using an adhesive. Using this new elastic fiber and / or fabric and a non-elastic component, before pleating and mounting the non-elastic component (as described in US Pat. No. '512) prior to installation Gathered or sheared elastic structures can be produced from the elastic components by stretching them in advance or attaching them and then thermally shrinking the elastic components.

  It is also possible to use the novel elastic fibers described herein in a spunlaced (or hydraulic entanglement) process to produce new structures. For example, the elastic sheet (12) disclosed in US Pat. No. 4,801,482 (Goggans) can be manufactured here using the novel elastic fibers / fabric described herein.

The continuous filaments exhibiting elasticity as described herein can also be used in weaving applications where high impact resilience is desired.
Also, the toughness and shrinkage of the novel elastic fibers and fabrics disclosed herein can be adjusted, which is the same as described, for example, in US Pat. No. 5,196,000 (Clear et al.) If necessary. In garments, the design can be flexible with respect to changing the contraction force.

US Pat. No. 5,037,416 (Allen et al.) Describes the advantages of a conformable topsheet by using elastic ribbons (see member 19 of US Pat. No. '416).
The novel elastic fiber can perform the function shown by the member 19 of US '416, or it can be used in the form of a fabric that provides the desired elasticity.

  Composites in which linear polyethylene or copolymer polyethylene having a very high molecular weight are utilized can also benefit from the use of the novel elastic fibers disclosed herein. For example, the new elastic fiber has a low melting point (the melting point of the polymer and the density of the polymer are in an essentially linear relationship), and as a result, described in US Pat. No. 4,584,347 (Harpell et al.). In the case of a blend of this new elastic fiber with a polyethylene fiber having a very high molecular weight such as Spectra ™ fiber manufactured by Allied Chemical, the low melting point elastic fiber has its high molecular weight The high molecular weight fibers are joined without melting the polyethylene fibers, thus maintaining the high strength and integrity exhibited by the high molecular weight fibers.

In US Pat. No. 4,981,747 (Morman), replacing the elastic sheet 122 forming a composite elastic material including a reversibly necked material with the novel elastic fibers and / or fabrics disclosed herein it can.

  This novel elastic fiber may also be a meltblown elastic component as described by reference numeral 6 in the figure of US Pat. No. 4,879,170 (Radwanski). U.S. Pat. No. '170 generally describes a co-molding material that exhibits elasticity and a method of manufacture.

It is also possible to produce elastic panels using the novel elastic fibers and fabrics disclosed herein, such as members 18, 20 of US Pat. No. 4,940,464 (Van Gompel).
, 14 and / or 26 and the like. The novel elastic fibers and fabrics described herein can also be used as an elastic component of a composite side panel (eg, layer 86 of US '464).

Foam molding:
The foamed molded product can be molded into various shapes including a rod shape, a tube shape, a tape shape, a sheet shape, and the like, and is used as a buffer, a heat insulating material, a base material for a poultice, and the like.

  The foamed molded article is obtained by mixing the ethylene copolymer composition (A), (A ′), (A ″) or (A ′ ″) and a foaming agent, and heating or decompressing the foamed foam. It is produced by generating bubbles in the resin molding by gasification of the agent or foaming of the decomposition gas.

As a manufacturing method of a foaming molding, the following manufacturing method is mentioned, for example.
(1) Extrusion foaming method The ethylene copolymer composition (A), (A '), (A'') or (A''') is placed in a hopper of an extruder, and the temperature is around the melting point of the resin. A method of continuously obtaining a foam by extruding a physical foaming agent from a press-fit hole provided in the middle of an extruder and extruding it from a die having a desired shape when extruding. Examples of the physical foaming agent include volatile foaming agents such as chlorofluorocarbon, butane, pentane, hexane, and cyclohexane, and inorganic gas foaming agents such as nitrogen, air, water, and carbon dioxide. In addition, a bubble nucleating agent such as calcium carbonate, talc, clay or magnesium oxide may be added during extrusion foaming.

The blending ratio of the physical foaming agent is usually 5 to 60 parts by weight, preferably 10 to 100 parts by weight of the composition (A), (A ′), (A ″) or (A ′ ″). ~ 50 parts by weight. When the blending ratio of the physical foaming agent is too small, the foaming property of the foam is lowered, and conversely when it is too much, the strength of the foam is lowered.
(2) The ethylene-based copolymer composition (A), (A ′), (A ″) or (A ′ ″), an organic pyrolytic foaming agent such as azodicarbonamide, and other if desired Using a kneading device such as a single-screw extruder, twin-screw extruder, Banbury mixer, kneader mixer, roll, etc., the additive and thermoplastic resin are melt-kneaded at a temperature below the decomposition temperature of the pyrolytic foaming agent, A method of preparing a foamable resin composition, generally forming it into a sheet, and then heating the sheet to a temperature equal to or higher than the decomposition temperature of the foaming agent to obtain a foam,
The blending ratio of the organic pyrolytic foaming agent is usually 1 to 50 parts by weight with respect to 100 parts by weight of the composition (A), (A ′), (A ″) or (A ′ ″). Preferably it is 4-25 weight part. If the blending ratio of the organic pyrolytic foaming agent is too small, the foaming property of the foam is lowered, and conversely if it is too much, the strength of the foam is lowered.
(3) Foaming method in a pressure vessel The ethylene-based copolymer composition (A), (A '), (A'') or (A''') is formed into a sheet or block by a press or an extruder. The molded body is then molded into a shape, and then the molded body is put into a pressure vessel, the physical foaming agent is sufficiently dissolved in the resin, and then the pressure is reduced to obtain a foamed body. It is also possible to fill the pressure vessel filled with the molded body with a physical foaming agent at room temperature, pressurize it, remove it after decompression, and heat it in an oil bath, oven or the like to foam.

If the ethylene copolymer composition (A), (A ′), (A ″) or (A ′ ″) is previously cross-linked, a cross-linked foam can be obtained.
Generally, crosslinking methods include thermal radical decomposition of a peroxide radical generator mixed in a resin, crosslinking by irradiation with ionizing radiation, crosslinking by irradiation with ionizing radiation in the presence of a polyfunctional monomer, and silane. Crosslinking etc. can be illustrated.

  In order to obtain a crosslinked foam by such a method, the composition (A), (A ′), (A ″) or (A ′ ″), an organic pyrolytic foaming agent, and a crosslinking aid The functional monomer and other compounding agents are melt-kneaded at a temperature lower than the decomposition temperature of the thermally decomposable foaming agent to form a sheet. The obtained foamable resin composition sheet is quantitatively irradiated with ionizing radiation to crosslink the composition (A), (A '), (A' ') or (A' ''), The foam is heated to a temperature higher than the decomposition temperature of the foaming agent. Examples of the ionizing radiation include α rays, β rays, γ rays, and electron beams. In addition, peroxide crosslinking or silane crosslinking can be performed instead of irradiation crosslinking with ionizing radiation.

  In the present invention, in the composition (A), (A ′), (A ″) or (A ′ ″), a weather resistance stabilizer, heat resistance stabilizer, anti-slip agent, as long as the object of the present invention is not impaired. Additives such as anti-blocking agents, anti-fogging agents, lubricants, pigments, dyes, nucleating agents, plasticizers, anti-aging agents, hydrochloric acid absorbents and antioxidants may be blended as necessary. Also, other polymers can be blended in small amounts without departing from the spirit of the present invention.

Such a foam is excellent in flexibility and toughness.
Form structure:
The foam structure is composed of the ethylene-based copolymer composition (A), (A ′), (A ″) or (A ′ ″).

Using a blend of ethylene copolymer composition (A), (A '), (A'') or (A''') and another suitable ethylene polymer or other natural or synthetic polymer Is possible. Other suitable ethylene-based polymers are low density polyethylene (LDPE), medium density polyethylene (MDPE) and high density polyethylene (HDPE) (eg, US Pat. No. 4,076,698).
), Ethylene / vinyl acetate copolymers, copolymers of ethylene and ethylenically unsaturated carboxylic acids, homo- and copolymers of α-ethylenes. Other suitable polymers include polystyrene (including high impact polystyrene), styrene-butadiene block copolymers, polyisoprene and other rubbers. Blends containing high melting point resins in a major proportion are preferred. The composition (A), (A ′), (A ″) or (A ′ ″) for producing a foam structure, or a blend containing these is referred to as an ethylene-based polymer material.

  Regardless of composition, the ethylene-based polymer material preferably contains 50 wt% or more, more preferably 70 wt% or more of ethylene monomer units. The ethylene-based polymer material may consist entirely or entirely of ethylene monomers. Preferred blends are ethylene copolymer compositions (A), (A ′), (A ″) or (A ′ ″) and other conventional ethylene polymers such as LDPE, HDPE, ethylene / acrylic. It contains acid copolymer (EAA) and LLDPE.

Additives such as antioxidants (eg hindered phenols (Irganox ™ 1010), phosphites (eg Irgafos ™ 168)), pigments have improved properties discovered by the applicant. It can also be contained in the ethylene-based copolymer composition (A), (A ′), (A ″) or (A ′ ″) to the extent that it does not inhibit.

An excellent teaching on how to make foam structures and how to process them is CPPark's “Polyolefin Foam” Chapter 9 Handbook edited by D. Klempner and KCFrisch
of Polymer Foams and Technology, Hanser Publishers, Munich, Viena, New York, Barcelona (1991).

  This foam structure can be produced by conventional extrusion foaming methods. This structure generally heats the ethylene-based polymer material to form a plasticized or molten polymer material, puts a blowing agent therein to form a foamable gel, and forms a foam product Can be prepared by extruding the gel through a die. Prior to mixing with the blowing agent, the polymeric material is heated to a temperature above its glass transition temperature or melting point. The blowing agent may be placed or mixed into the molten polymer material by any conventional means such as an extruder, mixer, blender. The blowing agent is mixed with the molten polymeric material at a high pressure sufficient to inhibit substantial foaming of the molten polymeric material and to disperse the blowing agent substantially homogeneously. If desired, the nucleating agent may be blended into the polymer melt or may be dry mixed with the polymer material prior to plasticization or melting. The foamable gel is usually cooled to a lower temperature in order to optimize the physical properties of the foam structure. The gel is then extruded or transported through a die of the desired shape into a vacuum or lower pressure zone to form a foam structure. The lower pressure zone is a pressure that is lower than the pressure maintained before the foamable gel is extruded through the die. The lower pressure may be higher than atmospheric pressure or lower (vacuum), but is preferably at atmospheric pressure level.

  This structure may be processed in the form of agglomerated strands by extrusion of ethylene-based polymer material through a multi-orifice die. The orifices are such that contact between adjacent streams of melt extrudate occurs during the foaming process, and the contacting surfaces adhere to each other with sufficient adhesion to form a unitary foam structure. Has been placed. The molten extrudate stream exiting the die takes the form of a strand or profile that desirably foams, agglomerates and adheres to each other to form a unitary structure. Desirably, the agglomerated individual strands or profiles should remain attached in a unitary structure so that the strands do not delaminate with the stresses encountered when preparing, shaping, and using the foam. Methods and apparatus for producing foam structures in the form of agglomerated strands can be found in US Pat. Nos. 3,573,152 and 4,824,720.

This foam structure may also be formed by a cumulative extrusion process, as found in US Pat. No. 4,323,528. In this method, a low density foam structure having a large side cross-sectional area 1) forms a gel of an ethylene-based polymer material and a blowing agent under pressure, where the viscosity of the gel is when the gel foams Forming at a temperature sufficient to hold the foaming agent, 2) extruding the gel into a holding zone maintained at a temperature and pressure that does not cause the gel to foam, wherein the holding zone foams the gel With an outlet die surrounding the orifice opening to the lower pressure zone, and an openable gate closing the die orifice, 3) Periodically opening the gate, 4) Moving onto the gel The mechanical pressure is applied substantially simultaneously by the ram, and it is passed through the die orifice from the holding zone to the lower pressure zone. Where the release occurs at a rate greater than the substantial foaming in the die orifice and at a lower rate than the substantial irregularity of the cross-sectional area or shape, and 5) prepared by foaming the released gel unconstrained in at least one direction to yield a foam structure.

  The foam structure can also be processed into uncrosslinked foam beads suitable for product molding. To produce foam beads, discrete resin particles such as granular resin pellets are suspended in a liquid medium in which the resin is substantially insoluble, such as water; high temperature in an autoclave or other pressure vessel And at high pressure, impregnated with the blowing agent by introducing the blowing agent into the liquid medium; and rapidly expelled into the atmosphere or vacuum zone to form foam beads. This method is well taught in US Pat. Nos. 4,379,859 and 4,464,484.

As a derivation of the above method, prior to impregnation with the blowing agent, styrene monomer may be impregnated into the suspended pellets so as to form a graft copolymer with the ethylene-based polymer material. The polyethylene / polystyrene copolymer beads are cooled and discharged from the container without being substantially foamed. The beads are then expanded and molded by conventional expanded polystyrene bead molding methods. A method for producing polyethylene / polystyrene copolymer beads is described in US Pat. No. 4,168,353.

  The foam beads may then be formed by any means known in the art, eg, the beads are agglomerated and fused to load the foam beads into a mold and form a product. For example, the beads are formed by heating the beads with steam. If desired, the beads may be impregnated with air or other blowing agent at elevated temperatures and pressures prior to loading into the mold. Furthermore, the beads can be heated prior to loading. The foam beads can then be formed into blocks or shaped articles by any suitable forming method known in the art (some methods are described in US Pat. Nos. 3,504,068 and 3,953,558). An excellent teaching of the above methods and molding methods can be found in the above publications of C.P. Park at p191, p-197-198 and p-227-229.

Blowing agents useful for making this foam structure include inorganic blowing agents, organic blowing agents and degradable chemical blowing agents. Suitable inorganic blowing agents include carbon dioxide, nitrogen, argon, water, air, nitrogen and helium. Organic blowing agents are aliphatic hydrocarbons having 1 to 6 carbon atoms, fatty alcohols having 1 to 3 carbon atoms, and fully or partially halogenated having 1 to 4 carbon atoms. Containing modified aliphatic hydrocarbons. Aliphatic hydrocarbons include methane, ethane, bropan, n-butane, isobutane, n-pentane, isopentane and neopentane. Fatty alcohols include methanol, ethanol, n-propanol and isopropanol. Fully or partially halogenated aliphatic hydrocarbons include fluorocarbons, chlorocarbons, and chlorofluorocarbons. Examples of fluorocarbons are methyl fluoride, perfluoromethane, ethyl fluoride, 1,1-difluoroethane (HFC-152a), 1,1,1-trifluoroethane (HFC-143a), 1,1,1,2-tetra Including fluoroethane, 2,2-difluoropropane, 1,1,1-trifluoropropane, perfluoropropane, dichloropropane, difluoropropane, perfluorobutane, perfluorocyclobutane. Partially halogenated chlorocarbons and chlorofluorocarbons for use in the present invention are methyl chloride, methylene chloride, ethyl chloride, 1,1,1-trichloroethane, 1,1-dichloro-1-fluoroethane (HCFC- 141b), 1-chloro-1,1-difluoroethane (HCFC-142b), 1,1-dichloro-2,2,2-trifluoroethane (HCFC-123) and 1-chloro-1,2,2,2 -Including tetrafluoroethane (HCFC-124). Fully halogenated chlorofluorocarbons are trichloromonofluoromethane (CFC-11), dichlorodifluoromethane (CFC-12), trichlorotrifluoroethane (CFC-113), 1,1,1-trifluoroethane, pentafluoroethane , Dichlorotetrafluoroethane (CFC-114), chloroheptafluoropropane and dichlorohexafluoropropane. Chemical blowing agents are azodicarbonamide, azodiisobutyro-nitrile, benzenesulfone hydrazide, 4,4-oxybenzenesulfonyl semicarbazide, p-toluenesulfonyl semicarbazide, barium azidocarboxylate, N, N'-dimethyl-dinitrosotephthalamide and trihydra Contains dinotriazine. Preferred blowing agents include isobutane, HFC-152a and mixtures thereof.

  The amount of blowing agent placed in the polymer melt to produce the foam-forming gel is 0.2-5.0 gram mole / kg polymer, preferably 0.5-3.0 gram mole / kg polymer. And most preferably 1.0 to 2.50 gram mole / kg polymer.

  Various additives such as stability control agents, nucleating agents, inorganic fillers, pigments, antioxidants, acid scavengers, UV absorbers, flame retardants, processing aids and extrusion aids are included in this foam structure May be put inside.

  Stability control agents may be added to the foam structure to improve dimensional stability. Preferred stability control agents include amides and esters of C10-C24 fatty acids. Such stability control agents are found in US Pat. Nos. 3,644,230 and 4,214,054. The most preferred stability control agents include stearyl stearamide, glycerol monostearate, glycerol monobehenate and sorbitol monostearate. Typically, such stability control agents are used in amounts ranging from about 0.1 to about 10 parts per 100 parts of polymer.

  This foam structure exhibits excellent dimensional stability. The preferred foam recovers to more than 80% of the initial volume, which is measured 30 seconds after foam foaming. Volume is measured by a suitable method such as volume exclusion of water.

  In addition, nucleating agents may be added to control the foam cell size. Preferred nucleating agents include inorganic materials such as calcium carbonate, talc, clay, titanium dioxide, silica, barium sulfate, diatomaceous earth, a mixture of citric acid and sodium bicarbonate, and the like. The amount of nucleating agent used may range from about 0.01 to about 5 parts by weight per 100 parts by weight of the polymer resin.

This foam structure is substantially uncrosslinked or uncrosslinked. The alkenyl aromatic polymer material comprising this foam structure is substantially uncrosslinked. The foam structure is ASTM D
No more than 5% gel by Method A of -2765-84. Some crosslinking that occurs naturally without the use of crosslinking agents or radiation is acceptable.

The foam structure than 250 kg / cm ^3, more preferably less than 100 kg / cm ^3, and most preferably has a density of less than 10 to 70 kg / cm ^3. The foam has an average cell size according to ASTM D3576 of 0.05 to 5.0, more preferably 0.2 to 2.0, and most preferably 0.3 to 1.8 millimeters.

  The foam structure may take any physical shape known in the art such as extruded sheets, rods, planks and profiles. The foam structure may be formed by molding expandable beads into any of the above shapes or any other shape.

The foam structure may be closed cell or open cell. Preferably, the foam comprises 80% or more closed cells according to ASTM D2856-A.
Such tougher and more elastic foam structures would be very useful for sports and leisure applications and cushion packaging applications.

Foam structure:
The foam structure is composed of the ethylene-based copolymer composition (A), (A ′), (A ″) or (A ′ ″), and is strong and elastic, and has a low density.
Also, the structure of the present invention is more thermally stable than EVA foam structure and does not generate unpleasant odor during foam expansion, fabrication and use. Soft strong cross-linked foam structures are useful for sports equipment, medical devices and cushioning equipment.

In forming the foam structure, the ethylene copolymer composition (A), (A '), (A'') or (A''') and a different ethylene polymer or other suitable It is also possible to use blends with natural or synthetic polymers. Suitable different ethylene-based polymers are described in low density polyethylene (LDPE) (eg high pressure, free radical polymerization technology), medium density polyethylene (MDPE), and high density polyethylene (HDPE) (eg US Pat. No. 4,076,698). ), Ethylene / ester copolymers, ethylene / vinyl acetate copolymers, copolymers of ethylene and ethylenically unsaturated carboxylic acids, homopolymers and copolymers such as α-ethylenic materials, Can be mentioned. Other suitable polymers include polystyrene (including high impact polystyrene), styrene-butadiene block copolymers, polyisobrene, and other rubbers. Blends containing a high melting point resin in a major proportion are preferred. Regardless of composition, the ethylenic polymer material preferably comprises 50 wt% or more, more preferably 70 wt% or more of ethylenic monomer units. The ethylene-based polymer material may be composed entirely of ethylenic monomer units. Preferred blends are the ethylene copolymer composition (A), (A ′), (A ″) or (A ′ ″) and other conventional ethylene polymers such as LDPE, HDPE, ethylene / acrylic acid copolymers. (EAA), and a blend with LLDPE.

  The foam structure of the present invention can take any physical form known in the art, for example, sheet, plank, or burn stock form. Other useful foams are expandable or expandable particles, moldable expandable particles, or beads, and articles produced by expansion and / or fusion and welding of these beads.

  The excellent teaching on how to make foam structures and how to treat them can be found in Hancock, C.P. Park's “Polyolefin Foam” chapter 9, Handbook of Polymer Foams and Technology, Munich, Beana, New York, Barcelona. Seen by D. Klempner and KCFrisch, published by Publishers (1991).

The foamed structure of the present invention is obtained by blending and heating the ethylene copolymer composition (A), (A ′), (A ″) or (A ′ ″) and a degradable chemical foaming agent. Making a foamable plasticized or molten polymer material, extruding the foamable molten polymer material from a die, including a cross-linking agent in the molten polymer material, and exposing the molten polymer material to elevated temperature to form a blowing agent Manufactured by releasing and creating a foam structure. The polymeric material and the chemical blowing agent can be mixed and melt blended by means known in the art, such as an extruder, mixer, or blender. The chemical blowing agent is preferably dry blended with the polymer material prior to heating the polymer material to a molten form, but can also be added when the polymer material is in the molten phase. Cross-linking can be induced by the addition of cross-linking agents or by radiation. Induction of cross-linking and exposure to elevated temperatures to effect expansion or foaming can occur simultaneously or sequentially. When using a cross-linking agent, it is incorporated into the polymeric material in the same way as a chemical blowing agent. Further, when a cross-linking agent is used, the foamable polymer melt is preferably heated or exposed to a temperature below 150 ° C. to prevent degradation of the cross-linking agent or blowing agent and prevent premature cross-linking. If radiation cross-linking is used, the foamable polymeric material is preferably heated or exposed to a temperature below 160 ° C. to prevent the foaming agent from decomposing. The foamable molten polymer material is extruded through a die of the desired shape to create a foam structure. This foamable structure is then cross-bonded and expanded at an elevated temperature such as an oven (typically 150 ° C. to 250 ° C.). When using radiation cross-linking, the foamable structure is irradiated to cross-link the polymer, which is then expanded at the elevated temperature described above. The structures of the present invention can be advantageously sheeted or laminated by the methods described above using either a cross-linking agent or radiation.

  The foamed structure of the present invention can be made into a continuous sheet structure by an extrusion process using a long land die as described in GB2,145,961A. In this method, the polymer, degradable blowing agent and blowing agent are mixed in an extruder, the mixture is heated to cross-link the polymer, and the blowing agent is foamed in a long land die; and foamed through the die. Molding is performed from the structure. The contact between the foam structure and the die is lubricated with a suitable lubricant.

  The foam structure of the present invention can also be a cross-linked foam bead suitable for article molding. To make expanded beads, separate resin particles, such as granular resin pellets, are suspended in a substantially insoluble liquid, such as water; the crosslinker and blowing agent are applied at elevated pressure and temperature in an autoclave or other pressure vessel. Impregnate; and release to atmospheric or reduced pressure area to make foam beads. The polymer beads are impregnated with a blowing agent, cooled, discharged from the container, and then expanded by heating or steam. In derivation of the above method, the styrene monomer can be impregnated into the suspension pellets with a cross-linking agent into a graft inter that includes an ethylenic polymer material. It is also possible to impregnate the resin pellets in a suspended or non-aqueous state with a foaming agent. Next, the expandable beads are expanded by heating with steam, and are formed into expandable polystyrene foam beads by a conventional method.

The expanded beads can be formed by means known in the art. For example, foam beads are filled into a mold, the mold is compressed to compress the bead, and the beads are heated, eg, with steam, to fuse and weld the beads to produce the article. Optionally, the beads can be preheated with air or other blowing agent prior to filling the mold. Excellent teachings on the above methods and molding methods can be found in C.P. Park, above publication, pp 227-233; U.S. Pat. Be looked at. Expanded beads can also be made by mixing a polymer, crosslinker and degradable mixture in a suitable mixing device or extruder, shaping the mixture into pellets, and heating the pellets to crosslink and expand. Can also be manufactured.

There are other methods of producing cross-linked foam beads suitable for forming into articles. The ethylene polymer material is melted and mixed with a physical blowing agent in a conventional foam extrusion apparatus to produce a substantially continuous foamed strand. This foamed strand is granulated or pelletized to make a foam bead. This foam bead is then cross-linked by radiation. This cross-linked expanded bead is then fused and shaped to make various articles as described above for other expanded bead methods. Additional teaching on this method can be found in US Pat.

The foam structure of the present invention can be manufactured in burn stock form by two different methods. One method involves the use of a cross-linking agent and the other method uses radiation.
The foamed structure of the present invention is a slab obtained by mixing the ethylene copolymer composition (A), (A ′), (A ″) or (A ′ ″) with a cross-linking agent and a chemical foaming agent. In a burn-stock configuration by heating the mixture in a mold so that the cross-linking agent can cross-link the polymer material and decompose the blowing agent and expand by the release of pressure in the mold. Can be made. Optionally, the pan stock produced upon pressure release can be reheated for further expansion.

  The cross-linked polymer sheet can be made by irradiation of the polymer sheet with a high energy beam or by heating a polymer sheet containing a chemical cross-linking agent. The cross-linked polymer sheet is cut into the desired shape, impregnated with high pressure nitrogen at a temperature above the softening point of the polymer, and the pressure is released to effect bubble nucleation and slight expansion in the sheet. The sheet is reheated at a low pressure above the softening point and then the pressure is released to expand the foam.

Blowing agents useful in the production of the foam structure of the present invention include degradable chemical blowing agents. Such chemical blowing agents decompose at high temperatures to produce gas or vapor, causing the polymer to expand into a foam. The chemical blowing agent is preferably in solid form so that it can be easily dry blended with the polymeric material. Chemical blowing agents: azodicarbonamide, azodiisobutyronitrile, benzenesulfohydrazide, 4,4-oxybenzenesulfonyl-semicarbazide, p-toluenesulfonyl-semicarbazide, barium azodicarboxylate, N, N'-dimethyl-N, N Examples include '-dinitrosoterephthalamide, N, N'-dinitrosopentamethylenetetramine, 4,4-oxybis (benzenesulfonylhydrazide), and trihydrazinotriazine, with azodicarbonamide being preferred. Additional teaching on chemical blowing agents can be found in C.P.Park's publication pp205-208 and F. Stobu's “Polyolefin Foam” Handbook of
Polymer Foams and Technology, pp.382-402, by Day Kay Flemper and Kay Sea Frisch, published by Hansar Publishers, Munich, Vienna, New York, Barcelona (1991).

  The chemical blowing agent is a polymer material in an amount sufficient to release 0.2 to 5.0, preferably 0.5 to 3.0, most preferably 1.2 to 2.50 moles of gas or vapor per kg of polymer. Blended with.

A useful cross-linking agent for producing the foam structure of the present invention is an organic peroxide. 1,1-di-t-butylperoxy-3,3,5-trimethylcyclohexane as a useful organic peroxide cross-linking agent; dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butyl Peroxy) hexane; 1-butylcumyl peroxide, α, α′-di (butylperoxy) -diisopropylbenzene, di-t-butyl peroxide, and 2,5-dimethyl-2,5-di- (t -Butylperoxy) hexane. Dicumyl peroxide is a preferred reagent. Additional teachings on organic peroxide cross-linking agents can be found in the above publication of PP Park, pp 198-204.

  Radiation cross-linking can be done by any of the usual types. Useful radiation types include electron beams or beta rays, gamma rays, x-rays, or neutron rays. Radiation crosslinks by generating polymer groups that are believed to gather and crosslink. Additional teachings on radiation cross-linking can be found in the above publication of PP Park, pp 198-204.

In some methods of making the foamed structures of the present invention, physical blowing agents can be used. Examples of physical blowing agents include organic and inorganic reagents. Suitable inorganic blowing agents include carbon dioxide, nitrogen, argon, water, air, and helium. Organic blowing agents include aliphatic hydrocarbons having 1 to 9 carbon atoms, aliphatic alcohols having 1 to 3 carbon atoms, and fully and partially halogenated hydrocarbons having 1 to 4 carbon atoms. Can be mentioned. Aliphatic hydrocarbons include methane, ethane, propane, n-butane, isobutane, n-pentane, isopentane, and neopentane. Aliphatic alcohols include methanol, ethanol, n-propanol and isopropanol. Full and partially halogenated aliphatic hydrocarbons include fluorocarbons, chlorocarbons and chlorofluorocarbons. Examples of fluorocarbons are methyl fluoride, perfluoromethane, ethyl fluoride, 1,1-difluoroethane (HFC-152a), 1,1,1-trifluoroethane (HFC-143a), 1,1,1,2- Tetrafluoroethane (HFC-134a), pentafluoroethane, difluoromethane, perfluoroethane, 2,2-difluoropropane, 1,1,1-trifluoropropane, perfluoropropane, dichloropropane, difluoropropane, perfluorobutane Perfluorocyclobutane. As the partially halogenated chlorocarbon and chlorofluorocarbon used in the present invention, methyl chloride, methylene chloride, ethyl chloride, 1,1,1-trichloroethane, 1,1-dichloro-1-fluoroethane (HCFC-141b), 1- Chloro-1,1-difluoroethane (HCFC-142b), chlorodifluoromethane (HCFC-22), 1,1-dichloro-2,2,2-trifluoroethane (HCFC-123), and 1-chloro-1, 2,2,2-tetrafluoroethane (HCFC-124) is mentioned. Trichloromonofluoromethane (CFC-11), dichlorodifluoromethane (CFC-12), trichlorotrifluoroethane (CFC-113), 1,1,1-trifluoroethane, pentafluoroethane, dichloromethane as fully halogenated chlorofluorocarbons Examples include tetrafluoroethane (CFC-114), chloroheptafluoropropane, and dichlorohexafluoropropane.

The amount of blowing agent to be incorporated into the polymer melt to make a foamable polymer gel is 0.2-0.2.
5.0, preferably 0.5 to 3.0, most preferably 1.0 to 2.50 mole / kg polymer.

The foam structure of the present invention is 5 to 90 as measured by ASTM D-2765-84, Method A.
%, More preferably 30 to 70%.
The foamed structure of the present invention has a density of less than 500, more preferably less than 250, most preferably less than 150 kg / cubic meter. The foamed structure has an average pore size as measured by ASTM D3576 of 0.05 to 5.0, more preferably 1.0 to 2.0, and most preferably 0.2 to 1.0 ml.

The foam structure of the present invention can be closed or open. Preferably, the foam structure of the present invention is greater than 90% closed cells as measured by ASTM D2856-A.
In addition, various additives can be mix | blended with the foaming structure of this invention. Such additives are, for example, inorganic fillers, stability control agents, nucleating agents, colorants, antioxidants, acid removal agents, UV absorbers, flame retardants, processing aids and extrusion aids.

gasket:
The gasket is composed of the ethylene-based copolymer composition (A), (A ′), (A ″) or (A ′ ″). This gasket has the ability to compress and seal a variety of containers without contaminating the contents. Liquid containers in particular benefit from the use of the novel gasket material disclosed herein.

Some gaskets need to withstand temperatures above room temperature (about 25 ° C.) for a short time, especially if this application is a “hot fill” application. For example, in the case of a product that needs to be sterilized, it is necessary to attach a gasket having a melting point of 100 ° C. or higher. Thus, a polymer suitable for the application can be specifically selected through the selection of an appropriate density for use in the gasket environment.

  Also, gaskets can be similarly produced by combining other polymers with an effective amount of substantially linear ethylene polymers, depending on the required end use properties. Such other polymers are thermoplastic polymers (ie melt processable), which include highly branched low density polyethylene, heterogeneously branched and linear low density polyethylene, ethylene / acetic acid. Polymers such as vinyl copolymers and ethylene / acrylic acid copolymers are included.

Gaskets made from this ethylene copolymer composition (A), (A '), (A'') or (A''') should be stiff enough to withstand compression. Still, it should be soft enough to form a suitable seal. Therefore, various gaskets can be manufactured by giving this polymer the hardness according to use. In this specification, the hardness is measured as “Shore A hardness” or “Shore D hardness” (ASTM D-2240).
Measure with). The range of Shore A hardness in the case of the ethylene copolymer composition (A), (A ′), (A ″) or (A ′ ″) constituting the gasket is the hardness of the polymer and the gasket obtained. Even when the petroleum oil usually added for the purpose of lowering is not used, it is in the range of 70 to 100. Table 2 summarizes the Shore A data for polymer density for the substantially linear ethylene polymers used in the manufacture of gaskets.

In addition, additives to the ethylene copolymer composition (A), (A '), (A'') or (A''') to the extent that they do not interfere with the improved properties found by the applicants. , For example, antioxidants, phosphites, cling additives (such as PIB), slip additives (such as erucamide),
It is also possible to include antiblock additives, pigments and the like.

Gaskets can take many different forms, including “o-rings” and flat seals (eg, “film-like” gaskets having a thickness appropriate for the intended use).
Suitable end uses include beverage cap liners, hot fill juice cap liners, polypropylene cap liners, metal cap liners, high density polyethylene cap liners, window glass gaskets, sealed containers, sealing caps, medical devices Gaskets, filter elements, pressure exhaust gaskets, hot melt gaskets, easy twist off caps, electrochemical battery gaskets, refrigerator gaskets, galvanic battery gaskets, leak proof cell gaskets , Tarpaulins, reusable gaskets, synthetic cork-like materials, thin cell electronic membrane separators, magnetic rubber materials, disc gaskets for alcoholic beverage bottle caps, freeze-resistant seal rings, gaskets for plastic casting , Telescopic joints and water stops, corrosion resistant conduit joints, soft magnetic plastics, pipe joint seals, integrated weatherproof plastic lids and hinges for electrical output, magnetic faced foamed articles, jarrings, soft gaskets, glass seals, Includes mischievous proof sealing liner, pressure applicator, bottle cap and straw structure, large seasoning bottle liner, metal cap for applesauce or salsa jar, household canning jar, “crown” etc. It is.

Gaskets made from this ethylene copolymer composition (A), (A ′), (A ″) or (A ′ ″) have numerous advantages, especially when used in food applications. The advantages include improved taste and odor compared to currently used polymer gaskets, such as ethylene / vinyl acetate, and low adhesion to polar substrates (eg, polyethylene terephthalate, glass, etc.) ( This is effective for lowering the torque when removing the sealed container / cap), the amount of extract is low (which is also particularly useful in food with respect to regulatory compliance), non-polar substrates (eg polypropylene and high density) Good adhesion to polyethylene (such as polyethylene as a linear homopolymer or linear non-uniform high density polyethylene), oxygen,
Sufficient barrier properties against carbon dioxide and water, high melting point compared to currently used polymers (eg ethylene / vinyl acetate, etc.), good stress crack resistance, chemical resistance Good, variable in hardness (in certain packaging, the gasket must be tight or tight depending on the degree of torque required to seal the container and the internal pressure of the container. Can be, but is effective for).

Various gasket manufacturing techniques include US Pat. No. 5,215,587 (McConnellogue et al.); US Pat. No. 4,085,186 (Rainer); US Pat. No. 4,619,848 (Kinght et al.); US Pat.
US Pat. No. 4,981,231 (Kinght); US Pat. No. 4,717,034 (Mumford); US Pat. No. 3,786,954 (Shull); US Pat. No. 3,779,965 (Lefforge et al.); US Pat. No. 3,493,453 (Ceresa et al.): US Pat. US Pat. No. 3,300,072 (Caviglia); US Pat. No. 4,984,703 (Burzynski); US Pat. No. 3,414,938 (Caviglia); US Pat. No. 4,939,859 (Bayer); US Pat. No. 5,137,164 (Bayer); ). Is included.

  The gaskets claimed herein also use, using conventional techniques, an extruded sheet or film, such as a blown film, cast film or extrusion coated film, and then punch or cut the gasket from this sheet or film. Can also be manufactured. Multilayer film structures are also suitable for use in the manufacture of the gaskets disclosed herein, provided that the ethylene-based copolymer is in at least one layer (preferably an inner layer located adjacent to the product). Composition (A), (A ′), (A ″) or (A ′ ″) is included. Also useful in the present invention is a foam multi-layer gasket containing the ethylene-based copolymer composition (A), (A ′), (A ″) or (A ′ ″).

Extruded product:
Extruded articles include extrusion coated articles, products in the form of extruded profiles and extruded cast films, which are ethylene copolymer compositions (A), ( A '), (A'') or (A''').

  It is also possible to blend the ethylene-based copolymer composition (A), (A ′), (A ″) or (A ′ ″) with other polymer materials, and with this, Single layer or multilayer products can be produced, and structures such as sealants, adhesives or tie layers can be produced. Ethylene copolymer composition (A), (A '), (A' ') or (A' '') to other polymer materials for the purpose of modifying processability, film strength, heat sealability or adhesion It is also possible to blend.

  Furthermore, the ethylene-based copolymer composition (A), (A ′), (A ″) or (A ′ ″) can be used in chemically and / or physically modified form. Such modification may be accomplished by any known technique, such as ionomerization and extrusion grafting.

As used herein, “drawdown” is defined as meaning that a molten polymer extrudate (web or filament) is stretched or stretched in the machine direction and sometimes also (to a lesser degree simultaneously) in the transverse direction. .

This specification defines “neck-in” as the difference between the die width and the width of the extruded product at the take-off position or the final width of the manufactured product, which is to a lesser extent with the expansion of the extruded product. Although affected by the surface tension effect. The measured neck-in value (at a constant output) remains constant as the drawdown rate increases or decreases with it, and the neck-in value for ordinary ethylene polymers is generally low. It is well known that it increases as the molecular weight distribution becomes narrower and / or.

  In addition, the ethylene-based copolymer composition (A), (A '), (A' ') or (A' '') has a high drawdown and a substantially reduced neck-in found by the applicants. Additives such as antioxidants, phosphites, cling additives such as PIB, Standostab PEPQ ™ (supplied by Sandoz), pigments, colorants and fillers Etc. can also be contained. Ethylene copolymer compositions (A), (A ′), (A ″) or (A ′ ″) and additives that improve antiblocking and coefficient of friction characteristics (to this) Includes, but is not limited to, untreated and treated silicon dioxide, talc, calcium carbonate and clay plus primary, secondary and substituted fatty acid amides), chill roll release agents, It is also possible to contain a silicon coating material or the like. It is also possible to add other additives that improve the anti-fogging properties of transparent cast films, for example as described by Niemann in US Pat. No. 4,486,552. Still other additives, such as quaternary ammonium compounds, alone or in ethylene, which improve the antistatic properties of the coatings, profiles and films of the present invention and enable the packaging or manufacture of, for example, electronic sensitive products. It can also be added in combination with acrylic acid (EAA) copolymers or other functional polymers.

  The multilayer structure comprising the ethylene-based copolymer composition (A), (A ′), (A ″) or (A ′ ″) may be produced by any known means, such as , Extrusion, lamination and combinations thereof. Furthermore, the ethylene copolymer composition (A), (A '), (A' ') or (A' '') can also be used in a coextrusion operation, in which case it exhibits a higher drawdown. The material is essentially “supported” with one or more materials with which it exhibits a lower drawdown.

  The ethylene-based copolymer composition (A), (A '), (A' ') or (A' '') is an extruded film regardless of whether it has a single layer structure or a multilayer structure. Can be used in the manufacture of extrusion profiles and extruded cast films. When the ethylene-based copolymer composition (A), (A '), (A' ') or (A' '') is used for coating or multi-layered purposes, the substrate or adjacent material layer is polar or non- They may be polar and include, for example, but not limited to, paper products, metals, ceramics, glass and various polymers, especially other polyolefins, and combinations thereof. In the case of extruded profile materials, a variety of products can be processed, such as, but not limited to, refrigerator gaskets, wire and cable jackets, wire coatings, medical tubing and water. For example, piping. Extruded cast films made using ethylene copolymer compositions (A), (A '), (A' ') or (A' '') are used in food packaging and industrial stretch wraps. ) Can be used for applications.

pipe:
The pipe is made of a silane-modified product of the ethylene copolymer composition (A), (A ′), (A ″) or (A ′ ″).

  Silane modification is performed by adding a radical generator and a silane compound to (A) or (A ′), (A ″) or (A ′ ″), and mixing them with an appropriate mixer such as a Henschel mixer. It can be manufactured by heating and kneading to about 140 to 250 ° C. with an extruder, a Banbury mixer or the like, followed by heat grafting.

As radical generators used for silane modification, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3 Etc. are preferable.
As the silane compound used for silane modification, a silane compound having a hydrolyzable organic group such as a terminal vinyl group and an alkoxy group is preferable, and vinyltrimethoxysilane, vinyltriethoxysilane, and the like are preferable.

  The pipe is formed by crosslinking the silane-modified product of the above (A) or (A ′), (A ″) or (A ′ ″). The molded body is blended with a silanol condensation catalyst and is usually molded into a pipe shape using a pipe molding machine.

  As the silanol condensation catalyst, a known compound used as a catalyst for promoting dehydration condensation between silanol groups can be used. Further, a master batch is separately prepared using a silanol condensation catalyst and a linear polyethylene before modification, and this and a silane-modified linear polyethylene are dry-blended with a mixer such as a Henschel mixer or a V blender, and then the mixture May be used for pipe forming.

  The formed pipe is usually brought into contact with moisture at about room temperature to about 130 ° C. in water, steam or in a humid atmosphere for about 1 minute to about 1 week. Thereby, a silane crosslinking reaction proceeds by the silanol catalyst, and a crosslinked pipe is obtained.

  Pipes should contain heat stabilizers, anti-aging agents, weathering stabilizers, hydrochloric acid absorbents, lubricants, organic or inorganic pigments, carbon blacks, eye-inhibitors, flame retardants, antistatic agents, fillers, etc. Can do.

Injection molded body:
The injection-molded product can be obtained by injection-molding the ethylene copolymer composition (A), (A ′), (A ″) or (A ′ ″). The injection-molded body can be manufactured by a conventionally known injection molding apparatus, and conventionally known conditions can be adopted as molding conditions.

Such an injection-molded article is excellent in heat resistance and environmental stress fracture resistance.
Wire sheath:
The sheath for electric wires is a sheath (outermost layer sheath) that protects electric wires or cables.

  The sheath for the electric wire is composed of the ethylene copolymer composition (A), (A ′), (A ″) or (A ′ ″) and, if necessary, a conventionally known heat resistance stabilizer, weather resistance stability. It is formed from agents, carbon black, pigments, flame retardants, anti-aging agents and the like.

The sheath for electric wires has a 50% crack generation time (F ₅₀ ) (ASTM D 1698) of 600 hours or more and is measured by a Taber abrasion test (JIS K 7204, load 1 kg, worn wheel CS-17, 60 rpm, 1000 times). It is preferable that the amount of wear applied is 10 mg or less, and the Izod impact strength (ASTM D 256, with notch) measured at −40 ° C. is 40 J / m ² or more.

The sheath for electric wires can be formed by a conventionally known extrusion coating forming method using the ethylene copolymer composition (A), (A ′), (A ″) or (A ′ ″).
Such a sheath for electric wires has stress crack resistance, wear resistance, and impact resistance at low temperatures.

The ethylene copolymer composition (A), (A ′), (A ″) or (A ′ ″) can be used in the following high drawdown extrusion method.
The high drawdown extrusion method includes the ethylene-based copolymer composition (A), (A ′), (A ″) or (A ″ ′), or the composition (A), (A ′), ( A ″) or a composition containing (A ′ ″) (hereinafter also referred to as “thermoplastic composition”) is a method for extrusion coating a substrate or producing a cast film. The method is
(I) supplying the thermoplastic composition to at least one extruder;
(Ii) producing at least one polymer stream melt-mixed with the thermoplastic composition;
(Iii) including extruding the molten polymer stream through a die to form a main web, the improvement here being: (i) operating the extruder at a line speed of 152 meters / minute or more. And (a) drawing the web onto the substrate, thereby coating the substrate with at least one layer of the thermoplastic composition, or (b) cooling the web. Producing the film with at least one layer of the thermoplastic composition by drawing down onto a take-off device, and (ii) the coated substrate or film to be used in a subsequent use. Including transportation or collection. With the present invention, lower neck-in, higher drawdown rate, and higher draw resonance resistance (draw resonance; melt flow instability) than obtained using ethylene polymers made using conventional Ziegler catalysts Phenomenon).

  As used herein, “drawdown” is defined as stretching or stretching a molten polymer extrudate (web or filament) in the machine direction and sometimes also (to a lesser degree simultaneously) in the transverse direction.

  This specification defines “neck-in” as the difference between the die width and the web width at the take-off position, which is affected by the extrudate expanding and to a lesser extent the effect of surface tension effects. receive. The measured neck-in value (at a constant output) remains constant or decreases as the drawdown rate increases, and the neck-in value for ordinary ethylene polymers is generally low in molecular weight. It is well known that it increases as the molecular weight distribution becomes narrower and / or.

  In the present invention, the composition (A), (A ′), (A ″) or (A ′ ″) is added to an additive such as an antioxidant, a phosphite, a cling additive (eg, PIB). Etc.), Standostab PEPQ ™ (supplied by Sandoz), pigments, colorants, fillers, and the like. The extrusion coatings and films can also include additives that improve antiblocking and coefficient of friction characteristics, including but not limited to untreated and treated silicon dioxide, talc, Included are calcium carbonate and clay, as well as primary, secondary and substituted fatty acid amides, chill roll release agents, silicone coatings and the like. It is also possible to add other additives that improve the anti-fogging properties of transparent cast films, for example as described by Niemann in US Pat. No. 4,486,552. Further, by improving the antistatic properties of the coatings and films of the present invention, for example, other additives that enable the packaging of sensitive items such as quaternary ammonium compounds alone or ethylene-acrylic can be used. It can also be added in combination with acid (EAA) copolymers or other functional polymers.

  The composition (A), (A ′), (A ″) or (A ′ ″) used in the manufacture of the compositions and products of the present invention is a monolayer structure of the resulting film or coating to be used. Or a multi-layer structure can be blended together with linear ethylene polymers and / or high pressure ethylene polymers or used as a single resinous polymer component. Further, by blending the composition (A), (A ′), (A ″) or (A ′ ″) or homopolymers together with other polymers, processability, film strength, Heat sealability or adhesion can be improved.

Some materials suitable for blending with this composition (A), (A '), (A'') or (A''') include, but are not limited to, for example, low density In addition to ethylene polymers such as high pressure low density ethylene homopolymer (LDPE), ethylene / vinyl acetate copolymer (EVA), ethylene-carboxylic acid copolymers and ethylene acrylate copolymers, olefin polymers produced at low to medium pressure, For example, polybutylene (PB) and ethylene / α-olefin polymers [including high density polyethylene, medium density polyethylene, polypropylene, ethylene / propylene interpolymers, linear low density polyethylene (LLDPE) and very low density polyethylene As well as graft-modified polymers, and combinations thereof It is included.

Suitable high pressure ethylene copolymers include ethylene with at least one α, β-ethylenically unsaturated comonomer (eg, acrylic acid as described by McKinney et al. In US Pat. No. 4,599,392). , Methacrylic acid, vinyl acetate and the like). Preferred high pressure ethylene copolymers are from 0.1 to 55% by weight of comonomer, more preferably from 1 to 35% by weight of comonomer, most preferably from 2 to 28% by weight of comonomer. Which may be chemically and / or physically modified by any known technique, such as ionomerization and extrusion grafting.

  However, suitable polymer blends include at least one ethylene-based copolymer composition (A), (A ′), (A ″) or (A ′ ″), and preferably this composition. Article (A), (A ′), (A ″) or (A ′ ″) comprises at least about 5 percent of the blend composition, more preferably at least about 10 percent of the blend composition.

  In the case of the multilayer coatings and films of the present invention, at least one composition (A), (A ′), (A ″) or (A ′ ″) may be included in any layer and in any number of layers. . However, very preferably nonetheless, in the case of multilayer films and coating structures, at least one composition in the outer layer (also referred to in the art as “skin layer” or “surface layer”) and sealant layer. Include object (A), (A '), (A' ') or (A' '').

  The blend composition of the present invention can be made by any suitable means known in the art, including tumble drive render means, melt blending means by compound or side arm extrusion, multiple reactor polymerization, etc. In addition to these combinations. In addition, the multilayer structure of the present invention can be produced by any known means, which includes coextrusion, lamination and combinations thereof. Furthermore, it is possible to use the compositions of the present invention in a coextrusion operation that uses a material that exhibits a higher drawdown, thereby essentially “supporting” one or more materials that exhibit a lower drawdown.

  Whether it is a single layer structure or a multilayer structure, the blended and non-blended compositions of the present invention can be used to coat various polar and non-polar substrates, This substrate includes, but is not limited to, for example, paper products, metals, ceramics, glass and various polymers, especially other polyolefins and combinations thereof.

EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples.
In the present invention, the physical properties of the film were evaluated as follows.

[Haze (Haze)]
Measured according to ASTM-D-1003-61.
[Gloss]
It measured according to JIS Z8741.

[Dirt impact strength]
Measured according to ASTM D 1709 A method.
[Production Example 1]
[Preparation of catalyst components]
After 5.0 kg of silica dried at 250 ° C. for 10 hours was suspended in 80 liters of toluene, it was cooled to 0 ° C. Thereafter, a toluene solution of methylaluminoxane (Al; 1.3
(3 mol / liter) 28.7 liters was added dropwise over 1 hour. At this time, the temperature in the system is 0 ° C.
Kept. The reaction was continued at 0 ° C. for 30 minutes, and then the temperature was raised to 95 ° C. over 1.5 hours.
The reaction was carried out at that temperature for 20 hours. Thereafter, the temperature was lowered to 60 ° C., and the supernatant was removed by a decantation method.

The solid component thus obtained was washed twice with toluene and then resuspended in 80 liters of toluene. To this system, 20.0 liters of a toluene solution (Zr; 14.0 mmol / liter) of bis (methylcyclopentadienyl) zirconium dichloride was added dropwise at 80 ° C. over 30 minutes, and further reacted at 80 ° C. for 2 hours. It was. Thereafter, the supernatant was removed and washed twice with hexane to obtain a solid catalyst containing 3.6 mg of zirconium per 1 g.

[Preparation of prepolymerization catalyst]
By adding 0.85 kg of the solid catalyst obtained above and 77 g of 1-hexene to 85 liters of hexane containing 1.7 mol of triisobutylaluminum, and prepolymerizing ethylene at 35 ° C. for 3.5 hours, A prepolymerized catalyst in which 3 g of polyethylene was prepolymerized per 1 g of the solid catalyst was obtained.

[polymerization]
Using a continuous fluidized bed gas phase polymerization apparatus, copolymerization of ethylene and 1-hexene was carried out at a total pressure of 20 kg / cm ² -G and a polymerization temperature of 80 ° C. In order to maintain a constant gas composition during the polymerization by continuously supplying the prepolymerized catalyst prepared above at 0.05 mmol / h in terms of zirconium atom and triisobutylaluminum at a rate of 10 mmol / h, ethylene, 1-hexene , Hydrogen and nitrogen were continuously supplied (gas composition; 1-hexene / ethylene = 0.020, hydrogen / ethylene =
9.5 × 10 ⁻⁴ , ethylene concentration = 50%). The polymer yield was 4.1 kg / h.
[Reference Example 1]
[Film forming]
Using the pellets of ethylene / α-olefin copolymer (A-1) produced in Production Example 1,
An inflation film was obtained under the following conditions. Using a single screw extruder of 20 mmφ · L / D = 26, using a 25 mmφ die, lip width 0.7 mm, single slit air ring, air flow rate = 90 liter / min, extrusion rate = 9 g / min, blow ratio = 1. 8. A film having a take-off speed of 2.4 m / min, a processing temperature of 200 ° C. and a thickness of 30 μm was obtained by inflation molding. The results are shown in Tables 1 and 3.
[Reference Example A]
The ethylene-α-olefin copolymer (A-1) and the high-pressure method low density polyethylene (D-1) shown in Table 2 were melt kneaded at a weight ratio (A-1) / (D-1): 96/4. Pelletized, and using this pellet, an inflation film was obtained in the same manner as in Reference Example 1. The results are shown in Table 3.
[Production Example 2]
[Preparation of catalyst components]
After 5.0 kg of silica dried at 250 ° C. for 10 hours was suspended in 80 liters of toluene, it was cooled to 0 ° C. Thereafter, a toluene solution of methylaluminoxane (Al; 1.3
(3 mol / liter) 28.7 liters was added dropwise over 1 hour. At this time, the temperature in the system is 0 ° C.
Kept. The reaction was continued at 0 ° C. for 30 minutes, and then the temperature was raised to 95 ° C. over 1.5 hours.
The reaction was carried out at that temperature for 20 hours. Thereafter, the temperature was lowered to 60 ° C., and the supernatant was removed by a decantation method.

  The solid component thus obtained was washed twice with toluene and then resuspended in 80 liters of toluene. In this system, 5.8 liters of a toluene solution of bis (1,3-n-butylmethylcyclopentadienyl) zirconium dichloride (Zr; 34.0 mmol / liter) and toluene of bis (methylcyclopentadienyl) zirconium dichloride are added. 6.0 liters of a solution (Zr; 14.0 mmol / liter) was added dropwise at 80 ° C. over 30 minutes, and further reacted at 80 ° C. for 2 hours. Thereafter, the supernatant was removed and washed twice with hexane to obtain a solid catalyst containing 3.6 mg of zirconium per 1 g.

[Preparation of prepolymerization catalyst]
By adding 0.85 kg of the solid catalyst obtained above and 77 g of 1-hexene to 85 liters of hexane containing 1.7 mol of triisobutylaluminum, and prepolymerizing ethylene at 35 ° C. for 3.5 hours, A prepolymerized catalyst in which 3 g of polyethylene was prepolymerized per 1 g of the solid catalyst was obtained.

[polymerization]
Using a continuous fluidized bed gas phase polymerization apparatus, copolymerization of ethylene and 1-hexene was carried out at a total pressure of 20 kg / cm ² -G and a polymerization temperature of 80 ° C. In order to maintain a constant gas composition during the polymerization by continuously supplying the prepolymerized catalyst prepared above at 0.05 mmol / h in terms of zirconium atom and 10 mmol / h of triisobutylaluminum, ethylene, 1-hexene , Hydrogen and nitrogen are continuously supplied (gas composition: 1-hexene / ethylene = 0.020, hydrogen / ethylene = 9.5 × 10 ⁻⁴ , ethylene concentration = 50%), ethylene / α-olefin copolymer (C-1) was obtained.
[Reference Example 2]
The ethylene / α-olefin copolymer (C-1) was pelletized by melt-kneading, and an inflation film was obtained in the same manner as in Reference Example 1 using the pellets. The results are shown in Tables 1 and 3.
[Reference Example B]
The ethylene / α-olefin copolymer (C-1) and the high-pressure low-density polyethylene (D-1) shown in Table 2 were melt kneaded at a weight ratio (C-1) / (D-1): 96/4. Pelletized, and using this pellet, an inflation film was obtained in the same manner as in Reference Example 1. The results are shown in Table 3.
[Reference Example 3]
Except that the gas composition was adjusted so that the density and MFR were the ethylene / α-olefin copolymer (C-2) described in Table 1, an ethylene / α-olefin copolymer ( C-2) was obtained. The ethylene / α-olefin copolymer (C-2) was pelletized by melt kneading, and an inflation film was obtained in the same manner as in Reference Example 1 using the pellets. The results are shown in Table 3.
[Reference Example C]
Melting and kneading ethylene / α-olefin copolymer (C-2) and high-pressure low-density polyethylene (D-1) shown in Table 2 at a weight ratio (C-2) / (D-1) = 96/4 Then, an inflation film was obtained in the same manner as in Reference Example 1 using this pellet. The results are shown in Table 3.
[Reference Example 4]
The ethylene / α-olefin copolymer (C) was prepared in the same manner as in Production Example 1 except that the gas composition was adjusted so that the density and MFR were the ethylene / α-olefin copolymer (C-3) described in Table 1. The ethylene / α-olefin copolymer (C-3) obtained was pelletized by melt kneading, and an inflation film was obtained in the same manner as in Reference Example 1 using this pellet. The results are shown in Table 3.
[Reference Example D]
Melt-kneading ethylene α-olefin copolymer (C-3) and high-pressure low-density polyethylene (D-1) shown in Table 2 at a weight ratio (C-3) / (D-1) = 96/4 And an inflation film was obtained using the pellets in the same manner as in Reference Example 1. The results are shown in Table 3.
[Comparative Example 1]
[Preparation of catalyst components]
Instead of 20.0 liters of a toluene solution of bis (methylcyclopentadienyl) zirconium dichloride (Zr; 14.0 mmol / liter) in [Preparation of catalyst component] of Production Example 1, bis (1,3-nbutyl) The solid catalyst component was prepared in the same manner except that 8.2 liters of a toluene solution of methylcyclopentadienyl) zirconium dichloride (Zr; 34.0 mmol / liter) was used.

[Preparation of prepolymerization catalyst]
A prepolymerized catalyst was obtained in the same manner as in Production Example 1 except that the solid catalyst component obtained in [Preparation of catalyst component] was used.

[polymerization]
Except for using the prepolymerization catalyst obtained in [Preparation of prepolymerization catalyst] and adjusting the gas composition so that the density and MFR are the ethylene / α-olefin copolymers (A-2) described in Table 1. Produced an ethylene / 1-hexene copolymer in the same manner as in Production Example 1. Table 1 shows the melt physical properties and the like of the obtained copolymer. The ethylene / α-olefin copolymer (A-2) was pelletized by melt kneading, and an inflation film was obtained in the same manner as in Reference Example 1 using this pellet. The results are shown in Table 3.
[Comparative Example 2]
The ethylene / α-olefin copolymer (A-2) and the high-pressure low-density polyethylene (D-1) shown in Table 2 are melt kneaded at a weight ratio (A-2) / (D-1) = 96/4. And an inflation film was obtained in the same manner as in Reference Example 1 using the pellets. The results are shown in Table 3.
[Comparative Example 3]
In [Preparation of catalyst component] in Production Example 1, bis (1,3-dimethylcyclohexane) was used instead of 20.0 liters of a toluene solution (Zr; 14.0 mmol / liter) of bis (methylcyclopentadienyl) zirconium dichloride. The solid catalyst component was prepared in the same manner except that 10.0 liter of a toluene solution (Zr; 28.0 mmol / liter) of pentadienyl) zirconium dichloride was used.

[Preparation of prepolymerization catalyst]
A prepolymerized catalyst was obtained in the same manner as in Production Example 1 except that the solid catalyst component obtained in [Preparation of catalyst component] was used.

[polymerization]
Except for using the prepolymerization catalyst obtained in [Preparation of prepolymerization catalyst] and adjusting the gas composition so that the density and MFR are the ethylene / α-olefin copolymer (A-3) described in Table 1. Produced an ethylene / 1-hexene copolymer in the same manner as in Production Example 1. Table 1 shows the melt physical properties and the like of the obtained copolymer. The ethylene / α-olefin copolymer (A-3) was pelletized by melt kneading, and an inflation film was obtained using the pellet in the same manner as in Reference Example 1. The results are shown in Table 3.
[Comparative Example 4]
The ethylene / α-olefin copolymer (A-3) and the high-pressure low-density polyethylene (D-1) shown in Table 2 are melt kneaded at a weight ratio (A-3) / (D-1): 96/4. And an inflation film was obtained using the pellets in the same manner as in Reference Example 1. The results are shown in Table 3.
[Reference Example 5]
Except that the gas composition was adjusted so that the density and MFR were the ethylene / α-olefin copolymers (C-5) and (C-6) described in Table 4, ethylene / α -Olefin copolymers (C-5) and (C-6) were obtained. The ethylene / α-olefin copolymer (C-5) and (C-6) were pelletized by melt kneading at a weight ratio (C-5) / (C-6): 60/40 (L-1), Using this pellet, an inflation film was obtained in the same manner as in Reference Example 1. The results are shown in Tables 5 and 6.

The ethylene / α-olefin copolymer composition (L-1) and the high-pressure low-density polyethylene (D-1) shown in Table 2 are in a weight ratio (L-1) / (D-1): 97/3. Pelletization was performed by melt-kneading, and an inflation film was obtained using the pellets in the same manner as in Reference Example 1. The results are shown in Table 6.
[Reference Example 6]
The ethylene / α-olefin copolymer (C) was prepared in the same manner as in Production Example 2 except that the gas composition was adjusted so that the density and MFR were ethylene / α-olefin copolymers (C-7) described in Table 4. C-7) was obtained. The ethylene / α-olefin copolymer (C-7) and (C-6) were pelletized by melt kneading at a weight ratio (C-7) / (C-6): 60/40 (L-2), Using this pellet, an inflation film was obtained in the same manner as in Reference Example 1. The results are shown in Tables 5 and 6.

The ethylene / α-olefin copolymer composition (L-2) and the high-pressure low-density polyethylene (D-1) shown in Table 2 at a weight ratio (L-2) / (D-1): 97/3 Pelletization was performed by melt kneading, and an inflation film was obtained using the pellets in the same manner as in Reference Example 1. The results are shown in Table 6.
[Reference Example 7]
The ethylene / α-olefin copolymer (C-8) and (C-9) listed in Table 4 were prepared in the same manner as in Production Example 2 except that the gas composition was adjusted to be the ethylene / α-olefin copolymers (C-8) and (C-9) -Olefin copolymers (C-8) and (C-9) were obtained. The ethylene / α-olefin copolymer (C-8) and (C-9) were pelletized by melt kneading at a weight ratio (C-8) / (C-9): 60/40 (L-3), Using this pellet, an inflation film was obtained in the same manner as in Example 1. The results are shown in Tables 5 and 6.

The ethylene / α-olefin copolymer composition (L-3) and the high-pressure low-density polyethylene (D-1) shown in Table 2 are in a weight ratio (L-3) / (D-1): 97/3. Pelletization was performed by melt-kneading, and an inflation film was obtained using the pellets in the same manner as in Reference Example 1. The results are shown in Table 6.

Claims (12)

(B) a copolymer of ethylene and an α-olefin having 6 to 8 carbon atoms,
(Bi) the density is in the range of 0.880 to 0.970 g / cm ³ ;
(B-ii) The melt flow rate (MFR) at 190 ° C. and a 2.16 kg load is in the range of 0.02 to 200 g / 10 min.
(B-iii) The decane-soluble component amount ratio (W) and density (d) at room temperature,
When MFR ≦ 10g / 10min,
W <80 × exp (-100 (d-0.88)) + 0.1
When MFR> 10g / 10min,
W <80 × (MFR-9) ^0.26 × exp (-100 (d-0.88)) + 0.1
Satisfy the relationship indicated by
(B-iv) The temperature (Tm) and density (d) at the maximum peak position of the endothermic curve measured by a differential scanning calorimeter (DSC) are Tm <400 × d−248.
Satisfy the relationship indicated by
(B-v) Melt tension (MT) and melt flow rate (MFR) at 190 ° C.
9.0 × MFR ^-0.65 >MT> 2.2 × MFR ^-0.84
Satisfy the relationship indicated by
(B-vi) Flow activation energy ((E _a ) × 10 ^-4 J / molK) obtained from shift factor of time-temperature superposition of flow curve and carbon atom of α-olefin in copolymer The relationship between the number (C) and the α-olefin content (x mol%) in the copolymer is
(0.039Ln (C-2) +0.0096) × x + 2.87 <E _a × 10 ^-4 ≦ (0.039Ln (C-2) +0.1660) × x + 2.87
Satisfy the relationship indicated by
(B-vii) Ratio of weight average molecular weight (Mw) and number average molecular weight (Mn) determined by GPC (Mw /
Mn)
2.2 <Mw / Mn <3.5
An ethylene / α-olefin copolymer represented by
(C) a copolymer of ethylene and an α-olefin having 6 to 8 carbon atoms,
(C-i) the density is in the range of 0.880 to 0.970 g / cm ³ ;
(C-ii) The melt flow rate (MFR) at 190 ° C. and a 2.16 kg load is in the range of 0.02 to 200 g / 10 minutes,
(C-iii) Decane-soluble component amount ratio (W) at room temperature and density (d) are MFR ≦ 10 g
/ At 10 minutes,
W <80 × exp (-100 (d-0.88)) + 0.1
When MFR> 10g / 10min,
W <80 × (MFR-9) ^0.26 × exp (-100 (d-0.88)) + 0.1
Satisfy the relationship indicated by
(C-iv) The temperature (Tm) and density (d) at the maximum peak position of the endothermic curve measured by a differential scanning calorimeter (DSC) are Tm <400 × d−248.
Satisfy the relationship indicated by
(Cv) The melt tension (MT) at 190 ° C. and the melt flow rate (MFR)
MT ≦ 2.2 × MFR ^-0.84
An ethylene / α-olefin copolymer represented by
(E)
(Ei) The melt flow rate measured at 190 ° C. and a 2.16 kg load is in the range of 0.1 to 50 g / 10 min.
(E-ii) The molecular weight distribution measured by gel permeation chromatography (Mw / Mn: Mw = weight average molecular weight, Mn = number average molecular weight) and melt flow rate (MFR) are 7.5 × log (MFR) − 1.2 ≦ Mw / Mn ≦ 7.5 × log (MFR) +12.5
A high-pressure radical process low-density polyethylene that satisfies the relationship represented by
A composition comprising
The ratio of (C) melt flow rate (MFR (C)) to (B) melt flow rate (MFR (B)) is 1 <(MFR (C)) / (MFR (B)) ≦ 20
An ethylene copolymer composition characterized by the above. The ethylene / α-olefin copolymers (B) and (C) are both ethylene / hexene-1 copolymers, and the composition comprises the ethylene / α-olefin copolymers (B) and (C). But,
(A′-i) The melt tension (MT) and melt flow rate (MFR) at 190 ° C.
9.0 × MFR ^-0.65 >MT> 2.2 × MFR ^-0.84
Satisfy the relationship indicated by
(A'-ii) Flow activation energy ((E _a ) × 10 ^-4 J / molK) obtained from the shift factor of time-temperature superposition of the flow curve, and copolymers (B) and (C) The relationship between the number of carbon atoms (C) in hexene-1 and the total content (x mol%) of hexene-1 in copolymers (B) and (C)
(0.039Ln (C-2) +0.0096) × x + 2.87 <E _a × 10 ^-4 ≦ (0.039Ln (C-2) +0.1660) × x + 2.87
Satisfy the relationship indicated by
(A'-iii) The ethylene copolymer composition according to claim 1, wherein when the composition is subjected to inflation molding to produce a film having a thickness of 30 µm, the haze of the film satisfies the following relationship: Object (A ');
When the fluidity index (FI) and melt flow rate (MFR) defined by the shear rate when the shear stress at 190 ° C. reaches 2.4 × 10 ⁶ dyne / cm ² are FI ≧ 100 × MFR
Haze <0.45 / (1-d) × log (3 × MT ^1.4 ) × (C-3) ^0.1
When the fluidity index (FI) defined by the shear rate when the shear stress at 190 ° C. reaches 2.4 × 10 ⁶ dyne / cm ² and the melt flow rate (MFR) are FI <100 × MFR
Haze <0.25 / (1-d) × log (3 × MT ^1.4 ) × (C-3) ^0.1
(Where d is density (g / cm ³ ), MT is melt tension (g), and C is the number of carbon atoms of hexene-1, that is, “6”). In addition to the requirements of (A′-i) to (A′-iii), the composition comprising the ethylene / α-olefin copolymers (B) and (C) may further comprise (A′-iv) GPC Ratio of the obtained weight average molecular weight (Mw) and number average molecular weight (Mn) (Mw /
Mn)
2.0 ≦ Mw / Mn ≦ 2.5
The ethylene-based copolymer composition according to claim 2 satisfying (A ′) the ethylene copolymer composition according to claim 1;
(D)
(a) an organoaluminum oxy compound;
(B-III) ethylene and an α-olefin having 3 to 20 carbon atoms in the presence of an olefin polymerization catalyst containing a transition metal compound of Group 4 of the periodic table containing a ligand having a cyclopentadienyl skeleton; Obtained by copolymerizing
(D-i) the density is in the range of 0.850 to 0.980 g / cm ³ ,
(D-ii) an ethylene / α-olefin copolymer having an intrinsic viscosity [η] measured in decalin at 135 ° C. in the range of 0.4 to 8 dl / g (however, an ethylene / α-olefin copolymer) (B) and (C) are not the same as ethylene / α-olefin copolymer (D))
An ethylene copolymer composition comprising:   A molded article comprising the ethylene copolymer composition according to any one of claims 1 to 4.   The molded body according to claim 5, wherein the molded body is a single-layer film or sheet.   The molded article according to claim 5, wherein the molded article is a multilayer film or sheet.   The molded body according to claim 5, wherein the molded body is an injection molded body.   The molded body according to claim 5, wherein the molded body is an extruded molded body.   The molded body according to claim 5, wherein the molded body is a fiber.   The molded body according to claim 5, wherein the molded body is a foam molded body. The molded body according to claim 5, wherein the molded body is a sheath for electric wires.