KR100354880B1 - A MOLDED PRODUCT COMPRISING AN ETHYLENE/α-OLEFIN COPOLYMER - Google Patents

Abstract

The present invention is to obtain a film, a sheet, a packaging material, an injection molded product, a foamed molded product, a fiber and the like excellent in mechanical strength, heat resistance and transparency, and these are copolymers of ethylene and α-olefins having 6 to 8 carbon atoms, Melt tension and MFR satisfy certain relations, and the flow activation energy determined from the time-temperature overlapping factor of the flow curve, the number of carbon atoms of the α-olefin in the copolymer, and the content of the α-olefin in the copolymer Ethylene-α-olefin copolymer (A) in which the haze of the film satisfies a specific relationship when a specific relationship is satisfied and the copolymer is prepared by inflation molding and a film having a thickness of 30 m, or (A) And (B) a copolymer of ethylene with an α-olefin having 6 to 8 carbon atoms and (C) a copolymer of ethylene with an α-olefin having 6 to 8 carbon atoms.It said, the MFR of the MFR (B) of (C) is an ethylene copolymer composition (A ') in a particular relationship.

Description

A molded article made of ethylene-α-olefin copolymer {A MOLDED PRODUCT COMPRISING AN ETHYLENE / α-OLEFIN COPOLYMER}

Ethylene-based copolymers are molded by various molding methods and are provided for various applications. Ethylene-based copolymers also require different properties depending on the molding method and application. For example, when trying to mold an inflation film at a high speed, in order to stably perform high-speed molding without bubble fluctuations or breakage, an ethylene-based copolymer must be selected to have a higher melt tension than the molecular weight. The same characteristics are necessary to prevent sag or breakage in blow molding, or to minimize the reduction in width in T die molding.

By the way, the method of improving the moldability by improving melt tension and expansion ratio (die expansion ratio) of an ethylene polymer obtained using a Ziegler-type catalyst, especially a titanium catalyst, is disclosed by Unexamined-Japanese-Patent No. 56-90810 or 60-106806. It is proposed in a call publication. In general, however, ethylene-based polymers, especially low-density ethylene-based copolymers obtained using titanium catalysts, have a broad compositional distribution and often contain components that cause adhesion when forming a molded article such as a film. Further reduction of the components was desired.

In addition, among the ethylene polymers produced using the Ziegler type catalyst, the ethylene polymers obtained using the chromium catalyst have a relatively high melt tension, but an improvement in thermal stability is desired.

The ethylene copolymer obtained by the catalyst for olefin polymerization containing a transition metal metallocene compound has high melt tension and good thermal stability, and is therefore expected to meet the above requirements. However, in the ethylenic copolymer obtained by the metallocene catalyst, in general, the melt tension (MT) and the flow activation energy (E _a ) are in proportion.

The polymer having a high melt tension has good moldability because of excellent bubble stability as described above. However, the flow activation energy E _a is high, which means that the temperature dependence of the molding conditions is large. For this reason, if the molding conditions are not controlled very strictly and uniformly, a stain will arise in the obtained molded object. For example, in the case of a film, transparency may fall.

On the other hand, when the flow activation energy E _a is low, the occurrence of spots in the molded body can be prevented, but the melt tension is low, the bubbles become unstable and the moldability is deteriorated.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a film, a molded article, and the like having excellent transparency and mechanical strength, and to provide a use of an ethylene-α-olefin copolymer having excellent moldability. It is an object of the present invention to provide a use of an ethylene copolymer composition having substantially the same composition and usability.

[Initiation of invention]

A molded article such as a single layer film or sheet, a multilayer film or sheet, an injection molded article, an extruded molded article, a fiber, a foamed molded article, a sheath for an electric wire, or the like is an ethylene-α-olefin copolymer (A ), An ethylene copolymer composition (A '), an ethylene copolymer composition (A' '), or an ethylene copolymer composition (A' '').

Ethylene-α-olefin copolymer (A):

It is a copolymer of ethylene and the alpha olefin of 6-8 carbon atoms,

(A-i) Melt tension (MT) and melt flow rate (MFR) at 190 ° C,

^{9.0 × MFR -0.65 MT> 2.2 ×} MFR -0.84

Satisfies the relationship indicated by

(A-ii) the flow activation energy ((E _a ) × 10 ^-4 J / molK) obtained from the shift factor of the time-temperature overlap of the flow curve, the number of carbon atoms (C) of the α-olefin in the copolymer, The relationship between the content rate (x mol%) of the α-olefin 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 represented by

(A-iii) When the copolymer is inflation-formed to produce a film having a thickness of 30 μm, haze of the film satisfies the following relationship.

The fluidity index (FI) and melt flow rate (MFR), defined as the shear rate at which the shear stress at 190 ° C reaches 2.4 × 10 ⁶ dyne / cm ² ,

When FI≥100 × MFR

When the number of carbon atoms (C) of the α-olefin is 6

Haze <0.45 / (1-d) × log (3 × MT ^1.4 ) × (C-3) ^0.1

When the number of carbon atoms (C) of the α-olefin is 7 or 8

Haze <0.50 / (1-d) × log (3 × MT ^1.4 )

The fluidity index (FI) and melt flow rate (MFR), defined as the shear rate at which the shear stress at 190 ° C reaches 2.4 × 10 ⁶ dyne / cm ² ,

When FI <100 × MFR

When the number of carbon atoms (C) of the α-olefin is 6

Haze <0.25 / (1-d) × log (3 × MT ^1.4 ) × (C-3) ^0.1

When the number of carbon atoms (C) of the α-olefin is 7 or 8

Haze <0.50 / (1-d) × log (3 × MT ^1.4 )

(Where d denotes density (g / cm ³ ) and MT denotes melt tension (g))

Such an ethylene-α-olefin copolymer (A) is, for example

(a) an organic aluminum oxy compound,

(b-I) at least one transition metal compound selected from the transition metal compounds represented by the following formula (I),

ML ¹ x... (I)

(Wherein M is a transition metal atom selected from Group 4 of the periodic table, L ¹ is a ligand that coordinates to the transition metal atom (M), and at least two ligands (L ¹ ) of these are hydrocarbons having 3 to 10 carbon atoms) A substituted cyclopentadienyl group having at least one group selected from the group, and ligands other than the substituted cyclopentadienyl group (L ¹ ) are a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, and a trialkylsilyl group , A halogen atom or a hydrogen atom, 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)

(Wherein M is a transition metal atom selected from Group 4 of the periodic table, L ² is a ligand that coordinates to a transition metal atom (M), and at least two of these ligands (L ² ) are methylcyclopentadienyl groups or ethylcyclo) The ligand (L ² ) other than the methylcyclopentadienyl group or the ethylcyclopentadienyl group is a pentadienyl group, and a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a trialkylsilyl group, a halogen atom or hydrogen X is the valence of the transition metal atom (M)

It is obtained by copolymerizing ethylene and an alpha olefin having 6 to 8 carbon atoms in the presence of a catalyst for olefin polymerization.

In the catalyst, the (a) organoaluminum oxy compound, (b-I) transition metal compound and (b-II) transition metal compound,

(c) It is preferable to be supported on a support.

Ethylene Copolymer Composition (A '):

(B) is a copolymer of ethylene and an α-olefin having 6 to 8 carbon atoms,

(Bi) density ranges from 0.880 to 0.970 g / cm ³ ,

(B-ii) Melt flow rate (MFR) at 190 ° C and 2.16 kg load is in the range of 0.02 to 200 g / 10 minutes,

(B-iii) Decane soluble component content rate (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

Satisfies the relationship indicated by

(B-iv) The temperature (Tm) and the density (d) of the maximum peak position of the endothermic curve measured by a differential scanning calorimeter (DSC)

Tm <400 × d-248

Satisfy the relationship represented 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

Satisfies the relationship indicated by

(B-vi) the flow activation energy ((E _a ) × 10 ⁻⁴ J / molK) obtained from the shift factor of the time-temperature overlap of the flow curve, the number of carbon atoms (C) of the α-olefin in the copolymer, The relationship between the content rate (x mol%) of the α-olefin 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

Satisfies the relationship indicated by

(B-vii) The ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) determined by GPC is

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,

(Ci) density ranges from 0.880 to 0.970 g / cm ³ ,

(C-ii) Melt flow rate (MFR) at 190 ° C and 2.16 kg load is in the range of 0.02 to 200 g / 10 minutes,

(C-iii) Decane soluble component content rate (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

Satisfies the relationship indicated by

(C-iv) The temperature (Tm) and the density (d) of the maximum peak position of the endothermic curve measured by a differential scanning calorimeter (DSC)

Tm <400 × d-248

Satisfies the relationship indicated by

(C-v) Melt tension (MT) and melt flow rate (MFR) at 190 ° C,

MT≤2.2 × MFR ^-0.84

Ethylene-α-olefin copolymer represented by

Composition,

The ratio of the melt flow rate (MFR (C)) of (C) to the melt flow rate (MFR (B)) of (B)

1 <(MFR (C)) / (MFR (B)) ≤20

to be. This ethylene-based copolymer composition (A ') has a composition and usefulness substantially the same as those of the ethylene-α-olefin copolymer.

In the ethylene copolymer composition (A '), the ethylene-α-olefin copolymers (B) and (C) are both ethylene-1-hexene copolymers,

(A'-i) Melt tension (MT) and melt flow rate (MFR) at 190 ° C,

^{9.0 × MFR -0.65 MT> 2.2 ×} MFR -0.84

Satisfies the relationship indicated by

(A'-ii) of the flow activation energy ((E _a ) × 10 ^-4 J / molK) obtained from the shift factor of the time-temperature overlap of the flow curve, and of 1-hexene in the copolymers (B) and (C) The relationship between the number of carbon atoms (C) and the total content (x mol%) of 1-hexene in the copolymer (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

Satisfies the relationship indicated by

(A'-iii) When the said copolymer composition is inflation-molded and the film of 30 micrometers in thickness is manufactured, it is preferable that the haze of the said film satisfy | fills the following relationship.

The fluidity index (FI) and melt flow rate (MFR), defined as the shear rate at which the shear stress at 190 ° C reaches 2.4 × 10 ⁶ dyne / cm ² ,

When FI≥100 × MFR

Haze <0.45 / (1-d) × log (3 × MT ^1.4 ) × (C-3) ^0.1

The fluidity index (FI) and melt flow rate (MFR), defined as the shear rate at which the shear stress at 190 ° C reaches 2.4 × 10 ⁶ dyne / cm ² ,

When FI <100 × MFR

Haze <0.25 / (1-d) × log (3 × MT ^1.4 ) × (C-3) ^0.1

(Wherein d represents density (g / cm ³ ), MT represents melt tension (g), and C represents 1-hexene carbon atom, that is, "6".

In addition, the ethylene copolymer composition (A ') is in addition to the requirements of the above (A'-i) to (A'-iii)

(A'-iv) The ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) determined by GPC is

2.0≤Mw / Mn≤2.5

It is desirable to satisfy.

To an ethylene-α-olefin copolymer (A) or an ethylene-based copolymer composition (A ')

(D)

(a) an organoaluminum oxy compound,

(b-III) obtained by copolymerizing ethylene and an α-olefin having 3 to 20 carbon atoms in the presence of a catalyst for olefin polymerization containing a transition metal compound of Group 4 of the periodic table including a ligand having a cyclopentadienyl skeleton Lose,

(Di) density ranges from 0.850 to 0.980 g / cm ³ ,

(D-ii) The intrinsic viscosity [η] measured in 135 degreeC and decalin is further mix | blended with the ethylene-alpha-olefin copolymer of the range of 0.4-8 dl / g, and the ethylene-alpha-olefin copolymer (A) Ethylene copolymer composition (A '') of ethylene-alpha-olefin copolymer (D), Ethylene copolymer composition (A ') of ethylene copolymer composition (A'), and ethylene-alpha-olefin copolymer (D) '').

However, the ethylene-α-olefin copolymer (A) and the ethylene-α-olefin copolymer (D) are not the same, and the ethylene-α-olefin copolymer (B) and (C) and the ethylene-α-olefin air Union D is not the same.

Best Mode for Carrying Out the Invention

Hereinafter, the use of the ethylene-alpha-olefin copolymer which concerns on this invention, and the use of an ethylene-type copolymer composition are demonstrated.

In addition, in the present invention, the term "polymerization" may be used not only for homopolymerization but also for copolymerization, and the term "polymer" is used not only for homopolymer but also for polymer. have.

The film, sheet, molded article, etc. according to the present invention are formed from the following ethylene-α-olefin copolymer (A) or ethylene-based copolymer composition (A '), (A' '), (A' ''). . First, an ethylene-alpha-olefin copolymer (A), an ethylene-type copolymer composition (A '), (A "), and (A'") are demonstrated.

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 for copolymerization with ethylene, a linear α-olefin having no branch is preferable, and specific examples thereof include 1-hexene, 1-heptene and 1-octene. In particular, 1-hexene is preferably used.

An ethylene-alpha-olefin copolymer (A) has the characteristics as shown to following (A-i)-(A-iii).

(A-i) Melt tension [MT (g)] and melt flow rate [MFR (g / 10min)]

^{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.

The ethylene-α-olefin copolymer having such characteristics has good moldability because of its high melt tension (MT).

In addition, MFR is measured under the conditions of 190 ° C, 2.16 kg load in accordance with ASTM D1238-65T.

In addition, melt tension (MT) is determined by measuring the stress when the melted polymer is stretched at a constant speed. That is, the produced polymer powder is melted by a conventional method, and then pelletized into a measurement sample, using a MT measuring instrument manufactured by Dongyang Seiki Co., Ltd., using a resin temperature of 190 ° C., an extrusion rate of 15 mm / min, a winding rate of 10 to 20 m / min, The nozzle diameter is 2.09 mm, and the nozzle length is 8 mm. At the time of pelletization, 0.05% by weight of tri (2,4-di-t-butylphenyl) phosphate as a secondary antioxidant was previously added to the ethylene-α-olefin copolymer and n-octadecyl-3- (4 ') as a heat stabilizer. 0.1 wt% of -hydroxy-3 ', 5'-t-butylphenyl) propionate and 0.05 wt% of calcium stearate as a hydrochloric acid absorbent were blended.

(A-ii) the flow activation energy ((E _a ) × 10 ^-4 J / molK) obtained from the shift factor of the time-temperature overlap of the flow curve, the number of carbon atoms (C) of the α-olefin in the copolymer, The relationship between the content rate (x mol%) of the α-olefin 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-12) +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 formability, it is necessary to improve melt tension, and for this reason, it is known that introduction of long-chain branching is effective. E _a of the ethylene-α-olefin copolymer without long chain branching is represented by E _a × 10 ⁻⁴ = (0.039Ln (C-2) +0.0096) × x + 2.87. If long chain branching exists, E _a becomes large, and in the case of E _a × 10 ⁻⁴ (0.039Ln (C-2) +0.0096) × x + 2.87, it is estimated that long chain branching exists, and film formability or transparency Is improved. On the other hand, when _a E a ^{× 10 -4 (0.039Ln (C-} 2) +0.1660) × x + 2.87, excellent in formability, but it is not preferable since the film strength and the film transparency deteriorates.

The measurement of the flow activation energy (E _a ) is described in, for example, Polymer Experimental Vol. 9 Thermodynamic Properties I (Polymer Society Polymer Experimental Editing Committee, Public Publications, pp. 25-28). The viscoelastic frequency dependence is measured to obtain the flow activation energy E _a from the shift factor of the time-temperature overlap. If the graph of storage modulus (vertical axis) versus angular velocity (horizontal axis) measured at a certain reference temperature is fixed and the data measured at different measured temperatures are moved parallel to the abscissa, it overlaps with the data of the reference temperature (thermodynamic simplicity). 2.303R (R is the gas constant) in the gradient of the straight line obtained by plotting the amount 1og (aT) for shifting the data at each measurement temperature to overlap with the data at the reference temperature with respect to the inverse 1 / T of the measured temperature (absolute temperature). By multiplying), the activation energy is obtained as an integer independent of temperature.

Specifically, E _a is measured as follows.

The angular velocity (ω (rad / sec)) dispersion of the storage modulus (G '(dyne / cm ² )) was measured using Rheometer RDS-II manufactured by Rheometrics. The sample holder used the parallel plate of 25 mm, and the sample thickness was about 2 mm. The measurement temperature was 130, 170, 200, 230 degreeC, and G 'was measured in the range of 0.04 <== <= 400 at each temperature. When measuring at 130 degreeC, in order to melt | dissolve a crystal | crystallization completely, after heating up to 150 degreeC, it measured as 130 degreeC. The deformation amount was appropriately selected in the range of 2 to 25% so that the torque in the measurement range was detectable and the torque did not become over. After measurement, the flow curve of four temperature conditions is superimposed on 130 degreeC as a reference temperature, and Ea is calculated | required from the Areneus type plot of _a shift factor. The calculation was performed using the analysis software RHIOS, which is attached to RDS-II.

(A-iii) When a film having a thickness of 30 μm is produced by inflation molding of the ethylene-α-olefin copolymer, the haze of the film satisfies the following relationship.

The fluidity index (FI) and melt flow rate (MFR), defined as the shear rate when the shear stress at 190 ° C. reaches 2.4 × 10 ⁶ dyne / cm ² ,

When FI≥100 × MFR

When the number of carbon atoms (C) of the α-olefin is 6,

Haze <0.45 / (1-d) × 1og (3 × MT ^1.4 ) × (C-3) ^0.1

When the number of carbon atoms (C) of the α-olefin is 7 or 8,

Haze <0.50 / (1-d) × 1og (3 × MT ^1.4 )

The fluidity index (FI) and melt flow rate (MFR), defined as the shear rate when the shear stress at 190 ° C. reaches 2.4 × 10 ⁶ dyne / cm ² ,

When FI <100 × MFR

When the number of carbon atoms (C) of the α-olefin is 6,

Haze <0.25 / (1-d) × log (3 × MT ^1.4 ) × (C-3) ^0.1

When the number of carbon atoms (C) of the α-olefin is 7 or 8,

Haze <0.50 / (1-d) × log (3 × MT ^1.4 )

(Where d denotes density (g / cm ³ ) and MT denotes melt tension (g)).

The ethylene-alpha-olefin copolymer which satisfy | fills these requirements is excellent in moldability and the transparency of the film obtained.

Haze uses a single screw extruder of 20mm ψL / D = 26, air flow rate = 90 liters / minute, using a 25mm ψ die, 0.7mm lip width, single layer slit air ring = 9 g / min, blow ratio = 1.8, draw rate = 2.4 m / min, processing temperature = 200 ° C., a film of thickness = 30 μm was prepared by inflation molding and measured according to ASTM-D-1003-61.

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 a sample such as MT measurement, using a TSP, capillary flow characteristics tester, the resin temperature of 190 ℃, shear stress range of about 5 × 10 ⁴ ~ 3 × 10 ⁶ dyne / cm ² Measure

In addition, according to MFR (g / 10min) of resin to measure, the diameter of a nozzle is changed and measured as follows.

0.5 mm when MFR> 20

1.0 mm when 20≥MFR> 3

2.0 mm when 3≥MFR> 0.8

3.0 mm when 0.8≥MFR

In addition, the density (d) is obtained by measuring the strand obtained at the melt flow rate (MFR) measurement at 2.16 kg load at 190 ° C. at 120 ° C. for 1 hour, and slowly cooling to room temperature over 1 hour, and then Measure with pipe.

It is preferable that an ethylene-alpha-olefin copolymer (A) satisfy | fills the following requirements in addition to the said 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, most preferably 70 to 96 Structural units present in an amount by weight, derived from α-olefins having 6 to 8 carbon atoms, are from 0 to 50% by weight, preferably from 1 to 45% by weight, more preferably from 2 to 35% by weight, in particular Preferably present in an amount of 4 to 30% by weight.

The composition of the ethylene-α-olefin copolymer is a ¹³ C-NMR spectrum of a sample in which approximately 200 mg of the copolymer is uniformly dissolved in 1 ml of hexachlorobutadiene in a ¹⁰ mm ψ sample tube. It is determined by measuring under the measurement conditions of 1500Hz of spectral width, 4.2sec of pulse repetition time and 6μsec of pulse width.

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 , more preferably 0.890 to 0.935 g / cm ³ , most preferably Is preferably in the range of 0.905 to 0.930 g / cm ³ .

The melt flow rate (MFR) of the ethylene-α-olefin copolymer (A) 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. .

N-decane soluble component amount fraction [W (% by weight)] and density [d (g / cm ³ )] of the ethylene-α-olefin copolymer (A) at 23 ° C.

When MFR≤10g / 10min,

W <80 × exp (-100 (d-0.88)) + 0.1

Preferably W <60 × exp (-100 (d-0.88)) + 0.1

More preferably, W <40 x 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 represented by.

In addition, the measurement of the amount of n-decane soluble components of a ethylene-α-olefin copolymer (the smaller the amount of soluble components is, the narrower the distribution of the composition) was measured. It carries out by removing n-decane insoluble part by filtration and collect | recovering n-decane soluble part from a filtrate.

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) of the ethylene-α-olefin copolymer (A)

Tm <400 × d-248

Preferably Tm <450 × d-296

More preferably, Tm <500 × d-343

Especially preferably, Tm <550 * d-392

It is good to satisfy the relationship indicated by.

In addition, the temperature (Tm) at the maximum peak position of the endothermic curve measured by a differential scanning calorimeter (DSC) was filled with about 5 mg of the sample in an aluminum dish, the temperature was raised to 200 ° C. at 10 ° C./min, and kept at 200 ° C. for 5 minutes. After that, the temperature is lowered to room temperature at 10 ° C./min, and then determined by the endothermic curve when the temperature is raised to 10 ° C./min. The measurement uses a DSC-7 device manufactured by Perkin Elma.

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

Said ethylene-alpha-olefin copolymer (A) can be used in combination of 2 or more type.

Ethylene-α-olefin copolymer (A) is, for example

(a) an organoaluminum oxy compound,

(b-I) at least one transition metal compound selected from the transition metal compounds represented by the general formula (I),

(b-II) ethylene and α having 6 to 8 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 above formula (II) It is obtained by copolymerizing an olefin.

In the above (a) an organoaluminum oxy compound,

(bI) at least one transition metal compound selected from the transition metal compounds represented by formula (I) and (b-II) at least one transition metal compound selected from transition metal compounds represented by formula (II) (c) It may be supported on a carrier (hereinafter, such a supported catalyst may be abbreviated as Cat-2).

Next, each catalyst component which forms the catalyst for olefin polymerization (Cat-1) and (Cat-2) is demonstrated.

(a) organoaluminum oxy compound

The organoaluminum oxy compound (a) (hereinafter may be described as "component (a)") may be a conventionally known benzene-soluble aluminoxane, and benzene as disclosed in Japanese Patent Laid-Open No. 2-276807. An insoluble organoaluminum oxy compound may be sufficient.

Such aluminoxane can be manufactured by the following method, for example, and is obtained as a solution of a hydrocarbon normally.

(1) Compounds containing adsorbed water or salts containing crystal water such as trialkylaluminum in a hydrocarbon medium suspension such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate and cerium chloride hydrate A method of reacting by adding an organoaluminum compound.

(2) A method in which water, ice, or water vapor is directly acted on an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether, tetrahydrofuran, or the like.

(3) A method in which an organic tin compound such as dimethyl tin oxide or dibutyl tin oxide is reacted with an organoaluminum compound such as trialkylaluminum in a medium such as decane, benzene or toluene.

Moreover, this aluminoxane may contain a small amount of organometallic components. The solvent or unreacted organoaluminum compound may be distilled off and removed from the recovered solution of aluminoxane and then redissolved in the solvent.

Specific examples of the organoaluminum compounds used in preparing the aluminoxanes include trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, trin-butylaluminum, triisobutylaluminum, tri-s-butylaluminum and tri- trialkyl aluminums such as t-butyl aluminum, tripentyl aluminum, trihexyl aluminum, trioctyl aluminum and tridecyl aluminum;

Tricycloalkyl aluminum, such as tricyclohexyl aluminum and tricyclooctyl aluminum;

Dialkyl aluminum halides such as dimethyl aluminum chloride, diethyl aluminum chloride, diethyl aluminum bromide and diisobutyl aluminum chloride;

Dialkyl aluminum hydrides such as diethyl aluminum hydride and diisobutyl aluminum hydride;

Dialkyl aluminum alkoxides such as dimethyl aluminum methoxide and ethyl aluminum ethoxide; Dialkyl aluminum aryl oxide, such as diethyl aluminum phenoxide, etc. are mentioned.

Of these, trialkylaluminum and tricycloalkylaluminum are particularly preferred. Moreover, as this organoaluminum compound, it is a following general formula

(iC ₄ H ₉ ) _x Al _y (C ₅ H ₁₀ ) _z

(x, y, z is positive, z≥2x)

The isoprenyl aluminum represented by can be used.

Such organoaluminum compounds are used alone or in combination. As a solvent used at the time of manufacture of an aluminoxane, Aromatic hydrocarbons, such as benzene, toluene, xylene, cumene, cymene; Aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane and octadecane; Alicyclic hydrocarbons such as cyclopentane, cyclohexane, cyclooctane and methylcyclopentane; And hydrocarbon solvents such as petroleum fractions such as gasoline, kerosene and diesel, or halides of the aromatic hydrocarbons, aliphatic hydrocarbons and cycloaliphatic hydrocarbons (for example, chlorides and bromides). In addition, ethers, such as ethyl ether and tetrahydrofuran, can be used. Of these solvents, aromatic hydrocarbons are particularly preferred.

In addition, the benzene-insoluble organoaluminum oxy compound is 10% or less, preferably 5% or less, particularly preferably 2% or less in terms of Al atoms dissolved in benzene at 60 ° C, insoluble or poorly soluble in benzene. to be.

The solubility in benzene of such an organoaluminum oxy compound was suspended in 100 ml of benzene and the organoaluminum oxy compound corresponding to 100 milligrams of Al was mixed for 6 hours at 60 ° C. under stirring, followed by jacketed G-5 glass. Thermal filtration was performed at 60 ° C. using a filter, and the amount of Al atoms present in the total filtrate after washing the solid part separated on the filter four times using 50 ml of benzene at 60 ° C. (x millimoles) was measured. Obtained by (x%).

(b-I) transition metal compounds and (b-II) transition metal compounds

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

ML ¹ _x ... (I)

(Wherein M is a transition metal atom selected from Group 4 of the periodic table, L ¹ is a ligand that coordinates to the transition metal atom (M), and at least two ligands (L ¹ ) of these are hydrocarbon groups having 3 to 10 carbon atoms) A substituted cyclopentadienyl group having at least one group selected from &lt; RTI ID = 0.0 &gt; and &lt; / RTI &gt; ligands other than the substituted cyclopentadienyl groups (L ¹ ) are hydrocarbon groups, alkoxy groups, aryloxy groups, trialkylsilyl groups, Is a halogen atom or a hydrogen atom, and X is the valence of the transition metal atom (M).)

ML ² _x ... (II)

(Wherein M is a transition metal atom selected from Group 4 of the periodic table, L ² is a ligand that coordinates to a transition metal atom (M), and at least two ligands (L ² ) of them are a methylcyclopentadienyl group or an ethylcyclopenta) The ligand (L ² ) other than the methylcyclopentadienyl group or the ethylcyclopentadienyl group is a hydrocarbon group, an alkoxy group, an aryloxy group, a trialkylsilyl group, a halogen atom or a hydrogen atom having 1 to 12 carbon atoms X is the valence of the transition metal atom (M).)

Hereinafter, the transition metal compound represented by the formula (I) or (II) will be described in more detail.

In the 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 for coordinating to the transition metal atom (M), and at least two ligands (L ¹ ) among them are substituted cyclopentadienyl groups having at least one substituent selected from a hydrocarbon group having 3 to 10 carbon atoms. . These ligands L ¹ may be the same or different, respectively.

In addition, the substituted cyclopentadienyl group may have 2 or more substituents, and 2 or more substituents may be same or different, respectively. 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 substituent is a methyl group, an 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, an aralkyl group, and the like. More specifically, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, pentyl group, hexyl group, octyl group, 2-ethylhexyl group, decyl group, etc. Alkyl groups; Cycloalkyl groups such as cyclopentyl group and cyclohexyl group; Aryl groups, such as a phenyl group and a tolyl group; Aralkyl groups, such as a benzyl group and a neofill group, can be illustrated.

Among these, alkyl groups are preferable, and n-propyl group and 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, and particularly preferably a 1,3-substituted cyclopentadienyl group.

In the above 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, and a trialkyl group. Silyl group, halogen atom or hydrogen atom.

Examples of the hydrocarbon group having 1 to 12 carbon atoms include alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, and the like, and more specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group and iso Alkyl groups such as butyl, s-butyl, t-butyl, pentyl, hexyl, octyl, 2-ethyl hexyl and decyl; Cycloalkyl groups such as cyclopentyl group and cyclohexyl group; Aryl groups, such as a phenyl group and a tolyl group; Aralkyl groups, such as a benzyl group and a neofill group, can be illustrated.

Examples of the alkoxy group include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, s-butoxy group, t-butoxy group, pentoxy group, hexoxy group and octoxy group. can do.

As an aryloxy group, a phenoxy group etc. can be illustrated.

Examples of the trialkylsilyl group include trimethylsilyl group, triethylsilyl group, triphenylsilyl group, and the like.

Halogen atoms are fluorine, chlorine, bromine and iodine.

Examples of the transition metal compound represented by formula (I) include bis (n-propylcyclopentadienyl) zirconium dichloride, bis (n-butylcyclopentadienyl) zirconium dichloride, and bis (n-hexylcyclopentadienyl Zirconium dichloride, bis (methyl-n-propylcyclopentadienyl) zirconium dichloride, bis (methyl-n-butylcyclopentadienyl) zirconium dichloride, bis (dimethyl-n-butylcyclopentadienyl) zirconium Dichloride, bis (n-butylcyclopentadienyl) zirconium dibromide, bis (n-butylcyclopentadienyl) zirconium methoxychloride, bis (n-butylcyclopentadienyl) zirconium ethoxychloride, 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 benzylchloride, bis (n-butylcyclopentadienyl) zirconium dibenzyl, bis (n-butylcyclopentadienyl ) Zirconium phenyl chloride, bis (n-butylcyclopentadienyl) zirconium hydride chloride, etc. are mentioned.

In the above examples, the disubstituted cyclopentadienyl ring includes 1,2- and 1,3-substituents, and the trisubstituent includes 1,2,3- and 1,2,4-substituents.

In the present invention, in the above zirconium compound, a transition metal compound in which a zirconium metal is substituted with a titanium metal or a hafnium metal can be used.

Among the transition metal compounds represented by these formulas (I), bis (n-propylcyclopentadienyl) zirconium dichloride, bis (n-butylcyclopentadienyl) zirconium dichloride, bis (1-methyl-3- Particular preference is given to n-propylcyclopentadienyl) zirconium dichloride, bis (1-methyl-3-n-butylcyclopentadienyl) zirconium dichloride.

In 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 may be the same or different.

In the above formula (II), the ligand (L ² ) other than the methylcyclopentadienyl group or the ethylcyclopentadienyl group coordinated to the transition metal atom (M) has the same number of carbon atoms as L ¹ in the formula (I). It is a 1-12 hydrocarbon group, an alkoxy group, an aryloxy group, a trialkylsilyl group, a halogen atom, or a hydrogen atom.

Examples of the transition metal compound represented by formula (II) include bis (methylcyclopentadienyl) zirconium dichloride, bis (ethylcyclopentadienyl) zirconium dichloride,

Bis (methylcyclopentadienyl) zirconium dibromide, bis (ethylcyclopentadienyl) zirconium dibromide, bis (methylcyclopentadienyl) zirconium methoxychloride,

Bis (ethylcyclopentadienyl) zirconium methoxychloride, bis (methylcyclopentadienyl) zirconium ethoxychloride, bis (ethylcyclopentadienyl) zirconium ethoxychloride, bis (methylcyclopentadienyl) zirconium dieth Said, bis (ethylcyclopentadienyl) zirconium diethoxide, bis (methylcyclopentadienyl) zirconium methyl chloride, bis (ethylcyclopentadienyl) zirconium methyl chloride, bis (methylcyclopentadienyl) zirconium dimethyl, Bis (ethylcyclopentadienyl) zirconium dimethyl, bis (methylcyclopentadienyl) zirconium benzylchloride, bis (ethylcyclopentadienyl) zirconium benzylchloride, bis (methylcyclopentadienyl) zirconium dibenzyl, bis (ethyl Cyclopentadienyl) zirconium dibenzyl, bis (methylcyclopentadienyl) zirconium phenylchloride, bis ( Butyl and the like can be mentioned cyclopentadienyl) zirconium phenyl chloride, bis (methylcyclopentadienyl) zirconium hydride chloride, bis (ethyl cyclopentadienyl) zirconium chloride hydride hard.

In the present invention, in the zirconium compound as described above, a transition metal compound in which zirconium metal is replaced with titanium metal or hafnium metal can be used.

Among the transition metal compounds represented by the general formula (II), bis (methylcyclopentadienyl) zirconium dichloride and bis (ethylcyclopentadienyl) zirconium dichloride are particularly preferable.

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

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

At least one transition metal compound (bI) selected from the transition metal compounds represented by formula (I) and at least one transition metal compound (b-II) selected from transition metal compounds represented by formula (II) Silver molar ratio (bI / b-II) is 99/1 to 40/60, preferably 95/5 to 45/55, more preferably 90/10 to 50/50, most preferably 85/15 to 55 It is preferable to use it in the quantity which becomes / 45 range.

A transition metal compound catalyst comprising at least one selected from the transition metal compounds (bI) represented by the formula (I) and at least one selected from the transition metal compounds (b-II) represented by the formula (II). A component may be described as "component (b)."

The catalyst for olefin polymerization (Cat-1) is formed from the organoaluminum oxy compound (a), the transition metal compound (bI) and the transition metal compound (b-II). The oxy compound (a), the transition metal compound (bI) and the transition metal compound (b-II) can be supported and used as a catalyst (Cat-2).

(c) carrier

(C) The carrier used according to necessity is an inorganic or organic compound, and a granular or particulate solid having a particle diameter of 10 to 300 µm, preferably 20 to 200 µm is used. Among these, a porous oxide is preferable. Specifically, SiO ₂ , Al ₂ 0 ₃ , MgO, ZrO ₂ , TiO ₂ , B ₂ 0 ₃ , CaO, ZnO, BaO, ThO _2, etc. or mixtures containing them, for example Si0 ₂ -MgO, Si0 ₂ -Al ₂ O ₃ , SiO ₂ -TiO ₂ , SiO ₂ -V ₂ O ₅ , SiO ₂ -Cr ₂ O ₃ , SiO ₂ -TiO ₂ -MgO, and the like.

Among these, from the group consisting of Si0 ₂ and Al ₂ 0 ₃ it is preferably composed mainly of at least one kind of component selected.

In addition, the inorganic oxide contains 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 0, K 2 0, may contain carbonates, sulfates, nitrates and oxide components such as Li ₂ O is no hindrance.

Such carriers (c) have different properties depending on the type and preparation method, but the carriers used preferably have a specific surface area of 50 to 1000 m ² / g, preferably 100 to 700 m ² / g, and a pore volume of 0.3 to 2.5. It is preferred that it is cm ³ / g. The carrier is used by firing at 100 to 1000 ° C, preferably 150 to 700 ° C, if necessary.

In such a carrier (c), the amount of adsorbed water is preferably less than 1.0% by weight, preferably less than 0.5% by weight, and the surface hydroxyl group is 1.0% by weight or more, preferably 1.5 to 4.0% by weight, particularly preferably 2.0 to 3.5% by weight. It is good to be.

Here, the amount of adsorbed water (% by weight) and the amount of surface hydroxyl groups (% by weight) of the carrier (c) are obtained as follows.

[Adsorption quantity]

At a temperature of 200 ° C, 100 parts by weight of the weight before drying of the weight reduction when dried for 4 hours under atmospheric pressure and nitrogen flow is used as the amount of adsorbed water.

[Surface hydroxyl amount]

The weight of the carrier obtained by drying at 4O &lt; 0 &gt; C for 4 hours under atmospheric pressure and nitrogen flow was X (g), and the weight of the fired product in which the surface hydroxyl group obtained by firing the carrier further at 1000 DEG C for 20 hours was Y ( It is calculated by the following formula as g).

Surface hydroxyl amount (% by weight) = {(X-Y) / X} × 100

Moreover, as a carrier (c) which can be used for this invention, the granular or particulate solid of an organic compound whose particle diameter is the range of 10-300 micrometers is mentioned. As these organic compounds, a main component is a (co) polymer or vinylcyclohexane, styrene produced by using a C2-C14? -Olefin such as ethylene, propylene, 1-butene and 4-methyl-1-pentene as a main component. The polymer or copolymer produced by this can be illustrated.

Moreover, as an ingredient which forms the catalyst for olefin polymerization (Cat-1) and (Cat-2), the following organoaluminum compound (d) can be used as needed.

d) organoaluminum compounds

As (d) organoaluminum compound (it describes as a "component (d) hereafter) used as needed, the organoaluminum compound represented by following General formula (i) can be illustrated, for example.

R ¹ _n AlX _3-n ... (i)

(In formula, R <^1> is a C1-C12 hydrocarbon group, X is a halogen atom or a hydrogen atom, n is 1-3.)

In the formula (i), R ¹ is a hydrocarbon group having 1 to 12 carbon atoms, for example, an alkyl group, a cycloalkyl group or an aryl group, but specifically, methyl, ethyl, n-propyl, isopropyl, isobutyl Group, pentyl group, hexyl group, octyl group, cyclopentyl group, cyclohexyl group, phenyl group, tolyl group and the like.

Specific examples of such (d) organoaluminum compounds include the following compounds.

Trialkyl aluminum, such as trimethyl aluminum, triethyl aluminum, triisopropyl aluminum, triisobutyl aluminum, trioctyl aluminum, and tri2-ethylhexyl aluminum; Alkenyl aluminum, such as isoprenyl aluminum; Dialkyl aluminum halides such as dimethyl aluminum chloride, diethyl aluminum chloride, diisopropyl aluminum chloride, diisobutyl aluminum chloride and dimethyl aluminum bromide; Alkyl aluminum sesquihalides such as methyl aluminum sesquichloride, ethyl aluminum sesquichloride, isopropyl aluminum sesquichloride, butyl aluminum sesquichloride and ethyl aluminum sesquibromide; Alkyl aluminum dihalide, such as methyl aluminum dichloride, ethyl aluminum dichloride, isopropyl aluminum dichloride, and ethyl aluminum dibromide; Alkyl aluminum hydride, such as diethyl aluminum hydride and diisobutyl aluminum hydride.

Moreover, the compound represented by following General formula (ii) can be used as (d) organoaluminum compound.

R ¹ _n AlY _3-n ... (ii)

Wherein R ¹ is as defined above, Y is -OR ² , -OSiR ³ ₃ , -OAlR ⁴ ₂ , -NR ⁵ ₂ , -SiR ⁶ ₃ or -N (R ⁷ ) AlR ⁸ ₂ is, n is 1 to 2, R ² , R ³ , R ⁴ and R ⁸ are methyl group, ethyl group, isopropyl group, isobutyl group, cyclohexyl group, phenyl group and the like, R ⁵ is hydrogen atom, methyl group, Ethyl group, isopropyl group, phenyl group, trimethylsilyl group and the like, and R ⁶ and R ⁷ are methyl group, ethyl group and the like.) Specific examples of such organoaluminum compounds include the following compounds.

(1) a compound represented by R ¹ _n Al (OR ² ) _3-n , for example, dimethyl aluminum methoxide, diethyl aluminum ethoxide, diisobutyl aluminum methoxide,

(2) a compound represented by R ¹ _n Al (0SiR ³ ₃ ) _3-n , for example Et ₂ A1 (OSiMe ₃ ), (iso-Bu) ₂ A1 (OSiMe ₃ ), (iso-Bu) ₂ Al (OSiEt ₃ ) and the like;

(3) compounds represented by R ¹ _n A1 (OAlR ⁴ ₂ ) _3-n , such as Et ₂ AlOAlEt ₂ , (iso-Bu) ₂ AlOAl (iso-Bu) _2, and the like;

(4) a compound 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 and the like;

(5) a compound represented by R ¹ _n Al (SiR ⁶ ₃ ) _3-n , such as (iso-Bu) ₂ AlSiMe ₃ and the like;

(6) a compound represented by 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 and the like.

Among the organoaluminum compounds represented by the formulas (i) and (ii), represented by the formulas R ¹ ₃ Al, R ¹ _n Al (OR ² ) _3-n , and R ¹ _n Al (OAlR ⁴ ₂ ) _3-n Preferred compounds are preferred, and in particular, compounds wherein R ¹ is an isoalkyl group and n = 2 are preferred.

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

In the catalyst for olefin polymerization (Cat-1), each catalyst component can be produced by mixing and contacting each catalyst component in the polymerization reactor or outside the polymerization reactor, but after the component (a) is made into a solid component, the component (b) is mixed and brought into contact with the solid phase catalyst. The solid catalyst may be added to the polymerization system after the solid catalyst is formed or the component (a) and the component (b) are mixed and contacted in advance.

The catalyst for olefin polymerization (Cat-1) can be formed by mixing and contacting component (a) and component (b) and component (d) as necessary in an inert hydrocarbon solvent. Although the contact order of each component is arbitrarily selected, in the case of mixing and contacting component (a) and component (b), it is preferable to add component (b) to the suspension of component (a). In addition, component (b) is preferably mixed in contact with other components after mixing two or more kinds of the transition metal compounds (components (b-I) and (b-II)) forming the component (b) in advance.

Specific examples of the inert hydrocarbon solvent used in the preparation of the catalyst for olefin polymerization (Cat-1) include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane and kerosene; Alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclopentane; Aromatic hydrocarbons such as benzene, toluene and xylene; Halogenated hydrocarbons, such as ethylene chloride, chlorobenzene, and dichloromethane, or a mixture thereof are mentioned.

When the component (a) and the component (b) and the component (d) are mixed and contacted as necessary, the concentration of the component (a) is converted into aluminum in the component (a) and is about 0.1 to 5 mol / liter (solvent). Preferably it is the range of 0.3-3 mol / liter (solvent). The atomic ratio (Al / transition metal) of aluminum (Al) in component (a) and 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 component (d) and the aluminum atom (A1-a) in component (a) to be used as necessary is usually 0.02 to 3, preferably Is in the range of 0.05 to 1.5. The mixing temperature at the time of mixing and contacting component (a), component (b), and component (d) as needed is -50-150 degreeC normally, Preferably it is -20-120 degreeC, and contact time is 1 minute-50 The time is preferably 10 minutes to 25 hours.

In the olefin polymerization catalyst (Cat-1) prepared as described above, the component (b) per 1 g of the catalyst is converted into a transition metal atom so that 5 × 10 ⁻⁶ to 5 × 10 ⁻⁴ moles, preferably 10 ⁻⁵ to It is contained in an amount of 2x10 ^-4 moles, and components (a) and (d) are converted into aluminum atoms in terms of 10 ^-2 to 2.5x10 ^-2 moles, preferably 1.5x10 ^-2 to 2x10 It is preferably contained in an amount of ^-2 moles.

Solid catalyst (Cat-2) can be manufactured by supporting component (a), component (b), and component (d) as needed on support (c).

The order of contacting of 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 (c) are preferred. ) Is brought into mixed contact, then component (b) is brought into mixed contact and component (d) is further brought into contact by mixing. In addition, the component (b) is preferably mixed with other components after mixing the two or more kinds of the transition metal compounds, the components (b-I) and (b-II) forming the component (b) in advance.

The contacting of the component (a), component (b), carrier (c) and component (d) can be carried out in an inert hydrocarbon solvent, and specifically for the olefin polymerization described above as an inert hydrocarbon solvent used in the preparation of the catalyst. The inert hydrocarbon solvent used at the time of manufacture of a catalyst (Cat-1) is mentioned.

When component (a), component (b) and carrier (c) and, if necessary, component (d) are mixed in contact, component (b) is usually converted into a transition metal atom per gram of carrier (c), usually 5 x 10 ^-6. ˜5 × 10 ⁻⁴ moles, preferably 10 ⁻⁵ to 2 × 10 ⁻⁴ water, and the concentration of component (b) is about 10 ⁻⁴ to 2 × 10 ⁻² moles / liter (solvent), Preferably it is the range of 2 * 10 <^-4> -10 <^-2> mol / liter (solvent). The atomic ratio (A1 / transition metal) of 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 component (d) and the aluminum atom (Al-a) in component (a) used as necessary is usually 0.02 to 3, preferably Is in the range of 0.05 to 1.5. The mixing temperature at the time of the mixed contact between the component (a), the component (b) and the carrier (c) and, if necessary, the component (d) is usually -50 to 150 ° C, preferably -20 to 120 ° C, and 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) per 5 g of the carrier (c) in terms of transition metal atoms, preferably 5 × 10 ⁻⁶ to 5 × 10 ⁻⁴ moles, preferably 10 ⁻⁵ to It is supported in an amount of 2 x 10 ^-4 moles, and the components (a) and (d) per 10 g of the carrier (c) are converted into aluminum atoms in terms of 10 ^-3 to 5 x 10 ^-2 moles, preferably 2 x 10 It is preferably supported in an amount of ^-3 to 2 × 10 ^-2 mol.

The catalyst for olefin polymerization (Cat-2) as described above may be a prepolymerization catalyst in which olefin is prepolymerized.

The prepolymerization catalyst can be prepared by introducing a olefin in an inert hydrocarbon solvent in the presence of the above components (a), (b) and carrier (c) and prepolymerizing. Moreover, it is preferable that the said solid catalyst component (Cat-2) is formed from the said component (a), the component (b), and the support | carrier (c). In this case, in addition to the solid catalyst component (Cat-2), the component (a) and / or the component (d) may be further added.

As the prepolymerization catalyst, olefin may be introduced into the suspension of the solid catalyst (Cat-2) (solid catalyst component) described above, and after the solid catalyst (Cat-2) is produced, the produced solid catalyst (Cat- After 2) is separated from the suspension, the solid catalyst (Cat-2) may be suspended again with an inert hydrocarbon, and olefins may be introduced therein.

When preparing the prepolymerization catalyst, the component (b) is usually converted into a transition metal atom in the component (b) in the range of 10 ⁻⁶ to 2 × 10 ⁻² mol / liter (solvent), preferably 5 × 10 ⁻⁵ to Used in an amount of 10 ⁻² mol / liter (solvent), and component (b) is usually 5 × 10 ⁻⁶ to 5 × 10 ⁻⁴ moles, preferably 10, per 1 g of carrier (c) in terms of transition metal atoms Used in amounts of ^-5 to 2 x 10 ^-4 moles. The atomic ratio (Al / transition metal) of aluminum in component (a) and 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) used as necessary is usually 0.02 to 3, preferably Is in the range of 0.05 to 1.5.

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

Prepolymerization temperature is -20-80 degreeC, Preferably it is 0-60 degreeC, and prepolymerization time is 0.5-100 hours, Preferably it is about 1-50 hours.

Examples of the olefins used in the preliminary polymerization include ethylene and α-olefins having 3 to 20 carbon atoms such as propylene, 1-butene, 1-pentene, 4-methyl-1-pentyl, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, etc. can be illustrated. Of these, ethylene or a combination of ethylene and an α-olefin used in polymerization is particularly preferable.

The prepolymerization catalyst is produced, for example, as follows. In other words, the carrier is suspended in an inert hydrocarbon. Next, an organoaluminum oxy compound (component (a)) is added to this suspension, and it is made to react for predetermined time. The supernatant is then removed and the solid component obtained is resuspended with inert hydrocarbon. After adding a transition metal compound (component (b)) to this system and reacting for a predetermined time, the supernatant is removed to obtain a solid catalyst component. Subsequently, the solid catalyst component obtained above is added to the inert hydrocarbon containing an organoaluminum compound (component (d)), and a prepolymerization catalyst is obtained by introducing an olefin therein. In the prepolymerization, the resulting olefin polymer is preferably 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 addition, in the prepolymerization catalyst, the component (b) per 1 g of the carrier (c) is about 5x10 ^-6 to 5x10 ^-4 moles, preferably 10 ^-5 to 2x10 ^-4 moles in terms of transition metal atoms. It is supported in an amount, and aluminum atoms (Al) in components (a) and (d) are 5 to 200, preferably 10 to 10, in molar ratio (Al / M) to transition metal atoms (M) in component (b). It is good to be supported in an amount in the range of 150.

The preliminary polymerization can be carried out either batchwise or continuously, and can be carried out either under reduced pressure, atmospheric pressure or under pressure. In prepolymerization, it is preferable to produce a prepolymer having hydrogen in the presence of intrinsic viscosity [?] Measured in decalin at least 135 ° C in the range of 0.2 to 7 d1 / g, preferably 0.5 to 5 d1 / g.

Copolymerization of ethylene and α-olefin is carried out in the presence of the catalyst for olefin polymerization as described above, in the gas phase or in the liquid phase in the slurry phase, and preferably in the gas phase. In slurry polymerization, an inert hydrocarbon may be used as a solvent and olefin itself can 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; Alicyclic hydrocarbons such as cyclopentane, methylcyclopentane, cyclohexane and cyclooctane; Aromatic hydrocarbons such as benzene, toluene and xylene; Petroleum fractions such as gasoline, kerosene and diesel. Among these inert hydrocarbon media, aliphatic hydrocarbons, cycloaliphatic hydrocarbons, petroleum fractions and the like are preferred.

In the slurry polymerization method or the gas phase polymerization method, the catalyst as described above is a concentration of transition metal atoms in the polymerization reaction system, and is usually 10 ^-8 to 10 ^-3 mol / liter, preferably 10 ^-7 to 10 ^-4 mol / It is recommended to use in the amount of liters.

In the catalyst for olefin polymerization formed from the component (a) and the component (b) and the component (d) as needed, the aluminum atom (A1) in the component (d) used as needed, and the transition metal compound (b) The atomic ratio (Al / M) with the transition metal atom (M) is in the range of 5 to 300, preferably 10 to 200, and more preferably 15 to 150.

In the catalyst for olefin polymerization formed from component (a), component (b) and carrier (c) and, if necessary, component (d), the organoaluminum oxy compound (component (a)) supported on the carrier during polymerization is In addition, an unsupported organoaluminum oxy compound may be further used. In this case, the atomic ratio (Al / M) between the aluminum atom (A1) in the unsupported organoaluminum oxy compound and the transition metal atom (M) in the transition metal compound (b) is 5 to 300, preferably 10 -200, More preferably, it is the range of 15-150. Component (d) to be used as necessary may be supported on the carrier (c) or may be added during polymerization. In addition, the component (d) may be supported on the carrier (c) and added at the time of polymerization. At this time, the component (d) supported on the carrier and the component (d) added during polymerization may be the same or different. The atomic ratio (Al / M) of the aluminum atom (A1) in the component (d) used as needed and the transition metal atom (M) in the transition metal compound (b) is 5 to 300, preferably 10 to 200, More preferably, it is the range of 15-150.

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., and when the gas phase polymerization method is carried out, the polymerization temperature is usually 0 to 120 ° C., preferably 20 to 100 ° C. Range. The polymerization pressure is usually at atmospheric pressure-100 kg / cm ² , preferably under a pressurized condition of 2 to 50 kg / cm ² , and the polymerization can be carried out in any of batch, semi-continuous and continuous manners.

Moreover, it is also possible to divide superposition | polymerization into two or more stages in which reaction conditions differ. In addition, the olefin polymerization catalyst may include other components useful for olefin polymerization in addition to the above components.

As an olefin which can superpose | polymerize with such an olefin polymerization catalyst, besides ethylene and the C6-C8 alpha olefin, For example, propylene, 1-butene, 1-pentene, 4-methyl-1- pentene, 1-decene Α-olefins such as 1-dodecese, 1-tetradecene, 1-hexadecene, 1-octadecene and 1-eicosene; C3-C20 cyclic olefins, for example cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, 2-methyl-1,4,5,8-di Metano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene and the like. Styrene, vinylcyclohexane, dienes, etc. can also be used.

In the ethylene-α-olefin copolymer obtained by the polymerization method of the olefin, 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 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 45% by weight, more preferably 2 to It is preferably present in an amount of 35% by weight, most preferably 4-30% by weight.

The ethylene-α-olefin copolymer thus obtained preferably has the characteristics as shown in (Ai) to (A-iii) described above, and is excellent in moldability and can produce a film excellent in transparency and mechanical strength. have.

Ethylene Copolymer Composition (A ')

The ethylene-based copolymer composition (A ') has substantially the same composition and utility as the ethylene-α-olefin copolymer (A), and the ethylene-α-olefin copolymer (B) and other ethylene-α-olefin copolymers. It is from coalescence (C).

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-olefins having 6 to 8 carbon atoms include those mentioned 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, most preferably 70 to 96 Structural units present in an amount by weight and derived from α-olefins having 6 to 8 carbon atoms are 0 to 50% by weight, preferably 1 to 45% by weight, more preferably 2 to 35% by weight, in particular Preferably present in an amount of 4 to 30% by weight.

It is preferable that the ethylene-alpha-olefin copolymer (B) has the characteristics as shown to the following (Bi)-(B-vii), and has the characteristics as shown to the following (Bi)-(B-viii). It is particularly desirable to have.

(Bi) 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 , and most preferably 0.905 to 0.930 g / cm ³ Range.

(B-ii) Melt flow rate (MFR) is 0.02-200g / 10min, Preferably it is 0.05-50g / 10min, More preferably, it is the range of 0.1-10g / 10min.

(B-iii) n-decane soluble component amount fraction [W (% by weight)] and density [d (g / cm ³ )] at 23 ° C.

When MFR≤10g / 10min,

W <80 × exp (-100 (d-0.88)) + 0.1

Preferably W <60 × exp (-100 (d-0.88)) + 0.1

More preferably, W <40 x 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

Especially preferably, Tm <550 * d-392

The relationship indicated by is satisfied.

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

(B-v) 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.

The ethylene-α-olefin copolymer having such characteristics has good moldability because of its high melt tension (MT).

(B-vi) the flow activation energy ((E _a ) × 10 ⁻⁴ J / molK) obtained from the shift factor of the time-temperature overlap of the flow curve, the number of carbon atoms (C) of the α-olefin in the copolymer, The relationship between the content rate (x mol%) of the α-olefin 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) The molecular weight distribution (Mw / Mn, where Mw: weight average molecular weight and Mn: number average molecular weight) measured by GPC is

2.2 <Mw / Mn <3.5

Preferably

2.4 <Mw / Mn <3.0

Range.

In addition, molecular weight distribution (Mw / Mn) is measured as follows using GPC-150C by Millipore.

The separation column is TSK GNH HT, the column size is 72mm in diameter, 600mm in length, the column temperature is 140 ℃, and in the mobile phase 0.025% by weight of o-dichlorobenzene (Hwangwang Chemical Co., Ltd.) and 0.025% by weight of BHT (electrochemical) as an antioxidant It was used to move at 1.0 ml / min, the sample concentration was 0.1 weight%, the sample injection amount was 500 microliters, and the differential refractometer was used as a detector. As the standard polystyrene, an isotropic company was used for the molecular weights Mw <1000 and Mw> 4 × 10 ⁶ , and a Fresha-Chemical company was used for 1000 <Mw <4 × 10 ⁶ .

The number of unsaturated bonds present in the molecule (B-viii) is 0.5 or less per 1000 carbon atoms, and less than 1 per molecule of the polymer.

In addition, the quantification of unsaturated bonds is performed using ¹³ C-NMR to integrate the area strength of a signal belonging to a double bond, that is, a signal ranging from 10 to 50 ppm, and a signal belonging to a double bond, that is, a signal ranging from 105 to 150 ppm, using a double bond. It finds from a curve and determines from the ratio.

The ethylene-α-olefin copolymer (B) is, for example, (a) an organoaluminum oxy compound, (b-II) ethylene in the presence of a catalyst for olefin polymerization containing a transition metal compound represented by the formula (II). It is obtained by copolymerizing the C6-8 alpha-olefin. The organoaluminum oxy compound (a) and the transition metal compound (b-II) are the same as those described in the production method of the ethylene-α-olefin copolymer (A). As in the case described above, the carrier (c) and the organoaluminum compound (d) may be used or prepolymerized. The usage-amount of each component, prepolymerization condition, and this polymerization condition are also the same as the case of manufacture of the said ethylene-alpha-olefin copolymer (A).

The ethylene-α-olefin copolymer (C) is a random copolymer of ethylene and an α-olefin having 6 to 8 carbon atoms. Examples of the α-olefins having 6 to 8 carbon atoms include those mentioned above.

As for the ethylene-alpha-olefin copolymer (C), the structural unit derived from ethylene is 50-100 weight%, Preferably it is 55-99 weight%, More preferably, it is 65-98 weight%, Most preferably, 70- It is present in an amount of 96% by weight, and the structural unit derived from 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, Especially preferably, it is present in the amount of 4-30 weight%.

It is preferable that an ethylene-alpha-olefin copolymer (C) has the characteristics as shown to the following (Ci)-(Cv), and what has the characteristics as shown to the following (Ci)-(C-vi) Particularly preferred.

(Ci) 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 , most preferably 0.905 to 0.930 g / cm ³ Range.

(C-ii) Melt flow rate (MFR) is 0.02 to 200 g / 10 minutes, Preferably it is 0.05-50 g / 10 minutes, More preferably, it is the range of 0.1-10 g / 10 minutes.

(C-iii) n-decane soluble component amount fraction [W (% by weight)] and density [d (g / cm ³ )] at 23 ° C.

When MFR≤10g / 10min,

W <80 × exp (-100 (d-0.88)) + 0.1

Preferably W <60 × exp (-100 (d-0.88)) + 0.1

More preferably, W <40 x 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

Especially preferably, Tm <550 * d-392

The relationship indicated by is satisfied.

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

(C-v) melt tension [MT (g)] and melt flow rate [MFR (g / 10min)]

And thus, it satisfies the relationship MT≤2.2 × MFR ^-0.84.

The number of unsaturated bonds present in the (C-vi) molecule is 0.5 or less per 1000 carbon atoms, and less than 1 per molecule of the polymer.

Such ethylene-α-olefin copolymer (C) is, for example, ethylene and carbon in the presence of a catalyst for olefin polymerization containing (a) an organoaluminum oxy compound and (bI) a transition metal compound represented by the formula (I). It is obtained by copolymerizing olefin of 6-8 atoms. The (a) organoaluminum oxy compound and (b-I) transition metal compound are as described in the preparation method of the said ethylene-alpha-olefin copolymer (A). As in the case described above, the carrier (c) and the organoaluminum compound (d) may be used or prepolymerization may be performed. The usage-amount of each component, prepolymerization condition, and this polymerization condition are also the same as the case of manufacture of the said ethylene-alpha-olefin copolymer (A).

The ethylene copolymer composition (A ') contains the ethylene-α-olefin copolymer (B) in an amount of 1 to 90% by weight, preferably 2 to 80% by weight, and includes an ethylene / α-olefin copolymer ( C) is preferably included in an amount of 10 to 99% by weight, preferably 20 to 98% by weight.

Melt flow of the ethylene-α-olefin copolymer (B) in the ethylene-based copolymer composition (A ') including the ethylene-α-olefin copolymer (B) and the ethylene-α-olefin copolymer (C) as described above. The ratio of the rate (MFR (B)) and the melt flow rate (MFR (C)) of the ethylene-α-olefin copolymer (C),

1 <(MFR (C)) / (MFR (B)) ≤20

Is preferably.

Especially in this invention, it is preferable that the said ethylene-alpha-olefin copolymer (B) and (C) are together an ethylene 1-hexene copolymer. In this case, the ethylene-based copolymer composition (A ') preferably has substantially the same physical properties as the ethylene-α-olefin copolymer (A) as shown below, and 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 ^-0.34

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.

The ethylene copolymer composition (A ') having such a property has good moldability because of its high melt tension (MT).

(A'-ii) of the flow activation energy ((E _a ) × 10 ^-4 J / molK) obtained from the shift factor of the time-temperature overlap of the flow curve, and 1-hexene in the copolymers (B) and (C) The relationship between the number of carbon atoms (C) and the total content (x mol%) of 1-hexene in the copolymer (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 the ethylene-based copolymer composition (A ') is produced by inflation molding with a film having a thickness of 30 µm, haze of the film satisfies the following relationship.

The fluidity index (FI) and melt flow rate (MFR), defined as the shear rate at which the shear stress at 190 ° C reaches 2.4 × 10 ⁶ dyne / cm ² ,

When FI≥100 × MFR

Haze <0.45 / (1-d) × log (3 × MT ^1.4 ) × (C-3) ^0.1

The fluidity index (FI) and melt flow rate (MFR), defined as the shear rate when the shear stress at 190 ° C reaches 2.4 x 10 ⁵ dyne / cm ² ,

When FI <100 × MFR

Haze <0.25 / (1-d) × log (3 × MT ^1.4 ) × (C-3) ^0.1

(Wherein d represents density (g / cm ³ ), MT represents melt tension (g), and C represents 1-hexene carbon atom, that is, "6".

The ethylenic copolymer composition (A ') satisfying these requirements is excellent in moldability and transparency of the resulting film.

Moreover, it is preferable that an ethylene copolymer composition (A ') satisfy | fills the following requirements in addition to the said requirements.

(A'-iv) The molecular weight distribution (Mw / Mn, Mw: weight average molecular weight, Mn: number average molecular weight) measured by GPC is

2.0≤Mw / Mn≤2.5

Preferably 2.0≤Mw / Mn≤2.4

Range.

In addition, in the ethylene copolymer composition (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, most preferably 70 to It is present in an amount of 96% by weight, and the structural unit derived from an α-olefin having 6 to 8 carbon atoms, preferably 1-hexene is 0 to 50% by weight, preferably 1 to 45% by weight, more preferably Is preferably present in an amount of 2 to 35% by weight, particularly preferably 4 to 30% by weight.

The density (d) of the ethylene copolymer composition (A ') 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 preferable that it is in the range of 0.905 to 0.930 g / cm ³ .

The melt flow rate (MFR) of the ethylene copolymer composition (A ') 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.

N-decane soluble component amount fraction [W (% by weight)] and density [d (g / cm ³ )] of the ethylene-based copolymer composition (A ') at 23 ° C,

When MFR≤10g / 10min,

W <80 × exp (-100 (d-0.88)) + 0.1

Preferably W <60 × exp (-100 (d-0.88)) + 0.1

More preferably, W <40 x 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 good 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 a differential scanning calorimeter (DSC) of the ethylene-based copolymer composition (A '),

Tm <400 × d-248

Preferably Tm <450 × d-296

More preferably, Tm <500 × d-343

Especially preferably, Tm <550 * d-392

It is good to satisfy the relationship indicated by.

Relationship between temperature (Tm) and density (d) of the maximum peak position of the endothermic curve measured by differential scanning calorimeter (DSC), n-decane soluble component amount fraction (W) and density (d) It can be said that the ethylene-based copolymer composition (A ') having a narrow compositional distribution.

The ethylene copolymer composition (A ') which consists of an ethylene-alpha-olefin copolymer (B) and an ethylene-alpha-olefin copolymer (C) can be manufactured using a well-known method, For example, It can be prepared in the same manner.

(1) The ethylene-α-olefin copolymer (B), the ethylene-α-olefin copolymer (C) and other components to be added as desired are mechanically added using a tumbler, an extruder, a kneader or the like. How to Blend or Melt Mix.

(2) Ethylene-α-olefin copolymer (B), ethylene-α-olefin copolymer (C), and other components to be added as desired, in an appropriate amount of solvent (for example, hexane, heptane, decane, Hydrocarbon solvents such as cyclohexane, benzene, toluene and xylene), and then the solvent is removed.

(3) preparing a solution obtained by separately dissolving an ethylene-α-olefin copolymer (B), an ethylene-α-olefin copolymer (C), and other components added as desired in an appropriate amount of solvent, respectively. Mixing and then removing the solvent.

(4) The method performed by combining the method of said (1)-(3).

As described above, the ethylene-α-olefin copolymer (A) and the ethylene-based copolymer composition (A ') according to the present invention together can produce a film having excellent moldability and excellent transparency and mechanical strength. However, in combination with other polymers, preferably an ethylene-α-olefin copolymer, for example, an ethylene-based copolymer composition of an ethylene-α-olefin copolymer (A) with another ethylene-α-olefin copolymer (A ''), an ethylene copolymer composition (A '' ') of an ethylene copolymer composition (A') and another ethylene-alpha-olefin copolymer, etc. can be used. As such another ethylene-alpha-olefin copolymer, the ethylene-alpha-olefin copolymer (D) demonstrated below is especially used preferably.

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 for copolymerization with ethylene include propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene and 1- Dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, etc. are mentioned.

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, most preferably 70 to 96 It is present in an amount of% by weight, and the structural unit derived from 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 present in an amount of 4 to 30% by weight.

It is preferable that such an ethylene-alpha-olefin copolymer (D) has the characteristics as shown to following (Di) and (D-ii), and has the characteristics as shown to following (Di)-(D-iv). It is more preferable to have.

(Di) 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 , and most preferably 0.920 to 0.950 g / cm ³ Range.

(D-ii) Intrinsic viscosity [eta] measured in 135 degreeC and decalin is 0.4-8 dl / g, Preferably it is 0.4-1.25 dl / g, More preferably, it is the range of 0.5-1.23 dl / g.

(D-iii) The temperature (Tm (° C.)) and the density (d (g / cm ³ )) at 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

Especially preferably, Tm <550 × d-391

It is good to satisfy the relationship indicated by.

(D-iv) n-decane soluble component amount fraction (W (% by weight)) and density (d (g / cm ³ )) at room temperature,

When MFR≤10g / 10min,

W <80 × exp (-100 (d-0.88)) + 0.1

Preferably W <60 × exp (-100 (d-0.88)) + 0.1

More preferably, W <40 x 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) of the maximum peak position in the endothermic curve measured by a differential scanning calorimeter (DSC), and the n-decane soluble component amount fraction (W) and the density (d) The ethylene-α-olefin copolymer (D) having the above relationship can be said to have a narrow compositional distribution.

However, the ethylene-α-olefin copolymer (A) and the ethylene-α-olefin copolymer (D) are not the same, and the ethylene-α-olefin copolymer (B) and (C) and the ethylene-α-olefin air Union D is not the same. Specifically, the ethylene-α-olefin copolymer (D) and the ethylene-α-olefin copolymer (A) to (C) can be distinguished in the following properties.

That is, an ethylene-alpha-olefin copolymer (D) is a copolymer which does not satisfy at least 1 requirement of the requirements (A-i)-(A-iii) which prescribe a copolymer (A).

Moreover, an ethylene-alpha-olefin copolymer (D) is a copolymer which does not satisfy | fill at least 1 requirement of requirements (B-iii)-(B-vii) which prescribe a copolymer (B).

In addition, an ethylene-alpha-olefin copolymer (D) is a copolymer which does not satisfy | fill at least 1 requirement of the requirements (C-iii)-(C-v) which prescribe a copolymer (C).

In addition, as the ethylene-α-olefin copolymer (D), the intrinsic viscosity [η] measured at 135 ° C and decalin is smaller than that of the ethylene-α-olefin copolymer (A), and the density is also lower. Dog. Moreover, it is also preferable that the intrinsic viscosity [η] measured in 135 degreeC and decalin is smaller than an ethylene-alpha-olefin copolymer (B) and (C), and its density is low as an ethylene-alpha-olefin copolymer (D). It is one of the aspects.

Such ethylene-α-olefin copolymer (D) is, for example, ethylene in the presence of a catalyst for olefin polymerization 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 an olefin having 3 to 20 carbon atoms. (a) An organoaluminum oxy compound is as having demonstrated in the manufacturing method of the said ethylene-alpha-olefin copolymer (A). As in the case described above, the carrier (c) and the organoaluminum compound (d) may be used or prepolymerized. The usage-amount of each component, prepolymerization conditions, and this polymerization condition are also the same as the case of manufacture of the said ethylene-alpha-olefin copolymer (A).

Hereinafter, the transition metal compound (b-III) will be described.

(b-III) Transition Metal Compounds

Transition metal compound of Group 4 of the periodic table containing a ligand having a (b-III) cyclopentadienyl skeleton used in the preparation of the ethylene-α-olefin copolymer (D) (hereinafter referred to as component (b-III) The transition metal compound of Group 4 of the periodic table containing a ligand having a cyclopentadienyl skeleton is not particularly limited, but is preferably a transition metal compound represented by the following general formula (III).

ML ³ _x ... (III)

Wherein 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 that coordinates to the transition metal atom (M), at least one of L ³ is a ligand having a cyclopentadienyl skeleton, and examples of the ligand having a cyclopentadienyl skeleton include a cyclopentadienyl group and methylcyclo Pentadienyl group, dimethylcyclopentadienyl group, trimethylcyclopentadienyl group, tetramethylcyclopentadienyl group, pentamethylcyclopentadienyl group, ethylcyclopentadienyl group, methylethylcyclopentadienyl group, propylcyclopentadienyl group, methyl Alkyl-substituted cyclopentadienyl groups or indenyl groups, such as a propyl cyclopentadienyl group, a butyl cyclopentadienyl group, a methylbutyl cyclopentadienyl group, and a hexyl cyclopentadienyl group, an indenyl group, 4,5,6,7-tetrahydroindenyl group, Fluorenyl group etc. can be illustrated. These groups may be substituted with a halogen atom, a trialkylsilyl group, or the like.

Among the ligands having these cyclopentadienyl skeletons, alkyl substituted cyclopentadienyl groups are particularly preferred.

When the compound represented by the formula (III) contains two or more ligands having a cyclopentadienyl skeleton, ligands having two cyclopentadienyl skeletons among them are alkylene groups such as ethylene and propylene, isopropylidene And substituted alkylene groups such as diphenylmethylene, silylene groups or dimethylsilylene groups, diphenylsilylene groups, and substituted silylene groups such as methylphenylsilylene groups.

In the above general formula (III), L ³ other than the ligand having a cyclopentadienyl skeleton is a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, or the same tree as L ¹ in the general formula (I). An alkylsilyl group, a halogen atom, a hydrogen atom, or a SO ₃ 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 p-toluenesulfonato group, methanesulfonato group, triple-oromethanesulfonato group and the like.

The transition metal compound represented by the above 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 ₁ R ⁴ _m R ⁵ _n M... (III ')

(Wherein M is the transition metal atom, R ² is a group having a cyclopentadienyl skeleton (ligand), R ³ , R ⁴ and R ⁵ are a group having an cyclopentadienyl skeleton, an alkyl group, a cycloalkyl group, Aryl group, aralkyl group, alkoxy group, aryloxy group, trialkylsilyl group, SO ₃ R group, halogen atom or hydrogen atom, k is an integer of 1 or more, k + 1 + m + n = 4.

In the present invention, in the formula, a metallocene compound in which one of R ³ , R ^4, and R ⁵ is a group having a cyclopentadienyl skeleton (for example), for example, R ² and R ³ is a cyclopentadienyl skeleton A metallocene compound which is a group (ligand) having an is preferably used. Groups having these cyclopentadienyl skeletons are substituted silyls such as alkylene groups such as ethylene and propylene, substituted alkylene groups such as isopropylidene and diphenylmethylene, silylene groups or dimethylsilylene, diphenylsilylene and methylphenylsilylene groups It may be coupled via a leng or the like. In this case, other ligands (for example, R ⁴ and R ⁵ ) may be a group 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, SO ₃ R, a halogen atom or a hydrogen atom.

Examples of the transition metal compound represented by formula (III) include bis (indenyl) zirconium dichloride, bis (indenyl) zirconium dibromide, bis (indenyl) zirconium bis (p-toluenesulfonato), 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 (methanesulfonato), ethylenebis (indenyl) zirconium bis (p Toluenesulfonato), ethylenebis (indenyl) zirconium bis (trifluoromethanesulfonato), ethylenebis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, isopropyl Den (cyclopentadienyl-fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl-methylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (cyclopenta dienyl) zirconium dichloride, dimethylsilyl Lenbis (methylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (dimethylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (trimethylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (indenyl Zirconium dichloride, dimethylsilylenebis (indeny) zirconiumbis (trifluoromethanesulfonato), dimethylsilylenebis (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) methyl zirconium monochloride, bis (cyclopentadienyl) ethyl zirconium Monochloride, bis (cyclopentadienyl) cyclohexylzirconium monochloride, bis (cyclopentadienyl) phenylzirconium monochloride, bis (cyclopentadienyl) benzylzirconium monochloride, bis (cyclopentadienyl) zirconium monochloride Monohydride, bis (cyclopentadienyl) methyl zirconium monohydrad, bis (cyclopentadienyl) dimethylzirconium, bis (cyclopentadienyl) diphenylzirconium, bis (cyclopentadienyl) dibenzylzirconium, bis (Cyclopentadienyl) zirconium methoxychloride, bis (cyclopentadienyl) zirconium Ethoxychloride, bis (cyclopentadienyl) zirconium bis (methanesulfonato), bis (cyclopentadienyl) zirconium bis (p-toluenesulfonato), bis (cyclopentadienyl) zirconium bis (trifluor Romethanesulfonato), bis (methylcyclopentadienyl) zirconium dichloride, bis (dimethylcyclopentadienyl) zirconium dichloride, bis (dimethylcyclopentadienyl) zirconium ethoxychloride, bis (dimethylcyclopentadiene Nil) zirconium bis (trifluoromethane-sulfonato), bis (ethylcyclopentadienyl) zirconium dichloride, bis (methylethylcyclopentadienyl) zirconium dichloride, bis (propylcyclopentadienyl) zirconium di Chloride, bis (methylpropylcyclopentadienyl) zirconium dichloride, bis (butylcyclopentadienyl) zirconium dichloride, bis (methylbutyl Clopentadienyl) zirconium dichloride, bis (methylbutylcyclopentadienyl) zirconium bis (methanesulfonato), bis (trimethylcyclopentadienyl) zirconium dichloride, bis (tetramethylcyclopentadienyl) zirconium di Chloride, bis (pentamethylcyclopentadienyl) zirconium dichloride, bis (hexylcyclopentadienyl) zirconium dichloride, bis (trimethylsilylcyclopentadienyl) zirconium dichloride, and the like.

Also in the above examples, the disubstituted cyclopentadienyl ring includes 1,2- and 1,3-substituents, and the trisubstituent includes 1,2,3- and 1,2,4-substituents. Alkyl groups such as propyl and butyl include isomers such as n-, i-, s- and t-.

Moreover, in the above zirconium compound, the compound which substituted zirconium by titanium or hafnium can be used.

In addition, the transition metal compound represented by Formula (III) includes a transition metal compound (b-I) represented by Formula (I) and a transition metal compound (b-II) represented by Formula (II).

The ethylene-α-olefin copolymer (D) is copolymerized such that ethylene and an α-olefin having 3 to 20 carbon atoms in the presence of the catalyst for olefin polymerization have a density of 0.850 to 0.980 g / cm ^3. It can manufacture.

The ethylene-α-olefin copolymer (D) is preferably 99 to 60 parts by weight, more preferably based on 100 parts by weight of the ethylene-α-olefin copolymer (A) or ethylene-based copolymer composition (A '). Preferably it is used in the ratio of 95-60 weight part.

The composition of the ethylene-α-olefin copolymer (D) and the above-described ethylene-α-olefin copolymer (A) or ethylene-based copolymer composition (A ') can be produced using the known method described above. have. Moreover, it can also manufacture by the multistage superposition | polymerization method which divided | segmented copolymerization into two or more stages in which reaction conditions differ using one or more polymerizers.

The molded article according to the present invention is formed from the above ethylene-α-olefin copolymer (A) or ethylene copolymer composition (A '), (A' '), (A' '').

Examples of the molded article include a single layer film, a multilayer film, an injection molded article, an extruded molded article, a fiber, a foam, an electric wire sheath, and more specifically, an agricultural film (single layer, multilayer), a waterproof sheet, a multilayer film, a packaging film (multilayer film, Stretch film, high load packaging film), multilayer barrier film, sealant for laminated film, heavy packaging film, grain bag, fluid packaging pouch, batch packaging package, bag in box inner container, medical container, heat resistant Containers, fibers, foam molded articles, gaskets, extruded products, pipes, various injection molded articles, wire sheaths, and the like.

Below, the molded object formed from the said ethylene-alpha-olefin copolymer (A) or ethylene-type copolymer composition (A '), (A "), (A'") is demonstrated in detail.

Agricultural Film (Single Layer):

Agricultural film is the said ethylene-alpha-olefin copolymer (A) or an ethylene-type copolymer composition (A '), (A "), (A'"), and a conventionally well-known antioxidant and ultraviolet absorber as needed. , Lubricants, slip agents, anti-blocking agents, anti-stick agents, antistatic agents, colorants, carbon black, medium density polyethylene, ethylene-vinyl acetate copolymers, ethylene-α-olefin air And additives such as copolymer rubber.

The agricultural film which concerns on this invention is 3-30 micrometers in thickness, Preferably it is the range of 7-20 micrometers.

Agricultural films are prepared from the ethylene-α-olefin copolymer (A) or the ethylene-based copolymer composition (A '), (A' ') and (A' ''), for example, by the inflation method and the T-die method. It can manufacture by film molding by this. Film molding by the inflation method is performed by extruding the copolymer (A) or the composition (A '), (A' '), (A' '') through a slit die and expanding with a predetermined air flow.

The agricultural film has excellent adhesion to soil, that is, flexibility, and excellent characteristics such as weather resistance, tensile property, tearing property, impact resistance, and rigidity, and is a mulch film mainly requiring a geothermal synergistic effect. It is effectively used for tunnel cultivation, house semi-promotion cultivation, processing non-cultivation cultivation, and early digging cultivation.

Agricultural Multilayer Film:

The agricultural multilayer film which concerns on this invention is a 3-layer laminated film which consists of an outer layer, an intermediate | middle layer, and an inner layer.

(Outer floor)

The outer layer which comprises the agricultural multilayer film which concerns on this invention is the said ethylene-alpha-olefin copolymer (A) or ethylene-type copolymer composition (A '), (A "), (A'"), an inorganic compound, If necessary, it is formed of a composition containing a weathering stabilizer and an anti-fogging agent.

Since the outer layer which consists of this copolymer (A) or a composition (A '), (A "), (A'") has a very small decline with time passing of light transmittance, the agricultural multilayer film which has such an outer layer is It can be in the state extended over a long term.

In addition, when the copolymer (A) or the composition (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. have.

(Inorganic compound)

The inorganic compound used when forming the outer layer of the multilayer film is an inorganic oxide, an inorganic hydroxide, hydrotalcites or the like containing at least one atom of Mg, Ca, Al and Si effective as a heat insulating agent.

Specifically, _{SiO 2, Al 2 0 3,} MgO, inorganic oxides such as CaO; Inorganic hydroxides such as Al (OH) ₃ , Mg (OH) ₂ and Ca (OH) ₂ ;

Formula M ²⁺ _1-x Al _x (OH) ₂ (A ^n- ) _{x /} nmH ₂ 0

[Wherein, M ²⁺ is Mg, Ca or a divalent metal ion of Zn, A ^n- is a ^{C1 -, Br -, I -} , NO 3 -, ClO 4-, SO 4 2-, CO 2 2-, Anions such as SiO ₃ ^2- , HPO ₄ ^2- , HBO ₃ ^2- , and PO ₄ ^3- , x is a numerical value satisfying the condition of 0 <x <0.5, and m satisfies the condition of 0 ≦ m ≦ 2. Is a number to say]

Hydrotalcite, such as the inorganic composite compound represented by this, and the baking product, etc. are mentioned. Among these, hydrotalcites are preferable, and the calcined product of the inorganic composite compound represented by the above formula is particularly preferable.

The above inorganic compounds may be used alone or in combination of two or more thereof.

The average particle diameter of the inorganic compound is 10 μm or less, preferably 5 μm or less, and more preferably 3 μm or less.

If the average particle diameter of an inorganic compound is within the said range, a multilayer film with favorable transparency can be obtained.

In the present invention, the inorganic compound is 1 to 20 parts by weight, preferably 1 to 18 parts by weight based on 100 parts by weight of the copolymer (A) or the composition (A '), (A' '), (A' ''). Parts, more preferably 2 to 15 parts by weight.

When forming an outer layer of a multilayer film, when an inorganic compound is used in the above ratio, the multilayer film excellent in heat retention can be obtained.

(Weather stabilizer)

When forming the outer layer of the multilayer film, weather stabilizers to be used as needed are largely divided into ultraviolet absorbers and light stabilizers, but is effective for agricultural films with a thinner light stabilizer, and has a significant effect of improving weather stability.

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.

Specifically as the hindered amine stabilizer, the following compounds are used.

(1) bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate,

(2) dimethyl succinate- (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-piperidinyl benzoate,

(5) bis- (1,2,6,6-tetramethyl-4-piperidinyl) -2- (3,5-di-t-butyl-4-hydroxybenzyl) -2-n-butyl malo Nate,

(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-tetra Oxaspiro (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 Tetraoxaspiro (5,5) undecane] diethyl} -1,2,3,4-butanetetracarboxylate,

(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 with 1,2-dibromoethane,

(14) [N- (2,2,6,6-tetramethyl-4-piperidyl) -2-methyl-2- (2,2,6,6-tetramethyl-4-piperidyl) No] propionamide, etc.

These hindered amine light stabilizers can be used individually or in combination of 2 or more types.

Such light stabilizer is 0.005 to 5 parts by weight, preferably 0.005 to 2 parts by weight, more preferably 100 parts by weight of the copolymer (A) or the composition (A '), (A' '), (A' ''). Preferably it is used in the ratio of 0.01-1 weight part.

Specifically as a ultraviolet absorber,

Salicylic acid-based ultraviolet absorbers such as phenyl salicylate, p-t-butylphenyl salicylate, and p-octylphenyl salicylate;

2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2,2 Benzos such as' -dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone and 2-hydroxy-4-methoxy-5-sulfobenzophenone Phenone ultraviolet absorbers;

2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-5'-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-3 ' , 5'-di-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-3'-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy Benzos such as -3 ', 5'-di-t-butylphenyl) -5-chlorobenzotriazole and 2- (2'-hydroxy-3', 5'-di-t-amylphenyl) benzotriazole Triazole-based absorbents;

And cyanoacrylate ultraviolet absorbers such as 2-ethylhexyl-2-cyano-3,3'-diphenyl acrylate and ethyl-2-cyano-3,3'-diphenyl acrylate. .

The ultraviolet absorber is 0.005 to 5 parts by weight, preferably 0.005 to 2 parts by weight, more preferably based on 100 parts by weight of the copolymer (A) or the composition (A '), (A' '), or (A' ''). Preferably it is used in the ratio of 0.01-1 weight part.

(Other ingredients)

In the copolymer (A) or the composition (A '), (A' ') and (A' ''), additives such as conventionally known antifogging agents, antistatic agents and heat stabilizers do not impair the object of the present invention. It can mix | blend in the range.

As the antifogging agent, an antifogging agent whose main component is a partial ester of polyhydric alcohol and higher fatty acid having 12 to 24 carbon atoms (including hydroxy fatty acid) is preferably used.

(Middle floor)

The intermediate layer constituting the agricultural multilayer film according to the present invention is formed from a composition containing an ethylene-vinyl acetate copolymer, an inorganic compound and, if necessary, an ethylene-α-olefin copolymer (A-1), a weathering stabilizer and an antifogging agent. have.

(Ethylene vinyl acetate copolymer)

The ethylene-vinyl acetate copolymer used in the present invention has a vinyl acetate content in the range of 2.0 to 30% by weight, preferably 3.0 to 25% by weight, more preferably 5.0 to 20% by weight.

When an intermediate | middle layer is formed with this ethylene vinyl acetate copolymer, the multilayer film excellent in heat retention can be obtained. Here, "thermal insulation" refers to the ability to absorb the solar heat during the day to absorb and reflect the radiation emitted at night from the ground where the temperature rises to maintain the temperature (temperature and geothermal) inside the house, tunnel and the like.

(Inorganic compound)

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 1 to 20 parts by weight, preferably 1 to 18 parts by weight, based on 100 parts by weight of the total amount of the ethylene / vinyl acetate copolymer and the ethylene / α-olefin copolymer (A-1) described later. More preferably, it uses in the ratio of 2-15 weight part. However, since component (A-1) is an arbitrary component, it may become 0 weight part.

When forming an intermediate | middle layer of a multilayer film, when an inorganic compound is used in the above ratio, the multilayer film excellent in heat retention can be obtained.

(Ethylene-α-olefin copolymer (A-1))

As for the ethylene-alpha-olefin copolymer (A-1) used as needed at the time of intermediate | middle layer formation of a multilayer film, the density is 0.925g / cm in the ethylene-alpha-olefin copolymer (A) used at the time of outer layer formation mentioned above. ³ or less, Preferably it is an ethylene-alpha-olefin copolymer of 0.880-0.920 g / cm <^3> .

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

When the intermediate layer is formed in the multilayer film, when the ethylene-α-olefin copolymer (A-1) is used in the above weight ratio with respect to the ethylene-vinyl acetate copolymer, the intermediate layer can be thinned.

(Weather stabilizer)

The weathering stabilizers used as necessary in forming the intermediate layer of the multilayer film are ultraviolet absorbers and light stabilizers used in forming the outer layer described above.

The light stabilizer is 0.005 to 5 parts by weight, preferably 0.005 to 2 parts by weight, more preferably 0.01 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 the ratio of -1 weight part. However, since component (A-1) is an arbitrary component, it may become 0 weight part.

The ultraviolet absorber is 0.005 to 5 parts by weight, preferably 0.005 to 2 parts by weight, more preferably 0.01 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 ˜1 parts by weight. However, since component (A-1) is an arbitrary component, it may become 0 weight part.

(Other ingredients)

To the ethylene-vinyl acetate copolymer for intermediate | middle layer formation, additives, such as a conventionally well-known antifoaming agent, an anti-mist agent, an antistatic agent, and a heat stabilizer, can be mix | blended in the range which does not impair the objective of this invention.

As the antifogging agent, an antifogging agent whose main component is a partial esterified product of the above-mentioned polyhydric alcohol and C12-C24 higher fatty acid (including hydroxy fatty acid) is preferably used.

The antifogging agent is 0.05 to 5 parts by weight, preferably 0.1 to 4 parts by weight, more preferably based on 100 parts by weight of the total amount of the ethylene-α-olefin copolymer (A-1) and the ethylene / vinyl acetate copolymer. 0.5 to 3 parts by weight is used. However, since component (A-1) is an arbitrary component, it may become 0 weight part.

(Inner layer)

The inner layer which comprises the agricultural multilayer film which concerns on this invention is formed from a copolymer (A) or a composition (A '), (A "), (A'"). An inorganic compound, a weathering stabilizer, and an antifogging agent can be mix | blended with this copolymer (A) or a composition (A '), (A "), and (A'").

In this invention, an inorganic compound is used in the ratio of 1-3 weight part with respect to 100 weight part of total amounts of a copolymer (A) or a composition (A '), (A "), and (A'").

When the inorganic compound (B) is used in the same ratio as described above in forming the inner layer of the multilayer film, a multilayer film having excellent heat retention can be obtained.

(Weather stabilizer)

The weathering stabilizers used as necessary in forming the inner layer of the multilayer film are the above-mentioned ultraviolet absorbers and light stabilizers.

The light stabilizer is 0.005 to 5 parts by weight, preferably 0.005 to 2 parts by weight, more preferably based on 100 parts by weight of the copolymer (A) or the composition (A '), (A' '), (A' ''). Preferably in an amount of 0.01 to 1 part by weight.

The ultraviolet absorber is 0.005 to 5 parts by weight, preferably 0.005 to 2 parts by weight, more preferably based on 100 parts by weight of the copolymer (A) or the composition (A '), (A' '), or (A' ''). Preferably in an amount of 0.01 to 1 part by weight.

(Other ingredients)

Additives, such as a conventionally well-known antifog additive, an antistatic agent, and a heat stabilizer, are seen in the copolymer (A) or composition (A '), (A "), (A'") used for inner-layer formation of a multilayer film. It can mix | blend in the range which does not impair the objective of this invention.

As an antifogging agent, the antifogging agent which uses the partial ester compound which consists of the above-mentioned polyhydric alcohol and C12-C24 higher fatty acid (including hydroxy fatty acid) as a main component is used preferably.

The antifogging agent is 0.05 to 5 parts by weight, preferably 0.1 to 3 parts by weight, more preferably 100 parts by weight of the copolymer (A) or the composition (A '), (A' '), (A' ''). Preferably it is used in the ratio of 0.5-2 weight part.

(Multilayer film)

The agricultural multilayer film according to the present invention comprising the outer layer, the middle layer and the inner layer as described above has a thickness of the outer layer is usually 3 ~ 100μm, preferably 10 ~ 80μm, more preferably 20 ~ 70μm, the thickness of the intermediate layer 10 ~ 150 micrometers, Preferably it is 20-120 micrometers, More preferably, it is the range of 30-100 micrometers, The thickness of an inner layer is 3-100 micrometers, Preferably it is 10-80 micrometers, More preferably, it is the range of 20-70 micrometers, These are The thickness of a conductor is 30-200 micrometers, Preferably it is 50-180 micrometers, More preferably, it is the range of 70-150 micrometers.

Agricultural multilayer film according to the present invention has the following physical properties and properties.

(i) Elmendorf tear strength is at least 90 kg / cm in the MD direction, preferably at least 100 kg / cm, and at least 90 kg / cm in the TD direction, preferably at least 100 kg / cm.

(ii) Dart impact strength in thickness of 100 micrometers is 900 g or more, Preferably it is 1,000 g or more.

(iii) tensile strength is more than 350kg / cm ² in the MD direction, and preferably at least 370kg / cm ^2, also, is 350kg / cm ² or more in the TD direction, and preferably at least 370kg / cm ^2.

(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.

In addition, Elmendorf tear strength is calculated | required by performing a tear strength test with respect to MD direction and TD direction of a multilayer film based on JISZ1702. The dart impact strength is obtained by performing an impact test in accordance with JIS Z 1707 (38 mm tip diameter). The tensile strength at break was determined by performing a tensile test using a crosshead moving speed constant tensile tester (manufactured by Instron Co., Ltd.) in the MD direction and the TD direction of the multilayer film based on JIS K 6781 under the following conditions. to be.

Moreover, the 50 micrometer-thick agricultural multilayer film which concerns on this invention has a gloss normally 60% or more, and haze is 15% or less normally.

In addition, the gloss of the film was measured at the incident angle of 60 ° according to ASTM D 523. In addition, the haze of the film was measured according to ASTMD1003-61.

(Manufacture of a multilayer film)

The agricultural multilayer film according to the present invention as described above is mixed with components such as polyethylene-based resin and additives used in each layer of the multilayer film, respectively, and melted in a Banbury mixer or roll mill or the like. It can mix and then manufacture by laminating | stacking an outer layer, an intermediate | middle layer, and an inner layer by co-extrusion inflation method or a co-extrusion T-die method.

Such an agricultural multilayer film is excellent in heat retention, dustproofness, and toughness, and can be installed in agricultural and horticultural facilities such as houses and tunnels, and can be used for a long time for the cultivation of useful crops.

Waterproof sheet:

The waterproof sheet includes the ethylene-α-olefin copolymer (A) or the ethylene-based copolymer composition (A '), (A' '), (A' ''), and carbon black, heat stabilizer, and weather stabilizer as necessary. And pigments, fillers (except carbon black), lubricants, antistatic agents, flame retardants, foaming agents and the like. The waterproof sheet may be a multilayer body having an inner layer or an outer layer as a layer made of the copolymer (A) or the composition (A '), (A' ') or (A' '') in combination with other substrates, reinforcing materials, drainage materials and the like. good.

Elongation at tear (JIS A 6008, Crepe method, speed 200mm / min) at 1.5mm thickness is 80% or more, and elongation at the time of sticking at thickness 1.5mm is 5mm or more. Peeling strength (JIS K 6328, speed 50mm / min) at the fusion | melting part when heat-sealing on condition of set temperature 500 degreeC and sealing speed 5m / min using the heat sealer of 10kg / 20mm It is preferable that it is above.

Since the waterproof sheet may come into contact with an uneven object, especially a sharp object, the elongation at tearing and elongation at the time of tearing are important factors in maintaining the performance of the waterproof sheet.

In addition, as a heat sealer for field use, Hot Air sheet welding machine 10E type made from Ryster Corporation is used. In addition, the peeling test was carried out using a Ryster Co., Ltd. hot air sheet welding machine type 10E, and fused two sheets under conditions of a set temperature of 500 ° C. and a speed of 5 m / min, and after adjusting the conditions at 23 ° C. for 48 hours or more to JIS K 6328. Therefore, the peeling strength test was done on condition of speed | rate 50mm / min, peeling strength was measured, and it was set as the index of fusion characteristic. The stab test uses an universal testing machine manufactured by Instron, and measures the breaking strength when the waterproof sheet is fixed to a fixture having a diameter of 5 cm, and a needle having a flat tip having a diameter of 0.7 mm is punctured at a speed of 50 mm / minute, Strength / sheet thickness (kg / mm) and elongation at break were determined.

Since the waterproof sheet which concerns on this invention can be heat-sealed easily and with high strength by the heat sealer actually used in the field, it is extremely preferable practically.

Such a waterproof sheet is excellent in mechanical strength, flexibility, and adhesion, such as tensile strength, tear strength, elongation at tear, sting strength, and elongation at stabbing.

Multilayer film:

The multilayer film is formed from a base film layer and a layer made of the ethylene-α-olefin copolymer (A) or the ethylene-based copolymer composition (A '), (A' ') and (A' '').

The material for forming the base film is not particularly limited as long as it has film forming ability, and any polymer or paper, aluminum foil, cellophane, or the like can be used. As such a polymer, for example, high density polyethylene, medium and low density polyethylene, ethylene vinyl acetate copolymer, ethylene acrylic acid ester copolymer, ionomer, polypropylene, poly-1-butene, poly-4-methyl-1-pentyl Vinyl polymers such as olefin polymers, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyacrylate, polyacrylonitrile, nylon 6, nylon 66, nylon 10, nylon 11, nylon 12, nylon 610, poly Polyamide-based polymers such as metha xylene adiamide, polyester-based polymers such as polyethylene terephthalate, polyethylene terephthalate / isophthalate, polybutylene terephthalate, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polycarbonate-based polymer Etc. can be mentioned.

Moreover, when a base film is made from a polymer, this polymer film may be unoriented or may be extended | stretched uniaxially or biaxially.

These base materials can be suitably selected by the use of a multilayer film. For example, in the case of a composite film for packaging, the substrate can be appropriately selected according to the packaged object. For example, when the package is a food which is easily corroded, a resin having excellent transparency, rigidity, and gas permeation resistance, such as polyamide, polyvinylidene chloride, ethylene / vinyl alcohol copolymer, polyvinyl alcohol, and polyester, can be used. have. In the case where the packaged object is a confectionery or a textile package, it is preferable to use polypropylene having good transparency, rigidity and water permeability.

When extrusion coating the ethylene-α-olefin copolymer (A) or ethylene-based copolymer composition (A '), (A' '), (A' '') on the substrate as described above, The copolymer (A) or the composition (A '), (A' '), (A' '') may be extrusion coated, and the substrate and the copolymer (A) or the composition (A ') or (A' '). , (A '' '), in order to enhance the adhesive force with a substrate, a known coating method, such as an organic titanium-based, polyethyleneimine-based, isocyanate-based anchor coating agent, or adhesive polyolefin, high-pressure polyethylene After the resin layer is provided, the copolymer (A) or the composition (A '), (A' '), or (A' '') may be extrusion coated.

Moreover, in order to ensure the adhesiveness between the base material and the resin (subcontracting resin or copolymer (A), the composition (A '), (A' '), (A' '')) in contact with the base material, the extruded resin is melted. It is also possible to force the oxidation of the membrane surface by blowing ozone into the membrane.

Such multilayer films include various packaging bags, for example, liquid soups, pickles, packaging bags for wet foods such as konjac spaghetti, packaging bags for fast foods such as miso and jam, powder packaging bags such as sugar, flour, and fish powder, and medicines. It is suitable for tablets and granule packaging bags, and serves as a sealant layer in such applications.

Packaging Multilayer Film:

The multilayer film for packaging consists of a film of at least three layer structure of an outer layer, one or two or more intermediate layers, and an inner layer. The resin composition used for an outer layer and an inner layer and the resin composition which comprises an intermediate | middle layer differ.

The outer layer and the inner layer are formed from the ethylene-α-olefin copolymer (A) or the ethylene copolymer composition (A '), (A' '), (A' ''). In addition, (A) or (A '), (A "), and (A'") which form an outer layer and an inner layer may be same, and may differ from each other.

Although the intermediate layer is arbitrarily selected from the resin composition used as a raw material of the said base film, For example, from 1-butene type | system | group (co) polymer and if needed, from resin or resin composition which consists of ethylene propylene 1-butene random copolymers. It is preferable that it is formed. The 1-butene-based (co) polymer is a 1-butene homopolymer or a 1-butene propylene copolymer having 75 to 85 mol% of 1-butene content and 15 to 25 mol% of propylene content.

Of the 1-butene unit (co) polymer had the following properties: MFR is 0.1 ~ 5g / 10 min, preferably 0.5 ~ 2g / 10 minutes and a density of 0.890 ~ 0.925g / cm ^3, preferably 0.895 ~ 0.920g / cm ³ Range. This 1-butene-based (co) polymer can be prepared using conventional Ziegler-Natta catalysts.

In the present invention, the 1-butene-based (co) polymer is 40 to 100% by weight, preferably 50 to 100% by weight of the total amount of the 1-butene-based (co) polymer and the ethylene-propylene-1-butene random copolymer. 90 weight%, More preferably, it is used in the ratio of 55 to 95 weight%.

The ethylene propylene 1-butene random copolymer preferably 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 minutes, preferably 1 to 30 g / 10 minutes, and a density of 0.890 to 0.910 g / cm ³ .

This ethylene propylene 1-butene random copolymer can be manufactured using a normal Ziegler-Natta catalyst.

In the present invention, the ethylene propylene 1-butene random copolymer is 0 to 60% by weight with respect to 100% by weight of the total amount of the 1-butene system (co) polymer and the ethylene propylene 1-butene random copolymer. 10 to 50% by weight, more preferably 5 to 45% by weight.

When the ratio of the 1-butene system (co) polymer and the ethylene propylene 1-butene random copolymer is within the range of the blending ratio, a multilayer film having excellent cutting property by an automatic packaging machine is obtained.

In the present invention, in addition to the 1-butene-based (co) polymer and the ethylene propylene-1-butene random copolymer in the resin or the resin composition constituting the intermediate layer, like the resin or the resin composition constituting the outer layer and the inner layer described above, Various stabilizers, compounding agents, fillers and the like can be added within a range not impairing the object of the present invention. In particular, an antifogging agent, an antistatic agent, or the like may be added so as to see the contents, or a sunscreen may be added to protect the contents, and an antioxidant and a lubricant may be added.

The intermediate layer may be composed of one layer or two 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 which concerns on this invention is shape | molded normally with the thickness of 10-20 micrometers, The intermediate | middle layer is 1-5 micrometers, and outer layer and inner layer are adjusted to the thickness of 2-8 micrometers, respectively. Moreover, according to a use, it is also possible to form another resin layer further outside of an inner layer and / or an outer layer.

The packaging multilayer film is mixed with each component forming each layer by using various blenders, and then used in a conventional molding method, that is, an inflation film molding machine having a plurality of die lips in an extruder, or a T-die molding machine. Manufactured by supply.

The multilayer film for packaging 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, since the film is cut by a knife passing in the transverse direction, the good or bad of the cutting property can be evaluated by the ratio of the Elmendorf tear strength in the longitudinal direction and the transverse direction. When the ratio of the Elmendorf tear strength is 9.1 or less, it is judged that the cutting property by the automatic packaging machine is good.

In the multilayer film for packaging according to the present invention, the Elmendorf tear strength ratio is 9.1 or less, so that cutting by an automatic packaging machine is easy, and continuous packaging can be performed at high speed. In addition, Elmendorf tearing strength is measured by the method according to JISZ-1702.

Moreover, the multilayer film for packaging which concerns on this invention is excellent in transparency, and haze value is usually 2.0% or less.

Moreover, the multilayer film for packaging which concerns on this invention is excellent in acupressure resilience, initial stage recovery rate is 70% or more, and residual distortion is 5.5 mm or less.

Moreover, the multilayer film for packaging which concerns on this invention is excellent in low temperature sealing property, and the sealing strength of the film heat-sealed at 90 degreeC is 100 kg / cm <^2> or more.

Such packaging multilayer films are excellent in mechanical strength properties, transparency, and low temperature heat sealability, and even after the contents are pressed, for example, with a finger, the resilience of the films thereafter is good, and is suitable for packaging foodstuffs and daily necessities.

Stretch Wrap Film:

Stretch packing film is the said ethylene-alpha-olefin copolymer (A) or ethylene-type copolymer composition (A '), (A "), (A'"), and another resin component example as needed. g., a density of 0.880 ~ 0.895g / cm ³ of ethylene-propylene random copolymer, a density of 0.880 ~ 0.895g / cm ^3, ethylene-butene random copolymer, a density of 0.910 ~ 0.924g / cm ³ high-pressure ethylene - It is formed from a vinyl acetate random copolymer.

Such other resin component is used in the quantity of 0-40 weight part with respect to 100 weight part of said copolymers (A) or a composition (A '), (A "), (A'").

In the present invention, the copolymer (A) or composition (A '), (A' '), (A' ''), or the copolymer (A) or composition (A ') (A' '), To the composition consisting of (A '' ') and other resin components, various additives, such as a slip agent, a blocking agent, an antifogging agent, an antistatic agent, or a sunscreen agent, are contained in a range which does not impair the object of the present invention in order to protect the contents. can do.

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 antiblocking agent, inorganic substances such as silica and talc are preferably used, for example.

As the antistatic agent, for example, glycerin fatty acid esters and sorbitol fatty acid esters are preferably used.

The film made from the copolymer (A) or the composition (A '), (A' '), (A' '') has the necessary proper tackiness, but when further tackiness is required, liquid polybutadiene, It is good to mix | blend poly isobutylene etc. about 2 to 10 weight%.

The stretch packaging film which concerns on this invention contains the film which consists of a copolymer (A) or composition (A '), (A "), (A'") as mentioned above.

The film for stretch packaging which concerns on this invention is 10-50 micrometers in thickness normally. The stretch packaging film may have a single layer structure or a multilayered structure.

The stretch packaging film of a single | mono layer structure can be manufactured by normal film forming methods, such as an inflation method and a T-die method.

The stretch-packaging film of a multilayer structure can be manufactured using a conventionally well-known shaping | molding method, for example, an inflation film forming machine equipped with a plurality of dies in an extruder, or a forming apparatus such as a T-die forming machine.

Stretch packaging film has a tensile tensile stress at break (JIS Z 1702) of 400 kg / cm ² or more, a tensile tensile elongation at break (JIS Z 1702) of 500% or more, and impact strength (ASTM D 3420). 2,500kgcm / cm or more, longitudinal tear strength (JIS Z 1720) is 50kg / cm or more, adhesive force (20kg, 50 ℃ × 1 day) is 3 ~ 25g / cm, 300% elongation The force after elapse of time is 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 tensile elongation at break than that of a conventional low density polyethylene or ethylene / vinyl acetate copolymer film, and can be stretched at 300 to 600%, so that it is highly stretched or releases (different in shape Suitable for stretch packaging of 2 or more objects.

Moreover, compared with the film of the conventional low density polyethylene or the ethylene-vinyl acetate copolymer, the stretch packaging film which concerns on this invention has a small stress applied after packaging, and does not deform a package, and the film strength after packaging is strong and a film The appearance is good.

The film for stretch packaging which concerns on this invention may be a film which consists of one said copolymer (A) or a composition (A '), (A "), (A'"), and this copolymer (A) Or the film of the multilayered structure which has 1 or 2 or more film layers other than the film layer which consists of compositions (A '), (A "), (A'") may be sufficient.

The multi-layered stretch packaging film, for example, the multi-layered film in which the non-adhesive side and the adhesive side are shared on the stretch-packaging film may be the copolymer (A) or the composition (A '), (A' '), (A' '') Film layer as an intermediate layer, and a film layer made of high density linear low density polyethylene as a non-adhesive layer on one surface of the intermediate layer is formed so as to have a thickness of about 5 to 30% of the total thickness of the film for stretch packaging. At the same time, 2 to 10 liquid polyisobutylene, liquid polybutadiene, or the like is added to the copolymer (A) or the composition (A '), (A' '), (A' '') as an adhesive layer on another surface. The film layer which consists of a composition mix | blended by weight% can be obtained by methods, such as forming so that it may become about 5 to 30% of thickness with respect to the total thickness of the film for stretch packaging.

Such a stretch packaging film is highly stretchable and has proper adhesiveness, no excessive stress is applied to the package after packaging, excellent strength properties and appearance after packaging, and no excessive adhesiveness to the film, and productivity and packaging properties. Excellent handling.

Packing film:

Packaging films are improved packaging or wrapping films, and more particularly exhibit improved transparency, toughness, extrusion processability and irradiation crosslinking efficiency, shrink, skin, stretch, hottack hot tack and vacuum wrap films. These films are provided with at least 1 type of ethylene-alpha-olefin copolymer (A) or ethylene-type copolymer composition (A '), (A "), (A'") layer, and It may be biaxially oriented, may be multilayer, and / or may be comprised so that it may have barrier property.

This ethylene-α-olefin copolymer (A) or ethylene-based copolymer composition (A '), (A' '), (A' '') has additives such that it does not interfere with the improved film properties disclosed by the present applicants. For example, antioxidant (for example, hindered phenol type (for example, Irganox (trademark) 1010 etc. made by Chiba Geigy Corp.), phosphites (for example Irgafos (trademark) 168, etc.) ), Etc., cling additives (e.g., polyisobutylene (PlB), etc.), PEPQ (trademark) (Sandoz Chemical's trademark, its main material is believed to be biphenylphosphonite), pigment , Colorants, fillers, and the like. The produced films may also include additives that enhance their antiblocking and friction coefficient characteristics, including, but not limited to, untreated and treated silicon dioxide, talc, calcium carbonate and clay, and the like. And primary and secondary fatty acid amides, silicone coatings and the like. It is also possible to add other additives that improve the anti-fogging properties exhibited by this film, as described, for example, in US Pat. No. 4,486,552 to Niemann et al. In addition, the addition of other additives, such as quaternary ammonium compounds or the like, alone or in combination with other functional polymers, which enables the packaging of electronic sensitive materials by improving the antistatic properties of the film, It is possible.

The ethylene-α-olefin copolymer (A) or ethylene-based copolymer composition (A '), (A' ') and (A' '') used for the production of the packaging and lapping olefin films of the present invention are Even if the structure used is a single layer or a multilayer structure, it can be used as only one polymer component of this film. By blending other polymers together with this ethylene-α-olefin copolymer (A) or ethylene-based copolymer composition (A '), (A' '), (A' ''), the processability of the film, the film strength, The heat sealability or adhesiveness can be improved. Packaging and lapping films prepared by appropriately blending this ethylene-α-olefin copolymer (A) or ethylene-based copolymer composition (A '), (A' '), (A' '') and other polymer components are It maintains improved performance and, in certain cases, provides improved combinations of properties. Although it is not limited to these various materials suitable for a blend with this ethylene-alpha-olefin copolymer (A) or ethylene-type copolymer composition (A '), (A "), (A'"), 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 polyethylene, polypropylene, ethylene / propylene copolymers, linear low density polyethylene (LLDPE) and ultra low density polyethylene and graft modified polymers and blends thereof, including but not limited to density, MWD and / or comonomer combinations. Changes, such as those disclosed in, for example, US Pat. No. 5,032,463 (described herein by reference), and the like. However, this ethylene-α-olefin copolymer (A) or ethylene-based copolymer composition (A '), (A' '), (A' '') is preferably at least 50%, more preferably of this blend composition. Preferably at least 80% of this blend composition. However, in the case of a multilayer film structure, very preferably the outer film layer (also referred to in the art as the "skin layer" or the "surface layer") and the sealant layer are these ethylene-α-olefin copolymers (A ) Or an ethylene-based copolymer composition (A '), (A' '), (A' '').

The oriented and unoriented film structures of the present invention can be prepared using conventional simple hot blown bubble, cast extrusion or extrusion coating techniques, particularly in the case of oriented films, more sophisticated techniques, for example, It can manufacture using a "tenter framing", a "double bubble", a "trapped bubble" method, etc.

In the present technology and in this specification, "stretched" and "oriented" are used in an interchangeable form, but the orientation is actually a tenter framing that presses the edge of the film or internal air pressure, for example, into the tube. It occurs as a result of the film being stretched by, for example.

A simple hot blown bubble film method is described, for example, in The Encyclopedia of Chemical Technology, Kirk-0thmer), 3rd Edition, John Wiley Sons, New York, 1981, 16, pp. 416-417 and 18, 191-. See page 192 and others. Sophisticated methods suitable for making biaxially oriented films, such as the "double bubble" method described in US Pat. No. 3,456,044 (Pahlke), and other methods suitable for making biaxially stretched or oriented films. U.S. Patent 4,865,902 (Golike et al.), U.S. Patent 4,352,849 (Mueller), U.S. Patent 4,820,557 (Warren), U.S. Patent 4,927,708 (Herran et al.), U.S. Pat. Patent No. 4,952,451 to Mueller et al.

As described by Pahlke in U.S. Patent No. 3,456,044, the "double bubble" or "trap bubble" film processing, compared to the simple bubble method, greatly increases the orientation of the film in both machine and transverse directions. Done. As the orientation increases in this manner, the free shrinkage value when the film is subsequently heated becomes higher. In addition, Pahlke in U.S. Patent No. 3,456,044 and Lustig et al. In U.S. Patent No. 5,059,481 produce inferior shrinkage properties in the machine and transverse directions, respectively, when low density polyethylene and ultra low density polyethylene materials are produced by a simple bubble method. For example, free shrinkage is about 3% inferior in both directions. However, known film materials, by contrast, in particular, in contrast to the film materials disclosed by Lustig et al. In US Pat. No. 5,059,481, US Pat. No. 4,976,898 and US Pat. No. 4,863,796, and in US Pat. No. 5,032,463 In contrast to the film materials disclosed by Smith, the ethylene-α-olefin copolymer (A) or ethylene-based copolymer compositions (A '), (A' ') and (A' '') of the present invention are simple With the bubble method, it shows a markedly improved shrinkage in both the machine and transverse directions. In addition, it is also possible to use a simple bubble method with a high blow up ratio, for example a blow up ratio equal to or greater than 2.5: 1, or more preferably Pahlke is disclosed in US Pat. No. 3,456,044, and in US Pat. No. 4,976,898. Using the "double bubble" method disclosed by Lustig et al., This ethylene-α-olefin copolymer (A) or ethylene-based copolymer composition (A '), (A' '), (A' '') When produced, good shrinkage can be achieved in the machine direction and in the transverse direction so that the resulting film is suitable for shrink wrap packaging purposes.

Equation: BUR = diameter of bubble ÷ die, using the diameter of the die, the blow-up ratio expressed in abbreviated form as "BUR" in this specification is calculated.

The olefin film for packaging and lapping of the present invention may be a single layer or a multilayer film. In an aspect in which the film structure is a monolayer, the monolayer is at least one ethylene-α-olefin copolymer (A) or an ethylene-based copolymer composition (A '), (A' '), (A' '') At least 10% by weight, preferably at least 30% by weight, and at least one ethylene-α-olefin copolymer (A) or ethylene-based copolymer composition (A '), (A' '), ( A '' ') may be included in an amount of 100% by weight.

The ethylene-α-olefin copolymer (A) or ethylene-based copolymer composition (A '), (A' '), or (A' ') used for the purpose of constructing this monolayer depends on the desired properties of this film. And in the aspect which uses 2 or more types of ethylene-alpha-olefin copolymer (A) or ethylene-type copolymer composition (A '), (A "), (A'") in the structure of this film, These polymers are selected based in part on both processing and use conditions being compatible with each other. Similarly, in the structure of this single layer, at least one ethylene-α-olefin copolymer (A) or ethylene-based copolymer composition (A '), (A' '), (A' ''), and at least one ordinary Ethylene polymers (e.g., conventional homogeneously branched linear ethylene / a-olefin copolymers prepared as described in US Pat. No. 3,645,992, or Ziegler method as described in US Pat. No. 4,076,698). In the case of using a blend with a conventionally produced nonuniformly branched ethylene / α-olefin copolymer, etc., these ethylene polymers are the ethylene / α-olefin copolymer (A) or the ethylene copolymer composition (A ′), These are selected based in part on the compatibility shown for (A '') and (A '' ').

Depending on the various properties of these monolayers, any of these five different packaging methods can be used for any of these monolayers, but in practice, the monolayer film is most suitable for use in tensile overlap and skin packaging methods. . As required for tensile lapping, single layer films made from the ethylene-α-olefin copolymers (A) or ethylene-based copolymer compositions (A '), (A' '), (A' '') of the present invention Shows a very good oxygen transmission rate.

Oxygen permeation means that when an individual wrap of red meat is tension wrapped for packaging (ie, a food vendor / butcher actually cuts the first meat for individual sales purposes, the smaller piece is “instore” It is particularly beneficial for packaged meats, and the permeation of oxygen makes it possible to "add" the desired bright red color to fresh red meats.) Films that are effective to package individual red meat slices usually have minimal shrinkage. In addition to showing good tensile properties. The film preferably exhibits oxygen permeability and exhibits good elastic recovery so that the meat can be inspected by the consumer without permanently deforming the film and making the meat unattractive. Pak-Wing Steve Chum and Nicole F. Whiteman, filed on April 28, 1993, filed in the pending US application entitled "Method of Packaging Food Products," how to package food containing these individual red meat parts. Is disclosed. However, even if shrinkage is not used in the current technology, a film used when packaging individual red meat portions can be produced as a heat shrinkable film.

One particularly preferred single layer suitable for use in the tensile overlap process is an ethylene-α-olefin copolymer (A) or an ethylene-based copolymer composition (A '), (A' '), (A' '') and ethylene / α, -unsaturated carbonyl copolymers such as EVA, EAA, ethylene / methacrylic acid / (EMAA), and blends thereof with their alkali metal salts (ionomers), esters and other derivatives, and the like.

In the case of a coextruded or laminated multilayer film structure (for example, a film structure of three and five layers), the ethylene-α-olefin copolymer (A) or ethylene-based copolymer composition (A ') described in the present specification, ( A ''), (A '' ') can be used as the core layer, outer surface layer, intermediate layer and / or inner sealant layer of this structure. In particular, in the hottack film of the present invention, at least one of the ethylene-α-olefin copolymer (A) or the ethylene-based copolymer composition (A '), (A' '), and (A' '') described herein. Is used as the heat sealable outer layer of at least one layer provided in this film structure. This heat sealable outer layer may be coextruded with another layer (stream), or the heat sealable outer layer may be laminated to another layer (stream) in a second operation, for example, by Wilmer A. Jenkins and As described by James P. Harrington, Packaging Foods With Plastics (1991), or by the Society of Plastics Engineers RETEC Proceedings, June 15-17 (1981), WJ Schrenk and pp. 211-229. It can be implemented as described in CRFinch Coextrusion For Barrier Packaging.

In the multilayer film structure, generally, the ethylene-α-olefin copolymer (A) or the ethylene-based copolymer composition (A '), (A' ') and (A' '') described in this specification are the multilayer films. It constitutes at least 10% of the entire structure. Other layers of this multilayer structure include, but are not limited to, barrier layers and / or tie layers and / or structural layers. Various materials can be used in these layers, and some of these may be used as two or more layers in the same film structure. 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 (e.g. maleic anhydride grafted polyethylene, etc.) And paper and the like. Generally, this multilayer film structure contains 2 to 7 layers.

The multilayer film structure in one aspect disclosed in this specification contains at least 3 layers (for example, "A / B / A" structure etc.), and each outer layer is at least 1 type of ethylene-alpha. -An olefin copolymer (A) or an ethylenic copolymer composition (A '), (A''),(A'''), and at least one core layer or hidden layer is formed by a high pressure method. Low density polyethylene (LDPE). Such multilayer film structures exhibit very good optical properties while maintaining good overall film strength properties. In general, the proportion of layers provided in this film structure is in terms of% of the entire structure, and the proportion in which the core layer is the main part of the film structure. The core layer must have at least 33% of the total film structure (for example, in the three-layer film structure, each "A" outer layer constitutes 33% by weight of the entire film structure, while the LDPE core layer (" B ”layer) constitutes 33% by weight of the previous film structure). In a three layer film structure, the core layer of the LDPE preferably comprises at least 70 percent of the previous film structure. In addition, as long as the optical properties are not deteriorated, a hidden additional layer may be assembled into the film structure. For example, using a bond or an intermediate layer made of ethylene / vinyl acetate copolymers, ethylene acrylic acid copolymers or anhydride graft modified polyethylene, or the like, or for example, vinylidene chloride / vinyl chloride copolymers or ethylene vinyl A barrier layer made of alcohol copolymers or the like can be used. As a more preferable three-layer film structure, each "A" outer layer is at least 1 type of ethylene-alpha-olefin copolymer (A) or ethylene-based copolymer composition (A '), (A''),(A''') In an amount of 15% by weight of the entire film structure, and the "B" core layer contains LDPE in an amount of 70% by weight of the entire film structure. By carrying out the orientation and / or irradiation (in any order) of the multilayer film structure, it is possible to produce a shrunk film structure consisting of multilayers or a shell package exhibiting controlled linear tearability. LDPE 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 , a melt index of 0.1 g / 10 minutes to 10 g / 10 minutes, and At least 1 gram of melt tension. In order to improve optical transparency, this ethylene-α-olefin copolymer (A) or ethylene-based copolymer composition (A '), (A'') and (A''') are generally 0.85 g / cm ³ to 0.96 a density of g / cm ³ , preferably a density of 0.9 g / cm ³ to 0.92 g / cm ³ , a melt index of 0.2 g / 10 to 10 g / 10 minutes, preferably 0.5 g / 10 minutes to 2 g / 10 minutes (I2) is shown.

These multilayer film structures are also ethylene-α-olefin copolymer (A) or ethylene-based copolymer composition (A '), (A' '), (A' '') (the following film structures) When used in combination with (A)), or in combination with another oxygen permeable film layer, for example, ethylene / vinyl acetate (EVA) and / or ethylene / acrylic acid (EAA), oxygen What shows permeability is obtained. Of particular interest are, for example, (A) / EAA / (A), (A) / VLDPE / (A) and LLDPE / (A) / LLDPE film structures, which at the same time become substitutes for conventional films such as PVC , A variety of fresh foods, such as red meat, fish, poultry, vegetables, fruits, cheeses, etc., cut out of the sleeve, and other foods that would benefit from the ingestion of oxygen around the retail display or that need to breathe properly. Very suitable for packaging Preferably, manufacturers and retailers produce such films as non-shrinkable films that exhibit good oxygen permeability, tensile properties, elastic recovery, and heat sealability (e.g., without having biaxial orientation induced by double bubble processing). They can be used in any of the usual forms, for example, in the form of a stock roll, and at the same time, it can be used as a normal packaging device.

In another aspect, these multilayer film structures may be formed from an oxygen barrier film (e.g., SARAN®, a film made from polyvinylidene chloride polymer manufactured by Dow Chemical Company, or a division of Kuraray of America, Inc.). EVAL (trademark) resin, which is an ethylene / vinyl alcohol copolymer manufactured by Eval Company of America (a division owned by Kuraray Ltd.), may be used. Oxygen barrier properties are important in film applications, such as when packaging large pieces of meat delivered to special stores for further cutting for consumer consumption, as described by Davis et al. In US Pat. No. 4,886,690. This oxygen barrier layer can also be designed to be "peelable" so that the first section can be removed at the arrival of the butcher / food vendor. And the peelable structure or design is particularly effective in the individual "case-ready" vacuum jacketed package, thereby eliminating the need to repack it in an oxygen permeable package for the purpose of adding bright red color. .

In any of the known methods, for example, by using an extrusion thermoforming method or the like, or the ethylene-α-olefin copolymer (A) or ethylene-based copolymer composition (A ') or (A' ') described herein. The film structure created from (A '' ') may be molded in advance according to the shape and contour of the product to be packaged. Advantages of using preformed film structures include given individual packaging operations, such as increased stretchability, thinner film thickness for a given stretch requirement, shorter heat-up and cycle times, etc. It can be supplemented or avoided.

The thickness of these single or multilayer film structures can be varied. However, the thicknesses of the monolayer and multilayer film structures described herein typically range from 0.1 mil (2.5 micrometers) to 50 mils (1270 micrometers), preferably from 0.4 mils (10 micrometers) to 15 mils (381 micrometers). ), Especially 0.6 mils (15 micrometers) to 4 mils (102 micrometers).

Film structures prepared from the ethylene-α-olefin copolymers (A) or ethylene-based copolymer compositions (A '), (A' ') and (A' '') described herein are surprisingly compared with conventional Irradiation crosslinking which is more efficient than the linear ethylene / alpha-olefin polymer superposed by Ziegler polymerization is shown. As one aspect of the present invention, by utilizing the advantages of irradiation efficiency exhibited by these unique polymers, it is possible to produce a film structure provided with a film layer that is crosslinked either selectively or selectively. For the purpose of utilizing another advantage of this finding, certain ethylene-α-olefin copolymers (A) or ethylene-based copolymer compositions (A '), (A' '), and (A' '') containing specific Film material of the pro-rad agents, for example, triallyl cyanurate and the like and / or anti-crosslinking inhibitors, for example as described by Warren in US Pat. No. 4,957,790, for example Combinations with butylated hydroxytoluene and the like as described by Evert et al. In US Pat. No. 5,055,328.

Moreover, the crosslinking by irradiation is also effective in the case where it is going to raise the shrinkage temperature range and hot sealing range of these film structures. For example, US Pat. No. 5,089,321 discloses a multilayer film structure having at least one heat sealable outer layer and at least one core layer exhibiting good radiation crosslinking performance. In the irradiation crosslinking technique, beta irradiation with an electron beam source and gamma irradiation with a radioactive element such as cobalt 60 are the most common methods for causing crosslinking of the film material.

In the irradiation crosslinking method, a thermoplastic film is produced by a blown film method, and then exposed to a radiation source (beta or gamma) with an irradiation dose of 20 Mrad, thereby causing crosslinking of the polymer film. When an oriented film is desired, irradiation crosslinking can be induced at any time, for example in the case of shrinkage and shell packaging, before or after the final film orientation, but preferably before the final orientation. Induce irradiation crosslinking. When the heat shrinkable film or the outer packaging film is produced by the method of irradiating pellets or films before the final film orientation, these films consistently exhibit higher shrinkage tension, so that the bending of the package and the bending of the cardboard There exists a tendency to become high, and conversely, when it oriented before irradiation, the shrinkage tension of the film obtained will become lower. Unlike the shrinkage tension, the free shrinkage characteristics exhibited by the ethylene-α-olefin copolymer (A) or the ethylene-based copolymer composition (A '), (A' '), (A' '') of the present invention are investigated. Regardless of whether it is done before or after the final film orientation, it is essentially unaffected.

Irradiation techniques effective for carrying out the treatment of the film structures described herein include techniques known to those skilled in the art. Preferably, irradiation is achieved by using an electron beam (beta) irradiation apparatus at a dose level of 0.5 Megarad (Mrad) to 20 Mrad. As described herein, the shrink film structure produced from the ethylene-olefin copolymer (A) or the ethylene-based copolymer composition (A '), (A' '), (A' '') is further investigated. It is expected that the improved physical properties will be exhibited due to the lower degree of chain breakage resulting from the treatment.

Hot-tack films of the present invention are oriented or unoriented single-layer or multi-layer structures, which show utility in bag-in-box and form-fill-seal operations. Examples of using the film of the present invention in foam-fill-silk operation are described in Wilmer A. Jenkins and James P. Harrington, Packaging Foods With Plastics, (1991), 32-83. C.G.Davis, Packaging Machinery 0perations: N0.8, Form-Fill-Sealing, A Self-Instructional Course by the Packaging Machinery Manufacturers Institute (April 1982); The Wiley Encyclopedia of Packaging Technology, by M. Bakker (Editor), John Wiley Sons (1986) (334, 364-369); And vertical or horizontal form / fill / seal packaging and thermography, as described in S. Sacharow and ALBrody, Packaging: An Introduction, Harcourt Brace Javanovich Publications, Inc. (1987), pp. 332-326. Packages can also be made using foam / fill / sealed packaging. A particularly effective device for foam / fill / thread operation is the vertical foam / fill / practice of Hayssen Ultima Super CMB, which is used to package typical products such as food, pharmaceuticals and hardware. Other manufacturers of apparatus for evacuating pouches by thermoforming include Cryovac and Koch.

Heavy Duty Packaging Films:

The high load packaging film is a film made of the ethylene-α-olefin copolymer (A) or the ethylene-based copolymer composition (A '), (A' '), (A' ''), and the thickness of the film is at least about 1.25 mil (31 microns), which has a film density in the range of 0.923-0.95 grams per cubic centimeter (g / cc) and typically exhibits at least 30% higher tensile strength or impact resistance than polyethylene films currently used in industry . The film can be used for heavy-duty packaging and transportation applications or for hot-fill packaging.

In the present specification, the term "medium modulus" is used to refer to the novel film in order to mean 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 for the purpose of meaning the film density as calculated from the known weight of the polymers or layers which are components and the measured density after annealing.

In the description of the novel film, the term "thickness" is used herein to mean a film thickness of about 1.25 mils (31 microns) or more.

The term "variable stoke extrusion" indicates that the distance between the annular die for the film and the height of the stoke, i.e., the bubble expansion point, can vary from 0 inches (0 centimeters) to 144 inches (366 centimeters) or more during blown film production. . The term includes both well known pocket blown film extrusion processing and stoke blown film extrusion processing. In this specification, the term "high stoke extrusion process" is used in a conventional sense, meaning that the distance between the annular die for the film and the air ring is equal to or larger than 30 inches (76 cm).

In the present specification, the term "heat charge" refers to packaging or product filling operation at a product temperature of 45 ° C or more. As used herein, the term "high load" generally refers to packaging an industrial item in bulk or with a single package weight of at least 10 pounds (4.5 kilograms).

The tear resistance exhibited by the film of the invention is measured in grams according to ASTM D 1922. 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 an 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 invention is measured according to ASTM D 1709. If the relationship shows that the performance value also increases as the thickness increases, it is normalized to exactly 3 mils by increasing or decreasing the tear and impact results proportionally based on the actually measured film thickness (micrometer), but The normalization calculations are reported only when the variation in thickness is within 10%, that is, when the measurement thickness is in the range of 2.7 to 3.3 mils.

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

The film thickness is generally in the range of about 1.25 mils or more, in particular 1.5 mils to 8.75 mils, and more particularly in the range of 2 mils to 8 mils.

The tear strength or impact resistance exhibited by this novel film is at least 30% higher than the tear strength or impact resistance exhibited by comparable prior art polyethylene films with approximately the same film density, melt index and film thickness.

This novel film is conveniently molded into a bag and is useful for use in thermally charged packaging applications in addition to high load packaging and transport applications, where such films exhibit good balance of properties, i.e. tear, impact and dimensional stability. In addition to being good, a film having a high strength and a moderate modulus is obtained.

This new film can be produced by variable-stalk blown extrusion. The production of films by blown film extrusion is well known. For example, see US Pat. No. 4,632,801 to Dowd, which describes a typical blown film extrusion process. Typical methods are to introduce a polymer into a screw extruder, melt the polymer therein, and move the inside of the extruder forward under pressure. The molten tube is formed by passing the molten polymer through an annular die for film and extruding it. Next, by supplying air into the annular die, the tube is inflated to produce a "bubble" having a desired diameter. Air is enclosed in the bubble with this annular die and nip rollers located downstream of the die, and then the bubble is compressed to produce a lay-flat film. The final thickness of the film is extruded. Rate, bubble diameter and nip speed are adjustable, which are adjustable with variables such as screw speed, haul-off rate and hoisting speed. If the bubble diameter and nip speed are constant to increase the extrusion rate, the final film thickness will be thicker.

Typical blown extrusion methods are generally categorized as "stock" or "pocket" extrusion. In the case of stalk extrusion, the bubble swells and expands at quite a high point of the annular die, and its adjustment is carried out. The air ring (which typically has a single layer structure) so that the tube remains about the same diameter as the annular die for the film until the molten tube swells to at least 5 inches (12.7 centimeters) above the annular die. Air flow is supplied to the outside of the pipe parallel to the machine direction. Moreover, it is also possible to cool the inside of a bubble in order to ensure the optimal stability of a bubble during manufacture, and it is also possible to use a bubble stabilization means inside.

It is known that the use of stalk extrusion improves molecular relaxation, thereby reducing the tendency of excessive orientation in one direction, thereby obtaining balanced film physical properties. Increasing the height of the stoke, ie, the inflation, generally improves the transverse direction (CD) properties, thereby improving the average film properties. Blown films from high molecular weight polyethylene compositions such as high molecular weight high density polyethylene (HMW-HDPE) and high molecular weight low density polyethylene (HMW-LDPE), etc. (they have sufficient melt strength to ensure sufficient bubble stability) In the case of the production of stocks, stock extrusion processing, in particular high stock extrusion, is very useful.

In the case of pocket extrusion, air is supplied from an air ring located immediately adjacent to the annular die so that the bubbles from the die immediately swell and expand. This air ring is typically double layered for the purpose of assuring the stability of the bubble after applying it. Pocket extrusion is more widely used than stoke extrusion, and is generally preferred in the case of polyethylene compositions having lower molecular weight and lower melt strength, such as linear low density polyethylene (LLDPE) and ultra low density polyethylene (ULDPE). Both the single layer film and the multilayer film can be produced by stoke and pocket extrusion, and the film of the present invention may be a single layer structure or a multilayer structure. Multilayer films can be prepared by any technique known in the art, which includes, for example, coextrusion, lamination or a combination of both. However, preferred thick heavy modulus polyethylene films of the present invention are single layer film structures.

Additives, for example, oxidation to the ethylene-α-olefin copolymer (A) or ethylene-based copolymer composition (A '), (A' '), (A' '') used in the production of the film of the present invention Preventive agents, phosphites, cling additives, Standostab PEPQ (trademark), pigments, colorants and fillers, etc., disclosed by the applicants for improved tear and impact resistance that do not interfere with the additives and materials. It can also be contained to an extent. Additives that are not generally required, but also improve anti-blocking and friction coefficient characteristics, including, but not limited to, untreated and treated silicon dioxide, talc, calcium carbonate and clay , Secondary and substituted fatty acid amides, and the like), a releasing agent, a silicone coating material and the like can also be contained in the film of the present invention. In addition, other additives, for example, quaternary ammonium compounds or the like, may be used alone or for the purpose of improving the antistatic properties of the film of the present invention to enable high load packaging of, for example, electron sensitive products. It is also possible to add it in combination with ethylene acrylic acid (EAA) copolymers or other functional polymers.

Advantageously, the strength properties of this new film have been improved, so that diluent polymers are typically used in the prior art polyethylene film compositions in addition to the reuse materials and scrap materials in the film compositions used in the manufacture of this new film. The new films can also be blended or blended in amounts greater than possible, and these new films can also impart or maintain the desired performance characteristics when successfully used for high load packaging and transportation applications. Suitable diluent materials include, for example, elastomers, rubbers and anhydride modified polyethylenes (e.g., LLDPE and HDPE grafted with polybutylene and maleic anhydride), as well as high pressure polyethylenes such as low density polyethylene (LDPE). Ethylene / acrylic acid (EAA) copolymers, ethylene / vinyl acetate (EVA) copolymers, ethylene / methacrylate (EMA) copolymers, and the like, and combinations thereof.

Stretched adhesive film:

The present invention is a multilayer film comprising at least two layers, having substantial adhesiveness on one side, and suitable for use as a stretch wrap material. This novel multilayer film comprises at least one ethylene-α-olefin copolymer (A) or ethylene-based copolymer composition (A '), (A' 'having a density of at least about 0.90 g / cc or about 0.90 g / cc. ), A backing layer from (A '' '), a surface layer from at least one film-forming olefin polymer composition having a density of about 0.90 g / cc, and at least one from any at least one high strength ethylene polymer composition Core or structural layer.

The surface layer exhibits significantly smaller adhesiveness than the back layer. The core or structural layer can be varied to meet specific film strength requirements.

According to the present invention, a film having a one-sided tackiness is particularly useful for stretching lapping, stretching bundling and tension winding operations for wrapping or holding small articles or objects. The single-sided adhesive film of the present invention is provided without the need for an adhesive additive or a functional polymer.

As an advantage of the present invention, the accumulation and accumulation of resin in the die lip and the reduction or disappearance of the movement of low molecular weight substances can be mentioned. This means that cleaning and storage time during film making and wrap operations are reduced. Problems with adhesion and contamination to adjacent articles and packages, as well as surface retention of dust or debris, are also reduced.

Another aspect of the invention provides a one-sided tacky film made from polymers having the same flow and monomer chemical properties, thereby facilitating consistent improved melt viscosity during coextrusion and good polymer compatibility for recycling. It is.

Another aspect of the present invention is to provide a single-sided tacky film in which the high tackiness does not decrease when the film is under stretching conditions, and the film exhibits remarkable stretching and non-stretching tackiness.

The amount of adhesion is related to the density of the polymer or blend combination forming the back layer and the surface layer of the film, and it has been found that the adhesion improves as the polymer density of the back layer decreases. In the back layer of the present invention, when the density of the back layer is 0.90 g / cc or less, preferably in the range of 0.85 g / cc to 0.99 g / cc, most preferably in the range of 0.86 g / cc to 0.98 g / cc, Substantial adhesion to the surface layer is shown. The density of the surface layer of this invention is 0.90g / cc or more, Preferably it is the range of 0.91g / cc-0.96g / cc, More preferably, it is the range of 0.93g / cc-0.95g / cc. Surface layers in a more preferred density range of 0.93 g / cc to 0.95 g / cc provide single sided adhesive films having the same stretched and unstretched tackiness.

The density of the core layer or the structural layer included in the multilayer film of the present invention can be changed to match the entire film strength requirements according to the end use.

Ethylene polymers having a density of less than 0.90 g / cc or less than 0.90 g / cc constituting the backing layer of the present invention are very low density polyethylene (VLDPE), the copolymer (A) or the composition (A '), (A' '), (A' '') and blend combinations thereof. Preferably, the back layer is made of copolymer (A) or composition (A '), (A' '), (A' '').

Film-forming olefin polymer compositions having densities greater than 0.90 g / cc constituting the surface layer of the present invention are propylene and ethylene polymers such as polypropylene, ethylene propylene copolymers, low density polyethylene (LDPE), medium density polyethylene (MDPE). ), High density polyethylene (HDPE), copolymer (A) or composition (A '), (A' '), (A' ''), non-uniform and uniformly branched linear low density polyethylene (LLDPE), non-uniform and uniformly branched Low density polyethylene (VLDPE), and blend combinations thereof. Preferably the surface layer is made from polypropylene in a blend combination with polypropylene, for example MDPE or HDPE MDPE alone, and is preferred because of its ability to give the same stretch and non-stretch adhesion.

The ethylene polymer constituting the core or structural layer of the present invention may be a low density polyethylene (LDPE), a medium density polyethylene (MDPE), a high density polyethylene (HDPE), a copolymer (A) or a composition (A '), (A' '), (A '' '), heterogeneous and uniformly branched linear low density polyethylene (LLDPE), heterogeneous and uniformly branched ultra low density polyethylene (VLDPE).

Heterogeneously branched VLDPE and LLDPE are known to those skilled in the art of linear polyethylene. They are prepared using Ziegler-Natta solution, slurry or gas phase polymerization, and coordination metal catalysts as described in U.S. Patent No. 4,076,698 to Anderson et al. These Ziegler-type linear polyethylenes are not homogeneous branches and they have a low melt tension. Moreover, these polymers do not exhibit substantial amorphous shape at low density. This is because they inherently have substantial high density (crystal) polymer parts. At densities of less than 0.90 g / cc, these materials are very difficult to produce using ordinary Ziegler-Natta catalysts, and are very difficult to pelletize. The pellets are tacky and tend to coagulate together.

Homogeneously branched VLDPE and LLDPE are also known to one of ordinary skill in the art of linear polyethylene. See, for example, the disclosure of US Pat. No. 3,645,992 to Erunston. They are prepared by solution, slurry or gas phase methods using zirconium and vanadium catalyst systems. Aywen et al., In US Pat. No. 4,937,299, disclose a preparation method using a metallocene catalyst. Although linear polyethylenes of this second class are homogeneously branched polymers, they, like Ziegler-type heterogeneous linear polyethylenes, have low melt tension. Commercial examples of these polymers are sold under the trade name "TAFMER" by Mitsui Chemicals, and under the trade name "EXACT" by Exxon Chemical.

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 homopolymerized with ethylene, or ethylene and a small amount of various monomers. It is an ethylene polymer manufactured by mutual polymerization with.

Additives such as adhesive additives, adhesives (eg PIB), slip and blocking agents, antioxidants (eg hindered phenols such as Irganox1010 or Irganox1076 supplied by Ciba-Geigy), phosphites (eg For example, Irgafos 168 supplied by Ciba-Geigy), Standpstep PEPQ (supplied by Sandoz), pigments, colorants, fillers, and processing aids are not necessary for the present invention to achieve the desired results, but the stretching disclosed herein It can be contained in the wrap material. However, the additives should be formulated to such an extent that they do not or do not interfere with the substantial stickiness and non-tackiness found in the present invention.

The multilayer film of the present invention can be produced by film lamination and / or coextrusion techniques, and blown or cast film extrusion apparatus known in the art, from two or more film layers comprising A / B and A / B / C structures. have. However, preferred structures are A / B / C structures produced by coextrusion techniques, more preferably by cast coextrusion techniques.

Preferred blown film methods are described, for example, in The Encyclopedia of Chemical Technology, Kirk-0thmer, 3rd Edition, John Willy & Sons, New York, 1981, Vo1.16, pp.416-417 and Vol.18, pp191-192. It is described in ". Preferred cast extrusion methods are described, for example, in Modern Plastics, mid-October 1989, Encyclopedia Issue, Vol. 66, N0.11, pages 256-257. Preferred coextrusion techniques and requirements are described by Tom I. Buttler in "Film Extrusion Manual: Process, Materials, Properties," Coextrusion ", Ch. 4, pp 31-80, TAPPI Press, (Atlanta, Ga. 1992). have.

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 minutes, preferably in the range of 0.5 to 12 g / 10 minutes, more preferably in the range of 0.8 to 6 g / 10 minutes.

The total film thickness of the multilayer film of the present invention is in the range of 0.4 to 20 mils (10 microns to 508 microns), preferably in the range of 0.6 to 10 mils (15 microns to 254 microns), more preferably 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, and more preferably in the range of 10:90 to 25:75. . The layer ratio of the multilayer film of two or more layers is maintained at the same thickness of the back layer and the surface layer of the film, 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, more preferably Is a layer ratio 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 further comprises a product made from the multilayer barrier film comprising ostomy bags, laminates for transdermal delivery of medication, and heat sealable bags. Include.

According to one aspect of the present invention there is provided an oxygen and moisture impermeable multilayer barrier film having a heat seal strength of at least 1.0 lb, preferably greater than 1.5 lb, per inch of film width. Oxygen impermeability means that a film has oxygen permeability of 90 cc / m <^2> / H * atm or less. Moisture impermeability means that the film has a water vapor transmission rate of ⁵ gm / m ² / H or less.

In one aspect the film comprises a barrier layer having at least one heat sealable skin layer thereon. The barrier layer includes, for example, a heat sealable skin layer (monolayer or multilayer) and any suitable barrier layer material that provides a suitable desired oxygen and moisture impermeability. Preferred barrier materials are copolymers of vinylidene chloride and vinyl chloride or methylmethacrylate. When the barrier layer comprises a copolymer of vinylidene chloride and vinyl chloride or methyl methacrylate, the barrier layer optionally contains 0 to 6% by weight of a copolymer of ethylene and vinyl acetate, more preferably 4 as a processing aid. May contain ~ 6%.

In one aspect of the invention the barrier layer is coextruded with at least one heat sealable skin layer. 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 an ethylene-α-olefin copolymer (A) or an ethylene-based copolymer composition (A '), (A' '), (A' ''). In order to assist in the processing of the film, the skin layer (single layer or multilayer) may comprise 0 to 10% by weight of a copolymer of ethylene and vinyl acetate, more preferably 0.5 to 5% of a copolymer as a processing aid. In addition, the skin layer may optionally include a slip agent / anti-stick agent. It may be desirable to coextrude an adhesive tie layer of the copolymer of ethylene and vinyl acetate between the skin layer and the barrier layer to improve the adhesion of those layers.

In a preferred aspect of the invention, the 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. Using this structure, you can create a reusable Ostomy bag or pouch. The barrier layer and skin layer (single layer or multilayer) can be made separately and then laminated together using a suitable adhesive polymer, liquid adhesive, or hot-melt adhesive. The multilayer blocking film of the present invention exhibits less than 85 dB of noise when bent at an angle of 65 ° at 0.45 Hz, preferably less than 83 dB when bent at an angle of 65 ° at 0.45 Hz, most preferably 0.45 Hz Curved at an angle of 65 ° at, produces less than 81dB of noise.

In another aspect of the present invention, additional layers may be added to the barrier layer to make a system for transdermal delivery of a medicament. Preferably the system comprises a backing layer of barrier film which serves as a gateway to the pharmaceutical system. The adhesive comprising the active agent is preferably attached to one surface of the film. Adjacent to the adhesive is a controlled release membrane adapted to contact the skin of the patient and to release the medicament while controlling.

In another form of this aspect, the backing layer can make a reservoir comprising the active agent, with a controlled release membrane that conceals the opening of the reservoir for controlling the diffusion of the drug into the skin of the patient. Adhesives may be used to adhere to the percutaneous delivery system to the patient's skin, either in or around. Preferably, a release liner is covered over the adhesive and the membrane to protect the structure before use.

Therefore, it is a feature of the present invention to provide an oxygen and moisture impermeable multilayer barrier film that can be produced using co-extrusion or lamination. Moreover, the characteristic of this invention is odor blocking property, flexibility, and low noise property. Also provided are heat sealable surfaces for use in making bags and pouches.

In one aspect, the multilayer barrier film of the present invention can be prepared 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 at the time of extrusion. Therefore, the entire thickness of the multilayer structure can be adjusted. Alternatively, the independent layers can be made separately and laminated together using an appropriate adhesive bonding layer.

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

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). 2% secant modulus is a measure of the stiffness or flexibility of the film. We found that the lower the value of 2% secant modulus for the 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 processable by conventional apparatus. As for the entire multilayer film, the 2% split 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 for ostomy 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 wt.%). Examples of suitable barrier materials include Saran® 469 and Saran MA, which are commercially available from Dow Chemical Company. In the case of using the saran barrier layer material, the barrier layer may contain, as a processing aid, a copolymer of ethylene and vinyl acetate, 0 to 6% by weight, more preferably 4 to 6% by weight. Suitable examples of ethylene / vinylacetate copolymer compositions are copolymers sold under the trademark Elvax® from E.I du Pont de Nemours Co., Inc.

Preferably the barrier layer comprises two heat sealable skin layers comprising an ethylene-α-olefin copolymer (A) or an ethylene-based copolymer composition (A '), (A' '), (A' ''); Co-extruded together or laminated between the two layers.

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

The multilayer barrier film of the present invention can be made by a lamination technique using a suitable adhesive. For example, the barrier layer and skin layer (monolayer or multilayer) may be made separately and then laminated together using an adhesive polymer, a liquid adhesive, or a hot melt adhesive. Suitable adhesive polymers for bonding the barrier layer and skin layer include, but are not limited to, ethylenically unsaturated copolymers of vinyl acetate, ethyl acrylate, ethyl methacrylate, methyl acrylic acid, acrylic acid, and carbon monoxide. Can be. As another acid, the ionomer of ethylene and methylacrylic acid or acrylic acid, and a graft anhydride copolymer are mentioned. Suitable liquid adhesives or hot melt adhesives include, but are not limited to, those based on copolymers of urethanes, copolyesters, and amide acrylates.

The five layers of oxygen and moisture impermeable barrier film include a barrier layer made from a suitable barrier material as discussed previously. Preferably the barrier layer is coextruded with the two outer heat sealable skin layers while sandwiching the adhesive layer between the two outer heat sealable skin layers. The heat-sealable skin layer in this five-layer aspect is the published PCT application N0. Substantially linear copolymers of ethylene with α-olefins described in PCT / US92 / 08812, or uniformly branched linear polyolefin resins, such as eg EXACT resins and TAFMER resins. It may include. Suitable adhesives include copolymers of ethylene and vinyl acetate which improve the adhesion between the barrier layer and the skin layer.

In the simplest form of another aspect of the present invention in which an additional layer is included with the barrier film to make a system for delivering the drug percutaneously, the barrier layer and the skin layer of the film are the back layer, which is a barrier to the drug system. It acts as a film. The barrier film also includes an adhesive layer comprising the active agent formulated in a matrix adhered to one side of the film. The adhesive chosen should be compatible with the active agent and also permeable to the active agent. Many active agents can be administered to the patient in this form, including, for example, estrogen, nitroglycerin, nicotine and scopolamine. Theoretically, most drugs can be administered in this form.

On contact with the skin of the patient, a controlled release membrane suitable for release while controlling the medication is on the adhesive layer. An additional layer of adhesive, which may be applied around the membrane or on the entire surface of the membrane, may be present to secure the transdermal delivery system against the patient's skin. The adhesive used in this embodiment of the present invention should be a medical adhesive such as a silicone adhesive, acrylic adhesive or vinyl acetate adhesive. In general, in this aspect, the system is sealed in a package or secured against a second barrier film, removing them before use.

Another embodiment of the transdermal drug delivery system according to the present invention is described. The barrier layer and skin layer form a barrier film into which the reservoir is molded, in order to contain the active agent therein. The opening of the reservoir is concealed with a controlled release membrane. Adhesives that can be applied to the perimeter of the membrane or over the entire area of the membrane act to secure the system to the skin layer of the patient. In addition, the adhesive of choice must be compatible with the active agent and must be permeable with respect to the agent. Preferably the release liner or the like hides and protects the adhesive and film prior to use.

A typical reusable Ostomy bag comprising an opening made from a multilayer barrier film can be made by folding the edge of the multilayer film and heat sealing the edge. The film is folded and sealed so that the inner surface of the bag or pouch is preferably provided by one heat sealable skin layer. The barrier film of the present invention provides the flexibility and tranquility desirable for ostomy applications, as well as the waterproof and odor barrier properties and oxygen barrier properties. As appreciated by those skilled in the art, the barrier films of the present invention can be applied to other packaging applications where barrier to moisture and oxygen is required.

Sealants for Laminated Films:

The sealant for laminated films can be molded by air-cooled inflation using the ethylene-α-olefin copolymer (A) or the ethylene-based copolymer composition (A '), (A' '), (A' ''). have.

The sealant for laminated films according to the present invention has a dart impact strength of 100 kg / cm or more, preferably 150 kg / cm or more. Moreover, this film has a complete sealing temperature of 130 degrees C or less, Preferably it is 110-130 degreeC.

Moreover, the blocking strength of the sealant for laminated | multilayer film which concerns on this invention is 1.5 kg / cm or less normally, and tensile Young's modulus is 3500 kg / cm <^2> or more normally.

The thickness of the sealant for laminated films according to the present invention is 10 to 150 m, preferably 10 to 60 m.

When the sealant for laminated films according to the present invention as described above is laminated on a substrate, a laminated film is obtained.

As said base material, the thin film body which consists of arbitrary materials which can form a film-form form can be used. As such a thin film, a polymer film or sheet, a cloth, paper, a metal thin film, and cellophane are mentioned.

Such a sealant for laminated films is excellent in low temperature heat sealability, hot tack resistance, impact resistance, blocking resistance and opening property.

Heavy Packaging Films:

The film for heavy packaging has a Young's modulus measured according to JIS K 6781 more than 4000 kg / cm <^2> , the dart impact strength measured according to ASTM D 1709A method is 55 kg / cm or more, and the film thickness is 30-200 m normally.

The heavy packaging film can be produced by the inflation method or the T-die method of the ethylene-α-olefin copolymer (A) or the ethylene-based copolymer composition (A '), (A' '), (A' ''). Can be. For example, it can laminate | stack with the film of polyester and polyamide, and can be set as a multilayer film.

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

Grain bags:

The bag for grains of this invention consists of the film of the said ethylene-alpha-olefin copolymer (A) or ethylene-type copolymer composition (A '), (A "), (A'"), Three directions of the film are blocked. This may be done if an opening is formed in one end and a bottom part is formed in the other end. For example, one film may be folded into two and the both sides may be sealed, and two synthetic resin films may be stacked and three directions inside thereof may be sealed, or a tubular shape may be formed by inflation or the like. One of the (tube-like) films may be sealed and the other may be an opening.

Moreover, when sealing one side of a film, it is preferable to weld together films, for example, but what kind of method may be used as long as it can seal in the state which can seal the content at the time of sealing films.

(Directed end)

The extension end is used as a base material for attaching the string to be described below, and is a winding place when closing the opening of the grain bag of the present invention.

This extension end may attach a separate film to one end of the opening end of an envelope-shaped film, and may form the film so that the extension end may be formed, when forming an envelope.

(String tied)

The tying string is to close the opening of the grain bag. The material of the string may be used in any kind, but if a material such as a film is used, it is preferable in that the convenience is improved when the bag for grain of the present invention is recycled.

(Sealing part for string)

The seal for the string is provided to mount the string to bind to the production end. This string sealing part is formed by folding a part of the production end to the opening end side of the other film, and folding it so as to enclose a string to be bound therein. For example, the string to be tied may be simply inserted by folding and sealing the end portions of the stretched ends. Alternatively, the strings tied together with the production ends may be sealed so that the strings do not move. However, for example, you may apply | attach an adhesive agent to the inner side of the string sealing part, and may bond the string and the sealing part for strings, and it may prevent the tie string from moving.

(Gap)

The gap is provided between the sealing portion for the string and the opening end of the other film. When the gap is provided, the opening is easy to open when the grain bag is used, and it is preferable in that it is a free space for winding when the grain bag is wrapped and closed. The width of this gap is 5 to 100 mm, preferably 10 to 30 mm.

Additional Components of the Invention

Although the bag for grains of this invention consists of said essential component mentioned above, it is satisfied also when the component described below is added.

(Flap part)

In the grain bag of the present invention, a flap portion having a predetermined width may be provided to extend from the string sealing portion to the opening end side to cover the opening. In this case, since a flap part presses the content of the vicinity of an opening part, and stops, it is preferable at the point which the received grain becomes difficult to overflow even when the grain bag is arrange | positioned laterally. Moreover, the width | variety of a flap part is at least the width | variety of the said gap, and is 30-150 mm, More preferably, it is 50-100 mm.

(Wrinkle part)

The said bottom part may be provided with the cross-sectional V-shaped wrinkle part in which one end of the said synthetic resin film was folded inward. In this case, when the grain is put inside the grain bag, the bottom of the bag is flat, which is preferable because the bag becomes stable.

At this time, if each side of the bottom side of the bag for grains is inclined sealing such that two sides form an inclined side of an isosceles triangle having a length substantially equal to the width length of each corrugation portion, the width of the bottom portion is the capacity of the grain. It is preferable at the point which becomes constant irrespective of it.

(Ventilation hole)

The film is preferably provided with a plurality of ventilation holes along both sides of the grain bag, in that the state of the stored grain can be properly maintained. A plurality of ventilation holes may be formed in accordance with at least either the opening end or the bottom end of the film. Moreover, each ventilation hole may be provided in a rectangle as an integral part in a film.

In addition, the ventilation hole may be provided only in either one of two films, or may be provided in both films.

In addition, since grain bags contain heavy grains and are frequently moved, grain bags are required to have excellent impact resistance and tear resistance.

The bag for grains which concerns on this invention is formed from the film shape | molded the copolymer (A) or a composition (A '), (A "), (A'") by the inflation method, for a grain, Since the strength suitable for a bag is obtained, it becomes possible to make thickness of the bag for grains thin compared with the conventional polyethylene. The film formed by the air-cooled inflation method from the copolymer (A) or the composition (A '), (A''),(A''') has (i) a tensile Young's modulus of 4,000 kg / cm ² or more, ( ii) If the dart impact strength is 55 kg / cm or more, it is suitable for use as a bag for grain.

Moreover, it is preferable that the gloss of the said film is 50% or more, and it is preferable that the thickness of the said film is 30-200 m as a bag for grains.

Moreover, since this film is excellent in low-temperature characteristics, such as low-temperature falling-bag strength characteristic which can be used enough for grain bags in the subzero cold region, film thickness can be made thin and high speed shaping | molding of a film is possible.

According to the grain bag of the present invention, first, an opening provided in the other end of the grain bag is opened, and an appropriate amount of grain is put therein. Next, the extension end is wound by an appropriate number of times on the open end side of the other film. Finally, the openings are blocked by joining and tying both sides of the tie string. Therefore, the method of using a grain bag is the same as that of a conventional paper grain bag, and there is no change in the working practices of producers or traders who are working with the conventional grain bags.

Moreover, since the envelope made of synthetic resin is used for the grain bag of this invention, it can manufacture at low cost compared with the conventional paper grain bag. In addition, each component mentioned above can be combined arbitrarily as much as possible.

(Method of manufacturing bag for grain)

Next, the manufacturing method of the bag for grains of this invention is comprised as follows. That is, in the film direction, the extension part formation process which provides the extension end which extended in the opening direction rather than the opening end of the other film in the two films, and the said extension end WHEREIN: The opening end of the said other film A string supply step of supplying a string to be bundled along the width direction of the bag at a portion with a predetermined gap; And a sealing step of overlapping and welding the reinforcing end portion bent and inverted, and overlapping in a state in which a gap remains between the opening end of the other film.

Here, three directions of the overlapped two synthetic resin films are blocked, and a grain bag having a bottom portion formed at one end and an opening formed at the other end may be formed by sealing three sides of two independent films. Although one film may be folded into two sheets and sealed in two directions, a film formed in a cylindrical shape, such as an inflation film, may be easily blocked since the two directions are blocked from the beginning.

Further, the bottom part may be provided by folding the bottom part inward to form a pleated part having a V-shaped cross section. Moreover, you may provide the drilling process which provides a some ventilation hole along both sides of the film of the said other stage. Moreover, you may provide the 2nd drilling process which forms a some ventilation hole along at least one of the said opening edge part and the bottom side edge part of the said other film.

Flexible Material Packaging Pouches:

Pouches for packaging liquid materials are pouches used in consumer packaging useful for packaging fluid materials (e.g. liquids such as milk), and the ethylene-α-olefin copolymers (A) or ethylene-based copolymer compositions (A It is formed from certain film structures, including '), (A' '), (A' '').

In the present invention, a flowable material is used by using a single-layer film structure of a polymer layer which is an ethylene-α-olefin copolymer (A) or an ethylene-based copolymer composition (A '), (A' '), or (A' ''). A pouch of the present invention is prepared for packaging.

Generally, the ethylene-α-olefin copolymer (A) or the ethylene-based copolymer composition (A '), (A' '), or (A' '') is used alone as the sealing layer of the film or film structure. . However, it is also possible to blend an ethylene-α-olefin copolymer (A) or an ethylene-based copolymer composition (A '), (A' '), (A' '') together with other polymers used as the heat-sealing layer. It is possible. In general, the ethylene-α-olefin copolymer (A) or the ethylene-based copolymer composition (A '), (A' ') and (A' '') are 10% by weight to 100% by weight of the film structure.

In addition, additives known to those skilled in the art, for example, antioxidants, phosphites, cling additives, and Standoztab PEPQ (trademark) supplied by Sandoz to the polymer as a raw material for manufacturing the pouch of the present invention. It is also possible to add antiblocking additives, slip additives, UV stabilizers, pigments, processing aids and the like.

The films and film structures disclosed herein comprise at least one layer, preferably an ethylene-olefin copolymer (A) or an ethylene-based copolymer composition (A '), (A' '), (A' ''). May be a single layer or a multilayer film structure provided that it is used as a sealing layer. The sealing layer has a thickness of at least about 0.1 mil (2.5 microns) and more, preferably 0.2 mil (5 microns) to 10 mils (254 microns), more preferably 0.4 mil (10 microns) to 5 mils (127). Micron).

A surprising feature of the film construction for pouches of the invention is the wide heat sealing range of the film. The heat-sealing range of this film structure may generally be from 50 ° C to 160 ° C, preferably from 75 ° C to 130 ° C. It has been found that the sealing layer of the present invention has a wider heat sealing range than the polyethylene film of the prior art made from ethylene polymers which are unevenly branched even when the density is about the same. In the heat sealing method of making a pouch from a film structure, it is important to widen the heat sealing range for higher flexibility. The melting point range of the copolymer (A) or the composition (A '), (A' '), (A' '') used in the production of the film structure having the heat sealing range specified above is generally 50 ° C to 130 ° C. Preferably, the temperature may be 55 ° C to 115 ° C.

Another unexpected feature of the film construction 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 at least about 1 N / inch within about 0.3 seconds at a sealing bar temperature of about 110 ° C. when using the DTC Hot Tack Strength Method, defined herein below. At least 11 bf within 0.4 seconds at a sealing bar temperature of about 110 ° C., when achieving a hot tack strength of 39.4 N / m) or using the DTC Heat Seal Strength Method defined below herein. Achieve a heat seal strength of 175 N / m. The film structure of the present invention also exhibits a hottack or heat seal initiation temperature of less than about 110 ° C. at a force of at least about 1 N / inch (39.4 N / m). Sealings made using the sealing layer of the present invention have been found to exhibit higher strength at lower sealing temperatures than seals in which prior art polyethylenes of higher density are used. It is important to give high heat sealing strength at low temperatures in order to be able to operate a conventional packaging device, for example a vertically-formed filling sealer or the like, at high speed to produce a pouch with little leakage.

When the ethylene-α-olefin copolymer (A) or the ethylene-based copolymer composition (A '), (A' ') or (A' '') is used as the sealing layer of the film structure for pouches of the present invention, When the pouches of the invention are compared with pouches made using linear low density polyethylene, linear ultra low density polyethylene, high pressure low density polyethylene, or a combination thereof, (1) a high speed workable pouch is obtained with a molded filling sealer and (2) It is believed that a small pouch package is obtained.

In one aspect of the present invention, a pouch is made from a tubular film structure and has a transversely sealed end thereof. This film structure

(I) 10-100 weight% of at least 1 layer containing an ethylene-alpha-olefin copolymer (A) or an ethylene-type copolymer composition (A '), (A "), (A'"), And

(II) 0 to 90% by weight of at least one polymer selected from the group consisting of heterogeneously branched linear ethylene / C ₃ -C ₁₈ α-olefin copolymers, high pressure low density polyethylene and ethylene-vinyl acetate copolymers It has at least 1 layer of film layers to make.

The heterogeneously branched linear ethylene / C ₃ -C ₁₈ α-olefin copolymer of this (II) is generally linear low density polyethylene (for example polyethylene produced using a Ziegler catalyst). These linear low density polyethylenes are often classified in subsets, which are represented as either very low density polyethylene (VLDPE) or ultra low density polyethylene (ULDPE). In the present specification, VLDPE and ULDPE are interchangeable terms, and those skilled in the art generally use them in this form. The density of the linear low density polyethylene of (II) is generally in the range ^{0.87g / cm 3 ~ 0.94g / cm} 3, preferably ^{0.87g / cm 3 ~ 0.915g / cm} 3. The heterogeneously branched linear low density ethylene / C ₃ to C ₁₈ α-olefin copolymer of (II) preferably exhibits a melt index of 0.1 to 10 g / 10 minutes.

The high pressure low density polyethylene of this (II) preferably shows a density of 0.916 to 0.93 g / cm ³ and a melt index of 0.1 to 10 g / 10 minutes.

Preferably, the ethylene: vinyl acetate copolymer of this (II) ethylene-vinyl acetate copolymer has a weight ratio of 2.2: 1 to 24: 1, which shows a melt index of 0.2 to 10 g / 10 minutes.

Another aspect of the invention,

(a) at least one copolymer (A) or composition (A '), (A''),(A''' having a density of 0.915 g / cm ³ or less and a melt index of 10.0 g / 10 minutes or less; ) Is 10-100% by weight

(b) 0 to 90 weight percent of at least one polymer selected from the group consisting of heterogeneously branched linear ethylene / C ₃ -C ₁₈ α-olefin copolymers, high pressure low density polyethylene and ethylene-vinyl acetate (EVA) copolymers Pouches prepared from blends which are%.

The heterogeneously branched linear ethylene / C ₃ -C ₁₈ α-olefin copolymer of this (II) is generally linear low density polyethylene (for example polyethylene produced using a Ziegler catalyst). This linear low density polyethylene includes very low density polyethylene (VLDPE) and ultra low density polyethylene (ULDPE), as described above. The density of the linear low density polyethylene of (II) is generally in the range ^{0.87g / cm 3 ~ 0.94g / cm} 3, preferably ^{0.87g / cm 3 ~ 0.915g / cm} 3. The heterogeneously branched linear low density ethylene / C ₃ -C ₁₈ α-olefin copolymer of (II) preferably has a melt index of 0.1 to 10 g / 10 minutes.

The high pressure low density polyethylene of this (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 minutes.

Preferably, the ethylene: vinyl acetate copolymer of this (b) ethylene: vinyl acetate copolymer has a weight ratio of 2.2: 1 to 24: 1, which shows a melt index of 0.2 to 10 g / 10 minutes.

The film structure of the pouch of the present invention also includes a multilayer or composite film structure, and preferably the polymer layer included in the structure is an inner layer of the pouch.

As will be appreciated by those skilled in the art, the multilayer film structure for pouches of the present invention may include various film layer combinations as long as the present sealing 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. This film structure is also used for barrier films such as polyester, nylon, ethylene-vinyl alcohol copolymers (EVOH), polyvinylidene dichloride (PVDC), for example Saran (trademark) (Dow Chemical Company (The Trademarks of Dow Chemical Company) and metal coating films and the like. Depending on the final use of this pouch, the choice of other materials or types of materials to be used in combination with the present sealing layer film greatly depends. The pouch described herein refers to the sealing layer used at least inside the pouch.

One aspect of the film structure for pouches of the present invention includes a sealing layer of at least one of an ethylene-olefin copolymer (A) or an ethylene-based copolymer composition (A '), (A' '), (A' ''). Two polymer outer layers. This polymer outer layer is preferably a polyethylene film layer, more preferably "linear low density polyethylene" ("LLDPE") and / or "linear ultra low density polyethylene" ("ULDPE") and / or very Low-density polyethylene "(" VLDPE ") is a heterogeneously branched linear polyethylene. An example of a commercial LLDPE is DOWLEX® 2045 (a trademark of Dow Chemical Company, commercially available from this company). An example of a commercially available ULDPE is ATTANE ™ 4201 (a trademark of Dow Chemical Company, commercially available from this company). LLDPE (including both VLDPE and ULDPE) useful herein is an olefin and an α-olefin having a small amount of 3 to 18 carbon atoms, preferably an α-olefin having 4 to 10 carbon atoms (eg Heterogeneously branched linear copolymers made from 1-butene, 4-methyl-1-pentyl, 1-hexene, 1-octene, 1-decene and the like). Generally, a Ziegler catalyst is used to prepare this heterogeneously branched LLDPE (for example, the method described in US Pat. No. 4,076,698 (Anderson et al.) Is used).

The density of LLDPE for the outer layer is generally at least 0.87 g / cm ³ , more preferably 0.9 to 0.93 g / cm ³ , and the melt index is generally 0.1 to 10 g / 10 minutes, preferably 0.5 to 2 g / 10 Minutes.

The thickness of the outer layer may be any thickness as long as the sealing layer has a minimum thickness of 0.1 mil (2.5 microns).

Another aspect of the film construction for pouches of the present invention includes a polymer layer between two polymer layers.

Another aspect of the film construction for pouches of the present invention includes at least one polymer core layer between at least one polymer outer layer and at least one polymer sealing layer. This polymer layer may be a film layer of LLDPE like the outer layer, or preferably another LLDPE, more preferably an LLDPE having a higher density than the outer layer. The thickness of the core layer may be any thickness as long as the sealing layer has a minimum thickness of 0.1 mil (2.5 microns).

Another aspect of the film structure for pouches of the present invention may be a structure including a sealing layer and another polyethylene film layer hereinafter referred to as "high pressure low density polyethylene"("LDPE"). Generally, 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 minutes. The thickness of this LDPE layer may be any thickness as long as the sealing layer has a minimum thickness of 0.1 mil (2.5 microns).

Another aspect of the pouch film structure of the present invention is a structure comprising an EVA copolymer layer having a weight ratio of sealing layer and ethylene: vinyl acetate of 2.2: 1 to 24: 1 and exhibiting a melt index of 0.2 to 20 g / 10 minutes. good. The thickness of this EVA layer may be any thickness as long as the sealing layer has a minimum thickness of 0.1 mil (2.5 microns).

The film structure used in the pouch manufacture of the present invention is 0.5 mil (12.7 microns) to 10 mils (254 microns), preferably 1 mil (25.4 microns) to 5 mils (127 microns).

The design of the film structure for the pouch of the present invention is flexible. Other LLDPEs (for example, VLDPE and ULDPE) can be used for the outer layer and the core layer for the purpose of optimizing specific film properties, for example, the rigidity of the film. In this manner, the film can be optimized to be suitable for a particular use, for example, a vertical molding filling sealer or the like.

Either of blow tube extrusion methods or cast extrusion methods, which are well known in the art, are used to prepare polyethylene film structures for use in the manufacture of pouches of the present invention. This blown tube extrusion method is described, for example, in Modern Plastcs Mid-0ctober 1989 Encyclopedia Issue, Vol. 66, Number 11, 264-266. Cast extrusion methods are described, for example, in Modern Plastics Mid-0ctober 1989 Encyclopedia Issue, Vol. 66, Numbers 11,256-257.

The pouch aspect of this invention is a hermetically sealed container which puts "fluid material." "Fluid material" means a material that can flow under gravity or is pumpable, but the term "fluid material" does not include gaseous materials. These flowable materials include non-acid solutions (e.g. milk, water, juice, wine, etc.) and carbonated liquids (e.g., soda, beer, water, etc.); Emulsions (eg ice cream mixes, soft margarine, etc.); Pastes (eg meat pastes, peanut butter, etc.); Preserved foods (eg jams, pie stuffing, marmalade and the like); jelly; Flour dough; Ground meat (eg sausage meat); Powder (eg gelatin powder, detergents, etc.); Granular solids (eg nuts, sugar, cereals, etc.); And similar materials. The pouches of the present invention are particularly useful for use in the packaging of liquids (for example milk). This flowable material may also include an oily liquid (eg cooking oil or motor oil, etc.).

At the time of producing the film structure for the pouch of the present invention, the film structure is cut to the width desired for use in a conventional pouch maker. Using the so-called molded filling sealers well known in the art, the pouch aspects of the present invention are prepared. In the pouch aspect of the present invention, there is a pouch which is a tubular member having a longitudinal wrap and a transverse seal so that a "pillow" pouch is formed when the pouch is filled with a fluid material.

The pouch aspect of the invention also has a pin seal around the three sides of the tubular member, i.e. a top seal and a side seal in the longitudinal direction, and in the cross-sectional view the longitudinal direction is filled with the flowable material in the pouch. There is a pouch that is a tubular member having a substantially sealed or "ball-shaped" bottom sealed in the bottom portion of the tubular member so that a substantially semicircular or "bow" bottom portion is formed. This pouch is a so-called "Enviro-Pak" pouch known in the art.

Pouches made according to the invention are preferably pouches made from so-called vertical molded filling seal (VFFS) groups which are well known in the art. Examples of commercially available VFFS groups include VFFS groups made by Hayssen or Prepac. VFFS groups are described in the literature: F.C. Lewis Form-Fill-Seal, Packaging Encyclopedia, 180, 1980.

In the VFFS packaging method, the sheet of the plastic film structure described herein is supplied to the VFFS machine, and the sheet is formed into a continuous tube in its inertial section. By sealing the longitudinal edges of the film together, the plastic film is folded and sealed inward / outward to seal the film, or the plastic film is sealed inward / inward to pin seal, thereby producing the tubular member. Next, after sealing a tube in the transverse direction at the place of the one terminal which becomes the bottom of this "pouch" using a sealing bar, a filling material, for example milk, etc. are put into this "pouch". Next, a sealing bar is used to seal the upper end of the pouch and the plastic film is incinerated or the film is cut to separate the resulting finished pouch from the tube. Methods of making pouches using this VFFS machine are generally described in US Pat. Nos. 4,503,102 and 4,521,437.

The capacity of the pouches of the invention can be varied. Generally 5 milliliters-10 liters, Preferably 10 milliliters-8 liters, More preferably, 1 liter-5 liters can contain a fluid material in this pouch.

When the ethylene-α-olefin copolymer (A) or the ethylene-based copolymer composition (A '), (A' ') or (A' '') sealing layer is used in a two- or three-layer coextruded film product, The use of the VFFS makes it possible to produce pouches at a faster rate and thus obtains a film structure which reduces the leakage of the pouches thus prepared.

Moreover, it is also possible to print on the pouch of this invention using the technique known in the art, for example, it is also possible to corona-process before printing.

The pouches of the present invention show excellent performance results when tested with a 5 foot (1.52 m) drop (test defined herein). Under this 5-foot (1.52 m) drop test, the percent breakage exhibited by the pouch is preferably 40 percent or less, more preferably 20 percent or less, especially 10 percent or less.

The use of this pouch in packaging for consumer liquids, such as milk, has many advantages over containers used in the past: glass bottles, paper cardboard and jug made of high density polyethylene. Previously used containers consumed a variety of natural resources in their manufacture, required large spaces in landfills, large storage spaces, and large amounts of energy in temperature control of the product. Due to the electrothermal properties of).

When the pouches of the present invention are made into thin films and used in liquid packaging, numerous advantages are gained over containers used in the past. This pouch has (1) low consumption of natural resources, (2) small footprint for landfilling, (3) reusability, (4) ease of processing, and (5) storage space required. Small, (6) uses less energy for storage (the heat transfer characteristics of the package), (7) makes incineration safe, and (8) reusable (for example, empty pouches for other uses, for example Other uses such as freezer bags, sandwich bags and general purpose storage bags).

Batch included package:

Batch inclusion packages include the ethylene-α-olefin copolymer (A) or the ethylene-based copolymer composition (A '), (A' '), (A' '') or any of these. It is a pouch included package made from. The package can be fabricated from a film and used to include powders, pellets and flowable materials to protect it, where the entire package (ie film and contents) can be added to the mixture during the manufacture of a product, for example For example, this package can be placed in an extruder / mixer at the same time as the product it contains.

Preferably the said ethylene-alpha-olefin copolymer (A) or ethylene-based copolymer composition (A '), (A''),(A''') used in the film of this batch containing package is only one. Used as a polymer component. However, other polymers may be blended and / or multilayered extruded together with the ethylene-α-olefin copolymer (A) or the ethylene-based copolymer composition (A '), (A''),(A'''). Alternatively, the multilayer film may be provided with workability, film hardness, film barrier properties, film strength, film melting properties, or other desired film properties. Batch-containing film made by using an appropriate blend of the ethylene-α-olefin copolymer (A) or ethylene-based copolymer composition (A '), (A''),(A''') and other polymer components Will also maintain improved performance. Some of the useful polymer blend components include, for example, ethylene / vinyl acetate copolymer (EVA), ethylene / vinyl alcohol copolymer (EVOH), polybutylene (PB), linear high density polyethylene with a density from 0.941 to 0.965 g / cm ³ . (HDPE), and linear low density polyethylene (LLDPE) produced by a conventional Ziegler catalyst having a density of 0.87 to 0.94 g / cm ³ , and the like. Preferably in the ethylene-α-olefin copolymer (A) or ethylene-based copolymer composition (A '), (A''),(A'''), at least about 50 percent of this blend composition, more preferably Preferably at least about 80 percent of this blend composition. However, very preferably the inner layer consists essentially of at least one of the ethylene-α-olefin copolymers (A) or ethylene-based copolymer compositions (A '), (A''),(A'''). Configure.

Moreover, to the said ethylene-alpha-olefin copolymer (A) or ethylene-type copolymer composition (A '), (A "), (A'"), the grade which does not disturb the function of this batch containing package, Other additives such as plasticizers, antioxidants, phosphites, cling additives, thermal stabilizers, light stabilizers (e.g. manufactured by Cyasorb (R) UV531 benzophenone and Chiba Geigy Corp. Tinubin® 622 hindered amine light stabilizer, etc.), pigments (e.g. titanium dioxide, calcium carbonate, carbol black, etc.), processing aids (e.g. polyethylene glycols, fluoropolymers, fluoroelastomers, Waxes), flame retardants (e.g., Amgard® CPC102, a phosphorus-based flame retardant manufactured by Albright and Wilson Americas), lubricants (e.g., waxes, stearates, mineral oils, etc.), slip Agent (eg erucamide, oleamide, etc.), antiblocking additive Agents (e.g. talc, silicon dioxide, etc.), cross-linking agents (e.g. peroxides (e.g. Booster (trade name) manufactured by DuPont), etc.), antifogging agents (e.g. Atmer manufactured by ICI) 100 sorbitan esters, etc.), impact modifiers (e.g. Paxon (trademark) Pax Plus, a rubber modified film resin manufactured by Allied Corp.), antistatic agents (e.g. Akzo Chemical, Inc.) Armostat 410, which is the third amine of the ethoxylating agent), and a filler (for example, talc, calcium carbonate, clay, fumed silica, etc.) may be contained. This list of additives is illustrative only and is not exhaustive or limiting.

Films and film structures having the novel properties described herein can be prepared using conventional hot blown film or cast film manufacturing techniques. It is also possible to use a biaxial orientation method, for example, a tenter frame or a double bubble method, in cooperation with this conventional manufacturing technique. Conventional hot blown film methods are described, for example, in The Encyclopedia of Chemical Technology, Kirk-0thmer, 3rd Edition, John Wiley Sons, NewYork, 1981, Vol. 16, pp. 416-417 and 18, pp. 191-192. Described. Processes for making biaxially oriented films, such as the "double bubble" method as described in US Pat. No. 3,456,044 (Pahlke), and US Pat. No. 4,865,920 (Golike et al.), US Pat. No. 4,352,849 (Mueller), The method described in US Pat. No. 4,820,557 (Warren), US Pat. No. 4,927,708 (Herran et al.), US Pat. No. 4,963,419 (Lustig et al.) And US Pat. No. 4,952,451 (Mueller), and the like are also used herein. The novel films and film structures described can be made. Moreover, it is also possible to manufacture this film and a film structure as described in tenter frame technology, for example, the technology used in the orientation of polypropylene.

Although this film may be a single | mono layer or a multilayer film, this film structure is the said ethylene-alpha-olefin copolymer (A) or ethylene-based copolymer composition (A '), (A') in at least 1 layer, Preferably an inner layer. Use at least one ')' or (A '' '). This inner layer is a layer adjacent to the material contained in the package. As described by WJSchrenk and CRFinch in the Society of Plastics Engineers RETEC Proceedings, June 15-17 (1981), pages 211-29, as described by WJSchrenk and CRFinch, ) And the inner layer may be laminated on another layer (stream) by coextrusion or secondary operation. As described by KR0sborn and WAJenkins in Plastic Films, Technology and Packaging Applications (Technnomic Publishing C0. Inc. (1992)), tubular film (ie blown film technology) or flat die (ie cast film) It is also possible to produce single layer films, and may optionally be subjected to further post extrusion steps to adhere or extrude the layers to layers of other packaging materials to produce a multilayer structure. Although the film may be two or more layers of coextruded (as described by 0sborn and Jenkins), the film may be further laminated to an additional layer of packaging material in accordance with other physical requirements for the film for final packaging. In addition, by D. Dumbleton, `` Laminations Vs. Coextrusion ”(Converting Magazine (September 1992)) also considers the contrast between coextrusion and lamination. Moreover, it is also possible to give another post-extrusion technique, for example, biaxial orientation processing, to a single | mono layer and a coextrusion process film.

Extrusion coating is another technique for making materials for multilayer packages. Like cast films, extrusion coating is a flat die technique. The film layer may be extruded onto the substrate in either monolayer or coextruded extrudate form.

In the case of polymer blends and / or multilayer film structures, generally, the ethylene-α-olefin copolymers (A) or ethylene-based copolymer compositions (A '), (A' '), (A' '') At least one layer, preferably the inner layer, of the entire multilayer film structure is constituted. Other layers of this multilayer structure include, but are not limited to, barrier layers and / or bonding layers and / or structural layers. Various materials may be used in this layer, some of which may 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 (e.g. polyethylene grafted with maleic anhydride) and paper Etc. are included. This multilayer film structure generally comprises 2 to 7 layers.

Single layer 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). In the case of coextrusion (or multilayer extrusion), the inner layer comprising this substantially linear ethylene / α-olefin polymer is typically from 0.2 mil (5 microns) to 15 mils (381 microns), preferably 1 Make from wheat (25.4 microns) to 5 mils (127 microns).

Films and film structures prepared from the above ethylene-α-olefin copolymers (A) or ethylene-based copolymer compositions (A '), (A' '), (A' '') may be prepared according to the end use requirements. Process into liner or packaging material. For example, a tube liner can be used to blend various materials sequentially, where the contents and liner are further blended with another component by moving it from one tube to another, and into any powerful mixer. send. In another example, the additive used in rubber production may be packaged in a bag, and the entire bag containing its contents is added to the process without being opened during rubber production. The use and manufacturing techniques for such batch containing bags are described in this industry, as described in US Pat. No. 4,394,473, US Pat. No. 5,120,787, US Pat. No. 4,248,348, European Patent Application Publication No. 0270902 and Canadian Patent No. 2,053,051. Well known from

When the ethylene-α-olefin copolymer (A) or ethylene-based copolymer composition (A '), (A' '), (A' '') is used in a batch-containing bag and a film, numerous advantages are obtained. The ethylene-α-olefin copolymer (A) or ethylene copolymer composition (A '), (A' '), (A' '') exhibits excellent processability in the production of blown films, and It has a lower melting point and softening range compared to polyethylene produced by Ziegler catalysts. In addition, since the said ethylene-alpha-olefin copolymer (A) or ethylene-type copolymer composition (A '), (A "), (A'") is comprised from carbon and a hydrogen atom, ethylene / acrylic acid or In contrast to using batch-containing films and bags made from ethylene / methacrylic acid copolymers (as described in European Patent Application Publication No. 0270902) or ethylene / vinyl acetate copolymers (US Pat. Nos. 5,120,787 and As compared to films and bags made from US Pat. No. 4,248,348), the ethylene-α-olefin copolymers (A) or ethylene-based copolymer compositions (A '), (A' '), (A '' 'Is compatible with a variety of elastomeric additives that are particularly useful in the rubber industry.

The material (class) to be placed in this batch containing bag (or packaging material, coating material or liner) may be a material exhibiting free flow (ie, the material easily flows under its own weight under gravity), or These may be materials that do not exhibit free flow (ie, this material does not flow under its own weight under gravity). These materials (varies) vary, but typically include materials that do not exhibit free flow, such as unvulcanized rubber, uncrosslinked elastomers, tars, and the like.

Typical materials showing free flow include clays, silicates, calcium carbonate, diethyldithiocarbamate cadmium, tetramethylthiuram disulfide, benzothiazyl disulfide, substituted thioesters and amine antioxidants, aniline antiozone derivatives, diamines And / or sulfur, a thiourea curing agent selected from compounds and peroxides, a UV pigment selected from substituted benzotriazoles and substituted benzophenones, color pigments selected from iron oxides, titanium dioxide and organic salts, carbon black, Reinforcing pigments selected from zinc oxide and hydrated silicon compounds, processing aids such as silicon dioxide, pumice, stearate and rubber processing oils, such as crosslinked elastomers, unvulcanized rubber compound materials, ground tires, herbicides, sterilization and flesh Fungicides, chlorinated polyethylene (CPE), and the like. Free flowing materials effectively included in the package of the present invention include solids in addition to liquids.

In the rubber industry, a small amount of rubber processing oil is typically used (for example 0.5 to 10% by weight), which is mixed with at least one other formulation material. Not all of the materials that can be packaged using the novel package of the present invention are included in the above-listed materials, but are not limited thereto.

The package of the present invention relates to materials for packaging or packaging formulations, and to mixtures of them with additives such as rubber processing oil and the like. In the case of unvulcanized rubber, a film is usually attached around the rubber, and in particular in the case of packaging, the film is normally wrapped so that the rubber is tightly wrapped with the film and then the film is heat sealed to itself to complete the package. Attach under. It is preferable to heat seal this film in the molding of this package, but it is not necessary.

The product produced from this batch containing package changes depending on the type of material contained in this package. Some products include asphalt animal feed and wire. For example, in the packaging of crushed tires in asphalt production, the packaging of titanium dioxide in animal feed production, and the packaging of CPE in wire coating production, enumerated thereon using the batch containing package of the present invention. Put one specific ingredient. Other products include various kinds of rubber (for example, by packaging rubber or additives for rubber in the batch-containing film described herein). It is also possible to produce energy by packaging waste materials (e.g. heavy tar effluent or waste plastics) and placing the entire package in an incinerator. In addition, by packaging and reusing waste plastics and other materials, it is also possible to mold other valid products, such as garbage bags or park benches.

Built-in container for bag in box:

The interior container for a bag in box is formed from the film which consists of said ethylene-alpha-olefin copolymer (A) or ethylene-type copolymer composition (A '), (A "), (A'"). Although the thickness of the film which forms the interior container for a bag in box changes with specific content or a manufacturing method, it is 30-1000m normally, Preferably it is 50-700m.

The container wall of the inner container for the bag in box according to the present invention

(i) the blocking force is less than 1.0 g / cm,

(ii) the number of pinhole occurrences in an area of 20.5 cm X 28.0 cm after 2000 times of repeated twisting in the Gerbo flex tester is 2 or less;

(iii) It is preferable that it is made from the film of 90,000 times or more of the internal bending times measured according to JIS P-8115. Moreover, the film whose neck in at the time of shaping | molding is 20 cm or less on one side is preferable.

The inner container for a bag in box may be formed from the single layer film which consists of said ethylene-alpha-olefin copolymer (A) or ethylene-type copolymer composition (A '), (A "), (A'"). And other resins (nylon, ethylene-vinyl alcohol copolymers, polyvinyl alcohol (EVOH), adhesive resins) consisting of the above (A) or the above (A '), (A' ') and (A' '') It may be formed from what is called a multilayer film which laminated | stacked the film used, etc.).

The inner container for a bag-in box, for example, is almost cuboidal in shape, and has a lid at its upper end, and a thick heat-sealed portion exists at a position corresponding to the periphery when the cube is cut at an angle. In addition, the inner container for the bag-in box is formed so that one container half body can be folded and inserted so as to overlap with the other container half body.

The inner container for the bag-in box is filled with liquid, and stored or transported in a rigid outer container such as a corrugated fiberboard box, and the empty container is placed in one container half to the other container half. Fold to overlap and store or transport in the inserted shape.

As described above, when the inner container for the bag in box is folded, inflated to form a cube, or filled and transported with the contents solution, various forces are added to the corner portion of the inner container for the bag in box. Receive excessive stresses beyond the envelope, and pinholes are generated easily. Therefore, this interior container requires high pinhole resistance, flex resistance, blocking resistance, and the like. And the bag-in box interior container according to the present invention satisfies the required physical properties as described above.

The inner container for a bag in box can be manufactured by the following method, for example.

(i) Vacuum molding using a mold having a shape capable of extruding two pieces of molten resin into a sheet by a T-die arranged in parallel in the longitudinal direction, and joining the peripheral portions of opposite sides of the container. How to.

(ii) A method of extruding cylindrically molten resin from a circular die (parison extrusion) and blow molding using a mold as described above.

(iii) A method of overlapping two or more resin films to heat-sealing four sides to form an envelope (in this case, the film is the copolymer (A) or the composition (A '), (A' '), (A'). A single layer film made of '') may be used, and a film made of the copolymer (A) or the composition (A '), (A' '), or (A' '') and another resin (nylon, ethylene vinyl alcohol air) A so-called multilayer film in which a film made of a copolymer resin (EVOH), polyvinyl alcohol, an adhesive resin, etc.) is laminated may also be used.

Such a bag-in box is excellent in thermal stability, blocking resistance, pinhole resistance and bending resistance, and excellent in economy, and thus is widely used as a container for accommodating various liquids such as alcoholic beverages, vinegar, photographic developer, bleach, and disinfectant solution.

Medical Containers:

The medical container is an envelope made of a multilayer film, an envelope made of a single layer film, a bottle made of a single layer, or the like, and at least one layer of the multilayer film, a single layer film, a single layer bottle is the ethylene-α-olefin copolymer (A) or an ethylene-based copolymer. It is formed from the composition (A '), (A' '), (A' '').

The medical container can be manufactured by water-cooled or air-cooled inflation method, T-die method, dry lamination method, extrusion lamination method, blow molding method and the like. As the molding method of the medical bag, the inflation method and the co-extrusion T-die method are preferable from the viewpoint of hygiene and economy, and the blow molding method is preferable as the molding of the 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, more preferably 0.15 to 0.3 mm. If the thickness of the container is 0.05 mm or more, the impact resistance is also good and there is no problem in practical use.

Such a medical container does not lose transparency even after sterilization treatment, has excellent heat resistance, and does not cause wrinkles or deformation.

Heat resistant container:

The heat-resistant container is an envelope made of a multilayer film, an envelope made of a single layer film, a multilayer bottle, a single layer bottle, or the like, wherein the multilayer film is at least one layer, a single layer film, at least one layer of the multilayer bottle, and the single layer bottle is the ethylene-α-olefin air. It is formed from the copolymer (A) or the ethylenic copolymer composition (A '), (A' '), (A' '').

When the heat-resistant container is a multilayer, there is no restriction | limiting in particular about layers other than copolymer (A) or a composition (A '), (A "), (A'"), Polypropylene, nylon, polyester, poly Vinyl 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 blow molding method or the like.

In the case where the heat-resistant container is in the form of an envelope, the inflation method and the co-extrusion T-die method are preferable in terms of hygiene and economy, and when the heat-resistant container is in the form of a bottle, a blow 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, more preferably 0.15 to 0.3 mm. If the thickness of the container is 0.05 mm or more, the impact resistance is also good and there is no problem in practical use.

The heat resistant container of this invention is 30% or less of haze (ASTM D-1003-61) after heat sterilization process, Preferably it is 20 to 0%.

Moreover, the heat distortion start temperature of a heat resistant container is 115 degreeC or more, and the thickness of the container for retort foods is the range of 0.05-1.00 mm normally.

In addition, heat distortion start temperature is measured as follows. That is, a sample of a bag or a bottle made from a molded film was subjected to hot water sterilization at a sterilization temperature x 30 minutes in a small heat-resistant high-pressure steam sterilizer manufactured by Alps, and visually observed the sample taken out of the sterilizer, and the change thereof. Evaluate. Starting with a sterilization temperature of 110 ° C., the sterilization temperature is increased by 1 ° C. after each sterilization is completed. When this deformation | transformation is confirmed for the first time to the sample taken out from the sterilizer by repeating this operation, the sterilization temperature is made into a strain start temperature.

Such a heat-resistant container, for example, a retort food container, is excellent in heat resistance and impact resistance without losing transparency even when sterilized.

Elastic fiber:

Elastic fibers are fibers exhibiting a recovery rate of at least 50% at 100% torsion, and are ethylene-α-olefin copolymers (A) or ethylene-based copolymer compositions (A '), (A' '), (A' '') From.

Fibers are typically classified according to their diameter. Monofilament fibers are generally defined as individual fiber diameters of at least about 15 denier per filament, usually at least about 30 denier. Small fine denier fibers are generally applied to fibers having a diameter of less than about 15 denier per filament. Fibers of micro denier are generally defined as fibers less than 100 microns in diameter. Fibers can also be classified by methods of making them, for example monofilaments, continuous wound fine filaments, staple or short cut fibers, spun bonds and mel It can be classified into melt blown fibers and the like.

The melt index in the case of the ethylene-olefin copolymer (A) or the ethylene-based copolymer composition (A '), (A' '), (A' '') used in the production of the elastic fibers used in the present specification is In the case of monofilaments (typically 15 denier / filament or more fibers), generally 0.01 g / 10 min to 1000 g / 10 min, preferably 0.1 g / 10 min to 5 g / 10 min, and small denier fibers (diameter generally Fibrous fiber equal to or less than 15 denier / filament), preferably 5 g / 10 min to 250 g / 10 min.

The ethylene-α-olefin copolymer (A) or ethylene-based copolymer composition (A '), (A' ') and (A' '') used in the production of this elastic fiber are further improved fibers found by the present applicants. And additives such as antioxidants, phosphites, cling additives, antiblock additives, pigments, and the like, to the extent that they do not interfere with fabric properties.

Various homofil fiber can be manufactured using this ethylene-alpha-olefin copolymer (A) or ethylene-type copolymer composition (A '), (A "), (A'"). Homophile fibers are fibers that have a single region (domain) and do not have other polymer regions (such as those of bicomponent fibers). Such homofill 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 United States). And systems such as those disclosed in US Pat. No. 4,413,110 (Kavesh et al.). Staple fibers can be melt spun (ie they can be directly extruded to the final fiber diameter without the use of additional stretching) or they can be melt spun to produce fibers with large diameters and then conventional fiber stretching techniques It can be made into a desired diameter by heat-stretching or cold-stretching using it. The novel elastic staple fibers disclosed herein can also be used as bonding fibers, and in particular, the novel elastic fibers have a lower melting point than the matrix fibers surrounding them. In the use of bonding fibers, typically, the bonding fibers are blended together with other matrix fibers and then heated throughout the structure, where the bonding fibers are melted to join the surrounding matrix fibers. Typical matrix fibers that benefit from the use of these new elastic fibers include, but are not limited to, poly (ethylene terephthalate) fibers, cotton fibers, nylon fibers, polypropylene fibers, other non-uniformly branched polyethylene fibers, and Linear polyethylene homopolymer fibers and the like. The diameter of this matrix fiber can be varied depending on the end use application.

Surprisingly, the recovery rate exhibited by the molten spun fiber made from this ethylene-α-olefin copolymer (A) or ethylene-based copolymer composition (A '), (A' '), (A' '') is the diameter of the melt It is almost equal to the recovery rate which the fiber which melted and spun the fiber so that it may become 2 or 3 times the diameter of a spun fiber, cold-stretched the fiber, and made the diameter the same. Since elasticity here is not a result of the orientation which becomes invalid by heat processing, the product which has the ability to maintain its elastic performance even if it heat-exposes later is obtained.

In the case of the novel elastic fibers disclosed herein, the ethylene-α-olefin copolymer (A) or the ethylene-based copolymer composition (A '), (A) while surprisingly reducing the influence on the elasticity of the fibers. The melt index of ''), (A '' ') can be varied widely. This makes it possible to change the strength and shrinkage of the fiber and the fabric independently of its elasticity, thereby making it possible to increase the flexibility regarding the design of the fabric and the final product. For example, by varying the melt index of the polymer, not the diameter of the fiber, it is possible to change the shrinkage of the fiber (a lower melt index results in a higher shrinkage), thus allowing the fabric to have the elastic / strength performance required for the fabric. It becomes possible to make the optimization of the texture more favorable.

Moreover, it is also possible to manufacture a bicomponent fiber using this ethylene-alpha-olefin copolymer (A) or ethylene-type copolymer composition (A '), (A "), (A'"). Let at least one part of bicomponent fiber be this ethylene-alpha-olefin copolymer (A) or ethylene-type copolymer composition (A '), (A "), (A'"). For example, in the case of a shell / core bicomponent fiber (that is, a fiber in which the shell concentrically surrounds the core), this ethylene-α-olefin copolymer (A) or ethylene-based copolymer composition (A ' ), (A ''), (A '' ') can be present on either the shell or core. In addition, another ethylene-α-olefin copolymer (A) or an ethylene-based copolymer composition (A '), (A' '), or (A' '') may be used independently of the shell and core in the same fiber. In this case, both components preferably exhibit elasticity. In this case, in particular, the melting point of the shell component is lower than that of the core component. Other kinds of bicomponent fibers are likewise within the scope of the present invention, including side-by-side fibers (for example, fibers having individual polymer regions), wherein the ethylene-α-olefin air Structures such as coalescing (A) or ethylene-based copolymer compositions (A '), (A' '), (A' '') to make up at least a portion of the fiber surface).

The shape of this fiber is not limited. For example, typical fibers have a circular cross-sectional shape, but sometimes they have other shapes, such as trilobal or flat (ie, "ribbon") shapes. The elastic fibers disclosed herein are not limited by the fiber shape.

The diameter of the fiber can be measured and reported in various forms. Generally, the diameter of the fiber 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 generally apply to extruded strands having at least 15 denier per filament, usually at least 30. Small denier fibers are generally applied to fibers having a denier of about 15 or less. Micro denier (also known as micro fiber) is generally applied to fibers having a diameter of about 100 micrometers or less. In the case of the novel elastic fibers disclosed herein, the diameter can be varied widely with little effect on the elasticity of the fibers. However, the denier of this fiber can be adjusted to suit the function of the finished product, whereby preferably 0.5-30 denier / filament for melt blown, 1-30 denier / filament for spunbond, continuous winding filament In the case of 1 to 2,000 denier / filament.

Fabrics made from the new fibers include both woven paper and nonwovens. Nonwoven fabrics, including spun laced (or hydraulically entangled) fabrics, as disclosed in U.S. Patent No. 3,485,706 (Evans) and U.S. Patent No. 4,939,016 (Radwanski et al.) Lint the staple fibers with heat, or spunbond the fibers in one continuous operation, or melt blown the fibers and calender or heat the resulting web. It can be produced by producing a fabric by bonding. Nonwoven fabric manufacturing techniques of this kind are well known to those skilled in the art, and the present disclosure is not limited to any individual method. Other structures made from the fibers are also included within the scope of the present invention, including, for example, blends of this new fiber with other fibers (e.g., poly (ethylene terephthalate) (PET) or cotton, etc.) This includes.

As used in the claims of this specification, the term "consisting essentially of" refers to an ethylene-α-olefin copolymer (A) or an ethylene-based copolymer composition (A '), (A' 'used in the production of this fiber and fabric. ), (A '' ') may contain additional materials that do not substantially affect the elasticity of this fiber or fabric. Such non-limiting additive materials include, but are not limited to, pigments, antioxidants, stabilizers, surfactants (e.g., U.S. Patent 4,486,552 (Niemann), U.S. Patent 4,578,414 (Sawyer et al.) Or U.S. Patent 4,835,194 (Bright et al.). As is).

Articles of manufacture that can be made using the novel elastic fibers and fabrics disclosed herein include composite fabric products (eg diapers, etc.) where it is desired to have a portion that exhibits elasticity. For example, a portion showing elasticity is desired, such as a waistband portion of a diaper which prevents the diaper from flowing down, a legband portion which prevents leakage, and the like (as shown in US Pat. No. 4,381,781 (Sciaraffa)). This resilient portion often helps to better shape fit and / or fixation systems for a good combination of comfort and reliability. The novel elastic fibers and fabrics disclosed herein can be used and structures can be fabricated that combine elasticity and breathability.

The novel elastic fibers and fabrics disclosed herein can also be used in a variety of structures, as described in US Pat. No. 2,957,512 (Wade). For example, layer 50 of the structure described in US Pat. No. 2,957,512 (i.e., a component that exhibits elasticity) (particularly flattened, crimped, and creped here, a material that does not exhibit elasticity) Back elastic structure) can be replaced with this novel elastic fiber and fabric. By melt bonding or using adhesives, these new elastic fibers and / or fabrics may be attached to fibers, fabrics or other structures that do not exhibit elasticity. Using this new elastic fiber and / or fabric and a non-elastic component, the non-elastic component prior to attachment (as described in US Pat. No. 2,957,512) can be crimped and By gathering a component that exhibits elasticity in advance or heat shrinking a component that exhibits its elasticity after attachment, a gather or shearing elastic structure can be produced from them.

It is also possible to use the novel elastic fibers described herein in the spun laced (or hydraulically entangled) method to produce new structures. For example, the elastic sheet 12 disclosed in US Pat. No. 4,801,482 (Goggans) can be made using the novel elastic fibers / fabrics described herein herein.

As described herein, continuous filaments exhibiting elasticity can also be used for fabric applications where high resilience is desired.

In addition, the rigidity and shrinkage force of the novel elastic fibers and fabrics disclosed herein can be adjusted, and from this, if necessary, the shrinkage force in the garment as described in, for example, US Patent No. 5,196,000 (Clear et al.) The design can be flexible in terms of changes.

U.S. Pat. No. 5,037,416 (A11en et al.) Describes the advantages of shape conforming top sheets by using a ribbon that exhibits elasticity (see member 19 of U.S. Pat. No. 5,037,416). This novel elastic fiber can exert the function indicated by member 19 of U.S. Patent 5,037,416, or use it in the form of a fabric so that the desired elasticity is obtained.

Benefits are also obtained by using the novel elastic fibers disclosed herein also in composites in which linear polyethylene or copolymer polyethylene having very high molecular weights are used. For example, the novel elastic fibers have a low melting point (the melting point of this polymer and the density of this polymer are essentially linear), and as a result, as described in US Pat. No. 4,584,347 to Harpell et al. Likewise, in the case of a blend of ultra high molecular weight polyethylene fibers (e.g., Spectra® fiber manufactured by Allied Chemical) with the novel elastic fibers, the low melting point elastic fibers do not melt high molecular weight polyethylene fibers. The high molecular weight fibers are bonded to each other, thereby maintaining the high strength and integrity exhibited by the high molecular weight fibers.

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

This novel elastic fiber may be an elastic component of meltblown processing, as described by reference number 6 in the drawing of US Pat. No. 4,879,170 to Radwanski. This U.S. Patent No. 4,879,170 generally describes a co-molded material and a method of making that exhibit elasticity.

It is also possible to use the novel elastic fibers and fabrics disclosed herein and to make elastic panels, which are for example members 18, 20, 14 and / or 26 of US Patent 4,940,464 (Van Gompel). Etc. can be used. It is also possible to use the novel elastic fibers and fabrics described herein and to use them as elastic components of composite side panels (eg, layer 86 of US Pat. No. 4,940,464).

Foam molded body:

The foamed molded article can be molded into various shapes including rods, tubes, tapes, sheets, and the like, and is used as a buffer, a heat insulating material, a foaming agent base, and the like.

The foamed molded article is a mixture of the above-mentioned ethylene-α-olefin copolymer (A) or ethylene-based copolymer composition (A '), (A' '), (A' '') and a blowing agent, and heated or reduced pressure It manufactures by making a bubble in a resin molding by foaming gasification or decomposition gas.

As a manufacturing method of a foamed molded object, the following manufacturing method is mentioned, for example.

(1) extrusion foaming method

The ethylene-α-olefin copolymer (A) or the ethylene-based copolymer composition (A '), (A' ') and (A' '') are put into a hopper of an extruder and extruded at a temperature near the melting point of the resin. At the time, the foam is continuously obtained by press-fitting a physical type foaming agent from the press hole provided in the middle of an extruder, and extruding from the mouthpiece of a desired shape. Examples of the physical blowing agent include volatile blowing agents such as freon, butane, pentane, hexane, and cyclohexane, and inorganic gas blowing agents such as nitrogen, air, water, and carbon dioxide. In addition, at the time of extrusion foaming, bubble nucleating agents such as calcium carbonate, talc, clay and magnesium oxide may be added.

The blending ratio of the physical blowing agent is usually 5 to 60 parts by weight, preferably 10 to 10 parts by weight of the copolymer (A) or the composition (A '), (A' '), (A' ''). 50 parts by weight. If the blending ratio of the physical foaming agent is too small, the foamability of the foam decreases, and if too large, the strength of the foam lowers.

(2) organic series decomposition type blowing agents such as the ethylene-α-olefin copolymer (A) or the ethylene-based copolymer composition (A '), (A' '), (A' '') and azodicarbonamide; And melt-kneading other additives and thermoplastic resins at a temperature below the decomposition temperature of the thermally decomposable blowing agent using a kneading apparatus such as a single screw extruder, a twin screw extruder, a Banbury mixer, a kneader mixer, a roll, or the like, if desired. And forming the sheet in a generally sheet form, and then heating the sheet above the decomposition temperature of the blowing agent to foam.

The blending ratio of the organic pyrolytic blowing agent is usually 1 to 50 parts by weight, preferably 4 to 100 parts by weight of the copolymer (A) or the composition (A '), (A' '), (A' ''). It is -25 weight part. If the blending ratio of the organic pyrolytic foaming agent is too small, the foamability of the foam decreases, and if too large, the strength of the foam decreases.

(3) Foaming method in pressure vessel

The ethylene-α-olefin copolymer (A) or ethylene-based copolymer composition (A '), (A' '), (A' '') is molded into a sheet or block shape by a press or an extruder. And then, injecting the molded body into a pressure vessel, sufficiently melting the physical foaming agent in the resin, and then obtaining a foam by reducing the pressure. Moreover, it is also possible to pressurize while filling the said molded object with a physical blowing agent at normal temperature, and to take out after pressure reduction, and to heat and foam in an oil bath, an oven, etc.

Moreover, when the said ethylene-alpha-olefin copolymer (A) or ethylene-type copolymer composition (A '), (A "), and (A'") are bridge | crosslinked previously, a crosslinked foam can be obtained.

Generally, as the crosslinking method, there can be exemplified a method of thermally decomposing and crosslinking a peroxide radical generator mixed in a resin, crosslinking by ionizing radiation, crosslinking by ionizing radiation in the presence of a polyfunctional monomer, and silane crosslinking. have.

In order to obtain a crosslinked foam by such a method, the copolymer (A) or the composition (A '), (A' '), (A' ''), an organic pyrolytic foaming agent, a polyfunctional monomer and other compounding agents as a crosslinking aid Is melt kneaded at a temperature below the decomposition temperature of the thermal decomposition foaming agent to form a sheet. After quantitatively irradiating the ionizing radiation to the obtained foamable resin composition sheet and crosslinking the copolymer (A) or the composition (A '), (A' '), (A' ''), the crosslinked sheet was subjected to the decomposition temperature of the blowing agent or higher. Heated to foam. Examples of the ionizing radiation include alpha rays, rays, gamma rays, and electron beams. Moreover, peroxide bridge | crosslinking and silane bridge | crosslinking can be performed instead of irradiation bridge | crosslinking by ionizing radiation.

In the present invention, a weathering stabilizer, a heat stabilizer, an anti-slip agent, and an anti-blocking agent within the range of not impairing the object of the present invention in the copolymer (A) or the composition (A '), (A' '), (A' ''). Additives such as antifogging agents, lubricants, pigments, dyes, nucleating agents, plasticizers, anti-aging agents, hydrochloric acid absorbers and antioxidants may be blended as necessary. In addition, small amounts of other polymers can be blended without departing from the spirit of the present invention.

Such foams are excellent in flexibility and toughness.

Foam structure:

The foam structure is made of an ethylene-α-olefin copolymer (A) or an ethylene-based copolymer composition (A '), (A' '), (A' ''). Using a blend of ethylene-α-olefin copolymers (A) or ethylene-based copolymer compositions (A '), (A' '), (A' '') and other suitable ethylene-based polymers or other natural or synthetic polymers It is also possible. Suitable other ethylene-based polymers include low density polyethylene (LDPE), medium density polyethylene (MDPE) and high density polyethylene (HDPE) (eg, prepared using Ziegler catalysts as described in US Pat. No. 4,076,698), ethylene / Vinyl acetate copolymers, copolymers of ethylene and ethylenically unsaturated carboxylic acids,? -Olefins alone and copolymers. Other suitable polymers include polystyrene (including impact resistant polystyrene), styrene-butadiene block copolymers, polyisoprene and other rubbers. Preference is given to blends comprising a high melting point resin in the major proportions. The copolymer (A) or composition (A '), (A' '), (A' '') or a blend containing these for producing a foam structure is referred to as an ethylene polymer material.

Regardless of the composition, the ethylene-based polymer material preferably comprises at least 50% by weight, more preferably at least 70% by weight of ethylene monomer units. The ethylene polymer material may be entirely or wholly from the ethylene monomer. Preferred blends are ethylene-olefin copolymers (A) or ethylene-based copolymer compositions (A '), (A' '), (A' '') and other conventional ethylene-based polymers such as LDPE, HDPE , Ethylene / acrylic acid copolymer (EAA) and LLDPE.

Additives such as antioxidants (e.g., hindered phenols (Irganox® 1010), phosphites (e.g. Irgafos® 168), pigments, to the extent that they do not interfere with the improved properties found by the applicant) It may be contained in an ethylene-alpha-olefin copolymer (A) or an ethylene-type copolymer composition (A '), (A "), (A'").

The teaching of how to manufacture a foam structure and how to process it is described in C.P. Park's "Polyolefin Foam" is described in Handbook of Polymer Foams and Technology, Hanser Publishers, Munich, Viena, New York, Barcelona (1991), edited by D. Klempner and K.C. Frisch in Chapter 9.

This foam structure can be produced by a conventional extrusion foaming method. This structure is generally extruded by heating an ethylene-based polymer material to form a plasticized or molten polymer material, placing a blowing agent therein to form a foamable gel, and passing the gel through a die to form a foam product. It can manufacture by doing. Prior to mixing with the blowing agent, the polymeric material is heated to its glass transition temperature or above its melting point. The blowing agent may be added or mixed into the molten polymer material by any means of the prior art such as extruders, mixers, blenders. The blowing agent inhibits substantial foaming of the molten polymer material and mixes with the molten polymer material at a high pressure sufficient to disperse the blowing agent approximately homogeneously. If desired, the nucleating agent may be blended into the polymer melt or dry mixed with the polymer material prior to plasticization or melting. Effervescent gels are typically cooled to lower temperatures in order to optimize the properties of the foam structure. The gel is then extruded or transported through a die of the desired shape to a region of reduced or lower pressure to form a foam structure. The region of lower pressure is a pressure lower than the pressure maintained before the expandable gel is extruded through the die. The lower pressure may be above or below atmospheric pressure (vacuum), but is preferably at atmospheric pressure.

This structure may be processed in the form of agglomerated strands by extrusion of the ethylene-based polymer material through a multi-orifice die. Contact between the adjacent streams of the molten extrudate occurs between foaming processes, and the orifices are arranged such that the surfaces in contact with each other have sufficient adhesion to adhere to one another. The stream of molten extrudate from the die takes the form of strands or profiles, which preferably foam, agglomerate, and adhere to each other to form an integral structure. Preferably, the individual strands or profiles which have been agglomerated should be as they are attached in an integral structure so as not to peel off the strands at the stresses given in forming, shaping and using the foam. Methods and apparatus for producing foam structures in the form of aggregated strands are described in US Pat. Nos. 3,573,152 and 4,824,720.

This foam structure may also be formed by a cumulative extrusion method, as shown in US Patent No. 4,323,528. In this method, a low density foam structure having a large lateral cross-sectional area is obtained by 1) forming a gel of ethylene-based polymeric material and blowing agent under pressure, where the viscosity of the gel is at a temperature sufficient to maintain the blowing agent when the gel foams. 2) extruding the gel into a holding zone maintained at a temperature and pressure that does not foam the gel, wherein the holding zone opens an orifice opening to a lower pressure zone that foams the gel. Having an openable gate closing the surrounding outlet die and the die orifice, 3) periodically opening the gel, 4) applying mechanical pressure substantially simultaneously by holding a movable ram on the gel and holding it Passing a die orifice from the zone and releasing it to a lower pressure zone, where substantial foaming occurs in the die orifice The release takes place at a high rate and also at a rate lower than that in which substantial irregularities in the cross-sectional area or shape occur, and 5) foaming the released gel unconstrained in at least one direction so that a foam structure is produced. Manufacture by.

The foam structure can be processed into uncrosslinked foam beads suitable for shaping the product. To prepare foam beads, discrete resin particles, such as granular resin pellets, are suspended in a liquid medium in which the resin, such as water, is substantially insoluble; Impregnated with the blowing agent by introducing the blowing agent into the liquid medium at high temperature and high pressure in an autoclave or other pressure vessel; In order to form foam beads, they are rapidly discharged into the atmosphere or a reduced pressure zone. This method is fully taught in US Pat. Nos. 4,379,859 and 4,464,484.

As a derivative of the method, prior to impregnation of the blowing agent, the styrene monomer may be impregnated in the suspended pellets to form a graft copolymer with the ethylene-based polymeric material. Polyethylene / polystyrene copolymer beads are cooled and discharged from the container without substantially foaming. The beads are then foamed and molded by conventional foamed polystyrene bead molding methods. Methods of making polyethylene / polystyrene copolymer beads are described in US Pat. No. 4,168,353. The foam beads may then be molded by any means known in the art, for example steam, to agglomerate and fuse the beads to load the foam beads into a mold and form a product, for example steam The beads are formed by heating the beads. If desired, the beads may be impregnated with air or other blowing agent at high temperature and high pressure prior to loading the mold. The beads can also be heated before loading. Foam beads can then be molded into blocks or shaped articles by appropriate molding methods known in the art (some methods are described in US Pat. Nos. 3,504,068 and 3,953,558). Teachings of the above methods and molding methods are described in p191, p197-198 and p227-229, in the above publications of C.P.Park.

Blowing agents useful in the production of this foam structure include inorganic blowing agents, organic blowing agents and degradable chemical blowing agents. Suitable inorganic foaming agents include carbon dioxide, nitrogen, argon, water, air, nitrogen and helium. Organic blowing agents include aliphatic hydrocarbons having 1 to 6 carbon atoms, aliphatic alcohols having 1 to 3 carbon atoms, and fully or partially halogenated aliphatic hydrocarbons having 1 to 4 carbon atoms. Aliphatic hydrocarbons include methane, ethane, propane, n-butane, isobutane, n-pentane, isopentane and neopentane. Aliphatic alcohols include methanol, ethanol, n-propanol and isopropanol. Fully or partially halogenated aliphatic hydrocarbons include fluorocarbons, chlorocarbons, and chlorofluorocarbons. Examples of fluorocarbons include methyl fluoride, perfluoromethane, ethyl fluoride, 1,1-difluoroethane (HFC-143a), 1,1,1-trifluoroethane (HFC-143a), 1,1 , 1,2-tetrafluoroethane, 2,2-difluoropropane, 1,1,1-trifluoropropane, perfluoropropane, dichloropropane, difluoropropane, perfluorobutane, perfluoro Rocyclobutane. Partially halogenated chlorocarbons and chlorofluorocarbons used in the present invention include 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-tetrafluoroethane (HCFC-124). Fully halogenated chlorofluorocarbons include trichloromonofluoromethane (CFC-11), dichlorodifluoromethane (CFC-12), trichlorotrifluoroethane (CFC-113), 1,1,1-trifluoro Roethane, pentafluoroethane, dichlorotetrafluoroethane (CFC-114), chloroheptafluoropropane and dichlorohexafluoropropane. Chemical blowing agents include azodicarbonamide, azodiisobutyronitrile, benzenesulfonhydrazide, 4,4-oxybenzenesulfonyl semicarbazide, p-toluenesulfonyl semicarbazide, azodicarboxylic acid barium, N, N'-dimethyl-dinitrosoterephthalamide and trihydrazinotriazines. Preferred blowing agents include isobutane, HFC-152a and mixtures thereof.

The amount of blowing agent in the polymer melt material to prepare the foam forming gel is 0.2-5.0 gram mol / kg polymer, preferably 0.5-3.0 gram mol / kg polymer, most preferably 1.0-2.50 gram mol / kg Polymer.

Various additives such as stability control agents, nucleating agents, inorganic fillers, pigments, antioxidants, acid removers, ultraviolet absorbers, flame retardants, processing aids and extrusion aids may be incorporated into this foam structure.

A stability control agent may be added to this foam structure to improve dimensional stability. Preferred stability control agents include amides and esters of C ₁₀ -C ₂₄ fatty acids. Such stability control agents are described in US Pat. Nos. 3,644,230 and 4,214,054. 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. Preferred foams recover to at least 80% of the initial volume, which is measured 30 seconds after foam foaming. Volume is measured by appropriate methods such as volume exclusion of water.

In addition, a nucleating agent may be added in order to control the size of the foam of the foam. Preferred nucleating agents include inorganic substances 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 is in the range of 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 comprising this foam structure is substantially not crosslinked. The foam structure comprises up to 5% gel by the method (A) of ASTMD-2765-84. Some crosslinking that occurs naturally without the use of crosslinkers or radiation is acceptable.

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

The foam structure may take on all kinds of physical shapes known in the art such as extruded sheets, rods, thick plates and release materials. The foam structure may be formed by molding the expandable beads in any or any of the above shapes.

This foam structure may be an independent bubble or a continuous bubble. Preferably this foam comprises at least 80% free bubbles by ASTM D2856-A.

Such stronger and at the same time more elastic foam structures are very useful for sports and leisure applications and cushion packaging applications.

Foam structure:

The foamed structure is made from an ethylene-α-olefin copolymer (A) or an ethylene-based copolymer composition (A '), (A' '), (A' ''), and is strong, elastic and low density. In addition, the structures of the present invention are more thermally stable than EVA foam structures and do not produce unpleasant odors during foam expansion, manufacture and use. Soft and strong crosslinked foam structures are useful in sporting goods, medical devices and cushioning goods.

When forming the foam structure, the ethylene-α-olefin copolymer (A) or the ethylene-based copolymer composition (A '), (A' '), (A' '') and other preferred ethylene-based polymers or other natural or It is also possible to use blends with synthetic polymers. Preferred other ethylene-based polymers include low density polyethylene (LDPE) (eg, high pressure, free radical polymerization technology), medium density polyethylene (MDPE), and high density polyethylene (HDPE) (eg, as described in US Pat. No. 4,076,698). Homopolymers and copolymers such as those prepared using the same Ziegler catalyst), ethylene / ester copolymers, ethylene / vinylacetate copolymers, copolymers of ethylene and ethylenically unsaturated carboxylic acids, and α-ethylenic materials. have. Other preferred polymers include polystyrene (including high impact polystyrene), styrene-butadiene block copolymers, polyisoprene, and other rubbers. Preference is given to blends comprising a high melting point resin in major proportions. Regardless of the composition, the ethylenic polymer material preferably comprises at least 50% by weight, more preferably at least 70% by weight of ethylenic monomer units. The ethylenic polymer material may be entirely composed of ethylenic monomer units. Preferred blends are the ethylene-α-olefin copolymers (A) or ethylene-based copolymer compositions (A '), (A' '), (A' '') and other conventional ethylene-based polymers such as LDPE, HDPE , Ethylene / acrylic acid copolymer (EAA), and blends with LLDPE.

The foam structure of the present invention may have any physical shape known in the art, such as the shape of a sheet, flank, or burn stock. Other useful foams are expandable or expandable particles, formable expandable particles, or beads, and articles produced by expansion and / or coalescence and welding of these beads.

Teachings on the preparation of foam structures and how to treat them are described in C.P. This is described in Park's 9th edition of Polyolefin Foam, Handbook of Polymer Foams and Technology, Munich, Vienna, New York, Barcelona (1991), D. Klempner and K. C. Frisch.

The foam structure of the present invention blends the ethylene-α-olefin copolymer (A) or ethylene-based copolymer composition (A '), (A' '), (A' '') with a decomposable chemical blowing agent and heats the foaming property. By making a plasticized or molten polymer material, extruding this expandable molten polymer material from a die, including a crosslinking agent in the molten polymer material, exposing the molten polymer material to elevated temperatures to release the blowing agent to create a foam structure Manufacture. Polymeric materials and chemical blowing agents can be mixed and melt blended by means known in the art, such as extruders, mixers, or blenders. Chemical blowing agents are preferably dry blended with the polymeric material prior to heating the polymeric material to make it meltable, but may be added when the polymeric material is in the molten phase. Crosslinking can be brought about by the addition of a crosslinking agent or by radiation. The exposure to elevated temperatures for causing crosslinking and for expanding or foaming can be simultaneously or sequentially. When using a crosslinking agent, it is formulated into a polymeric material like a chemical blowing agent. In addition, when a crosslinking agent is used, the expandable polymer molten material is preferably heated or exposed to a temperature of less than 150 ° C. to prevent degradation of the crosslinking agent or blowing agent and to prevent premature crosslinking. When using radiation crosslinking, the foamable polymeric material is preferably heated or exposed to temperatures below 160 ° C. to prevent degradation of the blowing agent. The foamable molten polymer material is extruded through a die of the desired shape to produce a foam structure. This expandable structure is then expanded by crosslinking at high temperatures such as an oven (typically 150 ° C. to 250 ° C.). When using spin crosslinking, the foam structure is irradiated to crosslink the polymer, which is then expanded at the above elevated temperatures. The structure of the present invention can advantageously be formed into a sheet or lamina by the above method using either a crosslinking agent or spinning.

The foamed structure of the present invention can be made into a continuous thin plate structure by an extrusion method using a die of long land as described in GB 2,145,961A. In this process, a polymer, a degradable blowing agent and a crosslinking agent are mixed in an extruder, the mixture is heated to crosslink the polymer, and the blowing agent is foamed in a die of long land; Pass through the die to form a foam structure. Contact between the foam structure and the die is lubricated with a suitable lubricant.

The foamed structure of the present invention may also be a crosslinked foamed beads that are suitable for article molding. In order to make foamed beads, individual resin particles such as granular resin pellets are suspended in substantially insoluble liquids such as water; Impregnating the crosslinker and blowing agent at elevated pressure and temperature in an autoclave or other pressure vessel; Release to atmospheric pressure or reduced pressure region to form foam beads. The polymer beads are impregnated with a blowing agent, cooled, released from the vessel, and then expanded by heating or steam. In the above method, the styrene monomer may be impregnated in the suspension pellet together with the crosslinking agent to form a graft copolymer comprising an ethylenic polymer material. The blowing agent may be impregnated with the resin pellets in the suspended or non-aqueous state. The expandable beads are then expanded by steam heating, molded by conventional methods to form expandable polystyrene foam beads.

The foam beads can be molded by means known in the art. For example, foamed beads are filled into a mold, the mold is compressed to compress the beads, and the beads are heated by, for example, steam, to fuse and weld the beads to make an article. Optionally, the beads may be preheated with air or other blowing agent prior to filling the mold. Teachings to the above methods and molding methods are pp227-233 of the above publication by C.P.Park; US Patent No. 3,886,100; US Patent No. 3,959, 189; US 4,168,353 and US 4,429,059. Foam beads can also be prepared by preparing a mixture of a polymer with a crosslinking agent and a degradable mixture in a suitable mixing apparatus or extruder, molding the mixture into pellets, heating the pellets to crosslink and swell.

There is another method of making crosslinked foam beads, which is desirable for molding into articles. The ethylene polymer material is melted and mixed with the physical blowing agent in a conventional foam extrusion apparatus to create a substantially continuous foam strand. The foamed strand is granulated or pelletized to form foamed beads. This foam beads are then crosslinked by spinning. The crosslinked foam beads are then coalesced and molded, and various articles are made as described above for the other foam beads method. Further teachings on this method are described in US Pat. Nos. 3,616,365 and pp. 224-228 of C.P.Park et al., Supra.

The foamed structure of the present invention can be produced in burr stock shapes by two different methods. One method involves the use of a crosslinker and the other method uses spinning.

The foam structure of the present invention is a slab by mixing the ethylene-α-olefin copolymer (A) or ethylene-based copolymer composition (A '), (A' '), (A' ''), a crosslinking agent and a chemical blowing agent The mixture may be heated in a mold to enable the crosslinker to crosslink the polymer material and to decompose the blowing agent and to be bourne-stock shaped by expanding by release of pressure in the mold. Optionally, the burr stock produced upon release of pressure can be reheated to effect further expansion.

The crosslinked polymer sheet can be made by irradiation of a polymer sheet with a high energy beam or by heating a polymer sheet comprising a chemical crosslinking agent. The crosslinked 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 nucleation and slight expansion of the bubbles 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 manufacture of the foam structures of the present invention include degradable chemical blowing agents. These chemical blowing agents decompose at high temperatures to produce gases or vapors, causing the polymer to swell into a foam form. This chemical blowing agent preferably takes the form of a solid so that it can be easily dry blended with the polymeric material. Azodicarbonamide, azodiisobutyronitrile, benzenesulfohydrazide, 4,4-oxybenzenesulfonyl semicarbazide, p-toluenesulfonyl semicarbazide, barium azodicarboxylate as chemical blowing agents , N, N'-dimethyl-N, N'-dinitrosoterephthalamide, N, N'-dinitrosopentamethylenetetramine, 4,4-oxybis (benzenesulfonylhydrazide), and trihydr Lazinotriazines are mentioned, Azodicarbonamide is preferable. Further teaching on chemical blowing agents is in the above publications pp205-208 by CPPark, and "Polyolefin Foam" Handbook of Polymer Foams and Technology by FAShutob, pp 382-402, by D.Klempner and KCFrisch, Hanser Publishers, Munich, Vienna , New York, Barcelona (1991).

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

Crosslinking agents useful for preparing the foam structures of the present invention are organic peroxides. Useful organic peroxide crosslinkers as 1,1-di-t-butylperoxy-3,3,5-trimethylcyclohexane; Dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane; 1-butylcumyl peroxide, '-di (butylperoxy) diisopropylbenzene, di-t-butylperoxide and 2,5-dimethyl-2,5-di- (t-butylperoxy) hexane Can be mentioned. Dicumyl peroxide is preferred. Further teachings on organic peroxide crosslinkers are described in the above publications pp198-204 to C.P.Park.

Crosslinking by radiation can be carried out by any conventional type. Useful types of radiation include electron beams or beta rays, gamma rays, X rays, or Neutron rays. Spinning performs crosslinking by generating polymer groups, and it is believed that these groups gather and crosslink. Further teaching regarding radiation crosslinking is described in C.P. Park, above publications pp. 198-204.

In some methods of making the foam structures of the present invention, physical blowing agents can be used. Examples of physical blowing agents include organic and inorganic reagents. Preferred inorganic blowing agents include carbon dioxide, nitrogen, argon, water, air and helium. Examples of the organic blowing agent 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. Examples of the aliphatic hydrocarbons include methane, ethane, propane, n-butane, isobutane, n-pentane, isopentane and neopentane. Examples of the aliphatic alcohols include methanol, ethanol, n-propanol and isopropanol. Fully 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 , 1,2,1-tetrafluoroethane (HFC-134a), pentafluoroethane, difluoromethane, perfluoroethane, 2,2-difluoropropane, 1,1,1-trifluoro Propane, perfluoropropane, dichloropropane, difluoropropane, perfluorobutane, perfluorocyclobutane. Partially halogenated chlorocarbons and chlorofluorocarbons used in the present invention include 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-tetraflouroethane (HCFC-124). Trichloromonofluoromethane (CFC-11), dichlorodifluoromethane (CFC-12), trichlorotrifluoroethane (CFC-113), 1,1,1-trifluoro as fully halogenated chlorofluorocarbons Ethane, pentafluoroethane, dichlorotetrafluoroethane (CFC-114), chloroheptafluoropropane and dichlorohexafluoropropane.

The amount of blowing agent to be blended into the polymer melt to make an expandable polymer gel is 0.2-5.0, preferably 0.5-3.0, most preferably 1.0-2.50 mol / kg polymer.

The foam structure of the present invention has a crosslink density of 5 to 90%, more preferably 30 to 70% as measured by ASTM D-2765-84, Method A.

The foam 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 foam structure has an average pore diameter of 0.05-5.0, more preferably 1.0-2.0, most preferably 0.2-1.0 mm as measured by ASTM D 3576.

The foam structure of the present invention may be a closed bubble or an open bubble. Preferably, the foam structure of the present invention is at least 90% closed air bubbles as measured by ASTM D 2856-A.

In addition, various additives may be blended into the foam structure of the present invention. Such additives are, for example, inorganic fillers, stability control agents, nucleating agents, colorants, antioxidants, acid removers, ultraviolet absorbers, flame retardants, processing aids and extrusion aids.

Gasket:

The gasket is made from an ethylene-α-olefin copolymer (A) or an ethylene copolymer composition (A '), (A' '), (A' ''). This gasket has the ability to compressively seal various containers without contaminating the contents. The use of the novel gasket material disclosed herein benefits in particular for containers for liquids.

Some gaskets need to withstand temperatures higher than room temperature (about 25 ° C.) for a short time, especially when the use is for “hot fill” applications. For example, in the case of products which need to be sterilized, it is necessary to attach a gasket having a melting point of 100 ° C or higher. Therefore, the polymer suitable for the application can be specifically selected through selecting a density suitable for use in the environment of the gasket.

In addition, according to the required end use characteristics, the gasket can be similarly prepared by combining other polymers with an effective amount of the copolymer (A) or the composition (A '), (A' '), (A' ''). have. These other polymers are thermoplastic polymers (i.e. melt processable), which include polymers such as highly branched low density polyethylene, heterogeneously branched linear low density polyethylene, ethylene / vinyl acetate copolymers and ethylene / acrylic acid copolymers, and the like. Included.

Gaskets prepared from this copolymer (A) or compositions (A '), (A' '), (A' '') should have a hardness sufficient to withstand compression, but nevertheless to form a suitable seal Make sure you have enough softness. Therefore, various gaskets can be manufactured by having this polymer have the hardness according to use. In this specification, hardness is measured as "Shore A hardness" or "Shore D hardness" (measured using ASTM D-2240). The range of Shore A hardness in the case of the ethylene-alpha-olefin copolymer (A) or ethylene-based copolymer composition (A '), (A "), and (A'") which comprises a gasket is obtained from a polymer and It is the range of 70-100 even when the petroleum oil normally added for the purpose of reducing the hardness of a gasket is not used.

In addition, to the ethylene-α-olefin copolymer (A) or ethylene-based copolymer composition (A '), (A' '), (A' ''), to the extent that it does not interfere with the improved properties found by the present applicants, It may also contain additives such as antioxidants, phosphites, cling additives (eg PIB), slip additives (eg erucamide), antiblock additives and pigments, etc. It is possible.

Gaskets can take many different forms, including "o-rings" and flat seals (e.g., "film-like" gaskets having a thickness corresponding to the intended use).

Suitable end use includes beverage cap liners, hot fill juice cap liners, polypropylene cap liners, metal cap liners, high density polyethylene cap liners, gaskets for window glass, sealed containers, sealing caps , Gaskets for medical devices, filter elements, gaskets for pressure exhaust, hot melt gaskets, easy twistoff caps, gaskets for electrochemical cells, gaskets for refrigerators, gaskets for galvanic cells, leak proof cells gasket for waterproof cell, waterproof sheet, reusable gasket, synthetic cork type material, thin cell membrane separator, magnetic rubber material, disc gasket for alcoholic beverage bottle cap, freezing sealing ring, gasket for plastic molding, expansion Joints and water stops, corrosion resistant conduit joints, soft magnetic plastic, pipe joint seals, integral weatherproof plastic lids and hinges for electrical output, rulers Magnetic faced foamed articles, ego rings, soft gaskets, glass seals, mischievous ring liners, pressure applicators, bottle caps and straws Structure, large seasoning bottle liner, apple sauce or metal cap for salsa ego, ego for home can, crown.

The gasket made from this ethylene-α-olefin copolymer (A) or ethylene-based copolymer composition (A '), (A' '), (A' '') has a number of advantages, especially when used in food applications. Have These advantages include improved taste and odor compared to polymer gaskets currently used, such as ethylene / vinyl acetate, and low adhesion to polar substrates (e.g. polyethylene terephthalate, glass, etc.). Effective for lowering torque when capped), small amounts of extracts (which are also particularly effective in foods in relation to compliance with regulations), nonpolar substrates (e.g. polypropylene and high density polyethylene (linear homopolymers) Good adhesion to phosphorus polyethylene or linear heterogeneous high density polyethylene, etc., sufficient barrier property against oxygen, carbon dioxide and water, and higher melting point compared to polymers currently used (e.g. ethylene / vinyl acetate). Thing, good stress cracking resistance, good chemical resistance, changeable hardness (in specific packaging Are included depending on the degree and the internal pressure of the vessel of torque required to seal the container, it is effective in that there may be increasing the hardness of the gasket agent, or to be low).

Various gasket manufacturing techniques include US Pat. No. 5,215,587 (McConnellogue et al.); U.S. Patent 4,085,186 to Rainer; U.S. Patent 4,619,848 to Kinght et al .; U.S. Patent 5,104,710 to Kinght; U.S. Patent 4,981,231 to Kinght; U.S. Patent 4,717,034 to Mumford; US Patent No. 3,786,954 (Shull); US Patent No. 3,779,965 to Lefforge et al .; U.S. Patent 3,493,453 (Ceresa et al.): U.S. Patent 3,183,144 to Caviglia; US Patent No. 3,300,072 to Caviglia; U.S. Patent 4,984,703 to Burzynski; US Patent No. 3,414,938 to Caviglia; U.S. Patent 4,939,859 to Bayer; U.S. Patent No. 5,137,164 to Bayer; And US Pat. No. 5,000,992 to Kelch. Included are techniques disclosed in.

The gasket claimed in this specification also uses conventional techniques, using an extruded sheet or film, such as a blown film, cast film, or an extrusion coated film, and then punching the gasket from this sheet or film, Or it can manufacture by cutting. Multilayer film structures are also suitable for use in the manufacture of the gaskets disclosed herein, although the ethylene-α-olefin copolymer (A) is provided in at least one layer (preferably an inner layer located adjacent to the product). Or an ethylenic copolymer composition (A '), (A' '), (A' ''). Foam multi-layer gaskets containing this ethylene-α-olefin copolymer (A) or ethylene-based copolymer composition (A '), (A' ') and (A' '') are also useful in the present invention.

Extrusion workpiece:

Extruded articles include extrusio coated articles, products in the form of extrusion profiles, and extrusion cast films, which are ethylene-α-olefin copolymers (A) or ethylene-based aerials. It is from a coalescing composition (A '), (A "), (A'").

Moreover, it is also possible to blend an ethylene-alpha-olefin copolymer (A) or an ethylene-type copolymer composition (A '), (A "), (A'") with another polymer material, using this, Single or multi-layered products can be produced, and structures, such as sealants, adhesives or bonding layers, can be produced. To the ethylene-α-olefin copolymer (A) or ethylene-based copolymer composition (A '), (A' '), (A' '') for the purpose of modifying workability, film strength, heat sealability or adhesiveness. It is also possible to blend other polymer materials.

In addition, the ethylene-α-olefin copolymer (A) or the ethylene-based copolymer composition (A '), (A' '), (A' '') can be used in chemical and / or physical modification forms. Such modification may be achieved by any known technique, and can be achieved, for example, by ionomerization and extrusion grafting.

In the present specification, "drawdown" is defined by meaning stretching or stretching a molten polymer extrudate (web or filament) in the machine direction and sometimes (but at the same time but in the transverse direction). .

In this specification, a "neck in" is defined as the difference between the die width and the width of the extruded workpiece or the final width of the manufactured product at the takeoff position, which defines the expansion and the low degree of influence of the surface tension of the extruded workpiece. Receive. The measured neck-in value (which can be placed at a constant output) is either constant or lowered even with a high drawdown rate, and in the case of normal ethylene polymers, the neck-in value is generally due to low molecular weight or narrow molecular weight distribution. It is well known to be high.

In addition, in the ethylene-α-olefin copolymer (A) or the ethylene-based copolymer composition (A '), (A' '), (A' ''), the high draw down and substantially lowered by the present applicants To the extent that neckin is not impaired, additives such as antioxidants, phosphites, cling additives (eg PIB, etc.), Standostab PEPQ (trademark), pigments, colorants and fillers, etc. It is also possible to contain it. Ethylene-α-olefin copolymer (A) or ethylene-based copolymer composition (A '), (A' '), (A' ''), and also to improve antiblocking and friction coefficient characteristics Additives (including, but not limited to, untreated and treated silicon dioxide, talc, calcium carbonate and clay, as well as primary, secondary and substituted fatty acid amides), release rolls for cold rolls, silicone coating materials, etc. It is also possible to contain it. It is also possible to add other additives, for example to improve the anti-fogging properties of the transparent cast film, as described, for example, in Niemann in US Pat. No. 4,486,552. Other additives, such as quaternary ammonium compounds, which enhance the antistatic properties of the coatings, profiles and films of the present invention, for example, enable packaging or manufacturing of electronic sensitive products, alone or ethylene acrylic acid (EAA ) It is also possible to add in combination with copolymers or other functional polymers.

The multilayer structure including the ethylene-α-olefin copolymer (A) or the ethylene-based copolymer composition (A '), (A' '), (A' '') may be produced by any known means, and such means Extrusions, laminations and combinations thereof are included. In addition, the ethylene-α-olefin copolymer (A) or the ethylene-based copolymer composition (A '), (A' '), (A' '') can also be used in coextrusion processing operation, in which case a higher By using a material showing a drawdown, at least one material showing a lower drawdown is essentially "supported".

The ethylene-α-olefin copolymer (A) or the ethylene-based copolymer composition (A '), (A' '), or (A' '') has a single layer structure or a multi-layer structure regardless of the extruded film or the extruded process. It can be used in the production of propyl and extrusion cast films. When the ethylene-α-olefin copolymer (A) or the ethylene-based copolymer composition (A '), (A' '), (A' '') is used for coating purposes or for the purpose of a multilayer structure, the substrate or adjacent The material layer may be polar or nonpolar, and they include, but are not limited to, for example, paper products, metals, ceramics, glass and various polymers, in particular other polyolefins, and combinations thereof. Extruded profiled materials can be processed into a variety of products, including, but not limited to, gaskets for refrigerators, jackets for wires and cables, wire coatings, medical pipes and receiving pipes, etc. do. Extruded cast films made using ethylene-α-olefin copolymers (A) or ethylene-based copolymer compositions (A '), (A' '), (A' '') are suitable for food packaging and industrial stretch wraps. stretchwrap).

pipe:

The pipe is made from the silane modified product of the ethylene-α-olefin copolymer (A) or the ethylene-based copolymer composition (A '), (A' '), (A' ''). In the silane modification, a radical generator and a silane compound are added to (A) or (A '), (A' ') and (A' ''), for example, mixed by an appropriate mixer such as a Henschel mixer, It can manufacture by heating to about 140-250 degreeC with an extruder, a Banbury mixer, etc., and kneading and heating-grafting.

As a radical generator 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 a silane compound used for silane modification, the silane compound which has hydrolyzable organic groups, such as a terminal vinyl group and an alkoxy group, is preferable, and vinyl trimethoxysilane, vinyl triethoxysilane, etc. are preferable.

The pipe is to crosslink the molded product of the silane modified products of the above (A) or (A '), (A' '), (A' ''). A molded object mix | blends a silanol condensation catalyst and shape | molds in a pipe form normally using a pipe molding machine.

As said silanol condensation catalyst, the well-known compound used as a catalyst which promotes dehydration condensation between silanol groups can be used. In addition, a master batch is separately prepared using a silanol condensation catalyst and a linear polyethylene before modification, and this and silane-modified linear polyethylene are dry blended by a mixer such as a Henschel mixer or a V blender, and then the mixture is pipe-molded. It may be used for.

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

Heat pipe stabilizers, anti-aging agents, weather stabilizers, hydrochloric acid absorbers, lubricants, organic or inorganic pigments, carbon black, flame retardants, antistatic agents, fillers and the like can be blended.

Injection molded body:

The injection molded product is obtained by injection molding the ethylene-α-olefin copolymer (A) or the ethylene copolymer composition (A '), (A' '), (A' ''). An injection molded body can be manufactured by a conventionally well-known injection molding apparatus, and molding conditions can also employ | adopt conventionally well-known conditions.

Such injection molded bodies are excellent in heat resistance and environmental stress fracture resistance.

Sheath for wires:

A wire sheath is a sheath (outermost sheath) which protects an electric wire or a cable.

Electric wire sheath is the said ethylene-alpha-olefin copolymer (A) or ethylene-type copolymer composition (A '), (A "), (A'"), a conventionally well-known heat stabilizer, and weather resistance as needed. It is formed from stabilizers, carbon blacks, pigments, flame retardants, anti-aging agents and the like.

The wire sheath has a 50% crack initiation time (F ₅₀ ) (ASTM D 1698) of 600 hours or more, and the amount of wear measured by the wear test (JIS K 7204, load 1 kg, wear wheel CS-17, 60 rpm, 1000 times). It is preferable that the Izod impact strength (ASTM D 256, notched type) measured at 140 degreeC is 10 mg or less, and is 40 J / m <^2> or more.

The wire seed is formed by a conventionally known extrusion coating forming method using the ethylene-α-olefin copolymer (A) or the ethylene-based copolymer composition (A '), (A' '), (A' ''). can do.

Such wire sheath has stress crack resistance, abrasion resistance, and impact resistance at low temperatures.

The ethylene-α-olefin copolymer (A) or ethylene-based copolymer composition (A '), (A' ') and (A' '') can be used in the following high drawdown extrusion method.

The high draw-down extrusion method is the ethylene-α-olefin copolymer (A) or ethylene-based copolymer composition (A '), (A' '), (A' ''), or copolymer (A) or composition ( A '), (A' '), (A' '') using a composition (hereinafter also referred to as a thermoplastic composition) is a method of extrusion coating a substrate or to produce a cast film,

(i) feeding the thermoplastic composition to at least one extruder,

(ii) melt mixing the thermoplastic composition to produce at least one polymer flow,

(iii) passing the molten polymer stream through a die and extruding to produce a main web, wherein the improvement here comprises (i) operating the extruder at a line speed of at least 152 meters / minute, and (a) the Draw down the web onto the substrate, whereby the thermoplastic composition covers the substrate in at least one layer, or

(b) cooling the web and drawing it down onto a takeoff device such that the thermoplastic composition makes the film using at least one layer; (ii) in the subsequent use, the coated substrate or the Transporting or collecting the film. With the present invention, a higher draw down ratio and higher draw resonance resistance (draw resonance; melt flow instability phenomenon), which is a lower neck than that obtained when using ethylene polymers produced using a conventional Ziegler catalyst Is obtained.

In the present specification, "draw down" is defined by stretching or stretching the molten polymer extrudate (web or filament) in the machine direction and sometimes (low but at the same time) the transverse direction.

The term "neck in" is defined herein as the difference between the die width and the web width of the takeoff position, which is affected by the expansion of the extrudate and to a low extent but by the surface tension. The measured neck-in value (for a constant output) remains constant or decreases even if the drawdown rate is high, and in the case of ordinary ethylene polymers, the neck-in value is generally high as the molecular weight is lower or the molecular weight is lower. It is well known.

In the present invention, the copolymer (A) or the composition (A '), (A' '), (A' ''), additives, for example, antioxidants, phosphites, cling additives (for example, PIB, etc.), Standostab PEPQ (trade name) (supplied by Sandoz), pigments, colorants, fillers and the like may also be included. It is also possible to include additives in the extruded coating and film that further improve antiblocking and friction coefficient characteristics, including, but not limited to, untreated and treated silicon dioxide, talc, calcium carbonate and clay, And primary, secondary and substituted fatty acid amides, chill roll release agents, silicone coatings and the like. As described, for example, by Niemann in US Pat. No. 4,486,552, it is also possible to add other additives which, for example, improve the antifogging properties of transparent cast films. In addition, other additives, such as quaternary ammonium compounds, which can improve the antistatic properties of the coating film and the film of the present invention, for example, enable the packaging of electronic sensitive articles alone or ethylene acrylic acid (EAA) It is also possible to add it in combination with copolymers or other functional polymers.

The copolymers (A) or compositions (A '), (A' '), (A' '') used in the preparation of the compositions and articles of the invention are the resultant films or coatings to be used are monolayer structures or multilayer structures. Even if it is, it can be blended together with the linear ethylene polymers and / or one high-pressure ethylene polymer or can be used as only one dendritic polymer component. Moreover, workability, film strength, heat-sealing property are blended by blending another polymer with this copolymer (A) or a composition (A '), (A "), (A'") or homopolymers. Or adhesiveness can be improved.

Some materials suitable for the blender with this copolymer (A) or compositions (A '), (A' '), (A' '') include, but are not limited to, for example, low density ethylene polymers, for example In addition to high pressure low density ethylene homopolymer (LDPE), ethylene / vinyl acetate copolymer (EVA), ethylenecarboxylic acid copolymer and ethylene acrylate copolymers, olefin polymers produced at low to medium pressure, for example polybutylene (PB) and ethylene / α-olefin polymers (which include high density polyethylene, medium density polyethylene, polypropylene, ethylene / propylene copolymers, linear low density polyethylene (LLDPE) and ultra low density polyethylene) and graft modified polymers and Combinations thereof.

Suitable high pressure ethylenic copolymers include ethylene as at least one, -ethylenically unsaturated copolymer (e.g. acrylic acid, methacrylic acid, vinyl acetate, etc.), as McKinney et al. Describe in US Pat. No. 4,599.392. The copolymers copolymerized together with) are included. Preferred high pressure ethylenic copolymers comprise from 0.1 to 55% by weight of comonomer, more preferably from 1 to 35% by weight of comonomer, and most preferably from 2 to 28% by weight of comonomer in total. Any of the techniques may be chemically and / or physically modified by, for example, ionomerization and extrusion grafting.

However, preferred polymer blends include at least one copolymer (A) or composition (A '), (A' '), (A' ''), and preferably this copolymer (A) or composition ( A '), (A' '), (A' '') the blend composition comprises at least about 5%, more preferably the blend composition constitutes at least about 10%.

The present invention relates to the use of ethylene-α-olefin copolymers.

The present invention also relates to the use of an ethylene copolymer composition having substantially the same composition and usability as the ethylene-α-olefin copolymer.

The present invention also relates to the use of the composition of the ethylene-α-olefin copolymer or ethylene copolymer composition with another ethylene copolymer.

In the multilayer coating and film of the present invention, at least one copolymer (A) or composition (A '), (A' '), (A' '') is included in any layer and any number of layers Also good. Nevertheless, very preferably, in the case of the multilayer film and the film structure, at least one copolymer (A) or the outer layer (also called a "skin layer" or "surface layer" in the art) and the sealant layer Compositions (A '), (A' '), (A' '').

Blend compositions of the present invention may be prepared by any suitable means known in the art, including combinations thereof, in addition to tumble dry blender means, melt blend means by compound or sidearm extrusion, multiple reactor polymerization, and the like. This includes. In addition, the multilayer structure of the present invention can be manufactured by any known means, which includes coextrusion, lamination and combinations thereof. Moreover, it is also possible to use the composition of this invention in the coextrusion operation which uses the material which shows higher drawdown, and essentially "supports" one or more materials which show low drawdown by this.

Even single or multi-layered structures, the blend compositions and non-blend compositions of the invention can be used and coated on a variety of polar and nonpolar substrates, including, but not limited to, paper products, Metals, ceramics, glass and various polymers, in particular other polyolefins and combinations thereof.

Claims (15)

A molded article characterized by the following ethylene-α-olefin copolymer (A): Ethylene-α-olefin copolymer (A): It is a copolymer of ethylene and the alpha olefin of 6-8 carbon atoms, (A-i) Melt tension (MT) and melt flow rate (MFR) at 190 ° C, ^{9.0 × MFR -0.65 MT> 2.2 ×} MFR -0.84 Satisfies the relationship indicated by (A-ii) the flow activation energy ((E _a ) × 10 ^-4 J / molK) obtained from the shift factor of the time-temperature overlap of the flow curve, the number of carbon atoms (C) of the α-olefin in the copolymer, The relationship between the content rate (x mol%) of the α-olefin 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 represented by (A-iii) When the copolymer is inflation-formed to produce a film having a thickness of 30 μm, haze of the film satisfies the following relationship. The fluidity index (FI) and melt flow rate (MFR), defined as the shear rate at which the shear stress at 190 ° C reaches 2.4 × 10 ⁶ dyne / cm ² , When FI≥100 × MFR When the number of carbon atoms (C) of the α-olefin is 6 Haze <0.45 / (1-d) × log (3 × MT ^1.4 ) × (C-3) ^0.1 When the number of carbon atoms (C) of the α-olefin is 7 or 8 Haze <0.50 / (1-d) × log (3 × MT ^1.4 ) The fluidity index (FI) and melt flow rate (MFR), defined as the shear rate at which the shear stress at 190 ° C reaches 2.4 × 10 ⁶ dyne / cm ² , When FI <100 × MFR When the number of carbon atoms (C) of the α-olefin is 6 Haze <0.25 / (1-d) × log (3 × MT ^1.4 ) × (C-3) ^0.1 When the number of carbon atoms (C) of the α-olefin is 7 or 8 Haze <0.50 / (1-d) × log (3 × MT ^1.4 ) (Where d denotes density (g / cm ³ ) and MT denotes melt tension (g)) The method of claim 1, The ethylene-α-olefin copolymer (A) is (a) an organoaluminum oxy compound, (b-I) at least one transition metal compound selected from the transition metal compounds represented by the following formula (I), ML ¹ x... (I) (Wherein M is a transition metal atom selected from Group 4 of the periodic table, L ¹ is a ligand that coordinates to the transition metal atom (M), and at least two ligands (L ¹ ) of these are hydrocarbons having 3 to 10 carbon atoms) A substituted cyclopentadienyl group having at least one group selected from the group, and ligands other than the substituted cyclopentadienyl group (L ¹ ) are a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, and a trialkylsilyl group , A halogen atom or a hydrogen atom, X is the valence of the transition metal (M)) (b-II) at least one transition metal compound selected from the transition metal compounds represented by the following formula (II), ML ² _x ... (II) (Wherein M is a transition metal atom selected from Group 4 of the periodic table, L ² is a ligand that coordinates to a transition metal atom (M), and at least two of these ligands (L ² ) are methylcyclopentadienyl groups or ethylcyclo) The ligand (L ² ) other than the methylcyclopentadienyl group or the ethylcyclopentadienyl group is a pentadienyl group, and a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a trialkylsilyl group, a halogen atom or hydrogen Is an atom, and X is the valence of the transition metal atom (M)) The molded object obtained by copolymerizing ethylene and the alpha-olefin of C6-C8 in presence of the catalyst for olefin polymerization which consists of. The method according to claim 1 or 2, The ethylene-α-olefin copolymer (A) is In the presence of a catalyst for olefin polymerization in which the (a) organoaluminum oxy compound, (bI) transition metal compound and (b-II) transition metal compound are supported on (c) the carrier, ethylene and 6 to 8 carbon atoms A molded product obtained by copolymerizing an α-olefin. delete delete delete delete delete The method according to claim 1 or 2, A molded article, wherein the molded article is a single layer film or sheet. The method according to claim 1 or 2, A molded article, wherein said molded article is a multilayer film or sheet. The method according to claim 1 or 2, A molded article wherein said molded article is an injection molded article. The method according to claim 1 or 2, A molded article wherein said molded article is an extrusion molded article. The method according to claim 1 or 2, A molded article wherein said molded article is a fiber. The method according to claim 1 or 2, A molded article wherein said molded article is a foam molded article. The method according to claim 1 or 2, A molded article, wherein said molded article is a sheath for electric wires.