JPH06240065A - Polyolefin composition and film made therefrom - Google Patents

Abstract

PURPOSE:To obtain a polyolefin composition fully satisfactory in and well- balanced among properties including mechanical properties, heat-sealability, hot tack, optical properties and processability and to provide a (composite) film made therefrom. CONSTITUTION:This polymer composition comprises 99-1 pt.wt. ethylene 4-10C alpha-olefin random copolymer having a density of 0.895-0.915g/cm<3> and giving a climbing temperature thermogram in which an endothermic peak appears in the region of 80-100 deg.C, and the heat absorption in this peak is at least 0.9 in terms of a ratio to the total heat absorption as measured with a differential scanning calorimeter after being completely melted and being slowly cooled, and 1-99 pts.wt. crystalline propylene polymer or its mixture.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention is a composition comprising a specific ethylene-α-olefin copolymer and a propylene-based polymer as essential components, and has heat-sealing properties, transparency, gloss, rigidity, tensile strength and tear strength. The present invention relates to a polyolefin composition which highly satisfies properties required for packaging applications such as impact resistance, a film made of the composition, and a composite film.

[0002]

2. Description of the Related Art Low-density polyethylene is widely used in the film field because it is highly waterproof, moisture-proof, moderately flexible, relatively transparent and relatively strong. Furthermore, since heat sealing is possible from a relatively low temperature and the sealing strength is good, it is often used as a packaging film in a single layer or in a multilayer form with other thin film materials.

In recent years, there has been a strong demand from the market for a polyethylene-based packaging film capable of increasing the filling speed of contents. Accelerating the filling speed of contents is
It means a higher film feeding speed, a shorter heat seal, and a shorter time until the load of the contents is applied to the sealing surface immediately after heat sealing. For this,
A film that has rigidity, develops heat seal strength at low temperature, and does not peel off even if the load of the contents is applied while the seal part is still hot immediately after heat sealing (so-called good hot tack property). It is necessary to be. Also, the composite film is manufactured by various methods,
Since a wide range of materials can be combined and beautifully printed composite films can be produced, the laminating method, which is widely used, tends to cause wrinkles when low-density polyethylene has poor rigidity and is not suitable for high-speed processing. The strength of is also important. Furthermore, transparency and gloss enhance the display value of the packaged contents, and tensile strength and resistance to tearing in any direction enhance the original function of the package for protecting the article, and are therefore equally important. Low-density polyethylene is roughly classified into the following two types depending on its manufacturing method or molecular structure.

One is an ethylene polymer which is produced by a radical polymerization method under high pressure and high temperature and which essentially has short chain branches and long chain branches. It is considered that short chain branching is generated by the intramolecular transfer reaction of the polymer radical during the growth reaction, and long chain branching is generated by the intermolecular transfer reaction. In radical polymerization, α-olefin causes a large chain transfer reaction, which lowers the molecular weight of the produced polymer and lowers its practical value.Therefore, even if it is present in the high-molecular-weight low-density polyethylene used as a synthetic resin, it is extremely polar. A small amount of α
-Only olefins are copolymerized.

The other is a copolymer of ethylene and α-olefin by a transition catalyst polymerization method represented by the Ziegler catalyst polymerization method. By the copolymerization of α-olefin,
A short-chain branch with two carbons less than that carbon is generated,
The density of the polymer is reduced. The latter usually does not have long chain branching, so linear low density polyethylene (L-LDP)
It is also called E). Since the former was invented historically earlier than the latter, it was conventionally called simply low density polyethylene, but in order to clearly distinguish it from L-LDPE,
It will be referred to as branched low-density polyethylene (B-LDPE).

Generally, a polymer substance is an aggregate of various molecules, and it is widely accepted as a general theory that various physical properties are changed depending on the distribution mode. The analysis of distribution patterns and the invention of polymer substances having improved physical properties by a new distribution pattern have become one of the central subjects of polymer chemistry both academically and industrially.

Regarding low-density polyethylene, the distribution concerning the molecular weight (molecular weight distribution) and the distribution concerning the short chain branching degree (short chain branching degree distribution) are important in terms of physical properties. B-LDP
While E has a broad molecular weight distribution and a relatively narrow short chain branching degree distribution, L-LDPE is generally known to have a relatively broad short chain branching degree distribution (eg, S. Hosod.
a: Polymer J., 20,383 (1988)). The short-chain branch in the L-LDPE molecule is produced by the copolymerization of α-olefin as a comonomer.
The short chain branching degree distribution of is also called comonomer distribution or (copolymerization) composition distribution.

The B-LDPE film has advantages such as optical properties such as transparency, moldability during processing, and good heat-sealing property, but rigidity (waist), impact strength,
Poor mechanical strength such as tensile strength and hot tack.

On the other hand, the L-LDPE film has the advantages of high mechanical strength and good drawdown property, but optical properties such as transparency, high load during processing, and molding stability. It has the drawback of being bad.

In recent years, it has been attempted to combine various physical properties required for these films in a highly balanced manner.
It is disclosed in various publications such as Japanese Patent Application Laid-Open No. 483 and Japanese Patent Application Laid-Open No. 2-153908, and some results have been achieved by devising the molecular weight distribution and composition distribution of L-LDPE. However, since these inventions are limited to improving the distribution pattern of polyethylene itself, it is not possible to expect a film that exceeds the physical properties peculiar to polyethylene.

On the other hand, the crystalline propylene-based polymer is excellent in transparency, gloss, rigidity, mechanical strength, heat resistance, chemical resistance and processability in addition to properties similar to those of low density polyethylene. Widely used as packaging material along with polyethylene. However, crystalline propylene-based polymers, especially propylene homopolymers, have the drawbacks of low impact strength at low temperatures and poor low-temperature heat-sealing properties and hot tack properties. It cannot be fully used for food packaging material applications for which the opportunities for handling are increasing.

Therefore, rubber is added to polypropylene (Japanese Patent Publication No. 357088) or polyethylene is added to improve the drawback of low impact strength (Japanese Patent Publication No. 37-6975). Alternatively, when propylene is polymerized, a small amount of ethylene is added to randomly copolymerize propylene and ethylene (Japanese Patent Publication No. 43-11).
No. 230) has been proposed.

However, these methods improve impact strength, but on the other hand, mechanical properties, especially tensile modulus decrease, and transparency and gloss deteriorate, so that the packaging material has sufficiently satisfactory performance. Was difficult to obtain.

[0014]

In order to achieve a high filling rate for contents, which has been strongly demanded in recent years, a polyolefin packaging film is excellent in low-temperature heat-sealing property and hot-tack property. In addition, transparency and luster are required to enhance the display value of the contents as a packaging film, and mechanical strength is required to enhance the original function of the packaging to protect articles. An object of the present invention is to provide a polyolefin composition and a film comprising the composition, which have been improved / optimized for packaging applications which further satisfy the comprehensive physical properties of conventionally known polyolefin films.

[0015]

Means for Solving the Problems As a result of detailed investigation of the expression mechanism of the low-temperature heat-sealing property, heat-sealing strength, and hot-tacking property, which are important properties particularly for polyolefins for packaging films, , The development of the strength of the heat-sealed portion is a necessary condition that the temperature of the film rises due to the heat from the seal bar heated to a predetermined temperature and they are fused to each other. It was found that it is closely related to the mechanical action during peeling.

Further, the inventors of the present invention have made diligent studies on melt properties, impact strength, mechanical strength, and crystallization behavior between incompatible resins and mixed systems. As a result, the ethylene-α-olefin copolymer and crystalline propylene are obtained. After mixing the polymer, the molded film has not only hot tack property but also comprehensive properties such as transparency, luster, waist strength (rigidity), impact strength, tensile strength and tear strength required as a packaging film. The inventors have found that they are highly balanced and have satisfactory workability at the same time, and have completed the present invention.

That is, according to the present invention, the density is 0.895 to 0.915 g / cm ³ , and the temperature rise thermogram measured by a differential scanning calorimeter after complete melting and slow cooling is in the range of 80 to 100 ° C. 99 to 1 part by weight of a random copolymer (I) of ethylene and an α-olefin having 4 to 10 carbon atoms, in which an endothermic peak is observed at an endothermic peak of 0.9 or more relative to the total calorific value. When,
The present invention provides a polyolefin composition comprising 1 to 99 parts by weight of a crystalline propylene polymer or a propylene polymer mixture (II), and a film comprising the composition.

The present invention will be described in detail below. The component (I) used in the present invention is a random copolymer of ethylene and an α-olefin having 4 to 10 carbon atoms. The α-olefin may be one kind or a plurality of kinds. Specific examples of such α-olefin include butene-1, pentene-1, hexene-1, heptene-1, octene-1, nonene-.
1, decene-1,4-methylpentene-1,4-methylhexene-1,4,4-dimethylpentene-1 and the like. In addition, vinyl cycloalkanes such as vinyl cyclohexane are also included. Among these α-olefins, butene-1, pentene-1, hexene-1, octene-1, 4-methylpentene-1 and the like are preferable in terms of availability of monomers, copolymerizability and quality of the obtained copolymer. . The content of α-olefin in the random copolymer is usually 2.0 to 20.0 mol%. The ethylene-α olefin random copolymer used in the present invention itself has transparency as a packaging film, gloss, mechanical strength,
Impact resistance, low temperature heat sealability, low temperature hot tack,
It is more preferable that the composition has high performance such as chemical resistance, heat resistance, and processability, so that it is preferable that the composition distribution is more uniform.

The component (II) used in the present invention is a propylene homopolymer, a copolymer of propylene and ethylene and / or α-olefin, or a mixture thereof.
Examples of the α-olefin include butene-1, pentene-
1, hexene-1, heptene-1, octene-1, nonene-1, decene-1, 4-methylpentene-1, 4-methylhexene-1,4,4-dimethylpentene-1 having 4 to 4 carbon atoms There are 10 α-olefins. In addition, vinyl cycloalkanes such as vinyl cyclohexane are also included. The ethylene or α-olefin content is usually 4
It is less than 5 mol%, preferably 40 mol% or less.

Each item will be described below. (1) Density and Melt Flow Rate The density of the ethylene-α-olefin random copolymer used in the present invention is measured according to JIS K6760 after annealing at 100 ° C. for 1 hour, and is 0.895 to 0.915.
g / cm ³ , preferably 0.900 to 0.915 g
/ Cm ³ , more preferably 0.900 to 0.910
It is g / cm ³ . If the density is lower than 0.895 g / cm ³ , the mechanical strength decreases, which is not preferable. on the other hand,
If the density is higher than 0.915 g / cm ^3, the temperature at which the heat-sealing property and the hot-tack property are exhibited becomes too high, and it becomes difficult to achieve high-speed packaging / filling, which is not preferable.

The melt flow rate (MFR) of the random copolymer (I) of ethylene and α-olefin and the crystalline propylene polymer or the crystalline propylene polymer mixture (II) used in the present invention is JIS K6760. At 190 ° C. The MFR of the random copolymer (I) of ethylene and α-olefin is preferably 0.1 to 15 g / 10 minutes, more preferably 0.
It is 2 to 10 g / 10 minutes, most preferably 0.3 to 5 g / 10 minutes. The weight average molecular weight (Mw) of the ethylene-α olefin random copolymer (I) is preferably in the range of 30,000 to 300,000. The MFR of the crystalline propylene-based polymer or the crystalline propylene-based polymer mixture (II) is preferably 0.1 to 15
g / 10 minutes, more preferably 0.2 to 10 g / 10
Min, most preferably 0.3 to 5 g / 10 min.

Furthermore, the random copolymer (I) of ethylene and α-olefin used in the present invention and a crystalline propylene-based polymer or a crystalline propylene-based polymer mixture (I
In the combination of I), the difference in MFR between them is preferably 10 g / 10 minutes or less, more preferably 7 g / 10 minutes or less, and most preferably 4 g / 10 minutes or less.

The preferred MF of the composition used in the present invention
R depends on the selection of the film production method, and is 0.1 to 10 g / 10 minutes in the inflation method, more preferably 0.2 to 5 g / 10 minutes, and 0.3 to 15 g / 10 minutes in the T-die method. More preferably 0.5
To 10 g / 10 min, 1 to 15 g / 10 min by extrusion lamination method, more preferably 2 to 10 g
/ 10 minutes.

(2) Thermal transition temperature The thermal transition behavior of a polymer is now commonly measured by a differential scanning calorimeter (DSC), and the relationship diagram between the exothermic or endothermic rate and the temperature is called a thermogram. Has been. This thermogram reflects the crystalline lamella thickness distribution of the polymer, which is known to be deeply influenced by the compositional distribution and thermal history of the polymer (eg S. Hosoda: Polymer J ., 20,383 (198
8)). The measurement of the thermal transition behavior in the present invention is divided into the case of obtaining the knowledge about the composition distribution inherent in the polymer and the case of obtaining the knowledge about the crystalline lamella thickness distribution of the formed film.

The method will be described below. To obtain information on the composition distribution inherent in the polymer In this case, measure the temperature rise thermogram after complete melting and slow cooling. The thermal transition behavior of a polymer depends on its thermal history and must therefore be eliminated and measured in advance. In the present invention, after holding (premelting) at 180 ° C. for 5 minutes in DSC, it is cooled to 40 ° C. at a temperature decreasing rate of 1 ° C./minute, and then heated to 180 ° C. at a temperature increasing rate of 10 ° C./minute to rise. Get the warm thermogram. 5 on each thermogram
A straight line connects 0 ° C. and the temperature at which all the heat absorption is completed, and is used as a baseline for obtaining the amount of heat. In the present invention, the “peak” clearly shows a maximum on the endothermic side and has a shoulder shape which is simply identified by an inflection point, or 2% of the maximum peak intensity in a thermogram. Anything that looks like a peak due to a small change of less than is not a "peak". This is because the present invention does not cause a minute change in the thermogram.

In the random copolymer (I) of ethylene and α-olefin used in the present invention, the maximum endothermic peak (A) was observed within the range of 80 to 100 ° C. in the temperature rising thermogram, and the endothermic peak It has a single peak with an endothermic amount of 0.9 or more, preferably 1.0 with respect to the total amount of heat. When the peak temperature of the endothermic peak is lower than this range, the maximum peel strength of the heat sealability and hot tack property is lowered, and when it is higher than this range, the heat seal property and hot tack property are not exhibited from a sufficiently low temperature, which is not preferable. Also,
When the endothermic amount of the endothermic peak (A) is lower than this range with respect to the total amount of heat, the maximum peel strength of heat sealability and hot tack property is lowered, and the effect of improving impact strength is small, which is not preferable.

The endothermic peak (A) of the random copolymer (I) of ethylene and α-olefin has a half width (Wa1).
/ 2) is preferably 30 ° C. or lower, more preferably 25 ° C.
Below, most preferably it is 20 degrees C or less. As shown in FIG. 1, Wa1 / 2 is the temperature difference between two points at which the melting thermogram intersects a line drawn from the midpoint of the perpendicular drawn from the peak (A) to the baseline and parallel to the baseline. If the line intersects with the boundary line with the adjacent peak (perpendicular line drawn from the minimum point on the heat absorption side to the baseline) before intersecting the thermogram, the temperature difference between this temperature and the other intersection is taken. To do.

Further, in the temperature rising thermogram of the crystalline propylene polymer used in the present invention, preferably 125
An endothermic peak is observed in the range of 175 to 175 ° C, more preferably in the range of 130 to 170 ° C.

When it is desired to obtain information on the crystalline lamella thickness distribution of the formed film, the temperature rising thermogram is measured directly from the film state in the polyolefin film of the present invention. The crystal melting behavior of a molded product is determined by the composition distribution of the polymer itself and various thermal histories during and after processing. Therefore, when it is desired to know the thermal melting behavior of the film itself, it is necessary to directly measure the film without subjecting it to thermal treatment before measurement. Therefore, in the present invention, the film is placed in a DSC measuring pan at 40 ° C.
To 10 ° C./min to obtain a temperature rising thermogram.

In the polyolefin film of the present invention, it is preferable that at least one endothermic peak (B) is observed in the range of 80 to 100 ° C. in the temperature rising thermogram.

(3) Composition The composition obtained in the present invention has a density of 0.895 to 0.
915 g / cm ³ , preferably 0.900 to 0.9
15 g / cm ³ , more preferably 0.900 to 0.
The maximum endothermic peak was observed in the range of 80 to 100 ° C. in the temperature rising thermogram measured by a differential scanning calorimeter after 910 g / cm ³ after complete melting and slow cooling, and the endothermic amount of the endothermic peak was the total calorific value. On the other hand, a single peak of 0.9 or more, preferably 1.0, ethylene and carbon number 4
99 to 1 part by weight, preferably 95 to 5 parts by weight, of a copolymer (I) of α-olefin of 1 to 10 and 1 to 99 parts by weight of a crystalline propylene polymer or a mixture of propylene polymers (II), preferably The essential component is 5 to 95 parts by weight. The melt flow rate (190 ° C.) of (I) is preferably 0.1 to 15 g / 10.
Min, more preferably 0.2 to 10 g / 10 min, most preferably 0.3 to 5 g / 10 min. The melt flow rate (190 ° C) of (II) is preferably 0.1.
To 15 g / 10 minutes, more preferably 0.2 to 1
0 g / 10 minutes, most preferably 0.3 to 5 g / 10
Minutes. Melt flow rate of (I) and (II) (19
0 ° C.) difference is preferably 10 g / 10 min or less, more preferably 7 g / 10 min or less, most preferably 4 g / 10.
It is less than a minute. In the case of a polyethylene-based composition in which the ethylene-α-olefin random copolymer serves as a matrix, the ethylene-α-olefin random copolymer is preferably 60 to 95 parts by weight, more preferably 65 to 95 parts by weight, and most preferably 70 to 95 parts by weight, and in the case of a crystalline propylene polymer composition in which the crystalline propylene polymer serves as a matrix, the propylene polymer is preferably 50 to 95 parts by weight, more preferably 60 to 95 parts by weight. 95 parts by weight, most preferably 7
0 to 95 parts by weight.

The tensile strength at 120 ° C. measured with a 1 mm press sheet molded after kneading from the composition of the present invention is 10 k in the case of a polyethylene composition having an ethylene-α-olefin random copolymer as a matrix.
g / cm ² or less, preferably 7 kg / cm ² or less, more preferably 3 kg / cm ² or less, most preferably 1 k
g / cm ² or less, in the case of a crystalline propylene-based polymer composition in which the crystalline propylene-based polymer serves as a matrix, 2
The mixture is 0 kg / cm ² or more, preferably 30 kg / cm ² or more, more preferably 50 kg / cm ² or more.

The method for producing the ethylene-α-olefin copolymer (I) is not particularly limited, and examples thereof include a high temperature / high pressure method, a gas phase polymerization method, a slurry polymerization method and a solution polymerization method. In order to sufficiently obtain the effects of the present invention, it is preferable to use a homogeneous catalyst known to bring about a resin having a narrow composition distribution.

The olefin polymerization catalyst used when producing the ethylene-α-olefin copolymer (I) according to the present invention is, for example, (i) a transition metal compound containing a ligand having a cycloalkadienyl skeleton. Or (ii) a transition metal containing at least two ligands having a cycloalkadienyl skeleton, and at least two ligands having the above cycloalkadienyl skeleton are bonded via a lower alkylene group. Examples of the catalyst include a compound and (iii) an organoaluminum oxy compound. The transition metal compound is represented by, for example, the following general formula (a). R ¹ _k R ² _l R ³ _m R ⁴ _n M (a) (In the formula, M is zirconium, titanium, hafnium, vanadium, or the like, and R ¹ is a group having a cycloalkadienyl skeleton. R ² , R ³ and R ⁴ are a group having a cycloalkadienyl skeleton, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, a halogen atom or hydrogen, and k is 1
The above integers and k + l + m + n = 4) Hereinafter, specific compounds will be exemplified as the transition metal compound (i) containing a ligand having a cycloalkadienyl skeleton in which M is zirconium. Bis (cyclopentadienyl) zirconium monochloride monohydride,
Bis (cyclopentadienyl) zirconium monobromide monohydride, bis (cyclopentadienyl) methyl zirconium hydride, bis (cyclopentadienyl) ethyl zirconium hydride, bis (cyclopentadienyl) phenyl zirconium hydride, bis (cyclopenta Dienyl) benzyl zirconium hydride, bis (cyclopentadienyl) neopentyl zirconium hydride, bis (methylcyclopentadienyl) zirconium monochloride, bis (indenyl) zirconium monochloride monohydride, bis (cyclopentadienyl) zirconium Dichloride, bis (cyclopentadienyl) zirconium dibromide, bis (cyclopentadienyl) methylzirconium mono Lolide, bis (cyclopentadienyl) ethyl zirconium monochloride, bis (cyclopentadienyl) cyclohexyl zirconium monochloride, bis (cyclopentadienyl) phenyl zirconium monochloride, bis (cyclopentadienyl) benzyl zirconium monochloride, Bis (methylcyclopentadienyl) zirconium dichloride, bis (t-butylcyclopentadienyl) zirconium dichloride,
Bis (indenyl) zirconium dichloride, bis (indenyl) zirconium dibromide, bis (cyclopentadienyl) zirconium dimethyl, bis (cyclopentadienyl) zirconium diphenyl, bis (cyclopentadienyl) zirconium dibenzyl, bis (cyclopenta) Dienyl) zirconium methoxy chloride, bis (cyclopentadienyl) zirconium ethoxy chloride, bis (methylcyclopentadienyl) zirconium ethoxy chloride, bis (cyclopentadienyl) zirconium phenoxycyclolide, bis (fluorenyl) zirconium dichloride. Further, specific examples of the transition metal compound (ii) in which at least two ligands having a cycloalkadienyl skeleton are bonded via a lower alkylene group are shown. Ethylene bis (indenyl) dimethyl zirconium, ethylene bis (indenyl) diethyl zirconium, ethylene bis (indenyl) diphenyl zirconium, ethylene bis (indenyl) methyl zirconium, ethylene bis (indenyl)
Ethyl zirconium monochloride, ethylenebis (indenyl) methylzirconium monobromide, ethylenebis (indenyl) zirconium dichloride, ethylenebis (indenyl) zirconium dibromide, ethylenebis (indenyl) zirconium methoxymonochloride,
Ethylene bis (indenyl) zirconium ethoxy monochloride, ethylene bis (indenyl) zirconium phenoxy monochloride, ethylene bis (cyclopentadienyl) zirconium dichloride, propylene bis (cyclopentadienyl) zirconium dichloride, ethylene bis (t-butylcyclopenta) Dienyl) zirconium dichloride, ethylenebis (4,5,6,7-tetrahydro-1-indenyl) dimethylzirconium, ethylenebis (4,5,6,7-tetrahydro-1-indenyl) methylzirconium monochloride, ethylenebis (4,5,6,7-Tetrahydro-1-indenyl) zirconium dichloride, ethylene bis (4,5,6,7
-Tetrahydro-1-indenyl) zirconium dibromide, ethylenebis (4-methyl-1-indenyl) zirconium dichloride, ethylenebis (5-methyl-1)
-Indenyl) zirconium dichloride, ethylenebis (6-methyl-1-indenyl) zirconium dichloride, ethylenebis (7-methyl-1-indenyl) zirconium dichloride, ethylenebis (5-methoxy-1)
-Indenyl) zirconium dichloride, ethylenebis (2,3-dimethyl-1-indenyl) zirconium dichloride, ethylenebis (4,7-dimethyl-1-indenyl) zirconium dichloride, ethylenebis (4,4)
7-dimethoxy-1-indenyl) zirconium dichloride. In the zirconium compound as described above, a transition metal compound in which zirconium metal is replaced with titanium metal, hafnium metal, chromium metal, vanadium metal or the like can also be used. Examples of the organoaluminum oxy compound (iii) include the general formula (b) and the general formula (c). The aluminoxane soluble in benzene represented by In such aluminoxane, R may be the same or different and is a hydrocarbon group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group and an isobutyl group, preferably methyl. A group, an ethyl group, an isobutyl group, particularly preferably a methyl group, and m is an integer of 2 or more, preferably 5 or more. As a method for producing the aluminoxane as described above, the following method can be exemplified. (A) Compounds containing adsorbed water, salts containing water of crystallization, such as magnesium chloride hydrate, copper sulfate hydrate,
A method in which a trialkylaluminum is added to a suspension of a hydrocarbon medium such as aluminum sulfate hydrate, nickel sulfate hydrate, and ceric chloride hydrate to react them. (B) A method in which water is allowed to act directly on a trialkylaluminum in a medium such as benzene, toluene, ethyl ether, or tetrahydrofuran. Among these methods, the method (A) is preferably adopted. The aluminoxane may contain a small amount of organic metal component.

Further, examples of other olefin polymerization catalysts used in producing the ethylene-α-olefin copolymer (I) according to the present invention include compounds represented by the following formula (d). _[R ⁵ _p R ⁶ _q MY _r] ⁺ A ^{- ·····} (d) (wherein, M is a zirconium, titanium, hafnium, or vanadium such as, R ⁵ is distribution having a cycloalkadienyl skeleton R ⁶ is a group having a ligand, R ⁶ is a group having a cycloalkadienyl skeleton, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, a halogen atom or hydrogen, and Y is inactive. Is a neutral donating ligand, p is an integer of 1 or 2, r is an integer of 0 or 1, and x is a transition metal M.
A case when the valency p + q = x-1 or R ⁵ is bound to M through a substituent optionally p + q = x-2, A - is a noncoordinating compatible anion of a Bronsted acid salt Is. )

Further, the ethylene-α olefins according to the present invention
Other olefins used in the production of copolymer (I)
Examples of the in-polymerization catalyst include the following general formula (e),
Vanadium compound represented by (f) and organic aluminum
Examples of the catalyst include a metal compound. VO (OR⁷)_SX_3-S(E) (In the formula, R⁷Is a hydrocarbon group and X is a halogen
And s is an integer satisfying 0 ≦ s ≦ 3. ) R⁸ _tAlX_3-t(F) (In the formula, R⁸Is a hydrocarbon group, X is halogen or
Is an alkoxy group, and t is a number 0 ≦ t ≦ 3.
It ) As the vanadium compound represented by the general formula (e),
For example, VOCl₃, VO (OCH₃) Cl₂, VO (O
CH₃)₂Cl, VO (OCH₃)₃ , VO (OC ₂H_Five) C
l₂, VO (OC₂H_Five)₂Cl, VO (OC₂H_Five)₃,
VO (OC₃H ₇) Cl₂, VO (OC₃H₇)₂Cl, V
O (OC₃H₇)₃, VO (Oiso C₃H ₇) Cl₂, VO
(Oiso C₃H₇)₂Cl, VO (Oiso C₃H₇)₃is there
Alternatively, a mixture of these can be exemplified. these
Among the compounds, VOCl represented by 0 ≦ s ≦ 1₃, VO
(OCH₃) Cl ₂, VO (OC₂H_Five) Cl₂, VO (O
C₃H₇) Cl₂, VO (Oiso C₃H₇) Cl₂Is the composition
Preferred for obtaining a copolymer having a narrow distribution, especially when s = 0
VOCl₃Is most preferred. Is represented by the general formula (f)
Examples of the organic aluminum compound include₂
H_Five)₂AlCl, (C_FourH₉)₂AlCl, (C₆H₁₃)₂
AlCl, (C₂H_Five)_{1. Five}AlCl_1.5, (C_FourH₉)
_1.5AlCl_1.5, (C₆H₁₃)_1.5AlCl_1.5, C₂
H_FiveAlCl₂, C_FourH₉AlCl₂, C₆H₁₃AlC
l₂Etc. can be illustrated. Of these compounds,
More preferred in terms of copolymerization reaction rate and copolymer yield
The compound satisfies 1 ≦ t ≦ 2, and is particularly preferable.
Some compounds are (C₂H_Five) _1.5AlCl_1.5Is. the above
In addition to vanadium compounds and organoaluminum compounds,
Halogen represented by the following general formula (g) as the third component
A catalyst composed of a combination of esterified compounds has a higher weight.
It is particularly preferable in that the total activity can be obtained. Expression(In the formula, R⁹Is a part of water of a hydrocarbon group having 1 to 20 carbon atoms
Organic in which elementary atoms or all hydrogen atoms are replaced by halogen
Group, R^TenIs a hydrocarbon group having 1 to 20 carbon atoms.
It ) A halogenated ester compound represented by the general formula (g)
Chi, R⁹Compounds in which all the substituents of are substituted with chloro are preferred.
Therefore, perchlor crotonic acid ester is particularly preferable.
Specifically, ethyl dichloroacetate, methyl tric
Lol acetate, ethyl trichloroacetate, methyl
Dichlorophenyl acetate, ethyldichlorophenyl
Acetate, methyl perchlor crotonate, ethylpa
ー Chlorcrotonate, Propyl Perchlor Crotone
G, isopropyl perchlor crotonate, butyl per
Chlorcrotonate, cyclopropyl perchlorate
, Phenyl perchlorchlortonate, etc.
However, the present invention is not limited to these.

As the α-olefin of the ethylene-α-olefin copolymer (I), those having 4 to 10 carbon atoms can be used. When an α-olefin having 6 or more carbon atoms is used, the following general formula ( It is preferable to use a vanadium compound obtained by reacting vanadium trichloride represented by h) with an alcohol. V (OR ¹¹ ) _u Cl _3-u · vR ¹² OH (h) (In the formula, R ¹¹ is a hydrocarbon group, R ¹² OH is an alcohol, and u is 0 ≦ u ≦ 1. .5, v is 0.5 ≦ v ≦ 8.
It is a number represented by 5. ) Examples of the alcohol used for the reaction with vanadium trichloride include methyl alcohol, ethyl alcohol,
n-propyl alcohol, i-propyl alcohol, n
-Butyl alcohol, i-butyl alcohol, tert
-Butyl alcohol, hexyl alcohol, octyl alcohol and the like, and preferably methyl alcohol, ethyl alcohol, i-propyl alcohol and the like having a low boiling point are used. As the crystalline propylene polymer (II), those produced by widely known methods can be used.

The polyolefin composition of the present invention is not particularly limited except that it is kneaded at a temperature at which all components are melted or higher. As the kneading device, for example, a batch type or a continuous type, a single-screw type or a multi-screw type can be used, and a screw type extruder in a film manufacturing apparatus can be used.

(4) Production of Film The polyolefin film of the present invention can be produced by using the polyolefin composition of the present invention as a raw material resin by a known technique such as an inflation method or a T-die method at a temperature at which the raw material resin melts or higher. Inflation method is also called blow molding method, the resin melt-kneaded in the extruder is extruded into a tube shape through the circular slit of the die,
By adjusting the pressure of the gas (usually air) blown into the tube, a film having a wide range of width can be manufactured. The film thickness depends on the resin extrusion speed and blown
It can be adjusted by the selection of Up-Race (BUR). The extruded tube is cooled from the outside by a gas (usually air) and / or a liquid (usually water). The method of cooling with water is called a water-cooled inflation method and is used for obtaining a film having excellent transparency, but changing the width of the film is troublesome. Further, a method of cooling with air is called an air cooling inflation method, and various cooling devices and methods have been proposed, but when roughly classified, there are a method of performing air cooling in one stage and a method of performing in multiple stages. Conventionally, a film obtained by the one-step air-cooling inflation method of L-LDPE has insufficient transparency, and a multi-step air cooling method has been proposed for this improvement. However, in the multi-step air cooling method, it is not easy to change the width of the film, and the water cooling inflation method is used. Similar to, the inflation process loses the ability to economically produce many types of films on a single machine. In the present invention, a film having excellent transparency can be obtained even by the one-step air-cooling inflation method. Further, in the present invention, it goes without saying that a film having excellent transparency can be obtained even by a water cooling inflation method or a multi-stage air cooling inflation method. The resin temperature during processing is usually selected within the range from the complete melting temperature to 280 ° C.

The T-die method is also called a cast method, in which the resin melt-kneaded by an extruder is extruded through parallel slits of a die and cooled by being brought into contact with a roll in which a coolant such as water is passed, Generally, a film having good transparency and good thickness accuracy can be produced.

The thickness of the film can be adjusted by selecting the extrusion rate of the resin and the pulling rate of the film. The resin temperature during processing is usually selected within the range from the complete melting temperature to 350 ° C.

In the case where the polyolefin film of the present invention is a single layer, the thickness of the film is 5 to 500 μm,
It is particularly desirable that the thickness is 10 to 200 μm. If the thickness is less than this range, it is difficult to process and handling is not easy when laminating. If the thickness is thick, the processing is difficult and the heat-sealing property is difficult to be exhibited.

(5) Film Structure The polyolefin film of the present invention has a structure in which the ethylene-α-olefin random copolymer forms a continuous phase and the crystalline propylene-based polymer forms a discontinuous dispersed phase, or the structure. It has the opposite structure. The present inventors have made a detailed study on the relationship between the structure and physical properties of the film. As a result, after kneading at a temperature equal to or higher than the temperature at which all components melt, 180
AST a 1mm press sheet press-formed at 5 ℃ for 5 minutes
A test piece punched out in the shape of MD1822 TYPE L, if the tensile strength measured under the conditions of a gripping interval of 20 mm, a pulling speed of 500 mm / min, and a measuring temperature of 120 ° C. is a specific value or less, an ethylene-α-olefin random copolymer Is a continuous phase, the crystalline propylene-based polymer is a dispersed phase, if the crystalline propylene-based polymer is a specific value or more, a crystalline propylene-based polymer is a continuous phase, low-density polyethylene a film having a structure forming a dispersed phase It was That is, in the former case, the tensile strength measured in this manner is 10 kg / cm ² or less, preferably 7 kg / cm ² or less, and more preferably 3 kg / cm ^2.
/ Cm ² or less, most preferably 1 kg / cm ² or less, and in the latter case 20 kg / cm ² or more, preferably 30
kg / cm ² or more, more preferably 50 kg / cm ²
That is all.

In the polyethylene-based film obtained in the present invention, a specific crystalline propylene-based polymer which is incompatible with polyethylene is finely dispersed in an ethylene-α-olefin random copolymer and oriented in a fixed direction. By the action of exhibiting the morphology, compared to the original polyethylene-based film, the stiffness is high (high rigidity), the tensile strength is strong,
High tear strength, wide temperature range where hot tack is developed, low processing load, and narrow composition distribution. Excellent transparency, gloss, and low temperature heat sealability of ethylene-α-olefin copolymer (I). In addition, it has a characteristic that physical properties such as low temperature hot tack property are not deteriorated so much, and the performance as a packaging film can be dramatically improved. Further, the crystalline propylene-based polymer film obtained in the present invention has a specific ethylene-α-olefin random copolymer, which is incompatible similarly to the polyethylene-based film, finely dispersed in the propylene-based polymer, By virtue of its directional morphology, it has a low temperature heat sealability and a low temperature hot seal without deteriorating the transparency, gloss, mechanical strength and impact resistance of the original crystalline propylene polymer film. It has the property of enhancing tackiness and tear strength balance, and can greatly improve the performance as a packaging film.

The kneading method is not particularly limited,
The kneader may be a batch type or a continuous type, a single-screw type or a multi-screw type, any of which can be used as long as all the components used in the present invention are at a melting temperature or higher, and a screw in a film manufacturing apparatus. Type extruders can also be used.

(6) Composite Film The polyolefin film of the present invention is in the form of a composite film with another substrate in order to fully exhibit its excellent heat-sealing properties, mechanical properties, optical properties and the like. It is particularly desirable that the polyethylene film of the present invention is present as a surface layer on at least one side. The substrate can be selected from, for example, any polymer capable of forming a film, cellophane, paper, paperboard, fiber structure, aluminum foil and the like. Examples of the film-forming polymer include polyamide resins such as nylon-6, nylon-66, nylon-11 and nylon-12, polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polypropylene and poly-1-.
Polyolefins such as butene, poly-4-methyl-1-pentene, polyethylene, ethylene / vinyl acetate copolymer, ethylene / methacrylic acid ester copolymer, ethylene / methacrylic acid copolymer, ethylene / acrylic acid copolymer, ionomer Considering the respective gas barrier properties, printability, transparency, rigidity, adhesiveness, etc. of resin, polyacrylonitrile, polyvinylidene chloride, polyvinyl chloride, polystyrene, polyvinyl alcohol, ethylene vinyl alcohol copolymer, etc. The composite film can be selected according to the purpose. If the substrate is stretchable,
In particular, when the performance of the film is improved by stretching such as polyamide resin, polyester resin, polypropyne, etc., the base material may be uniaxially or biaxially stretched. When in the form of a composite film, the thickness of the constituent layers of the polyolefin film of the present invention is from 1 to 50.
It is preferably 0 μm, particularly 10 to 100 μm. The thickness of the base material layer is arbitrary and can be selected according to the purpose. In addition, it is already widely practiced to combine a plurality of base materials with various configurations, and the present invention can also employ them.

In the present invention, the composite film having two or more layers is formed by a dry lamination method, a wet lamination method, a sandwich lamination method, a hot melt lamination method, a lamination method such as a thermal lamination method, a coextrusion method, an extrusion coating method. (Also referred to as extrusion lamination method) and combinations thereof, and the like. In the lamination method, the film of the present invention obtained by the method described in the description of the monolayer film and the composite film described here and other substrates, solvent-based adhesive, water-based adhesive, hot melt adhesion It is pasted with the agent, melt polymer, etc. In the co-extrusion method, another polymer melted and extruded is contacted with the inside and / or outside of the die. In the extrusion coating method, the melt coating on at least one surface of another substrate or the composite film described here
The extruded composition used in the present invention is coated to form a composite film. Further details of these are described in the "Handbook of Laminating Process" published by the Processing Technology Study Group.

(7) Additive The film of the present invention contains known additives such as an antioxidant, a weather resistance agent, a lubricant, an anti-blocking agent, an antistatic agent, an antifogging agent, an anti-drop agent, a pigment and a filler. can do.

[0049]

INDUSTRIAL APPLICABILITY As described above, the present invention is suitable for packaging in which various physical properties such as mechanical properties, heat seal properties, hot tack properties, optical properties, and processability are comprehensively balanced and highly satisfied. An optimum polyolefin composition, a film made of the composition, and a composite film can be provided. The polyethylene-based film obtained in the present invention has a specific crystalline propylene-based polymer, which is incompatible with polyethylene, finely dispersed in an ethylene-α-olefin random copolymer and oriented in a certain direction. By the action of showing, compared with the original polyethylene-based film, the waist is stronger (high rigidity), the tensile strength is stronger,
It has high tear strength, a wide temperature range where hot tack develops, a low load during processing, and properties such as transparency, luster, low temperature heat sealability, and low temperature hot tack that do not deteriorate so much. Therefore, the performance as a packaging film can be dramatically improved. Further, the crystalline propylene-based polymer film obtained in the present invention has a specific ethylene-α-olefin random copolymer, which is incompatible similarly to the polyethylene-based film, finely dispersed in the propylene-based polymer, By virtue of its directional morphology, it has a low temperature heat sealability and a low temperature hot seal without deteriorating the transparency, gloss, mechanical strength and impact resistance of the original crystalline propylene polymer film. It has the property of enhancing tackiness and tear strength balance, and can greatly improve the performance as a packaging film.

[0050]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. Physical property values in Examples and Comparative Examples were measured by the following methods. (1) Density According to the method specified in JIS K6760. 100
After annealing in water at ℃ for 1 hour, the density was measured. (2) Melt flow rate (MFR) According to the method specified in JIS K6760. However, the same method was used to measure the crystalline propylene-based polymer. (3) Weight average molecular weight (Mw) It was measured by gel permeation chromatography (GPC) under the following conditions. Equipment: Waters 150C type column: Tosoh Corp. TSK GHM-6 (6 mm φ × 600 mm) Solvent: o-dichlorobenzene (ODCB) Temperature: 135 ° C. Flow rate: 1.0 ml / min Injection concentration: 10 mg / 10 ml ODCB (Injection volume: 500 μl) The column elution volume was calibrated by the universal method using standard polystyrene manufactured by Tosoh Corporation and Pressure Chemical Co. (4) Tensile strength at 120 ° C. Using a Bravender PLV-151 type Brabender Plasticorder manufactured by Brabender Co., Ltd., after kneading at 180 ° C. and 60 rpm for 10 minutes, press molding was performed at 180 ° C. for 5 minutes to obtain a press sheet having a thickness of 1 mm. It was Press sheet is ASTM D18
22 TYPE was punched out to obtain a test piece. Grip the test pieces into the Toyo Seiki Seisakusho strograph T-type and set a gap of 20
After mounting the device in mm, the temperature inside the device was set to 120 ° C., and the tensile strength was measured under the condition of a pulling speed of 500 mm / min. (5) Endothermic peak temperature measured by a differential scanning calorimeter (DSC) DSC-7 manufactured by Perkin Elmer was used. When measuring the temperature rise thermogram after complete melting and slow cooling. About 10 mg of a test piece cut out from a sheet with a thickness of about 0.5 mm prepared by hot pressing was put in a sample pan for DSC measurement, and premelted at 180 ° C. for 5 minutes in DSC,
After cooling to 40 ° C at a rate of 1 ° C / min and holding for 5 minutes,
The temperature was raised to 180 ° C at a rate of 10 ° C / min to obtain a thermogram. When measuring the temperature rise thermogram directly from the film state. Approximately 10 mg of film laminated on several sheets was put in a sample pan for DSC measurement, held at 40 ° C for 5 minutes in DSC, and then heated to 180 ° C at a rate of 10 / min to obtain a thermogram. (6) Haze (Haze) According to the method specified in ASTM D1003. The smaller this value, the better the transparency. (7) Gloss (gloss) According to the method specified in JIS Z8741. The larger this value, the better the gloss. (8) 1% secant modulus (Secant Module)
s) Film processing direction (MD) or its orthogonal direction (TD)
A test piece with a width of 2 cm is cut out and attached to a tensile tester with a gripping distance of 6 cm and pulled at a speed of 5 mm / min, 1%
The stress when stretched was calculated by the formula of 100 × (stress) / (cross-sectional area). (9) Dirt impact strength According to ASTM D1709 method A. (10) Elmendorf tear strength According to the method specified in JIS Z1702. (11) Tensile strength According to the method specified in JIS Z1702. (12) Heat sealing property The polyolefin film layers of the two composite films were put together and a heat sealer manufactured by Tester Sangyo Co., Ltd. was used to form a sealing surface pressure of 1.3 kg / cm ² and a sealing time of 0.
Heat sealing with a seal width of 10 mm was performed under the condition of 3 seconds. The temperature of the seal bar (heat sealing temperature) was changed by 5 ° C. and heat sealing was performed in the same manner. From these, a test piece with a width of 15 mm was cut out in a direction perpendicular to the sealing surface, and 1 piece was cut at a speed of 200 mm / min using a Shopper-type tensile tester.
The 80 ° peel strength was measured at room temperature. (13) Low-temperature heat-sealing property When the measurement value measured by the method described in (12) above is shown in a line graph in the relation of heat-sealing temperature-peeling strength,
The comparison was made by the heat seal temperature on the lowest temperature side where the peel strength was 1 kg or more. The lower the temperature, the better the low temperature heat sealability. (14) Hot tack property The polyolefin film layers of the composite film cut out to a width of 15 mm are put together, and one side is connected with a pulley through 30
A load of g was applied, and a heat sealer manufactured by Tester Sangyo Co., Ltd. was used to perform heat sealing with a sealing width of 20 mm under the conditions of a sealing surface pressure of 1.3 kg / cm ² and a sealing time of 0.3 seconds. The load dropped at the same time as the end of the sealing, and the peeling force due to the load was applied to the sealing surface 0.14 seconds after the end of the sealing. Therefore, the actually peeled length was measured.
A similar test was conducted by changing the temperature of the seal bar (heat sealing temperature) in steps of 5 ° C. (15) Hot Tackability Suitable Range When the measurement value measured by the method described in (14) above is shown in a line graph in the relation of heat seal temperature-peeling distance,
The comparison was made by the heat seal temperature on the lowest temperature side and the heat seal temperature on the highest temperature side where the peeling distance continuously becomes 5 mm or less. The lower the heat sealing temperature on the low temperature side, the better the low temperature hot tack property. Further, the larger the difference between the heat sealing temperatures on the low temperature side and the high temperature side, the wider the temperature range suitable for hot tacking.

Example 1, Comparative Example 1 (1) Ethylene-α-olefin random copolymer (I)
The bottom of the tank reactor with a stirrer having an internal volume of 200 liters
A solution of predetermined ethylene and butene-1 dissolved in n-hexane was continuously supplied at a constant amount of 80 kg / hour of n-hexane and ethylene and butene-1, respectively. From another feed line, vanadyl trichloride, ethylaluminum sesquichloride, and n-butyl perchlorcrotonate were each continuously fed at a constant rate / hour. The temperature inside the reactor was controlled at 50 ° C. by circulating cooling water in a jacket attached to the outside of the reactor. Continuously withdraw the polymerization liquid from the upper part of the reactor so that the inside of the reactor is always full, add a small amount of methanol to stop the polymerization reaction, demonomerize and wash with water, and then steam strip the solvent. The solid copolymer was taken out and dried at 80 ° C. under reduced pressure to obtain an ethylene-1-butene random copolymer. Polymerization conditions, copolymer production rate, and obtained ethylene-1-butene random copolymer (IA)
Density, MFR, DSC measured after complete melting and slow cooling
Endothermic peak value in the thermogram, 80 to 10
Endotherm of the maximum endothermic peak observed within the range of 0 ° C (△
Table 1 shows the ratio of H (A)) to the total endotherm, the half-width (Wa1 / 2) of the maximum endothermic peak, and the α-olefin content. (2) Crystalline propylene-based polymer (II) As the crystalline propylene-based polymer (II), the ethylene content is 2.6 mol% and the butene-1 content is 11.2 mol%.
Ethylene-propylene-1-butene terpolymer (II
-A) was used. MFR of the terpolymer (II-A),
Table 3 shows endothermic peak values and α-olefin content in the DSC thermogram measured after complete melting and slow cooling. (3) Ethylene-1-butene random copolymer (I-
A) and crystalline propylene-based polymer (II-A) are mixed at a ratio of IA and II-A shown in Table 4 using a Nippon Roll Mfg. Co. #O type intensive mixer at 170 ° C.
And kneaded for 10 minutes. At this time, 2000 ppm of calcium stearate, 2500 ppm of antioxidant and 4000 ppm of silica-based antiblocking agent were added to the total weight of the above resins. (4) Production of Film Using an inflation molding machine K-40R manufactured by Placo Co., which is equipped with a spiral die having a die diameter of 125 mm, a die lip of 2.0 mm and a one-step air ring with an iris, 1
Extrusion rate of 5 kg / hour, die set temperature of 175 ° C.,
30 from the composition of (3) under the condition of BUR of 1.8
A film with a thickness of μm was obtained. Table 4 shows the endothermic peak temperature in the DSC thermogram obtained by directly raising the temperature of the film thus obtained, and the physical properties of the film. The film used for manufacturing the following composite film has a surface tension of 45d by a corona treatment machine attached to the apparatus.
Corona treatment was performed so as to be yne / cm. (5) Manufacture of composite film Using a Yasui Seiki desktop type test coater, the film obtained in (4) above was coated with a urethane-based adhesive so as to be ² g / m ² after drying. A dry lamination composite film was obtained by pressing the stretched nylon base film at 40 ° C. under a pressure of 3 kg / cm ² and then heat aging it at 40 ° C. for 2 days. Table 4 shows the temperatures of the composite film thus obtained, which are within a suitable range of low-temperature heat-sealing property and hot-tack property.

Examples 2-9, Comparative Examples 2-5 (1) Ethylene-α-olefin random copolymer (I) The ethylene-1-butene random copolymer (IA) of Example 1 (1). Was used. (2) Crystalline propylene-based polymer (II) As the crystalline propylene-based polymer (II), the propylene-based polymer (II-A) of (2) of Example 1 or butene-1 content 15.8 mol. % Propylene-1-butene copolymer (II-B), or ethylene content 0.6 mo
1% propylene-ethylene random copolymer (II-
C) was used. Crystalline propylene-based polymer (II-B, II
-C) MFR, DSC measured after complete melting and slow cooling
Table 3 shows the values of the endothermic peak and the α-olefin content in the thermogram. (3) Ethylene-α olefin random copolymer (I-
A) and a crystalline propylene polymer (II-A, II-B, or II-C) mixed IA and II-A, IA and II-B, or IA
And II-C at the ratios shown in Table 5 were kneaded and granulated at 190 ° C. and 80 rpm using a 30 mmφ non-belt single-screw extruder pellet manufacturing apparatus manufactured by Union Plastics.
At this time, the total weight of the above resins (IA, II-A, II-B
Or, in the case of II-C only, the total amount thereof is 2,000 ppm of calcium stearate and 25 ppm of antioxidant.
00ppm, 4000pp of silica-based anti-blocking agent
m was added. (4) Production of film A T-die film molding machine manufactured by Tanabe Plastic Co., Ltd. equipped with an extruder having an inner diameter of 50 mm, a T-die having a die width of 400 mm, a die gap of 0.7 mm and a semi-matt roll, a processing temperature of 240 ° C., and an extrusion amount of 9 0.2 kg / hour, chill roll temperature 3
A film with a thickness of 30 μm was obtained at 0 ° C. The surface tension is 45 dyne by the corona treatment machine attached to the device.
Corona treatment was performed so as to be / cm. Table 5 shows the physical properties of the film thus obtained. Table 5 shows the resin pressure under the above processing conditions. (5) Manufacture of composite film Using a Yasui Seiki desktop type test coater, the film obtained in (4) above was coated with a urethane-based adhesive so as to be ² g / m ² after drying. A dry lamination composite film was obtained by press-bonding the stretched nylon substrate film at 40 ° C. at 3 kg / cm ² and then aging it by heating at 40 ° C. for 2 days. Table 5 shows the temperatures of the composite film thus obtained, which are within a suitable range of low-temperature heat-sealing property and hot-tack property.

Example 10 (1) Ethylene-α-olefin random copolymer (I)
After the tank type reactor with an agitator having an inner volume of 214 liters was replaced with nitrogen, 17.4 kg of butane as a solvent and 35.1 kg of butene-1 as an α-olefin were charged, and the temperature of the reactor was raised to 40 ° C. After heating, hydrogen pressure is 0.1 kg / c
After adjusting m ² and ethylene pressure to 11.1 kg / cm ² , polymethylaluminoxane manufactured by Tosoh Akzo Co., Ltd. as an organoaluminum oxy compound was converted into Al atom and added in 600 mmol, and then bis as a transition metal compound. (Cyclopentadienyl) zirconium dichloride 0.03 mmol was added to initiate polymerization. Polymerization was carried out for 5 hours while adjusting the temperature to 40 ° C. and the ethylene pressure to 11.1 kg / cm ^2, and then a small amount of methanol was added to terminate the polymerization reaction. After the solvent and the monomer are discharged from the reactor until the pressure difference with the atmosphere is eliminated, a large amount of methanol is added, washed, filtered, and the powdery copolymer is taken out and dried to obtain ethylene-1-butene random. 11.3 kg of copolymer was obtained. Obtained ethylene-1-
The butene random copolymer (IE) has a density of 0.90.
6 g / cm ³ , MFR 2.0 g / 10 min, weight average molecular weight (Mw) 83000, maximum melting endothermic peak temperature in DSC thermogram measured after complete melting and cooling, 97.0 ° C., 80-100 The ratio of the endothermic amount (ΔH (A)) of the maximum endothermic peak observed in the range of ℃ to the total endothermic amount is 1.0, and the full width at half maximum (Wa1 /
2) is 15.3 ° C. and the butene-1 content is 5.26 mol%. (2) Ethylene-1-butene random copolymer (I-
Mixing of E) and crystalline propylene polymer (II-C) IE and II-C were kneaded and granulated in the same manner as in Example 2 in the proportions shown in Table 5. (3) Production of film A T-die film forming machine manufactured by Tanabe Plastic Co., Ltd. equipped with an extruder having an inner diameter of 50 mm, a T-die having a die width of 400 mm, a die gap of 0.7 mm, and a semi-matt roll, a processing temperature of 270 ° C., and an extrusion amount of 9 0.2 kg / hour, chill roll temperature 3
A film with a thickness of 30 μm was obtained at 0 ° C. The surface tension is 45 dyne by the corona treatment machine attached to the device.
Corona treatment was performed so as to be / cm. Table 5 shows the physical properties of the film thus obtained. Table 5 shows the resin pressure under the above processing conditions. (4) Manufacture of composite film Using a Yasui Seiki tabletop test coater, the film obtained in (3) above was coated with a urethane-based adhesive so as to be ² g / m ² after drying. A dry lamination composite film was obtained by press-bonding the stretched nylon substrate film at 40 ° C. at 3 kg / cm ² and then aging it by heating at 40 ° C. for 2 days. Table 5 shows the temperatures of the composite film thus obtained, which are within a suitable range of low-temperature heat-sealing property and hot-tack property.

Comparative Examples 6 to 8 (1) Ethylene-α-olefin random copolymer (I)
Production of Sumitomo Chemical Co., Ltd. Excellen (VL102) was used as an ethylene-1-butene random copolymer (IB). Ethylene-1-butene random copolymer (I-
B) density, MFR, DS measured after slowing after complete melting
Table 2 shows the value of the endothermic peak in the C thermogram and the α-olefin content. The maximum endothermic peak value of IB is 10
Higher than 0 ℃. (2) Ethylene-1-butene random copolymer (I-
B) and crystalline propylene polymer (II-B) mixed IB and II-B in the proportions shown in Table 6 in Examples 2-1
0 or kneading and granulating in the same manner as in Comparative Examples 2 to 5. (3) Production of film A T-die film molding machine manufactured by Tanabe Plastic Co., Ltd. equipped with an extruder having an inner diameter of 50 mm, a T-die having a die width of 400 mm, a die gap of 0.7 mm and a semi-matt roll, a processing temperature of 280 ° C., and an extrusion amount of 9 0.2 kg / hour, chill roll temperature 3
A film with a thickness of 30 μm was obtained at 0 ° C. The surface tension is 45 dyne by the corona treatment machine attached to the device.
Corona treatment was performed so as to be / cm. The physical properties of the film thus obtained are shown in Table 6. (4) Manufacture of composite film Using a Yasui Seiki tabletop test coater, the film obtained in (2) above was coated with a urethane-based adhesive so as to be ² g / m ² after drying. A dry lamination composite film was obtained by press-bonding the stretched nylon substrate film at 40 ° C. at 3 kg / cm ² and then aging it by heating at 40 ° C. for 2 days. Table 6 shows the temperature of the composite film thus obtained, which is within a suitable range of low-temperature heat-sealing property and hot-tack property.

Comparative Example 9 Sumikasen (L211) [B- manufactured by Sumitomo Chemical Co., Ltd.
LDPE] was used as the ethylene-α olefin random copolymer (IC). Table 2 shows the density, MFR, and endothermic peak values in the DSC thermogram measured after complete melting and slow cooling after ethylene-α olefin random copolymer (IC). Except that the ethylene-α-olefin random copolymer (IC) is used instead of the ethylene-1-butene random copolymer (IA) of Example 2,
It carried out like (3) of Example 2, (4), and (5).
However, only the processing temperature in film production (4) is 2
The temperature was changed to 80 ° C. The properties of the film and composite film thus obtained are shown in Table 6.

Comparative Examples 10 to 12 (1) Ethylene-α-olefin random copolymer (I) Sumikasen L (FA201- manufactured by Sumitomo Chemical Co., Ltd.)
0) to ethylene-1-butene random copolymer (I-
Used as D). Density of ethylene-1-butene random copolymer (ID), MFR, value of endothermic peak in DSC thermogram measured after complete melting and slow cooling,
Table 2 shows the α-olefin content. (2) Ethylene-1-butene random copolymer (I-
D) and crystalline propylene-based polymer (II-B) mixed I-D and II-B in the proportions shown in Table 6 were obtained in Examples 2 and 4.
Alternatively, kneading and granulation were performed as in Comparative Example 2. (3) Production of film A T-die film molding machine manufactured by Tanabe Plastic Co., Ltd. equipped with an extruder having an inner diameter of 50 mm, a T-die having a die width of 400 mm, a die gap of 0.7 mm and a semi-matt roll, a processing temperature of 250 ° C., and an extrusion amount of 9 0.2 kg / hour, chill roll temperature 3
A film with a thickness of 30 μm was obtained at 0 ° C. The surface tension is 45 dyne by the corona treatment machine attached to the device.
Corona treatment was performed so as to be / cm. The physical properties of the film thus obtained are shown in Table 6. (4) Manufacture of composite film Using a Yasui Seiki tabletop test coater, the film obtained in (3) above was coated with a urethane-based adhesive so as to be ² g / m ² after drying. A dry lamination composite film was obtained by press-bonding the stretched nylon substrate film at 40 ° C. at 3 kg / cm ² and then aging it by heating at 40 ° C. for 2 days. Table 6 shows the temperature of the composite film thus obtained, which is within a suitable range of low-temperature heat-sealing property and hot-tack property.

[0057]

[Table 1]

[0058]

[Table 2]

[0059]

[Table 3]

[0060]

[Table 4]

[0061]

[Table 5]

[0062]

[Table 6]

[Brief description of drawings]

FIG. 1 is a diagram illustrating a half-value width (Wa1 / 2) of an endothermic peak of an ethylene-α olefin random copolymer.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI technical display area C08L 23/18

Claims (12)

[Claims] 1. A density of 0.895 to 0.915 g / cm.sup.2.
³ , which was 80 to 10 in the temperature rising thermogram measured by a differential scanning calorimeter after complete melting and slow cooling.
A random copolymer of ethylene and an α-olefin having 4 to 10 carbon atoms, in which an endothermic peak is observed in the range of 0 ° C. and the endothermic amount of the endothermic peak is 0.9 or more with respect to the total calorific value (I). A polyolefin composition comprising 99 to 1 part by weight and 1 to 99 parts by weight of a crystalline propylene polymer or propylene polymer mixture (II). 2. The ethylene-α olefin random copolymer (I) has a melt flow rate (190 ° C.) of 0.1 to 15 g / 10 minutes, and (I) and a crystalline propylene-based polymer or a propylene-based polymer. The polyolefin composition according to claim 1, wherein the difference in melt flow rate (190 ° C) of the combined mixture (II) is 10 g / 10 minutes or less. 3. A crystalline propylene polymer or a propylene polymer mixture (II) is a propylene homopolymer,
Propylene and ethylene and / or C4-10
Is a copolymer with α-olefin or a mixture thereof and has a melt flow rate (190 ° C.) of 0.1 to 1.
5 g / 10 min, which was 12 in a temperature rising thermogram measured by a differential scanning calorimeter after complete melting and slow cooling.
The polyolefin composition according to claim 1 or 2, wherein an endothermic peak is observed in the range of 5 to 175 ° C. 4. A crystalline propylene-based polymer or propylene-based polymer mixture (II) containing 60 to 95 parts by weight of an ethylene-α-olefin random copolymer (I).
Is 5 to 40 parts by weight. The polyolefin composition according to any one of claims 1 to 3. 5. The ethylene-α-olefin random copolymer (I) is 50 to 5 parts by weight, and the crystalline propylene polymer or propylene polymer mixture (II) is 50 to 95 parts by weight. Item 5. The polyolefin composition according to any one of items 1 to 3. 6. Tensile strength at 120 ° C. measured with a 1 mm thick sheet press-formed after melt-kneading.
/ Cm ² or less, the polyolefin composition according to any one of claims 1 to 4. 7. Tensile strength at 120 ° C. measured on a 1 mm thick sheet press-formed after melt-kneading is 20 kg.
/ Cm ² or more, the polyolefin composition according to any one of claims 1 to 3 and 5. 8. An ethylene-.alpha.-olefin random copolymer (I) has a temperature rise thermogram measured by a differential scanning calorimeter of 80 to 10 after complete melting and slow cooling.
The polyolefin according to any one of claims 1 to 7, wherein an endothermic peak is observed in the range of 0 ° C, and the endothermic amount of the endothermic peak is 1.0 relative to the total amount of heat of the ethylene-α olefin random copolymer. Composition. 9. A film comprising the polyolefin composition according to any one of claims 1 to 8. 10. A temperature-increasing thermogram measured directly from a film state by a differential scanning calorimeter with at least 1.
More than one endothermic peak was observed in the range of 80 to 100 ° C, and the tensile strength at 120 ° C measured by a 1 mm thick press sheet formed from the film was 10 kg / c.
The film according to claim 9, which is not more than m ² . 11. A temperature-increasing thermogram measured directly from a film state by a differential scanning calorimeter with at least 1.
More than one endothermic peak was observed within the range of 80 to 100 ° C, and the tensile strength at 120 ° C measured by a 1 mm thick press sheet formed from the film was 20 kg / c.
The film according to claim 9, which is at least m ² . 12. A composite film, wherein at least one layer in the laminated film is a layer comprising the film according to any one of claims 9 to 11.