WO2016010400A1 - Ethylene-1-hexene-1-butene terpolymer and film comprising same - Google Patents

Abstract

The present invention relates to an ethylene-1-hexene-1-butene terpolymer and a film comprising the same. The ethylene-1-hexene-1-butene terpolymer according to the present invention has optimized ranges of density and melting index, comprises 1-hexene and 1-butene as comonomers, and can provide a polymer with excellent physical properties by adjusting the content ratio of the comonomers to a predetermined range. Therefore, the film manufactured using the same retains excellent adhesiveness, processability, and dart impact strength so as to be suitable for, especially, a stretch film, and thus can be favorably used.

Description

 【Specification】

 [Name of invention]

 Ethylene-1-Nucene-1-butene Ternary Copolymer and Film Comprising the Same

 [Cross Citation with Related Application (s)]

 The present application is the Korean Patent Application No. 10-2014-0091055 dated July 18, 2014 and

Claims the benefit of priority based on Korean Patent Application No. 10-2015-0100965 filed on July 16, 2015, the entire contents of which are disclosed in the literature of the Korean Patent Application.

 Technical Field

 The present invention relates to an ethylene-1-nuxene-1-butene ternary co-polymer and a film comprising the same. More specifically, the present invention relates to an ethylene-1-nuxene-1-butene ternary copolymer suitable for stretch films having excellent physical properties such as adhesiveness and falling layer stratification strength, and a film comprising the same.

 Background Art

 In general, a polymer film refers to a non-fibrous flat plastic molding having a thickness of 0.25 mm (l / 100 inch) or less. Polymer is light, good barrier property, excellent transparency and relatively low price. It is used in almost all fields such as packaging materials, household goods, automobiles, electronic devices, aircraft, etc. It is easy to process and easy to make into film. Synthetic polymers such as polyethylene, polypropylene, polyvinyl chloride, and polyethylene terephthalate have been developed at home and abroad, and are widely used as polymer films. Currently, many synthetic polymers are used alone or as a blending material.

 In particular, polyethylene (PE) is divided into low density polyethylene, high density polyethylene, and linear low density polyethylene according to density, copolymerization, and branching type, and various polyethylene products have been introduced in the metallocene catalyst system which has been commercialized recently.

Low-density polyethylene is one of general purpose resins that was used as an insulating material for military radars because of its excellent electrical properties, after being successfully synthesized by ICI in 1933. The main uses are general packaging, agriculture, shrink film, paper coating, etc. Excellent melt tension, suitable for coating applications.

 Linear low density polyethylene is prepared by copolymerizing ethylene and alpha olefin at low pressure using a polymerization catalyst, and has a narrow molecular weight distribution, a short length branch of a constant length, and a long chain branch. Linear low density polyethylene film has high fracture strength and elongation as well as characteristics of general polyethylene, and it is excellent in tear strength and fall stratification strength, so it is not suitable for use of stretch film or overlap film that is difficult to apply to existing low density polyethylene or high density polyethylene. It is increasing.

 In such linear low density polyethylene, the breaking strength, tear strength, and falling layer strength, which are important properties of the film, are largely influenced by alpha olepin used as comonomer, and alpha olepin used as 1-butene, 1 -Nuxene, 1-octene and the like.

 Generally, the physical properties of the linear low density polyethylene film are known to be excellent when 1-octene is used, but the price of 1-octene comonomer is expensive and disadvantageous in terms of economics. On the other hand, in the case of stretch films requiring adhesion, it is required to use polyethylene of significantly low density. On the other hand, the slurry loop process, which is one of general polymerization processes of polyethylene, is known to use 1-butene as a comonomer to obtain polyethylene of low density. However, in the case of 1-butene, the physical properties are lower than that of other comonomers, and thus, low-density linear polyethylene products using low-density linear polyethylene products other than 1-butene are industrially demanded technologies.

 Therefore, in this background, there is a constant demand for manufacturing a better product having a balance between physical properties and economics, and improvements are needed.

 [Content of invention]

 Problem to be solved

The present invention is to solve the problems of the prior art as described above, to provide an ethylene-1-nuxene-1-butene terpolymer having an excellent balance of physical properties. ^'

 Still another object of the present invention is to provide a film comprising the ethylene ᅳ 1-nuxene -1-butene terpolymer.

[Measures of problem] One aspect of the present invention for achieving the above _{object, CI (C 0 -mon 0 m} er Incorporation) Index of 0.5 to 5; Density is 0.900 to 0.916 g / cm ³ ; Melt flow index (Ml) measured at 190 ^° C., 2.16 kg loading conditions in accordance with ASTM D1238; 2.0 to 5.0 g / 10 min; An ethylene-1-nuxene-1-butene terpolymer is provided wherein the weight ratio of 1-nuxene to 1-butene is 1-5.

 A second aspect of the present invention for achieving the above object, provides a film comprising the ethylene-1-nuxene-1_butene terpolymer.

 【Effects of the Invention】

Ethylene-1-nuxene-1′butene terpolymer according to the present invention has an optimized range of CI Index, density and melt index, and includes 1-nuxene and 1-butene as comonomers, and between comonomers by adjusting the content ratio in a predetermined _range. It is possible to provide a polymer having low density and excellent physical properties. Therefore, the film produced using the same has excellent adhesiveness, processability, and dart impact strength characteristics, particularly suitable for stretch films, and thus can be usefully used.

 [Brief Description of Drawings]

 1 is a graph illustrating an example of a method of measuring a CI index using a molecular weight distribution curve.

 [Specific contents to carry out invention]

 As the invention allows for various changes and numerous modifications, particular embodiments will be illustrated and described in detail below. However, this is not intended to limit the present invention to a specific disclosed form, it should be understood to include all modifications, equivalents, and substitutes included in the spirit and scope of the present invention.

 Hereinafter, the present invention will be described in more detail.

 One aspect of the present invention, CI (Co-monomer Incorporation) represented by the following formula 1

Index is 0.5 to 5; ¾ degree is 0.900 to 0.916 g / cm ³ ; Melt flow index (Ml) measured at 190 ^° C., 2.16 kg loading conditions in accordance with ASTM D1238, 2.0-5.0 g / 10 min; ethylene-1- with a weight ratio of 1-nuxene to 1-butene 1-5 Nucleene-1-butene terpolymer is provided:

[Equation 1] (SCB content of high molecular weight side SCB box of low molecular weight side)

Q Index = — — ^■

 (Low molecular weight ¾ 5 (: 8 ¾ quantity)

 Ethylene-1-nuxene-1-butene terpolymer of the present invention has a Co-monomer Incorporation (CI) Index calculated from the formula 1 of about 0.5 to about 5, or about 1.0 to about 5, or about 1.5 to about 5 Can be.

 As used herein, the CI structure is a structure in which the content of comonomers such as alpha olepin is concentrated in the high molecular weight main chain, that is, a new structure in which the content of short chain branch (SCB) increases toward the higher molecular weight. Means.

 The CI Index can measure the molecular weight, molecular weight distribution and SCB content simultaneously using the GPC-FTIR apparatus, and the log value (log M) of the molecular weight (M) is the X-axis, and the molecular weight of the log. When the molecular weight distribution curve is plotted with the y-axis distribution (dwt / dlog M), the SCB (Short Chain Branch) content (the number of carbons per 1,000 carbons) at the left and right boundaries of 60% except for 20% of the left and right ends of the total area. 2 to 7 branch content (unit: dog / 1,000C) can be measured and calculated by Equation 1 below. In this case, the high molecular weight side SCB content and the low molecular weight side SCB content mean the SCB content values at the right boundary and the left boundary in the middle 60% range except for the left and right ends 20%.

 An example of a measurement method of such a CI index is shown in FIG. 1.

 [Equation 1]

 (SC & High Molecular Weight-SCB Content on Low Molecular Weight)

Q Index = —— — —— ^{■ ■}

 (See low molecular weight i)

 At this time, if the CI Index is 0 or less, it is not a polymer of CI structure, and if it is larger than 0, it can be regarded as a polymer of CI structure.

 Ternary copolymers according to the invention, together with ethylene, are comonomers of

Includes all 1-butenes.

 The weight ratio of 1-nuxene to 1-butene in the comonomer may be about 1 to about 5, preferably about 1.5 to about 3.5, more preferably about 2.0 to about 3.5.

In addition, according to an embodiment of the present invention, the ethylene-1-nuxene-1-butene 3-membered The content of 1-butene and 1-haeksen from about 5 to about 15 parts by weight _^0/0 of the total weight of the copolymer, preferably from about 8 to about 13% by weight.

 When the total content and the increase ratio of 1-nucleene to 1-butene are in the above ranges, low density polyethylene can be obtained by lowering the density of the copolymer without deteriorating other physical properties, and excellent adhesion of about 8 kgf / mm or more can be realized.

Terpolymers according to the invention have a density ranging from about 0.900 to about 0.916 g / cm ³ , preferably from about 0.900 to about 0.915 g / cm ³ , more preferably from about 0.905 to about 0.915 g / cm ³ . Have When the density of the ethylene-1-nuxene-1-butene ternary copolymer is in the above range, it may exhibit excellent adhesive strength and falling layer stratification strength.

 In general, the density of polyolefins is affected by the amount of alpha olepin comonomer used. In other words, when the amount of the alpha olefin copolymer comonomer is large, the density decreases, and when the amount of the alpha olefin comonomer is small, the density increases. However, it is not easy to implement various physical properties suitable for stretch films, including density, using only a single comonomer.

 Accordingly, the present invention, alpha olepin comonomer comprising 1-nuxene and 1-butene

By providing a ternary copolymer, by optimizing the content of the 1-nuxene and 1-butene and the relative weight ratio of each, as described above, the physical properties suitable for the film such as low density, excellent processability, adhesion and fall impact strength.

Further, the melt flow index (Ml) at 190 ^° C. and 2.16 kg loading conditions of the ethylene-1-nuxene-1-butene terpolymer of the present invention is about 2.0 to about 5.0 g / 10 min, preferably Can be from about 2.5 to about 4.5 g / 10 minutes, more preferably from about 2.5 to about 3.5 g / 10 minutes. When the melt flow index is in the above range, it may be preferable as an optimum point capable of harmonizing molding processability and mechanical properties.

 According to one embodiment of the invention, the weight average molecular weight of the terpolymer of the invention is about 50,000 to about 150,000 g / mol, preferably about 60,000 to about 120,000 g / mol, more preferably about 60,000 to about 100,000 g / md, but is not limited thereto.

In addition, according to one embodiment of the present invention, the molecular weight distribution (weight average molecular weight / number average molecular weight) of the terpolymer of the present invention is about 1.5 to about 5, preferably about 2.5 to about 4, more preferably about 2.5 To about 3.5, but is not limited thereto. It is not.

 The ethylene-1-nuxene-1-butene ternary copolymer according to the present invention is suitable for film applications such as low density, excellent workability, adhesion and fall stratification strength, and can be particularly useful for producing stretch films.

 Ternary copolymers according to the present invention may be prepared according to, for example, the production method described below, but are not limited thereto.

 According to one embodiment of the invention, the ethylene-1-nuxene-1-butene terpolymer can be prepared in the presence of a supported metallocene catalyst. More specifically, when the carrier catalyst particles are cut in cross section, an outer layer comprising up to one third of the total diameter of the particles from each surface towards the center, and the remainder from one third of the particles to the inner center A silica carrier composed of an inner layer comprising a portion, wherein the alkylaluminoxane is supported on the inside and the surface of the carrier; At least one metallocene compound supported on the silica carrier, wherein the Al / Si element content ratio (weight%) of the inner layer is at least 65% of the Al / Si element content ratio (weight%) of the outer layer , In the presence of a supported metallocene catalyst, by copolymerizing ethylene, 1-nuxene, and 1-butene.

 In the specification of the present invention, the supported catalyst particles include a silica carrier on which an alkylaluminoxane as a promoter is supported. In addition, when these supported catalyst particles are cut in cross section, one third of the total diameter of the particles from each surface toward the center is A portion including up to the point where defined is defined as the outer layer, and the remaining portion from one third of the particle to the inner center, that is, a portion including two thirds of the remaining inner center is defined as the inner layer. Thus, the inner layer comprises a portion 70% of the longest radius from the center of the silica carrier in the supported metallocene catalyst and the outer layer comprises the remaining outer portion of the silica carrier.

 In addition, the inside of the silica carrier mentioned in the present invention includes pores.

 In addition, unless otherwise stated throughout the present specification, the term "water content" of a carrier is defined as the percentage of the weight of water contained in the carrier relative to the total weight of the carrier.

In addition, in the present invention, the supported metallocene catalyst refers to a catalyst on which one or more metallocene compounds are supported. In addition, the supported metallocene catalyst of the present invention may further include a borate-based compound as a second cocatalyst. The supported metallocene catalyst has a large amount of alkylaluminoxane penetrated into the inside of the silica carrier and pores to be chemically bonded, and a considerable amount of alkylaluminoxane is physically bonded to the surface. In other words, the alkyl aluminoxane that penetrates into the carrier and is chemically bonded is small. However, the supported metallocene catalyst is to allow the promoter to be supported on the inner layer more than before. Therefore, the supported metallocene catalyst contains a large amount of alkylaluminoxane in the inner layer in the configuration consisting of the inner layer and the outer layer, thereby improving the apparent density and controlling the catalyst activity easily.

 In the supported metallocene catalyst having such a characteristic, the Al / Si element content ratio (wt%) of the inner layer is the Al / Si element content of the outer layer when elemental analysis of an alkyl aluminoxane-supported silica carrier is performed. It becomes 65% or more of ratio (weight%), Preferably it is 90 to 150%. This means that the amount of aluminum penetrated deeply into the inner layer of the silica carrier is large.

 The metallocene compound is a metallocene compound well known in the art of one or more of the following. ^ "Available.

 The method for producing the supported metallocene catalyst includes the steps of preparing a silica carrier; Contacting the silica carrier with an alkylaluminoxane as a promoter component to support the alkylaluminoxane on the inside and the surface of the silica carrier; And sequentially supporting one or more metallocene compounds on the silica carrier on which the alkylaluminoxane is supported, wherein the alkali aluminoxane may be supported on the silica carrier by a split dosing method at different temperatures.

 That is, the preparation method of the supported metallocene catalyst is characterized in that, when preparing the supported metallocene catalyst, the promoter is divided into the silica carrier so that the promoter is distributed in a relatively large amount, and the temperature range is varied. have.

According to this method, it is possible to provide a supported metallocene catalyst having a specific parameter with respect to the content of Al / Si in the carrier. Preferably, the supported metallocene catalyst has an outer layer comprising a point that, when the carrier catalyst particles are cut cross-sectionally, from each surface to a point that is one third of the total diameter of the particles, and a third point of the particles. A silica carrier comprising an inner layer comprising the remainder from the inner to the inner center, wherein the alkyl aluminoxane is supported on the inside and the surface of the carrier; The silica One or more metallocene compounds supported on the carrier, wherein the Al / Si element content ratio (weight%) of the inner layer is at least 65% of the Al / Si element content ratio (weight%) of the outer layer. Metallocene catalysts can be provided.

 Hereinafter, each step that may be included in the method will be described in more detail.

 First, a step of preparing a silica carrier is performed. According to one embodiment, a silica carrier having a morphology suitable for the Philips loop slurry process can be selected. By selectively controlling the amount of silane groups and siloxane groups on the silica carrier through calcinations conditions, the binding of the supported metallocene catalyst and alkylaluminoxane, the promoter, is optimized.

In addition, after the chemical reaction of the OH group of the silica and the viscosity of the co-catalyst (for example, MAO) in the high silver so as to penetrate to the inside after the chemical reaction proceeds, in order to physically adsorb on the silica surface, The firing temperature of the silica can range from the temperature at which moisture disappears from the surface of the silica to the silver range from which the OH groups are completely removed from the surface. According to a preferred embodiment, the firing conditions of the silica carrier is preferably baked at a temperature of 100 to 700 ^° C. Through the firing, the water content of the silica carrier is preferably 0.1 to 7 weight ⁰ /.

 In addition, as the carrier exhibits a water content in the above-described range, the carrier may include 0.5 to 5 mmol / g of hydroxyl group, preferably () .7 to 2 mmol / g of hydroxyl group, on the surface of the carrier.

 Such a carrier may be at least one member selected from the group consisting of silica, silica-alumina and silica-magnesia, preferably silica. In addition, any carrier that satisfies the above water content range can be used without limitation.

 In addition, if necessary, the surface of the carrier may be surface treated with a small amount of trialkylaluminum to exhibit more enhanced activity.

The trialkylaluminum may be at least one selected from the group consisting of trimethylaluminum (TMA1), triethylaluminum (TEA1) and tributylaluminum (TBA1), preferably triethylaluminum (TEA1). have. In addition, in the surface treatment step of the carrier, a solvent may be used to induce smooth contact reaction between the carrier and trialkylaluminum, and may be repeated without solvent.

The solvent includes aliphatic hydrocarbons such as nucleic acids, pentane and heptane; Aromatic hydrocarbons such as toluene and benzene; Hydrocarbons substituted with chlorine atoms such as dichloromethane; Ethers such as diethyl ether and tetrahydrofuran (THF); Most organic solvents such as acetone and ethyl acetate can be used. Preferably, a nucleic acid, heptane, toluene or dichloromethane may be used as the solvent. In addition, the surface treatment step of the carrier may be carried out at a temperature condition of 0 to 120 ^° C, preferably 10 to 100 ^° C, more preferably 30 to 9 (C in terms of process efficiency improvement.

 In addition, the amount of trialkylaluminum reacted on the surface of the carrier by the above step is not particularly limited, but in relation to the alkylaluminoxane described later, the molar ratio of alkylaluminoxane to trialkylaluminum is 1:10 to 1:20. , Preferably 1:12 to 1:18. That is, the molar ratio of alkylaluminoxane to trialkylaluminum is preferably 1: 10 or more, in order to be able to properly react with water on the surface of the carrier, and silanol groups on the surface of the carrier to react with alkylaluminoxane. In order not to be removed, the molar ratio is preferably 1:20 or less.

 According to one embodiment of the invention, the additional surface treatment step of the carrier is added to the solvent and the carrier in the reactor, and then mixed, trialkylaluminum is added to react with stirring for 30 minutes to 3 hours in the above-described temperature range It can be done by the method. However, the present invention is not limited thereto.

 Meanwhile, the method for preparing the supported metallocene catalyst includes contacting the silica carrier with alkylaluminoxane, which is a promoter component, to support the alkylaluminoxane on the silica carrier and the surface.

 In particular, the method for preparing a supported metallocene catalyst according to one embodiment of the present invention is characterized by splitting the temperature while changing the temperature from high temperature to low temperature when the alkylaluminoxane is supported on a silica carrier.

That is, the alkylaluminoxane is a primary at a high temperature of a part of the total charge It is added to the silica carrier by the divided addition method, which is added and the remaining content of the total amount is added at a low temperature secondly. The high temperature may include a range of 50 ^° C or more, preferably 50 to 150 ^° C., and the low temperature may include a range of 40 ^° C or less, or -10 to 40 ^° C.

Therefore, according to one embodiment of the present invention, the alkylaluminoxane is divided into 5 parts of the total input amount in the first input in the silver of rc or more, and the second content in the second input in the silver content of 40 ^° C or less. It can be supported on the silica carrier by the addition method.

In addition, the most according to a preferred embodiment, the said alkyl aluminoxane silica carrier-supported, 50 ^° C to amount of 50 to 90 parts by weight _^0/0 of the total alkyl aluminoxane at 150 ^° C of the present invention the silica support It can be obtained by a method of carrying out the first reaction by carrying out the first reaction, and supporting the remaining alkylaluminoxane at -KTC to 40 ^° C with a second addition to the silica carrier to carry out the second reaction.

More specifically, the contact a ^'to obtain a silica in the above step and the co-catalyst component is an alkyl aluminoxane. At this time, the contacting method according to an embodiment of the present invention by contacting the alkyl aluminoxane by dividing the alkyl aluminoxane in two parts as described above in the silica carrier, as described above, the alkylaluminoxane in a larger amount than the conventional It is allowed to penetrate, and also a considerable amount of alkylaluminoxane is supported on the surface. According to this method, the alkylaluminoxane is pore-filled into the silica carrier composed of the inner layer of the silica carrier supported on the inside and the surface and the outer layer surrounding it.

 In the method for preparing the supported metallocene catalyst according to an embodiment of the present invention, in order to increase the content of the promoter in the silica, chemical attachment is superior, and the viscosity of the reactant is lowered to increase the pore inside the silica. By contacting the alkylaluminoxane and the silica carrier in advance at a high temperature, which is a condition that is easy to diffuse, and contacting the alkylaluminoxane at a low temperature, the promoter component is supported by physical adsorption on the silica surface. Therefore, according to one embodiment of the present invention, the walk density and the catalytic activity of the polymer can be adjusted according to the amount of alkylaluminoxane and the contact silver as well as the dosing method.

The supporting conditions of such alkylaluminoxanes are alkylaluminoxanes as described above. At least two or more split-injections are used at high and low temperatures. For example, the alkylaluminoxane may be divided into two inputs, and the first injection may be performed in a range of a minimum temperature of 50 ^° C to a maximum temperature of 150 ^° C. In addition, at the time of the second addition, in the range of -KTC to 40 ^° C, the alkylaluminoxane is supported while being dividedly added to carry out post-reaction. In addition, the alkyl aluminoxane is added to the first input when the first bearing and the second input during the remaining residual amount was added to 50 to 90 parts by weight _^0/0 of the total amount of the alkyl aluminoxane is supported secondary.

 At this time, when the alkyl aluminoxane, which is the cocatalyst, is added at once without being divided into, the aluminum alumina is excessively present on the surface of the carrier because the alkyl aluminoxane is unevenly supported on the carrier. On the other hand, metallocene compounds with small molecules are uniformly supported inside and outside. Therefore, due to the batch of the alkylaluminoxane, the metallocene compound supported therein cannot be activated to reduce the total catalyst activity, and thus the polymerization by the catalyst activated only on the outside proceeds to lower the density. There is a problem.

 On the other hand, the alkyl aluminoxane (alkylaliminoxane) is a cocatalyst component to assist the activity of the metallocene compound to be described later.

 The step may be carried out by mixing the carrier and the alkylaluminoxane in the presence or absence of a solvent and reacting with stirring.

 Here, the alkyl aluminoxane may be at least one selected from the group consisting of methyl aluminoxane, ethyl aluminoxane, butyl aluminoxane and isobutyl aluminoxane.

 The amount of the alkylaluminoxane supported on the silica carrier by the above step may be 5 to 15 mmol / g based on the carrier lg. That is, within the supported amount range, by dividing at high temperature and low temperature to support the alkylaluminoxane on the silica carrier, the above-described linear reaction and post reaction of the alkylaluminoxane can be performed.

 In this case, a solvent may be used to induce a smooth reaction reaction between the carrier and the alkylaluminoxane, or may be repeated without a solvent.

The solvent includes aliphatic hydrocarbons such as nucleic acids, pentane and heptane; Aromatic hydrocarbons such as toluene, benzene; Hydrocarbons substituted with chlorine atoms such as dichloromethane; Ethers such as diethyl ether and tetrahydrofuran (THF); Acetone, Most organic solvents such as ethyl acetate can be used. Preferably, nucleic acid, heptane, toluene or dichloromethane may be used as the solvent.

 In this process, a silica carrier in which a larger amount of a promoter (alkylaluminoxane) penetrates into the silica carrier than before, and a considerable amount of a promoter (alkylaluminoxane) is bound to the outside of the silica carrier.

 On the other hand, the method for producing a supported metallocene catalyst according to an embodiment of the present invention includes the step of supporting two or more metallocene compounds on the silica carrier on which the alkylaluminoxane is supported.

 According to the present invention, the catalyst is supported by sequentially supporting one or more metallocene catalysts on the silica carrier on which the alkylaluminoxane is supported, thereby interacting with the supported promoters according to the reaction conditions of the respective metallocene compounds. Allow this to be adjusted. The supported metallocene catalyst prepared in this manner can be seen by controlling the depth profile in the carrier of the catalyst by SEM / EDS analysis, thereby controlling the amount of external support in the silica of the alkylaluminoxane.

 In addition, according to the supported metallocene catalyst, it is possible to greatly improve the productivity of polyolefin when the polyolefin is prepared using the improved density and catalytic activity.

 The metallocene compound is a main moiety component capable of exhibiting activity as a catalyst together with the aforementioned alkylaluminoxane.

 The step may be carried out by mixing the carrier and the metallocene compound in the presence of a solvent and reacting with stirring.

 In this case, the amount of the metallocene compound supported on the silica carrier by the above step may be 0.01 to lmmol / g based on the carrier lg. That is, in consideration of the contribution effect of the catalyst activity by the metallocene compound, it is preferable to fall within the above-described supporting amount range.

 In addition, the temperature condition in the supporting step of the metallocene compound is not particularly limited.

Meanwhile, as the metallocene compound, one or more kinds of those conventional in the art may be used without limitation. For example, the metallocene compound may include 1) a metallocene compound comprising a combination of non-bridged Cp and Cp-based compounds, 2) Metallocene compound comprising a combination of Si bridge Cp and Cp system, 3) Metallocene compound comprising a combination of C bridge Cp and Cp system, 4) Si bridge Cp ( Si bridge Cp) and a metallocene compound comprising a combination of an amine, 5) a metallocene compound comprising a combination of an ethylene bridge Cp and a Cp system, 6) a phenylene bridge Cp ) And metallocene compounds containing a combination of amine-based, 7) a metallocene compound containing a CC, Si-C, or Si-Si bridge and the like can be used. The Cp may be cyclopentadienyl, indenyl, fluorenyl, indenoindole (Mn), or the like, and the structure thereof is not limited. In the case of the Si-based bridge _t _ appendix when - may include haeksil substituents and the like structures, if it contains the structure-inden-tetrahydro- may include indene structure. In addition, the metallocene compound of the present invention includes a low molecular metallocene compound (Cp-based) and a high molecular metallocene compound (eg, CGC type or ansa type).

 For example, the metallocene compound may be at least one selected from the group consisting of the following Chemical Formulas 1 to 5:

 [Formula 1]

 In Chemical Formula 1,

M ¹ is a Group 4 transition metal;

Cp ¹ and Cp ² are the same as or different from each other, and are each independently selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl, and fluorenyl radicals One, they may be substituted with a hydrocarbon of 1 to 20 carbon atoms;

R ^a and R ^b are the same as or different from each other, and each independently hydrogen, C1 to C20 alkyl, C1 to C10 alkoxy, C2 to C20 alkoxyalkyl, C6 to C20 aryl, C6 to C10 aryloxy, C2 Alkenyl to C20, alkylaryl of C7 to C40, arylalkyl of C7 to C40, arylalkenyl of C8 to C40, or alkynyl of C2 to C10;

Z ¹ is a halogen atom, C1 to C20 alkyl, C2 to C10 alkenyl, C7 to C40 alkylaryl, C7 to C40 arylalkyl, C6 to C20 aryl, substituted or unsubstituted C1 to C20 alkylidene , Substituted or unsubstituted amino group, C2 Alkylalkoxy to C20, or arylalkoxy of C7 to C40;

 n is 1 or 0;

 [Formula 2]

^ ρ Β ^ ρ ⁴ _ί ^) Μ ² Ζ ² _3-ιη

 In Chemical Formula 2,

Μ ² is a Group 4 transition metal;

Cp ³ and Cp ⁴ are the same as or different from each other, and are each independently selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl and fluorenyl radicals They may be substituted with a hydrocarbon having 1 to 20 carbon atoms;

R ^c and R ^d are the same as or different from each other, and each independently hydrogen, C1 to C20 alkyl, C1 to C10 alkoxy, C2 to C20 alkoxyalkyl, C6 to C20 aryl, C6 to C10 aryloxy, C2 Alkenyl to C20, alkylaryl of C7 to C40, arylalkyl of C7 to C40, arylalkenyl of C8 to C40, or alkynyl of C2 to C10;

Z ² is a halogen atom, C1 to C20 alkyl, C2 to C10 alkenyl, C7 to C40 alkylaryl, C7 to C40 arylalkyl, C6 to C20 aryl, substituted or unsubstituted C1 to C20 alkylidene , A substituted or unsubstituted amino group, C2 to C20 alkylalkoxy, or C7 to C40 arylalkoxy;

B ¹ cross-links the Cp ³ R ^c ring and the Cp ⁴ R ^d ring, or one Cp ⁴ R ^d ring

One or more or a combination of carbon, germanium, silicon, phosphorus or nitrogen atom containing radicals, which crosslink to M ² ;

 m is 1 or 0;

 [Formula 3]

(Cp ⁵ R ^e ) B ² (J) M ³ Z ³ ₂

 In Chemical Formula 3,

M ³ is a Group 4 transition metal;

Cp ⁵ is any one selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl and fluorenyl radicals, which may be substituted with hydrocarbons having 1 to 20 carbon atoms Can be; R ^e is hydrogen, alkyl of C1 to C20, alkoxy of C1 to C10, alkoxyalkyl of C2 to C20, aryl of C6 to C20, aryloxy of C6 to C10, alkenyl of C2 to C20, alkylaryl of C7 to C40 C7-C40 arylalkyl, C8-C40 arylalkenyl, or C2-C10 alkynyl;

Z ³ is a halogen atom, C1 to C20 alkyl, C2 to C10 alkenyl, C7 to C40 alkylaryl, C7 to C40 arylalkyl, C6 to C20 aryl, substituted or unsubstituted C1 to C20 alkylidene Or a substituted or unsubstituted amino group, C2 to C20 alkylalkoxy, or ^' C7 to C40 arylalkoxy;

B ² is at least one or a combination of carbon, germanium, silicon, phosphorus or nitrogen atom containing radicals which crosslink the Cp ⁵ R ^e ring and J;

J is any one selected from the group consisting of NR ^f , O, PR ^f and S, wherein R ^f is C1 to C20 alkyl, aryl, substituted alkyl or substituted aryl,

 [Formula 4]

 In Chemical Formula 4,

 R10 to R13 and R10 'to R13' are the same as or different from each other, and each independently hydrogen, C1 to C20 alkyl group, C2 to C20 alkenyl group, C6 to C20 aryl group, C7 to C20 alkylaryl group, C7 An arylalkyl group of C20 to C20 or an amine group of C1 to C20, and two or more adjacent ones of R10 to R13 and R10 'to R13' may be connected to each other to form one or more aliphatic rings, aromatic rings, or hetero rings. Can;

 Z1 and Z2 are the same as or different from each other, and each independently hydrogen, C1 to

C20 alkyl group, C3 to C20 cycloalkyl group, C1 to C20 alkoxy group, C6 to An aryl group of C20, an aryloxy group of C6 to C10, an alkenyl group of C2 to C20, an alkylaryl group of C7 to C40, or an arylalkyl group of C7 to C40;

 Q is C1 to C20 alkylene group, C3 to C20 cycloalkylene group, C6 to C20 arylene group, C7 to C40 alkylarylene group, or C7 to C40 arylalkylene group;

 M 2 is a Group 4 transition metal;

 X3 and X4 are the same as or different from each other, and each independently halogen, C1 to C20 alkyl group, C2 to C20 alkenyl group, C6 to C20 aryl group, nitro group, amido group, C1 to C20 alkylsilyl group, C1 To C20 alkoxy group, or C1 to C20 sulfonate group;

 [

In Chemical Formula ₅ ,

R ¹ and R ² are each independently hydrogen, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, silyl having 6 to 20 carbon atoms, alkylaryl having 7 to 20 carbon atoms, and having 7 carbon atoms. Substituted with 20 to 20 arylalkyl or hydrocarbyl

Metalloid of Group 4 metals; R ¹ and R ² or two R ² may be connected to each other by an alkylidine including alkyl having 1 to 20 carbon atoms or aryl having 6 to 20 carbon atoms to form a ring;

R ³ is each independently hydrogen, a halogen atom, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, alkylaryl having 7 to 20 carbon atoms, arylalkyl having 7 to 20 carbon atoms, and carbon atoms. Alkoxy of 1 to 20, aryloxy or amido of 6 to 20 carbon atoms; Two or more R ³ in the R ³ increase may be connected to each other to form an aliphatic ring or an aromatic ring;

CY ¹ is a substituted or unsubstituted aliphatic or aromatic ring, and Substituents substituted in CY ¹ are a halogen atom, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, alkylaryl having 7 to 20 carbon atoms, arylalkyl having 7 to 20 carbon atoms, and 1 carbon atom. Alkoxy of 20 to 20, aryloxy of 6 to 20 carbon atoms, amido; When there are a plurality of substituents, two or more substituents in the substituents may be linked to each other to form an aliphatic or aromatic ring;

 M is a Group 4 transition metal;

Q ¹ and Q ² are each independently halogen, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, alkylaryl having 7 to 20 carbon atoms, arylalkyl having 7 to 20 carbon atoms, and carbon atoms. Alkyl amido having 1 to 20 carbon atoms, aryl amido having 6 to 20 carbon atoms, or alkylidene having 1 to 20 carbon atoms.

 In this case, the metallocene compound including a combination of the non-bridged Cp and the Cp-based may include the compound represented by Chemical Formula 1.

 A metallocene compound comprising a combination of the Si bridge Cp and a Cp system and a metallocene compound including a combination of a C bridge Cp and a Cp system are represented by Formula 2 above. It may include a compound.

 The metallocene compound including a combination of the Si bridge Cp and the amine may include a compound represented by Chemical Formula 3.

 The metallocene compound including a combination of the ethylene bridge Cp and the Cp-based may include the compound represented by Chemical Formula 4.

 In addition, hydrocarbyl, as defined in Formula 5, is a monovalent group in a form in which hydrogen atoms are removed from hydrocarbons, and includes ethyl, phenyl, and the like. In addition, the metalloid is a metalloid and an element showing intermediate properties between metal and nonmetal, and include arsenic, boron, silicon, tellurium, and the like.

According to one embodiment of the present invention, specific examples of the compound represented by Chemical Formula 1 may include a compound represented by one of the following structural formulas, but the present invention is not limited thereto.

According to one embodiment of the present invention, specific examples of the compound represented by Chemical Formula 2 may include a compound represented by one of the following structural formulas, but the present invention is not limited thereto.

According to one embodiment of the present invention, specific examples of the compound represented by Chemical Formula 3 may include a compound represented by one of the following structural formulas, but the present invention is not limited thereto.

In the supported metallocene catalyst, Q in Formula 4 is an alkylene group of C1 to C20, Z1 and Z2 are each independently hydrogen, an alkyl group of C1 to C20 or an alkoxy group of C1 to C20, and X3 and X4 are It may be a halogen, but is not limited thereto.

In addition, the compound represented by Formula 5 may include a compound represented by one of the following structural formula, but the present invention is not limited thereto.

 In the above structural formula,

Each R ⁷ is independently hydrogen or methyl; Q ⁵ and Q ⁶ may each independently be methyl, dimethylamido or chloride.

The metallocene compound represented by Chemical Formula 5 has a narrow Cp-MN structure due to the metal site being linked by a cyclopentadienyl ligand in which an amido group is linked to a phenylene bridge in a ring form. The Q ⁱ ᅳ MQ ² angle approaching can be kept wide.

 In addition, the preparation method of the supported metallocene catalyst may be performed by further including, in addition to the above-described steps, steps that may be conventionally performed in the art to which the present invention pertains before or after each step, The above-mentioned steps do not limit the polymerization process of the present invention.

 In addition, according to a preferred embodiment of the present invention, when one or more metallocene compounds are used, one or more metallocene compounds may be sequentially supported on the silica carrier.

Meanwhile, according to one embodiment of the present invention, as a second promoter, a borate-based The compound may be further supported. That is, the method may further include supporting a borate-based compound as a crab cocatalyst on a silica carrier on which an alkylaluminoxane and at least one metallocene compound are supported.

 Therefore, according to a preferred embodiment of the present invention, the carrier may be supported with an alkylaluminoxane as a first cocatalyst, a borate compound as a second cocatalyst, and at least one metallocene compound. When the second catalyst is included in the supported metallocene catalyst, the polymerization activity of the final prepared catalyst may be improved.

 The second cocatalyst, the borate compound, may include a borate compound in the form of a trisubstituted ammonium salt, a borate compound in the form of a dialkyl ammonium salt, or a borate compound in the form of a trisubstituted phosphonium salt. Specific examples of such a second catalyst include trimethylammonium tetraphenylborate, methyldioctadecylammonium tetraphenylborate, triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tri (n-butyl) ammonium tetraphenylborate ， Methyltetracyclooctadecylammonium tetraphenylborate, Ν, Ν-dimethylanilium tetraphenylborate, diethylanilium tetraphenylborate ，

Ν, Ν-dimethyl (2,4,6-trimethylaninynium) tetraphenylborate, trimethylammonium tetrakis (pentafluorophenyl) borate, methylditetradecylammonium tetrakis (pentaphenyl) borate, methyldioctadecylammonium Tetrakis (pentafluorophenyl) borate, triethylammonium tetrakis (pentafluorophenyl) borate, tripropylammonium tetrakis (pentafluorophenyl) borate, tri (η-butyl) ammonium tetrakis (pentafluorophenyl Brate,

Tri (secondary-butyl) ammonium tetrakis (pentafluorophenyl) borate, Ν, Ν-dimethylaninium tetrakis (pentafluorophenyl) borate,

Ν, Ν-diethylanilium tetrakis (pentafluorophenyl) borate ，

 Ν, Ν-dimethyl (2,4,6-trimethylanilium) tetrakis (pentafluorophenyl) borate,

Trimethylammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate, triethylammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate, tripropylammonium tetrakis (2,3 , 4,6-tetrafluorophenyl) borate, tri (η-butyl) ammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate ， _Ν , Ν_dimethylanilium Tetrakis (2,3,4,6-tetrafluorophenyl) borate, Ν, Ν-diethylanilium tetrakis (2,3,4,6-tetrafluorophenyl) borate, or Ν, Ν-dimethyl Borate compounds in the form of trisubstituted ammonium salts such as-(2,4,6-trimethylaninynium) tetrakis (2,3,4,6-tetrafluorophenyl) borate; Borate type in the form of dialkylammonium salt, such as dioctadecyl ammonium tetrakis (pentafluorophenyl) borate, ditetradecyl ammonium tetrakis (pentafluorophenyl) borate, or dicyclonuclear ammonium tetrakis (pentafluorophenyl) borate compound; Or triphenylphosphonium tetrakis (pentafluorophenyl) borate, methyldaoctadecylphosphonium tetrakis (pentafluorophenyl) borate or tri (2,6-dimethylphenyl) phosphonium tetrakis (pentafluorophenyl) Borate compounds in the form of trisubstituted phosphonium salts, such as a borate, etc. are mentioned.

 In addition, the borate compound may be supported in an amount of 0.01 to 1 mmol / g based on the silica carrier lg. In addition, when the borate compound is used as the second cocatalyst in the method of the present invention, the supporting order is not particularly limited. For example, the present invention can support the borate-based compound last on the silica carrier after supporting one or more metallocene compounds. In addition, the present invention can optionally be carried out in the order of supporting b) alkyl aluminoxane on a silica carrier, then carrying a borate compound, followed by one or more metallocene compounds.

 The ethylene-1-nuxene-1-butene terpolymer of the present invention can be prepared by copolymerizing ethylene, 1-nuxene, and 1-butene in the presence of the supported metallocene catalyst.

 The method for preparing the ethylene-1-nuxene-1-butene terpolymer may include preparing the supported metallocene catalyst; And polymerizing reaction of ethylene, 1-nuxene, and 1-butene in the presence of the catalyst.

 The supported metallocene catalyst may itself be used in the polymerization reaction. In addition, the supported metallocene catalyst may be prepared and used as a prepolymerized catalyst by contacting with an olefinic monomer. For example, the supported metallocene catalyst may be separately contacted with an ethylene, 1-butene, or 1-nuxene monomer to prepare a prepolymerized catalyst. It can also manufacture and use.

In addition, the supported metallocene catalyst is an aliphatic hydrocarbon solvent having 5 to 12 carbon atoms (for example, pentane, nucleic acid, heptane, nonane, decane and isomer thereof), aromatic hydrocarbon solvent such as toluene, benzene, dichloromethane, Chlorine, such as chlorobenzene Dilution may be carried out by dilution with a hydrocarbon solvent substituted with an atom. At this time, it is preferable to use after removing a small amount of water or air which can act as a catalyst poison by adding a small amount of alkylaluminum to the solvent.

 The polymerization reaction may be performed using one continuous slurry polymerization reactor, a loop slurry reaction vessel, or a gas reaction reactor.

In addition, the polymerization can be carried out by reacting at a temperature of about 25 to about 500 ^° C and about 1 to about 100 kgf / cm ² for about 1 to about 24 hours. Specifically, the polymerization may be carried out at a temperature of about 25 to about 500 ^° C, preferably about 25 to about 200 ^° C, more preferably about 50 to about 100 ^° C. The reaction pressure may also be carried out at about 1 to about 100 kgf / cm ² , preferably at about 1 to about 50 kgf / cm ² , more preferably at about 5 to about 40 kgf / cm ² .

The ethylene-1-nuxene—1-butene terpolymer prepared according to the above method may be obtained as a terpolymer having the above-described physical properties while maintaining high activity ₍ equivalent or higher than the conventional one).

 According to another aspect of the present invention, there is provided a film comprising the ethylene-1-nuxene-1-butene terpolymer.

The film has the above-described characteristics, that is, a CI (Co-monomer Incorporation) Index represented by the following Formula 1 is 0.5 to 5; Density is 0.900 to 0.916 g / cm ³ ; Melt flow index (Ml) measured at 190 ^° C., 2.16 kg loading conditions in accordance with ASTM D1238; 2.0 to 5.0 g / 10 min; Ethylene-1'nucleene-1-butene terpolymer having a weight ratio of 1-nuxene to 1-butene in the range of 1 to 5, and prepared using the same.

 [Equation 1]

 Molecular weight side s content -Low molecular weight side scB content

 CI Index = — ————

 (¾ molecular weight side)

 More specific description of the above formula 1 and other properties of the ethylene-1-nuxene-1-butene terpolymer are as described above.

The film according to the present invention may be prepared according to a method of inflation molding a ethylene-1-nuxene-1-butene ternary copolymer peltiff into a single thickness extruder so as to have a constant thickness, but is not limited thereto. In the technology belonging It may be prepared according to the method commonly used.

 The film of the present invention thus prepared has excellent fall-off layer strength and adhesion.

 According to one embodiment of the present invention, the film of the present invention has a fall fall strength measured by ASTM D 1709 [Method A] of 600 g or more, for example, about 600 to about 1,500 g, preferably about 700 to About 1,200 g.

 In addition, according to an embodiment of the present invention, the film may have an adhesive force of 7 or more, for example, about 7 to about 20, preferably about 7 to about 15, measured according to ASTM D 3330.

 Hereinafter, preferred embodiments are provided to help understanding of the present invention. However, the following examples are only for illustrating the present invention, and the present invention is not limited thereto.

<Example>

 Preparation Example of Supported Catalyst

 Preparation Example 1

Silica (manufacturer: Grace Davision, product name: Sylopol 952) was prepared as a carrier, which was calcined at 100 ^° C. for 30 minutes.

Thereafter, 100 ml of toluene and 10 g of the silica were dispersed in a glass reaction vessel, and a portion of methylaluminoxane (MAO) solution was added by dividing with a cocatalyst, and the shelf was stirred at 80 ^° C. Then, at a low temperature, the remaining content of methylaluminoxane was added and then reacted. Subsequently, washing with a sufficient amount of toluene to remove unreacted methylaluminoxane (MAO supported amount: 5 mmol / g carrier (line reaction), 3 mmol carrier (post reaction)).

 As a metallocene compound of the formula (1) on the silica supported methyl aluminoxane as described above

Toluene solution in which bis (n-butylcyclopentadienyl) -zirconium dichloride (Bis (n-butylcyclopentadienyl) -zirc onium dichloride) was added was added and stirred at 40 ^° C. for 1 hour. Then, t-secondary nucleosil methylsilyl (Nt-butyl amido) (2,3,4,5-tetramethylcyclopentadienyl) -titanium as a metallocene compound of formula 3 Dichloride (t-butoxyhexylmethylsilyl (^ - t -buthylamido) (2, 3, 4,5-tet ^

Toluene solution in which nyl) -titanium dichloride) was dissolved was added, and stirred at 40 ^° C. for 1 hour to react. This was washed with a layered amount of toluene and dried under vacuum to obtain a solid powder yarn supported metallocene catalyst.

At this time, the amount of the metallocene compound supported is 0.1 mmol / g of the metallocene of Formula 1, 0.1 mmol / g of the metallocene of Formula 3, and the Al / Si content of the supported metallocene catalyst is The inner layer had 29.5 weight ⁰ /. And the outer layer had 43.5 weight%. Comparative Production Example 1

Silica (manufacturer: Grace Davision, product name: Sylopol 948) was prepared as a carrier, which was calcined at 100 ^° C. for 30 minutes.

Then, 100 ml of toluene and 10 g of the silica were added to the glass reactor and dispersed therein, and a methylaluminoxane (MAO) solution was used as a promoter. It was added and stirred slowly at 40 ^° C. Subsequently, washing with a sufficient amount of toluene to remove unreacted methylaluminoxane (MAO supported amount: 8mtnol / g carrier).

 As described above, bis (n-butylcyclopentadienyl) -zirconium dichloride (Bis (n-butylcyclopentadienyl) -zirconium dichloride) ° 1 is dissolved in a metallocene compound represented by Chemical Formula 1 on silica loaded with methylaluminoxane. The solution was added and stirred to react. Then, as a metallocene compound of the formula (3), t-butoxynuxylmethylsilyl (Nt-butylamido) (2,3,4,5-tetramethylcyclopentadienyl) -titanium dichlorolay H (t-butoxyhexylmethylsilyl Toluene was dissolved by adding a solution of toluene containing (Nt-buthylamido) (2,3,4,5-tetramethylcyclopentadie nyl) -titanium dichloride). This was washed with a layered amount of toluene and dried in vacuo to obtain a supported metallocene catalyst as a solid powder.

 At this time, the supported amount of the metallocene compound was 0.1 mmol / g-carrier of the metallocene of formula (1), and 0.1 mmol / ^ carrier of the metallocene of formula (3). Polymerization Example

 Example 1

The catalyst of Preparation Example 1 was added to a single loop slurry polymerization process and Linear low density polyethylene was prepared. 1-butene and 1-nuxene were used as comonomers. Example 2

 Example except that the content of comonomers 1-butene and 1-nuxene were changed

Linear low density polyethylene was prepared in the same manner as 1. Example 3

 A linear low density polyethylene was prepared in the same manner as in Example 1 except that the contents of comonomers 1-butene and 1-nuxene were changed. Example 4

 A linear low density polyethylene was prepared in the same manner as in Example 1 except that the contents of comonomers 1-butene and 1-nuxene were changed. Comparative Example 1

 Of Comparative Preparation Example 1. The catalyst was introduced into a single loop slurry polymerization process to produce linear low density polyethylene according to the conventional method. 1-nuxene was used as comonomer. Experimental Example

 Property measurement

The polyolefin copolymers obtained in Examples and Comparative Examples were 180 to 210 ^° using a biaxial extruder (W & P Twin Screw Extruder, 75 pie, L / D = 36) after prescription of antioxidant (Iganox 1010 + Igafos 168, CIBA). It was granulated at an extrusion temperature of C. Film molding was inflation-molded using a single screw extruder (Shinhwa Industrial Single Screw Extruder, Blown Film M / C, 50 pie, L / D = 20) to a thickness of 0.05 mm at an extrusion temperature of 165 to 200 ^° C. The die gap (Die Gap) is ² .0 mm, blow up ratio (Ratio Blown-Up) was set to 0.3 ^second.

The physical properties and film properties of the polyolefin copolymer were measured according to the following evaluation method, and the results are shown in Table 1 below. 1) Density: ASTM 1505

2) Melt Index (MI, 2.16 kg / 10 min): ASTM D1238, 2.16 kg, 190 ^° C

 3) Weight average molecular weight and molecular weight distribution: The number average molecular weight, the weight 'average molecular weight, and the Z average molecular weight were measured using a measurement temperature of 160 ° C. and gel permeation chromatography-FTIA (GPC-FTIR). Molecular weight distribution was shown by the ratio of a weight average molecular weight and a number average molecular weight.

 4) Falling layer striking strength: 20 drops or more per film sample based on ASTM D 1709 [Method A] was measured to determine the fall impact strength.

 5) Adhesive force: The adhesive force was obtained by measuring 10 times or more per film sample based on ASTM D 3330.

6) CI Index: When the molecular weight distribution curve is drawn with the log value (log M) of the molecular weight (M) as the x-axis and the molecular weight distribution (dwt / dlog M) for the log value as the y-axis, Short Chain Branch (SCB) content at the left and right borders of 60% excluding the left and right ends ₂ 0% (branch content of 2 to 7 carbon atoms per 1,000 carbons, unit / 1,000C) The CI Index was calculated based on Equation 1 below.

 At this time, the high molecular weight side SCB content and the low molecular weight side SCB content mean SCB content values at the right and left boundary of 60% range, respectively, and the sample contains BHT 0.0125% using PL-SP260. After pretreatment with 1, 2, 4-Trichlorobenzene at 160 ° C for 10 hours, it was measured at 160 ° C using a PerkinElmer Spectrum 100 FT-IR connected to a high temperature GPC (PL-GPC220).

 Equation 1

 (High molecular weight SCS content-Low molecular weight SCB box ¾

 Q Index = ^^^ ―—— — —

 (That proud 5CB ship

Table 1

 Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comonomer 1 -Butene 2.7 2.7 2.9 3.2

(weight %)

 1-Necksen 6.9 7.2 7.9 8.3 10.3

(weight %)

Referring to Table 1, Examples 1 to 4 of the present invention showed a low density while including 1-nuxene and 1-butene as a comonomer in a constant weight ratio, showing high fall impact strength and adhesion. Therefore, it can be usefully used for applications such as stretch films requiring such physical properties.

Claims

Claims Claims 1 The CI (Co-monomer Incorporation) Index represented by the following formula 1 is 0.5 to 5; Density is 0.900 to 0.916 g / cm 3; Melt flow index (Ml) measured at 190 ° C., 2.16 kg loading conditions in accordance with ASTM D1238; 2.0 to 5.0 g / 10 min; Ethylene-1-nuxene-1-butene terpolymer having a weight ratio of 1-nuxene to 1-butene of 1-5:

 [Equation 1]

 (SCB content of high molecular weight side-SCB¾ low molecular weight side)

 Q Index = ■ — ― ~

 (Low molecular ¾ 8 ¾¾ Equation 1,

 SCB (Short Chain Branch) content means the branch content of 2 to 7 carbon atoms per 1,000 carbons (unit: 1,000C),

 The low molecular weight side SCB content and the high molecular weight side SCB content are the X-axis log value (log M) of the molecular weight (M) of the ethylene-1-nuxene-1-butene terpolymer, and the molecular weight with respect to the said log value When the molecular weight distribution curve is drawn with the y-axis distribution (dwt / dlog M), 60% of the left boundary (low molecular weight side SCB content) and the right boundary (high molecular weight side SCB content), except for the left and right ends 20% of the total area. ) Means the SCB content in.

[Claim 2]

 The method of claim 1,

 Ethylene-1-nuxene-1-butene terpolymer having a weight average molecular weight of 50,000 to 150,000 g / m.

[Claim 3]

 In U,

Ethylene-1-nuxene-1-butene ternary copolymer having a molecular weight distribution (weight average molecular weight / number average molecular weight) of 1.5 to 5.

[Claim 4]

 The method of claim 1,

 Ethylene-1-nuxene-1-butene terpolymer, wherein the content of 1-butene and 1-nuxene is 5 to 15% by weight relative to the total weight of the ethylene-1-nuxene-1-butene terpolymer.

[Claim 5]

 The method of claim 1,

 When the carrier catalyst particles are cut in cross section, the outer layer comprises from each surface to a point that is one third of the total diameter of the particle, and the remaining portion from one third point of the particle to the inner center A silica carrier composed of an inner layer and having an alkylaluminoxane supported on and in the surface of the carrier; At least one metallocene compound supported on the silica carrier,

 In the presence of a supported metallocene catalyst, wherein the Al / Si elemental content ratio (weight%) of the inner layer is at least 65% of the Al / Si elemental content ratio (weight%) of the outer layer,

 Ethylene-1-nuxene-1-butene terpolymer prepared by copolymerizing ethylene, 1-nuxene, and 1-butene.

[Claim 6]

 The method of claim 5,

 Ethylene-1-nuxene-1-butene ternary copolymer, wherein the Al / Si elemental content ratio (weight%) of the inner layer is 90 to 150% of the Al / Si elemental content ratio (weight%) of the outer layer.

[Claim 7]

 The method of claim 5,

. The metallocene compound may be a metallocene compound including a combination of non-bridged Cp and Cp-based, a metallocene compound including a combination of Si bridge Cp and Cp-based; Metallocene compound including a combination of C bridge Cp and Cp system, Metallocene compound including a combination of Si bridge Cp and amine system, Ethylene bridge Cp Metallocene compound including a combination of and Cp-based, comprising a combination of phenylene bridge Cp (phenylene bridge Cp) and amine-based Ethylene-1-nuxene-1-butene terpolymer which is at least one member selected from the group consisting of metallocene compounds and metallocene compounds including CC, Si-C, or Si-Si bridges.

[Claim 8]

 The method of claim 5,

 The silica carrier is at least one member selected from the group consisting of silica, silica-alumina and silica-magnesia, ethylene-1-nuxene-1-butene terpolymer.

【Claim ⁹ 】

 The method of claim 5,

 The alkyl aluminoxane is at least one member selected from the group consisting of methyl aluminoxane, ethyl aluminoxane, butyl aluminoxane and isobutyl aluminoxane, ethylene-1-nuxene-1-butene terpolymer.

[Claim 10]

 The method of claim 5,

 The supported amount of the metallocene compound on the silica carrier is 0.01-1 mmol / g ethylene-1-nuxene-1-butene terpolymer.

[Claim 11]

 A film comprising the ethylene-1-nuxene-1-butene terpolymer of claim 1.

[Claim 12]

 The method of claim 11,

The film having a fall fall strength of 600 to l, 500 g as measured based on ASTM D 1709 [Method A]. ^'

[Claim 13]

 The method of claim 11,

 A film with an adhesion of at least 7 as measured according to ASTM D 3330.