KR20190127564A - Ethylene/alpha-olefin Copolymer, Method For Preparing The Same And Resin Composition For Optical Film Comprising The Same - Google Patents

Abstract

The present invention provides an ethylene/alpha-olefin copolymer satisfying conditions (a) to (d): (a) density: 0.850 to 0.910 g/cc; (b) melt index (MI) (190°C, 2.16 kg load conditions; MI_(2.16)): 0.1 to 100 dg/min; (c) molecular weight distribution (MWD): 1.5 to 3.0; and (d) Rtv value according to formula 1, R_(tv)=N_(tv)/N_v+N_(tv)+N_(vl)+N_(vd), is 0.12 or more. In the formula 1, Nv, Ntv, Nvl, and Nvd each represent the number of vinyl groups, trivinyl groups, vinylene groups, and vinylidene groups per 1,000 carbon atoms as measured by nuclear magnetic resonance spectrometry, respectively.

Description

Ethylene / alpha-olefin copolymer, method for preparing the same, and a resin composition for an optical film including the same {Ethylene / alpha-olefin copolymer, Method For Preparing The Same And Resin Composition For Optical Film Comprising The Same}

In the present invention, the molecular weight distribution is narrow, the trivinyl content in the polymer is maintained at a certain ratio or more, the ethylene / alpha-olefin copolymer having excellent physical properties and a method for preparing the same, and an optical including the ethylene / alpha-olefin copolymer It relates to a resin composition for films.

Olefin polymerization catalyst systems can be classified into Ziegler-Natta and metallocene catalyst systems, and these two highly active catalyst systems have been developed for their respective characteristics. The Ziegler-Natta catalyst has been widely applied to existing commercial processes since the invention in the 50s, but is characterized by a wide molecular weight distribution of the polymer because it is a multi-site catalyst having multiple active sites. There is a problem that there is a limit in securing the desired physical properties because the composition distribution is not uniform.

On the other hand, the metallocene catalyst is composed of a combination of a main catalyst composed mainly of a transition metal compound and a cocatalyst composed of an organometallic compound composed mainly of aluminum, and such a catalyst is a single site catalyst as a homogeneous complex catalyst. The polymer has a narrow molecular weight distribution according to the characteristics of a single active site, and a polymer having a uniform composition of the comonomer is obtained, and the stereoregularity, copolymerization characteristics, molecular weight, It has the property to change the crystallinity.

U.S. Patent No. 5,914,289 describes a method for controlling the molecular weight and molecular weight distribution of a polymer using a metallocene catalyst supported on each carrier, but the amount of solvent used and the time required for preparing the supported catalyst are high. The hassle of having to support the metallocene catalyst to be used on the carrier, respectively.

Korean Patent Application No. 10-2003-0012308 discloses a method for controlling the molecular weight distribution by supporting a dual-nuclear metallocene catalyst and a mononuclear metallocene catalyst on a carrier together with an activator to polymerize by changing the combination of catalysts in the reactor. Is starting. However, this method is limited in realizing the characteristics of each catalyst at the same time, and also has the disadvantage of freeing the metallocene catalyst portion in the carrier component of the finished catalyst, causing fouling in the reactor.

On the other hand, 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 chain branch of a constant length, and a long chain branch. Linear low density polyethylene film has high breaking strength and elongation as well as properties of general polyethylene, and it has excellent tearing strength and fall impact strength. Therefore, the use of stretch film and overlap film that is difficult to apply to existing low density polyethylene or high density polyethylene is increasing. Doing.

However, linear low density polyethylenes using 1-butene or 1-hexene as comonomers are mostly produced in single gas phase reactors or single loop slurry reactors, and are more productive than processes using 1-octene comonomers, but these products are also used. Due to the limitations of catalyst technology and process technology, physical properties are inferior to those of using 1-octene comonomer, and molecular weight distribution is narrow, resulting in poor processability.

US Pat. No. 4,935,474 reports on the preparation of polyethylenes having a broad molecular weight distribution using two or more metallocene compounds. U.S. Patent No. 6,828,394 reports a process for producing polyethylene with good comonomer binding properties and mixtures with and without good comonomer bonding, particularly suitable for films. In addition, US Pat. No. 6,841,631 and US Pat. No. 6,894,128 produce polyethylene having bimodal or polycrystalline molecular weight distribution with a metallocene catalyst using at least two kinds of metal compounds, for use in films, blow molding, pipes, and the like. It is reported to be applicable. However, these products have improved processability, but there is a problem in that the extrusion appearance is coarse and the physical properties are not stable even under relatively good extrusion conditions because the dispersion state by molecular weight in unit particles is not uniform.

In this context, there is a constant demand for producing a better product having a balance between physical properties and processability, and in particular, a need for a polyethylene copolymer having excellent processability is further required.

U.S. Patent 5,914,289 Korean Patent Publication No. 2004-0076965 U.S. Patent 4,935,474 U.S. Patent 6,828,394 U.S. Patent 6,841,631 U.S. Patent 6,894,128

The present invention is to solve the problems of the prior art, ethylene / alpha -olefin copolymer having a narrow molecular weight distribution, the trivinyl content in the polymer is maintained above a certain ratio, having excellent physical properties, particularly excellent crosslinking behavior properties and It is intended to provide a method of manufacturing the same.

In addition, an object of the present invention is to provide a resin composition for an optical film including the ethylene / alpha olefin copolymer is improved optical properties such as yellow index (YI), total light transmittance (Tt).

One embodiment of the present invention provides an ethylene / alpha-olefin copolymer that meets the following conditions (a) to (d):

(a) Density: 0.850 to 0.910 g / cc

(b) Melt Index (Melt Index, MI, 190 ° C., 2.16 kg loading conditions): 0.1 to 100 dg / min

(c) molecular weight distribution (MWD): 1.5 to 3.0

(d) Rtv value according to Equation 1 below 0.12.

[Equation 1]

In Equation 1, Nv, Ntv, Nvl, and Nvd are the vinyl, trivinyl, vinylene, and vinylidene functional groups per 1000 carbon atoms measured by nuclear magnetic spectroscopy, respectively. It means the number.

Another embodiment of the present invention, the ethylene comprising the step of polymerizing ethylene and alpha-olefin-based monomer by adding hydrogen at 5 to 100 cc / min in the presence of a catalyst composition comprising a transition metal compound of Formula 1 Provided are methods for preparing the alpha / olefin copolymer:

[Formula 1]

In Chemical Formula 1,

R ₁ is hydrogen; C1-20 alkyl; C3-20 cycloalkyl; C2-20 alkenyl; C1-20 alkoxy; C6-20 aryl; C7-20 arylalkoxy; C7-20 alkylaryl; Or C7-20 arylalkyl,

R _2a to R _2e are each independently hydrogen; halogen; C1-20 alkyl; C3-20 cycloalkyl; C2-20 alkenyl; C1-20 alkoxy; Or C6-20 aryl,

R ₃ is hydrogen; halogen; C1-20 alkyl; C3-20 cycloalkyl; C2-20 alkenyl; C6-20 aryl; C6-20 alkylaryl; C7-20 arylalkyl; C1-20 alkyl amido; C6-20 aryl amido; C1-20 alkylidene; Or phenyl substituted with one or more selected from the group consisting of halogen, C1-20 alkyl, C3-20 cycloalkyl, C2-20 alkenyl, C1-20 alkoxy and C6-20 aryl,

R ₄ to R ₉ are each independently hydrogen; Silyl; C1-20 alkyl; C3-20 cycloalkyl; C2-20 alkenyl; C6-20 aryl; C7-20 alkylaryl; C7-20 arylalkyl; Or a metalloid radical of a Group 14 metal substituted with C 1-20 hydrocarbyl; Two or more adjacent to each other of the R ₆ to R ₉ may be connected to each other to form a ring,

Q is Si, C, N, P or S,

M is a Group 4 transition metal,

X ₁ and X ₂ are each independently hydrogen; halogen; C1-20 alkyl; C3-20 cycloalkyl; C2-20 alkenyl; C6-20 aryl; C7-20 alkylaryl; C7-20 arylalkyl; C1-20 alkylamino; C6-20 arylamino; Or C1-20 alkylidene.

Another embodiment of the present invention provides a resin composition for an optical film comprising the ethylene / alpha -olefin copolymer.

The ethylene / alpha-olefin copolymer of the present invention has a narrower molecular weight distribution than the prior art, and exhibits excellent crosslinking properties by maintaining the trivinyl content in the polymer at a certain ratio or more.

In addition, the resin composition for an optical film containing the ethylene / alpha-olefin copolymer of the present invention is excellent in optical properties such as a yellow index (YI) and a total light transmittance (Tt). Therefore, the ethylene / alpha-olefin copolymer of the present invention can be usefully applied to the production of a resin composition for an optical film which requires excellent optical properties.

1 shows the crosslinking behavior of Example 1 and Comparative Example 1 according to the crosslinking recipe (a) as an embodiment of the present invention.

The terminology used herein is for the purpose of describing exemplary embodiments only and is not intended to be limiting of the invention. Singular expressions include plural expressions unless the context clearly indicates otherwise. As used herein, the terms "comprise", "comprise" or "have" are intended to indicate that there is a feature, step, component, or combination thereof that is practiced, and that one or more other features or steps, It should be understood that it does not exclude in advance the possibility of the presence or the addition of components, or combinations thereof.

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 the specific disclosed form, it should be understood to include all modifications, equivalents, and substitutes included in the spirit and scope of the present invention.

The term "composition" as used herein includes a mixture of materials comprising the composition as well as reaction and decomposition products formed from the material of the composition.

The term "polymer," as used herein, refers to a polymer compound prepared by polymerizing monomers, whether of the same or a different kind. The generic term polymer thus encompasses the term homopolymers commonly used to refer to polymers made from only one monomer, and the term interpolymer as defined below.

The term "interpolymer" as used herein refers to a polymer prepared by the polymerization of at least two different monomers. As such, the generic term interpolymer includes copolymers commonly used to refer to polymers made from two different monomers, and polymers made from two or more different monomers.

1. Ethylene / alpha-olefin copolymer

Hereinafter, the ethylene / alpha-olefin copolymer of the present invention will be described in detail.

Ethylene / alpha-olefin copolymers according to one embodiment of the present invention satisfy the following conditions (a) to (d):

(a) Density: 0.850 to 0.910 g / cc

(b) Melt Index (Melt Index, MI, 190 ° C., 2.16 kg loading conditions; MI _2.16 ): 0.1 to 100 dg / min

(c) molecular weight distribution (MWD): 1.5 to 3.0

(d) Rtv value according to Equation 1 below 0.12.

[Equation 1]

In Equation 1, Nv, Ntv, Nvl, and Nvd are the vinyl, trivinyl, vinylene, and vinylidene functional groups per 1000 carbon atoms measured by nuclear magnetic spectroscopy, respectively. It means the number.

The present invention uses a catalyst as described below, by introducing an optimum amount of hydrogen during polymerization to simultaneously satisfy the conditions of (a) to (d), thereby physical properties, in particular crosslinking properties of the ethylene / alpha olefin copolymer Can be greatly improved.

Specifically, the ethylene / alpha-olefin copolymer of the present invention is a polymer having a low density in the range of 0.850 to 0.910 g / cc, as measured according to ASTM D-792. Specifically, the density may be at least 0.850 g / cc, or at least 0.855 g / cc, or at least 0.86 g / cc, or at least 0.865, and at most 0.91 g / cc, or at most 0.90 g / cc, or 0.89 g / cc. It may be:

In general, the density of the olefin polymer is affected by the type and content of the monomers used in the polymerization, the degree of polymerization, etc., and in the case of the copolymer, the effect of the comonomer is large, and the higher the content of the comonomer, the lower the density of ethylene / alpha- Olefin copolymers can be prepared and the amount by which comonomers can be introduced into the copolymer can depend on the copolymerizability of the catalyst, ie the properties of the catalyst.

In the present invention, a large amount of comonomer can be introduced by using a catalyst composition including a transition metal compound having a specific structure. As a result, the ethylene / alpha-olefin copolymer according to one embodiment of the present invention may have a low density as described above, and as a result may exhibit excellent processability. More specifically, the ethylene / alpha-olefin copolymer may have a density of 0.850 to 0.910 g / cc, in which case the effect of maintaining mechanical properties and improving the impact strength by the density control is more remarkable.

In addition, the ethylene / alpha-olefin copolymers of the present invention have a narrow molecular weight distribution (MWD) in the range of 1.5 to 3.0. As an example, the molecular weight distribution may be at least 1.6, or at least 1.7, or at least 1.8, and may be at most 2.7, or at most 2.4, or at most 2.2.

In general, when two or more kinds of monomers are polymerized, molecular weight distribution (MWD) increases, and as a result, impact strength, mechanical properties, and the like decrease, and a blocking phenomenon occurs. On the other hand, in the present invention, by introducing an optimum amount of hydrogen during the polymerization reaction, the molecular weight and molecular weight distribution of the produced ethylene / alpha -olefin copolymer is reduced, and as a result, the crosslinking properties, impact strength, mechanical properties and the like are improved.

In the present invention, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are polystyrene equivalent molecular weights analyzed by gel permeation chromatography (GPC), and the molecular weight distribution is based on the ratio of Mw / Mn. Can be calculated.

The ethylene / alpha-olefin copolymer according to one embodiment of the present invention may be a polymer having a weight average molecular weight (Mw) of 40,000 to 150,000 g / mol. More specifically, the weight average molecular weight may be at least 45,000 g / mol, or at least 49,000 g / mol, or at least 52,000 g / mol, and may be at most 130,000 g / mol, or at most 90,000 g / mol, or at most 65,000 g / mol. Can be.

In addition, the ethylene / alpha-olefin copolymer of the present invention has a melt index (Melt Index, MI, 190 ° C., 2.16 kg loading conditions) in the range of 0.1 to 100 dg / min. As an example, the ethylene / alpha-olefin copolymer of the present invention has a melt index (MI) of at least 1 dg / min, or at least 1.5 dg / min, or at least 3 dg / min, or at least 5 dg / min, or 12 dg / min or more, or 16 dg / min or more, 90 dg / min or less, or 70 dg / min or less, or 40 dg / min or less, or 35 dg / min or less.

In addition, the ethylene / alpha-olefin copolymer may have a melt index in the range of 5 to 230 dg / min (Melt Index, MI, 190 ° C., 10 kg loading condition by ASTM D1238).

Further, the ethylene / alpha-olefin copolymer may have a MI ₁₀ / MI _2.16 value of 8.5 or less, or 7.9 or less, which is a melt index value (190 ° C., 10 kg load condition) with respect to a melt index (190 ° C., 2.16 kg load condition). It may be 7.5 or less, and may be 5.0 or more, or 5.5 or more, or 6.0 or more. MI ₁₀ / MI _2.16 is an index of the long chain branching degree of the copolymer, and if the MI ₁₀ / MI _2.16 value is 8.5 or less, it means that the long chain branching is small.

When the weight average molecular weight and the melt index to satisfy the above range may be suitable to be applied to the resin composition for an optical film.

That is, the mechanical properties and impact strength of the ethylene / alpha-olefin copolymer can be controlled by controlling the amount of catalyst used together with the type of catalyst used in the polymerization process, and by satisfying the above conditions, it is possible to improve while maintaining excellent mechanical properties. Exhibited processability.

In addition, the ethylene / alpha-olefin copolymer of the present invention is characterized in that the trivinyl content per 1000 carbon atoms in the copolymer is controlled at a certain ratio or more. Specifically, the ethylene / alpha-olefin copolymer of the present invention has an Rtv value of at least 0.12 according to Equation 1 below.

[Equation 1]

In Equation 1, Rtv is a ratio of the number of trivinyl groups to the number of functional groups per 1000 carbon atoms measured by nuclear magnetic spectroscopic analysis.

The content of trivinyl in the copolymer is possible through control of the polymerization temperature and the hydrogen input amount in the preparation. The double bond in the copolymer binds to the radicals generated by the crosslinking agent to activate the crosslinking reaction, and the crosslinking properties are excellent as the ratio of the number of trivinyl groups to the number of functional groups per 1000 carbon atoms is higher than a certain ratio.

The ethylene / alpha-olefin copolymer according to the present invention may exhibit a narrow molecular weight distribution, excellent crosslinking properties and thus optical properties by maintaining the trivinyl content above a certain ratio as described above.

For example, the Rtv value may be at least 0.08, or at least 0.10, or at least 0.12, or at least 0.15, and may be at most 0.30, at most 0.29, or at most 0.27, or at most 0.26, or at most 0.25. When the trivinyl content satisfies the numerical range, it may exhibit narrow molecular weight distribution, excellent crosslinking properties, and thus optical properties.

In addition, the ethylene / alpha-olefin copolymer of the present invention may satisfy the above Rtv value and at the same time the number of unsaturated functional groups including vinyl, trivinyl, vinylene and vinylidene in the copolymer may be 0.65 or less per 1000 carbon atoms. And more specifically, 0.6 or less, or 0.5 or less, or 0.45 or less, or 0.4 or less, and 0.1 or more, or 0.15 or more, or 0.2 or more, or 0.23 or more. When the number of the unsaturated functional groups satisfies the numerical range, it may exhibit a narrow molecular weight distribution, excellent crosslinking properties and thus optical properties.

In addition, the number of vinyl functional groups in the copolymer may be 0.3 or less per 1000 carbon atoms. Specifically 0.29 or less, or 0.25 or less, or 0.2 or less, or 0.15 or less, or 0.1 or less, 0.01 or more, or 0.02 or more, or 0.04 or more, or 0.06 or more. When the number of the unsaturated functional groups satisfies the numerical range, it may exhibit a narrow molecular weight distribution, excellent crosslinking properties and thus optical properties.

Also, the number of vinylene functional groups in the copolymer is 0.3 or less, or 0.29 or less, or 0.25 or less, or 0.2 or less, or 0.15 or less, or 0.1 or less, 0.01 or more, or 1000 carbon atoms. Or 0.02 or more, or 0.04 or more, or 0.06 or more. When the number of the unsaturated functional groups satisfies the numerical range, it may exhibit a narrow molecular weight distribution, excellent crosslinking properties and thus optical properties.

In addition, the number of vinylidene functional groups in the copolymer may be 0.07 or less, or 0.05 or less, 1,000 or more, or 0.02 or more per 1000 carbon atoms. When the number of the unsaturated functional groups satisfies the numerical range, it may exhibit a narrow molecular weight distribution, excellent crosslinking properties and thus optical properties.

In the present invention, the vinyl group has a structure of R-CH = CH ₂ , the trivinyl group has a structure of RCH = CR′R ″, and the vinylene has RCH = CHR ′ (E-form) or Z-RCH = CHR ′ ( Z-form), wherein the vinylidene refers to the structure RR'C = CH ₂ , wherein R, R 'and R "may each independently be a branched chain according to an alpha-olefin which is a polymer chain or a comonomer. .

In the present invention, the content of each of vinyl, vinylidene, vinylene and trivinyl in the copolymer can be calculated from the results of NMR analysis. Specifically, the copolymer may be dissolved in 1,1,2,2-tetrachloroethane D2 (TCE-d2) solvent and then measured using a Bruker AVANCE III 500 MHz NMR instrument at 393K. The TCE-d2 peak is corrected to 6.0 ppm in the 1 H NMR spectrum, and the content ratio of the comonomer is calculated using the integrated values of 1.4 ppm and 0.96 ppm. Calculate the contents of the vinyl group, vinylidene group, vinylene group and trivinylene group observed at 4.7 ppm to 5.6 ppm (analysis method: AMT-3863). Peak assignment see Macromolecules 2014, 47, 3282-3790 .

In addition, the ethylene / alpha-olefin copolymer according to one embodiment of the present invention may have a crystallization temperature (Tc) of 35 ° C to 80 ° C. More specifically, the crystallization temperature may be 40 ° C or more, or 45 ° C or more, 75 ° C or less, or 70 ° C or less, or 65 ° C or less. This high crystallization temperature is due to the uniform distribution of comonomers in the ethylene / alpha-olefin copolymer, and can exhibit excellent structural stability by having the above temperature range.

In addition, the ethylene / alpha-olefin copolymer according to one embodiment of the present invention may have a melting temperature (Tm) of 50 to 110 ° C. More specifically, the melting temperature may be 55 ° C or higher, or 60 ° C or higher, or 70 ° C or higher, and may be 110 ° C or lower, or 105 ° C or lower, or 95 ° C or lower. By having a melting temperature of such a temperature range it can exhibit excellent thermal stability.

In the present invention, the crystallization temperature and the melting temperature of the ethylene / alpha-olefin copolymer can be measured using a differential scanning calorimeter (DSC). Specifically, the copolymer is heated to 150 ° C and then maintained for 5 minutes, lowered again to 20 ° C and then increased again. At this time, the rising rate and the falling rate of the temperature are respectively adjusted to 10 ℃ / min, the second temperature is measured in the section of the rising temperature to the melting temperature, and the result measured in the section appearing while reducing the temperature is the crystallization temperature.

In addition, in the ethylene / alpha-olefin copolymer according to one embodiment of the present invention, the alpha-olefin monomer as a comonomer is C4-20 It may be an olefin monomer. Specific examples include propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetra Decene, 1-hexadecene, or 1-eicosene, and the like, and one of these alone or a mixture of two or more thereof may be used.

Among these, the alpha-olefin monomer may be 1-butene, 1-hexene or 1-octene, and most preferably 1-butene, considering that the improvement effect is remarkable when applied to the resin composition for an optical film. .

In addition, in the ethylene / alpha-olefin copolymer, the content of the comonomer alpha-olefin may be appropriately selected within a range that satisfies the above physical property requirements, specifically, greater than 0 and 99 mol% or less, or It may be 10 to 50 mol%.

2. Resin Composition for Optical Film

Another embodiment of the present invention provides a resin composition for an optical film comprising the ethylene / alpha-olefin copolymer. The resin composition for an optical film may be extruded into a sheet or film shape, but is not particularly limited thereto.

The resin composition comprising the ethylene / alpha olefin copolymer may exhibit excellent crosslinking behavior characteristics. For example, the degree of crosslinking of the resin composition for an optical film of the present invention may be at least 55%, or at least 58%, or at least 63%, or at least 67%, or at least 69%.

The resin composition for an optical film may have a glass transition temperature of -55 ° C to -45 ° C, or -53 ° C to -42 ° C, or -50 ° C to -40 ° C.

The resin composition comprising the ethylene / alpha olefin copolymer measured the yellow index (YI) and the total light transmittance (Tt) before and after crosslinking of the ethylene / alpha olefin copolymer, respectively. As a result, the yellow index (YI) and The value of the total light transmittance (Tt) may satisfy a range suitable for use in the optical film.

Specifically, the Yellowness Index (YI) value of the resin composition for an optical film may be 0.5 or more, or 1.0 or more, or 1.25 or more, or 1.30 or more, 5.5 or less, or 4.9 or less, or 4.5 or less, Or 3.9 or less, or 2.9 or less, or 1.5 or less, or 1.2 or less. The smaller the YI value, the more correct the quality stability of the optical film.

In particular, when the yellow index is measured after crosslinking is performed on the resin composition including the ethylene / alpha-olefin copolymer, an excellent value may be exhibited. By way of example, the yellow index after the crosslinking may be at least 0.5, or at least 0.7, or at least 0.8, or at least 0.9, or at least 1.0, at most 1.5, or at most 1.34, or at most 1.3, or at most 1.2, or at most 1.0, Or 0.9 or less.

The yellow index is a value quantifying the yellowing phenomenon of the resin composition when exposed to ultraviolet rays, and may be measured using a UV / Vis spectrometer in accordance with ASTM D1925. For example, by using the UV / Vis spectrometer, the reflectance of the wavelength range of 400 nm to 700 nm of the resin composition may be measured, and the yellow index value may be calculated by using Equation 2 below.

[Equation 2]

YI = [100 (1.28XCIE-1.06ZCIE)] / YCIE

In Equation 2, YI is a value calculated using a color difference analysis program in a UV / VIS / NIR spectrometer, and XCIE, YCIE, and ZCIE are relative values represented by red, green, and blue color coordinates, respectively.

In addition, the resin composition for an optical film of the present invention may have excellent light transmittance. As an example, the total light transmittance (Tt) measured by a haze meter after crosslinking the sheet-shaped resin composition at a temperature of 150 ° C may satisfy the following Equation 3.

[Equation 3]

Tt ≥ 90.0%

The total light transmittance may be a value measured with a haze meter for a light having a wavelength of 200 nm or more, for example, 300 nm, 350 nm, 400 nm, 450 nm, 500 nm, 550 nm or 600 nm. For light having a wavelength of preferably 550 nm, the measured value may be a haze meter. The total light transmittance of the resin composition of the present invention measured above represents the total light transmittance after the sheet-shaped resin composition is crosslinked, and the sheet-shaped resin composition may be laminated through a vacuum laminator.

The total light transmittance of the resin composition is 90% or more, or 90.2% or more, or 90.5% or more, or 90.9% or more, or 91% or more, measured after crosslinking the sheet-shaped resin composition at a temperature of 150 ° C. Or 92% or more. In addition, in consideration of the photoelectric efficiency of the optical device, it can be adjusted to have a total light transmittance in the above-described range.

Moreover, a modified resin composition, for example, a silane modified resin composition or an amino silane modified resin composition, can be manufactured using the resin composition for optical films of this invention.

As an example, the resin composition for an optical film of the present invention may further include a known unsaturated silane compound, an amino silane compound, a crosslinking agent and a crosslinking aid in addition to the ethylene / alpha-olefin copolymer of the present invention.

The unsaturated silane compound may be included in a polymerized form in a silane-modified resin composition or an amino silane-modified resin composition by being grafted to a main chain including a polymerized unit of a monomer of the copolymer of the present invention in the presence of a radical initiator or the like.

As an example, the unsaturated silane compound may be vinyl trimethoxy silane, vinyl triethoxy silane, vinyl tripropoxy silane, vinyl triisopropoxy silane, vinyl tributoxy silane, vinyl tripentoxy silane, vinyl triphenoxy Silane, or vinyltriacetoxy silane, and the like, and as one example, vinyltrimethoxy silane or vinyltriethoxy silane may be used, but is not limited thereto.

In addition, the amino silane compound may be a reactive functional group such as an alkoxy group of an unsaturated silane compound grafted on the main chain of the copolymer of the present invention, such as vinyltriethoxysilane, in the grafting modification step of the ethylene / alpha-olefin copolymer. By acting as a catalyst for promoting the hydrolysis reaction to be converted, it is possible to further improve the adhesive strength with the back sheet composed of a glass substrate or a fluorine resin in the upper and lower parts. At the same time, the amino silane compound may also be involved as a reactant in the direct copolymerization reaction, thereby providing a moiety having an amine functional group in the amino silane-modified resin composition.

The amino silane compound is not particularly limited as long as it is a amine compound containing an amine group and is a primary amine or a secondary amine. For example, aminotrialkoxysilane, aminodiakoxysilane, etc. may be used as the amino silane compound, and examples thereof include 3-aminopropyltrimethoxysilane (APTMS) and 3-aminopropyltriethoxysilane. (3-aminopropyltriethoxysilane; APTES), bis [(3-triethoxysilyl) propyl] amine, bis [(3-trimethoxysilyl) propyl] amine, 3-aminopropylmethyldiethoxysilane, 3-aminopropylmethyl Dimethoxysilane, N- [3- (trimethoxysilyl) propyl] ethylenediamine (N- [3- (Trimethoxysilyl) propyl] ethylenediamine; DAS), aminoethylaminopropyltriethoxysilane, aminoethylaminopropylmethyldimeth Methoxysilane, aminoethylaminopropylmethyldiethoxysilane, aminoethylaminomethyltriethoxysilane, aminoethylaminomethylmethyldiethoxysilane, diethylenetriaminopropyltrimethoxysilane, diethylenetriaminopropyltrie Methoxysilane, diethylenetriaminopropylmethyldimethoxysilane, diethyleneaminomethylmethyldiethoxysilane, (N-phenylamino) methyltrimethoxysilane, (N-phenylamino) methyltriethoxysilane, (N-phenyl Amino) methylmethyldimethoxysilane, (N-phenylamino) methylmethyldiethoxysilane, 3- (N-phenylamino) propyltrimethoxysilane, 3- (N-phenylamino) propyltriethoxysilane, 3- 1 selected from the group consisting of (N-phenylamino) propylmethyldimethoxysilane, 3- (N-phenylamino) propylmethyldiethoxysilane, and N- (N-butyl) -3-aminopropyltrimethoxysilane Or more species. The amino silane compounds may be used alone or in combination.

In the resin composition, the content of the unsaturated silane compound and / or amino silane compound is not particularly limited.

The crosslinking agent may act as a radical initiator in the preparation of the silane-modified resin composition to initiate a reaction in which the unsaturated silane compound is grafted to the resin composition. In addition, by forming crosslinking between the silane-modified resin composition or between the silane-modified resin composition and the non-modified resin composition in the step of lamination during the manufacture of the optoelectronic device, the heat resistance durability of the final product, such as the encapsulant sheet, can be improved. have.

If the crosslinking agent is a crosslinkable compound capable of initiating radical polymerization of the vinyl group or forming a crosslink, various crosslinking agents known in the art may be variously used. For example, organic peroxides and hydroperoxides may be used. And one or two or more selected from the group consisting of azo compounds can be used.

Specifically, t-butyl cumyl peroxide, di-t-butyl peroxide, di-cumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl Dialkyl peroxides such as -2,5-di (t-butylperoxy) -3-hexine; Hydroperoxides such as cumene hydroperoxide, diisopropyl benzene hydroperoxide, 2,5-dimethyl-2,5-di (hydroperoxy) hexane and t-butylhydroperoxide; Diacyl peroxides such as bis-3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, benzoyl peroxide, o-methylbenzoyl peroxide, and 2,4-dichlorobenzoyl peroxide; t-butylperoxy isobutylate, t-butylperoxy acetate, t-butylperoxy-2-ethylhexanoate, t-butylperoxy pibarate, t-butylperoxy octoate, t-butylperoxy Isopropyl carbonate, t-butylperoxybenzoate, di-t-butylperoxyphthalate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, 2,5-dimethyl-2,5-di Peroxy esters such as (benzoyl peroxy) -3-hexine; And azo compounds such as ketone peroxides such as methyl ethyl ketone peroxide and cyclohexanone peroxide, lauryl peroxide, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile). One or more selected from, but is not limited thereto.

The organic peroxide may be an organic peroxide having a half-life temperature of 120 ° C to 135 ° C, for example, 120 ° C to 130 ° C, 120 ° C to 125 ° C, and preferably 121 ° C. As used herein, the term "1 hour half-life temperature" means a temperature at which the half-life of the crosslinker is 1 hour. Depending on the one-hour half-life temperature, the temperature at which the radical initiation reaction occurs efficiently becomes different. Therefore, when an organic peroxide having a one-hour half-life temperature in the above-described range is used as a crosslinking agent, a lamination process temperature for manufacturing an optoelectronic device The radical initiation reaction, ie the crosslinking reaction, can proceed effectively.

The crosslinking agent is included in an amount of 0.01 to 1 parts by weight, for example, 0.05 to 0.55, 0.1 to 0.5 or 0.15 to 0.45 parts by weight, based on 100 parts by weight of the resin composition, when the crosslinking agent is included in less than 0.01 parts by weight, The effect of improving heat resistance is insignificant, and when included in an amount exceeding 1 part by weight, the moldability of the encapsulant sheet is reduced, which may cause a problem in the process, and may affect the physical properties of the encapsulant.

Moreover, the resin composition of this invention can contain a crosslinking adjuvant in addition to the said crosslinking agent. By including the crosslinking aid in the resin composition, it is possible to increase the degree of crosslinking between the resin compositions by the above-mentioned crosslinking agent, thereby further improving the heat resistance durability of the final product, for example, the encapsulant sheet.

The crosslinking aid is included in an amount of 0.01 to 0.5 parts by weight, for example, 0.01 to 0.3, 0.015 to 0.2, or 0.016 to 0.16 parts by weight based on 100 parts by weight of the resin composition, when the crosslinking aid is included in less than 0.01 parts by weight. In addition, the effect of improving heat resistance is insignificant, and when it is included in an amount exceeding 0.5 parts by weight, problems affecting the physical properties of the final product such as the encapsulant sheet may occur and the production cost may increase.

The crosslinking aid can be used a variety of crosslinking aids known in the art, for example, a compound containing at least one or more unsaturated groups such as allyl groups or (meth) acryloxy groups can be used as the crosslinking aid.

The compound containing the allyl group may be exemplified by a polyallyl compound such as triallyl isocyanurate, triallyl cyanurate, diallyl phthalate, diallyl fumarate or diallyl maleate, for example. The compound containing a meta) acryloxy group is, for example, ethylene glycol diacrylate, ethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, t-butyl 1- (2-ethylhexyl) monoperoxycarbonate ( TBEC), methacryloxypropyltrimethoxysilane (MEMO) and the like can be exemplified, but is not particularly limited thereto.

Moreover, the resin composition of this invention can further contain 1 or more types of additives chosen from a light stabilizer, a UV absorber, a heat stabilizer, etc. as needed.

The light stabilizer may serve to prevent photooxidation by capturing the active species of the photodegradation start of the resin depending on the use to which the composition is applied. The kind of light stabilizer that can be used is not particularly limited, and for example, a known compound such as a hindered amine compound or a hindered piperidine compound can be used.

According to the use of the composition, the UV absorber may play a role of absorbing ultraviolet rays from sunlight or the like, converting them into harmless thermal energy in the molecule, and preventing the active species of photodegradation initiation in the resin composition from being excited. . The specific kind of UV absorber that can be used is not particularly limited, and for example, inorganic UV such as benzophenone series, benzotriazole series, acrylonitrile series, metal complex salt system, hindered amine series, ultrafine titanium oxide or ultrafine zinc oxide, etc. One kind or a mixture of two or more kinds such as an absorbent may be used.

Examples of the heat stabilizer include tris (2,4-di-tert-butylphenyl) phosphite, bis [2,4-bis (1,1-dimethylethyl) -6-methylphenyl] ethyl ester phosphorous acid, tetra Keith (2,4-di-tert-butylphenyl) [1,1-biphenyl] -4,4'-diylbisphosphonate and bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite and the like Phosphorus-based heat stabilizer; Lactone-type heat stabilizers, such as the reaction product of 8-hydroxy-5,7-di-tert- butyl-furan-2-one and o-xylene, are mentioned 1 type, or 2 or more types can be used. have.

In the resin composition, the content of the light stabilizer, UV absorber and / or heat stabilizer is not particularly limited. That is, the content of the additive can be appropriately selected in consideration of the use of the resin composition, the shape and density of the additive, and the like, and is usually suitably within the range of 0.01 parts by weight to 5 parts by weight based on 100 parts by weight of the total solid content of the resin composition. Can be adjusted.

In addition to the above components, the resin composition may further appropriately include various additives known in the art, depending on the use to which the resin component is applied.

In addition, the resin composition for an optical film of the present invention may be used as an encapsulant encapsulating a device in various optoelectronic devices, but is not limited thereto. For example, an industrial material applied to an elevated temperature lamination process, etc. It can also be used as.

3. Process for preparing ethylene / alpha-olefin copolymer

Another embodiment of the present invention, the ethylene comprising the step of polymerizing ethylene and alpha-olefin-based monomer by adding hydrogen at 5 to 100 cc / min in the presence of a catalyst composition comprising a transition metal compound of Formula 1 Provided are methods for preparing the alpha / olefin copolymer:

[Formula 1]

In Chemical Formula 1,

R ₁ is hydrogen; C1-20 alkyl; C3-20 cycloalkyl; C2-20 alkenyl; C1-20 alkoxy; C6-20 aryl; C7-20 arylalkoxy; C7-20 alkylaryl; Or C7-20 arylalkyl,

R _2a to R _2e are each independently hydrogen; halogen; C1-20 alkyl; C3-20 cycloalkyl; C2-20 alkenyl; C1-20 alkoxy; Or C6-20 aryl,

R ₃ is hydrogen; halogen; C1-20 alkyl; C3-20 cycloalkyl; C2-20 alkenyl; C6-20 aryl; C6-20 alkylaryl; C7-20 arylalkyl; C1-20 alkyl amido; C6-20 aryl amido; C1-20 alkylidene; Or phenyl substituted with one or more selected from the group consisting of halogen, C1-20 alkyl, C3-20 cycloalkyl, C2-20 alkenyl, C1-20 alkoxy and C6-20 aryl,

R ₄ to R ₉ are each independently hydrogen; Silyl; C1-20 alkyl; C3-20 cycloalkyl; C2-20 alkenyl; C6-20 aryl; C7-20 alkylaryl; C7-20 arylalkyl; Or a metalloid radical of a Group 14 metal substituted with C 1-20 hydrocarbyl; Two or more adjacent to each other of the R ₆ to R ₉ may be connected to each other to form a ring,

Q is Si, C, N, P or S,

M is a Group 4 transition metal,

X ₁ and X ₂ are each independently hydrogen; halogen; C1-20 alkyl; C3-20 cycloalkyl; C2-20 alkenyl; C6-20 aryl; C7-20 alkylaryl; C7-20 arylalkyl; C1-20 alkylamino; C6-20 arylamino; Or C1-20 alkylidene.

In the transition metal compound of Formula 1 according to an embodiment of the present invention,

R ₁ is hydrogen; C1-20 alkyl; C3-20 cycloalkyl; C1-20 alkoxy; C6-20 aryl; C7-20 arylalkoxy; C7-20 alkylaryl; Or C7-20 arylalkyl,

R _2a to R _2e are each independently hydrogen; halogen; C1-12 alkyl; C3-12 cycloalkyl; C2-12 alkenyl; C1-12 alkoxy; Or phenyl,

R ₃ is hydrogen; halogen; C1-12 alkyl; C3-12 cycloalkyl; C2-12 alkenyl; C6-20 aryl; C7-13 alkylaryl; C7-13 arylalkyl; Or phenyl substituted with one or more selected from the group consisting of halogen, C1-12 alkyl, C3-12 cycloalkyl, C2-12 alkenyl, C1-12 alkoxy and phenyl,

R ₄ to R ₉ are each independently hydrogen; C1-20 alkyl; C3-20 cycloalkyl; C6-20 aryl; C7-20 alkylaryl; Or C7-20 arylalkyl,

Two or more adjacent to each other of R ₆ to R ₉ may be connected to each other to form an aliphatic ring of C 5-20 or an aromatic ring of C 6-20; The aliphatic ring or aromatic ring may be substituted with halogen, C1-20 alkyl, C2-12 alkenyl, or C6-12 aryl,

Q may be Si,

M may be Ti,

X ₁ and X ₂ are each independently hydrogen; halogen; C1-12 alkyl; C3-12 cycloalkyl; C2-12 alkenyl; C6-12 aryl; C7-13 alkylaryl; C7-13 arylalkyl; C1-C13 alkylamino; C6-12 arylamino; Or C1-12 alkylidene.

In addition, in the transition metal compound of Formula 1 according to another embodiment of the present invention,

R ₁ is hydrogen; C1-12 alkyl; C3-12 cycloalkyl; C1-12 alkoxy; C6-12 aryl; C7-13 arylalkoxy; C7-13 alkylaryl; Or C7-13 arylalkyl,

R _2a to R _2e are each independently hydrogen; halogen; C1-12 alkyl; C3-12 cycloalkyl; C2-12 alkenyl; C1-12 alkoxy; Or phenyl,

R ₃ is hydrogen; halogen; C1-12 alkyl; C3-12 cycloalkyl; C2-12 alkenyl; C7-13 alkylaryl; C7-13 arylalkyl; Phenyl; Or phenyl substituted with one or more selected from the group consisting of halogen, C1-12 alkyl, C3-12 cycloalkyl, C2-12 alkenyl, C1-12 alkoxy and phenyl,

R ₄ to R ₉ are each independently hydrogen; C1-12 alkyl; C3-12 cycloalkyl; C6-12 aryl; C7-13 alkylaryl; Or C7-13 arylalkyl,

Two or more adjacent to each other of R ₆ to R ₉ may be connected to each other to form an aliphatic ring of C 5-12 or an aromatic ring of C 6-12;

The aliphatic ring or aromatic ring may be substituted with halogen, C1-12 alkyl, C2-12 alkenyl, or C6-12 aryl,

Q may be Si,

M may be Ti,

X ₁ and X ₂ are each independently hydrogen; halogen; C1-12 alkyl group; Or C2-12 alkenyl.

In addition, in the transition metal compound of Formula 1 according to another embodiment of the present invention,

R ₁ may be hydrogen or C1-12 alkyl,

R _2a to R _2e are each independently hydrogen; C1-12 alkyl; Or C1-12 alkoxy,

R ₃ is hydrogen; C1-12 alkyl; Or phenyl,

R ₄ and R ₅ are each independently hydrogen; Or C1-12 alkyl,

R ₆ to R ₉ may be each independently hydrogen or methyl,

Q may be Si,

M may be Ti,

X ₁ and X ₂ may be each independently hydrogen or C1-12 alkyl.

In the transition metal compound of Formula 1, cyclopentadiene fused with benzothiophene by cyclic bond, and amido group (NR ₁ ) are stably crosslinked by Q (Si, C, N or P), Group 4 transition metals form a coordinated structure. When applied to olefinic polymerization using the catalyst composition, it is possible to produce polyolefins with characteristics such as high activity, high molecular weight and high copolymerizability even at high polymerization temperatures.

Furthermore, the transition metal compound of Formula 1 has a structure in which a substituted or unsubstituted phenyl group is bonded to Q in the amido group (NR ₁ ) is crosslinked by Q (Si, C, N, P), It can be more stably crosslinked and can have excellent electronic stability when coordinating with a transition metal.

In addition, by placing a phenyl group, which is a bulky substituent, around the center metal, it suppresses β-Hydrogen transfer, thereby making it possible to produce a higher molecular weight olefin polymer and have excellent copolymerizability.

That is, in the present invention, by using the transition metal compound described above, by introducing hydrogen in an optimized content during the polymerization reaction, it is possible to provide an ethylene / alpha -olefin copolymer having a narrow molecular weight distribution and excellent crosslinking properties, the transition Due to the electronic / structural stability of the metal compounds, the incorporation of hydrogen is advantageous. In addition, since the initial molecular weight of the polymer formed by the catalyst addition before hydrogen injection is high, it is also possible to produce a product having a high molecular weight while having a narrow molecular weight distribution after hydrogen injection.

The compound represented by Chemical Formula 1 may specifically be any one of compounds represented by the following chemical formulas.

[Formula 1-1] [Formula 1-2] [Formula 1-3] [Formula 1-4]

[Formula 1-5] [Formula 1-6] [Formula 1-7] [Formula 1-8]

[Formula 1-9] [Formula 1-10]

Meanwhile, in the preparation of the ethylene / alpha-olefin copolymer according to one embodiment of the present invention, the catalyst composition may further include a promoter for activating the transition metal compound of Chemical Formula 1.

The promoter is an organometallic compound including a Group 13 metal, and specifically, may include one or more of a compound of Formula 2, a compound of Formula 3, and a compound of Formula 4.

[Formula 2]

R _41- [Al (R ₄₂ ) -O] _n -R ₄₃

In Chemical Formula 2,

R ₄₁ , R ₄₂ and R ₄₃ are each independently hydrogen, halogen, a hydrocarbyl group having 1 to 20 carbon atoms and a hydrocarbyl group having 1 to 20 carbon atoms substituted with halogen,

n is an integer of 2 or more,

[Formula 3]

D (R ₄₄ ) ₃

In Formula 3, D is aluminum or boron,

Each R ₄₄ is independently a halogen, a hydrocarbyl group having 1 to 20 carbon atoms, and a hydrocarbyl group having 1 to 20 carbon atoms substituted with halogen,

[Formula 4]

^{[LH] + [Z (A} ) 4] - or ^{[L] + [Z (A} ) 4] -

In Chemical Formula 4,

L is a neutral or cationic Lewis base, H is a hydrogen atom,

Z is a Group 13 element, A each independently represent a hydrocarbyl group having 1 to 20 carbon atoms; Hydrocarbyloxy group having 1 to 20 carbon atoms; And one or more hydrogen atoms of these substituents are substituted with one or more substituents of halogen, a hydrocarbyloxy group having 1 to 20 carbon atoms, and a hydrocarbylsilyl group having 1 to 20 carbon atoms.

More specifically, the compound of Formula 2 may be an alkylaluminoxane compound having a repeating unit bonded in a linear, circular, or reticular form. Specific examples thereof include methylaluminoxane (MAO), ethylaluminoxane, isobutylaluminoxane or tert-butyl aluminoxane, etc. are mentioned.

In addition, specific examples of the compound of Formula 3 may include trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylchloroaluminum, triisopropylaluminum, tri-s-butylaluminum, tricyclo Pentyl aluminum, tripentyl aluminum, triisopentyl aluminum, trihexyl aluminum, trioctyl aluminum, ethyl dimethyl aluminum, methyl diethyl aluminum, triphenyl aluminum, tri-p-tolyl aluminum, dimethyl aluminum methoxide, dimethyl aluminum ethoxide , Trimethylboron, triethylboron, triisobutylboron, tripropylboron or tributylboron, and the like, in particular, may be selected from trimethylaluminum, triethylaluminum or triisobutylaluminum.

In addition, the compound of Formula 4 may include a borate compound in the form of a trisubstituted ammonium salt, or a dialkyl ammonium salt, a trisubstituted phosphonium salt. More specific examples include trimetalammonium tetraphenylborate, methyldioctadecylammonium tetraphenylborate, triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tri (n-butyl) ammonium tetraphenylborate, methyltetracyclo Octadecylammonium tetraphenylborate, N, N-dimethylaninynium tetraphenylborate, N, N-diethylaninynium tetraphenylborate, N, N-dimethyl (2,4,6-trimethylaninium) tetraphenylborate, Trimethylammonium tetrakis (pentafluorophenyl) borate, methylditetradecylammonium tetrakis (pentaphenyl) borate, methyldioctadecylammonium tetrakis (pentafluorophenyl) borate, triethylammonium, tetrakis (pentafluoro Phenyl) borate, tripropylammonium tetrakis (pentafluorophenyl) borate, tri (n-butyl) ammonium tetrakis (pen) Tafluorophenyl) borate, tri (secondary-butyl) ammonium tetrakis (pentafluorophenyl) borate, N, N-dimethylaninium tetrakis (pentafluorophenyl) borate, N, N-diethylaninium Tetrakis (pentafluorophenyl) borate, N, N-dimethyl (2,4,6-trimethylaninium) tetrakis (pentafluorophenyl) borate, trimethylammoniumtetrakis (2,3,4,6-tetra Fluorophenyl) borate, triethylammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate, tripropylammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate, tri ( n-butyl) ammonium tetrakis (2,3,4,6-, tetrafluorophenyl) borate, dimethyl (t-butyl) ammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate, N , N-dimethylaninium tetrakis (2,3,4,6-tetrafluorophenyl) borate, N, N-diethylaninium tetrakis (2,3,4,6-tetrafluorophenyl) bolay Or N, N- dimethyl- (2,4,6-trimethyl not iodonium) tetrakis-tri-substituted ammonium salt form borate-based compounds such as (with 2,3,4,6-tetra fluorophenyl) borate; Borates in the form of dialkylammonium salts such as dioctadecylammonium tetrakis (pentafluorophenyl) borate, ditetradecylammonium tetrakis (pentafluorophenyl) borate or dicyclohexylammonium tetrakis (pentafluorophenyl) borate compound; Or triphenylphosphonium tetrakis (pentafluorophenyl) borate, methyldioctadecylphosphonium tetrakis (pentafluorophenyl) borate or tri (2,6-, dimethylphenyl) phosphonium tetrakis (pentafluorophenyl And a borate compound in the form of a trisubstituted phosphonium salt such as) borate.

By the use of such a promoter, the polymerization activity can be improved while the molecular weight distribution of the finally prepared ethylene / alpha-olefin copolymer becomes more uniform.

The promoter may be used in an appropriate amount so that the activation of the transition metal compound of Formula 1 may proceed sufficiently.

In addition, the catalyst composition may include the transition metal compound of Formula 1 supported on a carrier.

When the transition metal compound of Formula 1 is supported on the carrier, the weight ratio of the transition metal compound to the carrier may be 1:10 to 1: 1,000, more specifically 1:10 to 1: 500. When the carrier and the transition metal compound are included in the above-mentioned ratio of rain, the optimum shape can be exhibited. In addition, when the promoter is supported on the carrier together, the weight ratio of the promoter to the carrier may be 1: 1 to 1: 100, more specifically 1: 1 to 1:50. When including the promoter and the carrier in the weight ratio, it is possible to improve the catalytic activity and to optimize the microstructure of the polymer to be produced.

On the other hand, as the carrier, silica, alumina, magnesia, or a mixture thereof may be used, or by drying the material at a high temperature to remove moisture on the surface, in a state containing a highly reactive hydroxyl group or siloxane group on the surface. May be used. In addition, the high temperature dried carriers may further include oxides, carbonates, sulfates, or nitrates, such as Na ₂ O, K ₂ CO ₃ , BaSO _4, and Mg (NO ₃ ) ₂ .

The drying temperature of the carrier is preferably 200 to 800 ° C, more preferably 300 to 600 ° C, and most preferably 300 to 400 ° C. When the drying temperature of the carrier is less than 200 ° C., the moisture is too much to react with the surface of the carrier and the promoter reacts. When the carrier temperature exceeds 800 ° C., the pores on the surface of the carrier are combined to reduce the surface area, and more hydroxyl groups are present on the surface. It is not preferable because it disappears and only siloxane groups remain and the reaction site with the promoter decreases.

In addition, the amount of hydroxy groups on the surface of the carrier is preferably 0.1 to 10 mmol / g, more preferably 0.5 to 5 mmol / g. The amount of hydroxyl groups on the surface of the carrier can be controlled by the method and conditions for preparing the carrier or by drying conditions such as temperature, time, vacuum or spray drying.

Meanwhile, the polymerization of the ethylene / alpha-olefin copolymer may be performed by continuously adding hydrogen in the presence of the catalyst composition described above and continuously polymerizing ethylene and alpha-olefin monomers.

At this time, the hydrogen gas serves to suppress the rapid reaction of the transition metal compound in the initial stage of polymerization, and to terminate the polymerization reaction. Accordingly, by controlling the use and usage of such hydrogen gas, an ethylene / alpha-olefin copolymer having a narrow molecular weight distribution and having a predetermined proportion or more of trivinyl in the copolymer can be effectively produced.

For example, the hydrogen gas may be at least 5 cc / min, or at least 7 cc / min, or at least 10 cc / min, or at least 15 cc / min, or at least 19 cc / min, or at least 22 cc / min and , Up to 100 cc / min, or up to 50 cc / min, or up to 45 cc / min, or up to 35 cc / min, or up to 29 cc / min. When added under the above conditions, the produced ethylene / alpha-olefin polymer can realize the physical properties in the present invention. If the content of hydrogen gas is introduced at less than 5 cc / min, the termination of the polymerization reaction may not occur uniformly, making it difficult to prepare an ethylene / alpha-olefin copolymer having the desired physical properties, and also exceeding 100 cc / min. In this case, the termination reaction may occur too quickly to produce an ethylene / alpha-olefin copolymer having a low molecular weight.

In addition, the polymerization reaction may be carried out at 80 to 200 ℃, it is possible to more easily control the trivinyl content in the ethylene / alpha -olefin copolymer by controlling the polymerization temperature with the hydrogen input amount described above. Accordingly, specifically, the polymerization reaction temperature may be 100 ° C. or higher, or 120 ° C. or higher, or 140 ° C. or higher, and may be 190 ° C. or lower, or 180 ° C. or lower, or 170 ° C. or lower, or 160 ° C. or lower.

In addition, during the polymerization reaction, an organoaluminum compound for removing water in the reactor may be further added, and the polymerization reaction may proceed in the presence thereof. Specific examples of such organoaluminum compounds include trialkylaluminum, dialkyl aluminum halides, alkyl aluminum dihalides, aluminum dialkyl hydrides or alkyl aluminum sesqui halides, and more specific examples thereof include Al (C _2). H ₅ ) ₃ , Al (C ₂ H ₅ ) ₂ H, Al (C ₃ H ₇ ) ₃ , Al (C ₃ H ₇ ) ₂ H, Al (iC ₄ H ₉ ) ₂ H, Al (C ₈ H ₁₇ ) ₃ , Al (C ₁₂ H ₂₅ ) ₃ , Al (C ₂ H ₅ ) (C ₁₂ H ₂₅ ) ₂ , Al (iC ₄ H ₉ ) (C ₁₂ H ₂₅ ) ₂ , Al (iC ₄ H ₉ ) ₂ H, Al (iC ₄ H ₉ ) ₃ , (C ₂ H ₅ ) ₂ AlCl, (iC ₃ H ₉ ) ₂ AlCl, (C ₂ H ₅ ) ₃ Al ₂ Cl ₃ , and the like. Such organoaluminum compounds may be continuously added to the reactor and may be added at a rate of about 0.1 to 10 moles per kilogram of reaction medium introduced to the reactor for proper water removal.

In addition, the polymerization pressure may be about 1 to about 100 Kgf / cm ² , preferably about 70 to about 96 Kgf / cm ² , more preferably about 80 to about 93 Kgf / cm ² .

In addition, when a transition metal compound is used in a form supported on a carrier, the transition metal compound may be an aliphatic hydrocarbon solvent having 5 to 12 carbon atoms, such as pentane, hexane, heptane, nonane, decane, and isomers thereof, toluene and benzene. Aromatic hydrocarbon solvents, such as dichloromethane, hydrocarbon solvents substituted with chlorine atoms such as chlorobenzene may be dissolved or diluted and added. The solvent used herein is preferably used by removing a small amount of water or air that acts as a catalyst poison by treating a small amount of alkyl aluminum, and may be carried out by further using a promoter.

Example

Hereinafter, preferred examples are provided to aid in understanding the present invention. However, the following examples are merely provided to more easily understand the present invention, and the contents of the present invention are not limited thereto.

Synthesis Example 1 Preparation of Transition Metal Compound

Step 1: Preparation of Ligand Compound (1a-1)

To a 250 mL Schlenk flask, 10 g (1.0 eq, 49.925 mmol) of 1,2-dimethyl-3H-benzo [b] cyclopenta [d] thiophene and 100 mL of THF were added and 22 mL of n-BuLi (1.1 eq, 54.918 mmol, 2.5 M in hexane) was added dropwise at -30 ° C, and then stirred at room temperature for 3 hours. The stirred Li-complex THF solution was cannulated in a Schlenk flask containing 8.1 mL (1.0 eq, 49.925 mmol) of dichloro (methyl) (phenyl) silane and 70 mL of THF and then stirred at room temperature overnight. After stirring and dried in vacuo, extracted with hexane 100 mL.

To 100 mL of extracted chloro-1- (1,2-dimethyl-3H-benzo [b] cyclopenta [d] thiophen-3-yl) -1,1- (methyl) (phenyl) silane hexane solution t-BuNH ₂ 42 mL (8 eq, 399.4 mmol) was added at room temperature, followed by stirring at room temperature overnight. After stirring and dried in vacuo, the mixture was extracted with 150 mL of hexane. 13.36 g (68%, dr = 1: 1) of a yellow solid was obtained after drying the solvent.

(1a-1)

¹ H NMR (CDCl ₃ , 500 MHz): δ 7.93 (t, 2H), 7.79 (d, 1H), 7.71 (d, 1H), 7.60 (d, 2H), 7.48 (d, 2H), 7.40 to 7.10 (m, 10H, aromatic), 3.62 (s, 1H), 3.60 (s, 1H), 2.28 (s, 6H), 2.09 (s, 3H), 1.76 (s, 3H), 1.12 (s, 18H), 0.23 (s, 3H), 0.13 (s, 3H)

Step 2: Preparation of the Transition Metal Compound (1a)

4.93 g (12.575 mmol, 1.0 eq) of the ligand compound of Formula 2-4 and 50 mL (0.2 M) of toluene were added to a 100 mL Schlenk flask, and 10.3 mL (25.779 mmol, 2.05 eq, 2.5 M in hexane) of n-BuLi was added. It was added dropwise at -30 ℃, then stirred overnight at room temperature. After stirring, 12.6 mL (37.725 mmol, 3.0 eq, 3.0 M in diethyl ether) of MeMgBr was added dropwise, and then 13.2 mL (13.204 mmol, 1.05 eq, 1.0 M in toluene) of TiCl ₄ was added thereto, followed by stirring at room temperature overnight. . After stirring, dried in vacuo, extracted with 150 mL of hexane, and after removing the solvent to 50 mL 4 mL (37.725 mmol, 3.0eq) was added dropwise, and stirred overnight at room temperature. After vacuum drying, the mixture was extracted with 150 mL of hexane. After drying the solvent, 2.23 g (38%, dr = 1: 0.5) of a brown solid.

(1a)

¹ H NMR (CDCl ₃ , 500 MHz): δ 7.98 (d, 1H), 7.94 (d, 1H), 7.71 (t, 6H), 7.50-7.30 (10H), 2.66 (s, 3H), 2.61 (s , 3H), 2.15 (s, 3H), 1.62 (s, 9H), 1.56 (s, 9H), 1.53 (s, 3H), 0.93 (s, 3H), 0.31 (s, 3H), 0.58 (s, 3H), 0.51 (s, 3H), -0.26 (s, 3H), -0.39 (s, 3H)

Synthesis Example 2: Preparation of Transition Metal Compound

Step 1: Preparation of Ligand Compound (2a-1)

(i) Preparation of Lithium Carbamate

1,2,3,4-tetrahydroquinoline (13.08 g, 98.24 mmol) and diethyl ether (150 mL) were placed in a Schlenk flask. The Schlenk flask was immersed in a -78 ° C low temperature bath made of dry ice and acetone and stirred for 30 minutes. Then n-BuLi (39.3 mL, 2.5 M, 98.24 mmol) was injected into the syringe under a nitrogen atmosphere to form a pale yellow slurry. Then, after the flask was stirred for 2 hours, the flask was heated to room temperature while removing the generated butane gas. After the flask was again immersed in Article -78 ℃ low temperature lowers the temperature was charged with a CO ₂ gas. As the carbon dioxide gas was added, the slurry disappeared and became a transparent solution. The flask was connected to a bubbler to raise the temperature to room temperature while removing carbon dioxide gas. Thereafter, excess CO ₂ gas and solvent were removed under vacuum. The flask was transferred to a dry box, and then pentane was added thereto, stirred vigorously, and filtered to obtain lithium carbamate, a white solid compound. The white solid compound is coordinated with diethyl ether. The yield is then 100%.

¹ H NMR (C ₆ D ₆ , C ₅ D ₅ N): δ 1.90 (t, J = 7.2 Hz, 6H, ether), 1.50 (br s, 2H, quin-CH ₂ ), 2.34 (br s, 2H , quin-CH ₂ ), 3.25 (q, J = 7.2 Hz, 4H, ether), 3.87 (br, s, 2H, quin-CH ₂ ), 6.76 (br d, J = 5.6 Hz, 1H, quin-CH ) ppm

¹³ C NMR (C ₆ D ₆ ): δ 24.24, 28.54, 45.37, 65.95, 121.17, 125.34, 125.57, 142.04, 163.09 (C = O) ppm

(ii) 8- (2,3,4,5-tetramethyl-1,3-cyclopentadienyl) -1,2,3,4-tetrahydroquinoline (8- (2,3,4,5- Preparation of Tetramethyl-1,3-cyclopentadienyl) -1,2,3,4-tetrahydroquinoline)

The lithium carbamate compound (8.47 g, 42.60 mmol) prepared in step (i) was placed in a Schlenk flask. Subsequently, tetrahydrofuran (4.6 g, 63.9 mmol) and 45 mL of diethyl ether were added sequentially. The Schlenk flask was immersed in a -20 ° C. low temperature bath made of acetone and a small amount of dry ice, stirred for 30 minutes, and then t-BuLi (25.1 mL, 1.7 M, 42.60 mmol) was added thereto. At this time the color of the reaction mixture turned red. Stir for 6 hours while maintaining -20 ° C. CeCl ₃ · 2LiCl solution (129 mL, 0.33 M, 42.60 mmol) dissolved in tetrahydrofuran and tetramethylcyclopentinone (5.89 g, 42.60 mmol) were mixed in a syringe, and then introduced into a flask under a nitrogen atmosphere. After slowly raising the temperature of the flask to room temperature, the thermostat was removed after 1 hour, and the temperature was kept at room temperature. Subsequently, water (15 mL) was added to the flask, ethyl acetate was added, and the filtrate was obtained by filtration. The filtrate was transferred to a separatory funnel and hydrochloric acid (2 N, 80 mL) was added thereto, followed by shaking for 12 minutes. After neutralizing with saturated aqueous sodium hydrogen carbonate solution (160 mL), the organic layer was extracted. Anhydrous magnesium sulfate was added to this organic layer to remove water and filtered, and the filtrate was taken out and the solvent was removed. The obtained filtrate was purified by column chromatography using hexane and ethyl acetate (v / v, 10: 1) solvent to give a yellow oil. Yield 40%.

(2a-1)

¹ H NMR (C ₆ D ₆ ): δ 1.00 (br d, 3H, Cp-CH ₃ ), 1.63-1.73 (m, 2H, quin-CH ₂ ), 1.80 (s, 3H, Cp-CH ₃ ), 1.81 (s, 3H, Cp-CH ₃ ), 1.85 (s, 3H, Cp-CH ₃ ), 2.64 (t, J = 6.0 Hz, 2H, quin-CH ₂ ), 2.84-2.90 (br, 2H, quin -CH ₂ ), 3.06 (br s, 1H, Cp-H), 3.76 (br s, 1H, NH), 6.77 (t, J = 7.2 Hz, 1H, quin-CH), 6.92 (d, J = 2.4 Hz, 1H, quin-CH), 6.94 (d, J = 2.4 Hz, 1H, quin-CH) ppm

Step 2: Preparation of Transition Metal Compound (2a)

(i) Preparation of [(1,2,3,4-tetrahydroquinolin-8-yl) tetramethylcyclopentadienyl- η ⁵ , κ- N] dilithium compounds

8- (2,3,4,5-tetramethyl-1,3-cyclopentadienyl) -1,2,3,4-tetrahydroquinoline (8.07 g) prepared through step (1) in a dry box. , 32.0 mmol) and 140 mL of diethyl ether were added to a round flask, and the temperature was lowered to −30 ° C., and n-BuLi (17.7 g, 2.5 M, 64.0 mmol) was added slowly with stirring. The reaction was carried out for 6 hours while raising the temperature to room temperature. Thereafter, the mixture was washed with diethyl ether several times to obtain a solid. The remaining solvent was removed by vacuum to obtain a dilithium compound (9.83 g) as a yellow solid. Yield 95%.

¹ H NMR (C ₆ D ₆ , C ₅ D ₅ N): δ 2.38 (br s, 2H, quin-CH ₂ ), 2.53 (br s, 12H, Cp-CH ₃ ), 3.48 (br s, 2H, quin-CH ₂ ), 4.19 (br s, 2H, quin-CH ₂ ), 6.77 (t, J = 6.8 Hz, 2H, quin-CH), 7.28 (br s, 1H, quin-CH), 7.75 (brs , 1H, quin-CH) ppm

(ii) (1,2,3,4-tetrahydroquinolin-8-yl) tetramethylcyclopentadienyl- η ⁵ , κ -N] titanium dimethyl ([(1,2,3,4-Tetrahydroquinolin-8 -yl) tetramethylcyclopentadienyl-eta5, kapa-N] titanium dimethyl)

In a dry box, TiCl ₄ · DME (4.41 g, 15.76 mmol) and diethyl ether (150 mL) were placed in a round flask, and MeLi (21.7 mL, 31.52 mmol, 1.4 M) was slowly added with stirring at −30 ° C. After stirring for 15 minutes, the [(1,2,3,4-tetrahydroquinolin-8-yl) tetramethylcyclopentadienyl- η ⁵ , κ- N] dilithium compound prepared in step (i) 5.30 g, 15.76 mmol) was added to the flask. Stir for 3 hours while raising the temperature to room temperature. After the reaction was completed, vacuum was applied to remove the solvent, dissolved in pentane, and filtered to obtain a filtrate. Removal of pentane through vacuum yielded a dark brown compound (3.70 g). The yield was 71.3%.

(2a)

¹ H NMR (C ₆ D ₆ ): δ 0.59 (s, 6H, Ti-CH ₃ ), 1.66 (s, 6H, Cp-CH ₃ ), 1.69 (br t, J = 6.4 Hz, 2H, quin-CH ₂ ), 2.05 (s, 6H, Cp-CH ₃ ), 2.47 (t, J = 6.0 Hz, 2H, quin-CH ₂ ), 4.53 (m, 2H, quin-CH ₂ ), 6.84 (t, J = 7.2 Hz, 1H, quin-CH), 6.93 (d, J = 7.6 Hz, quin-CH), 7.01 (d, J = 6.8 Hz, quin-CH) ppm

¹³ C NMR (C ₆ D ₆ ): δ 12.12, 23.08, 27.30, 48.84, 51.01, 119.70, 119.96, 120.95, 126.99, 128.73, 131.67, 136.21 ppm.

[Production of Ethylene / Alpha-olefin Copolymer]

Example 1

After filling the 1.5 L autoclave continuous process reactor with hexane solvent (5.5 kg / h) and 1-butene (0.8 kg / h), the temperature at the top of the reactor was preheated to 155 ° C. Triisobutylaluminum compound (0.05 mmol / min), transition metal compound (1a) (0.15 µmol / min) prepared in Synthesis Example 1 as a catalyst, dimethylanilinium tetrakis (pentafluorophenyl) borate cocatalyst (0.15 μmol / min) were simultaneously introduced into the reactor. Subsequently, ethylene (0.87 kg / h) and hydrogen gas (25 cc / min) were introduced into the autoclave reactor to maintain the copolymerization reaction continuously for 60 minutes at a pressure of 89 bar and a polymerization temperature of 140 ° C. Was prepared.

Next, the remaining ethylene gas was removed, and the resulting copolymer-containing solution was dried in a vacuum oven for 12 hours or more, and then the physical properties of the obtained bale-type copolymer were measured.

Examples 2-9

The polymers of Examples 2 to 9 were prepared in the same manner as in Example 1, except that the reactants were added in the amounts shown in Table 1 below.

Comparative Examples 1 and 2

Meanwhile, as Comparative Example 1, LC Chemical's LC885X product was purchased, In Comparative Example 2, Mitsui Corp.'s DF8200 product was purchased and used.

Comparative Examples 3 and 4

Using the transition metal compound (2a) prepared in Synthesis Example 2, except that the reactants were added to the content shown in Table 1 to prepare a polymer of Comparative Examples 3 and 4 in the same manner as in Example 1 It was.

Comparative Examples 5 and 6

The polymers of Comparative Examples 5 and 6 were prepared in the same manner as in Example 1, except that the reactants were added in the amounts shown in Table 1 below.

C2 C6 1-C4 H2 Cat. Co-cat. Polymerization temperature catalyst Kg / h sccm μmol / min ℃ Example 1 0.87 5.5 0.8 25 0.15 0.15 140 Synthesis Example 1 Example 2 0.87 5.5 0.7 22 0.075 0.5 140 Synthesis Example 1 Example 3 0.87 5.5 0.85 24 0.25 0.375 155 Synthesis Example 1 Example 4 0.87 5.5 0.8 10 0.25 0.375 148 Synthesis Example 1 Example 5 0.87 5.5 0.8 10 0.25 0.375 146 Synthesis Example 1 Example 6 0.87 5.5 0.85 24 0.25 0.375 152 Synthesis Example 1 Example 7 0.87 5.5 0.85 24 0.25 0.375 161 Synthesis Example 1 Example 8 0.87 5.5 0.85 24 0.25 0.375 172 Synthesis Example 1 Example 9 0.87 7.0 0.83 16 0.17 0.34 140 Synthesis Example 1 Comparative Example 3 0.87 5.5 0.45 6 0.30 0.90 160 Synthesis Example 2 Comparative Example 4 0.87 5.5 0.43 6 0.24 0.72 160 Synthesis Example 2 Comparative Example 5 0.87 5.5 0.7 0 0.33 0.74 165 Synthesis Example 1 Comparative Example 6 0.87 5.5 0.7 2 0.35 0.55 160 Synthesis Example 1

In addition, Examples 1 to 9 and Comparative Examples 1 to 6 The number of each functional group of vinylene, trivinyl, vinyl and vinylidene per 1000 carbon atoms in the copolymer was measured by nuclear magnetic spectroscopic analysis according to the following method and shown in Table 2.

① The copolymer was dissolved in 1,1,2,2-tetrachloroethane D2 (TCE-d2) solvent and measured using a Bruker AVANCE III 500 MHz NMR instrument at 393K.

② The TCE-d2 peak was corrected to 6.0 ppm in the 1H NMR spectrum, and the content ratio of the comonomer was calculated using the integral values of 1.4 ppm and 0.96 ppm. The content of vinyl group, vinylidene group, vinylene group and trivinyl group observed at 4.7 ppm to 5.6 ppm was calculated (analytical method: AMT-3863). Peak assignment is referred to Macromolecules 2014, 47, 3282-3790 .

Relative content (number / 1000 C) Trivinyl / Total (%) Vinylene Trivinyl vinyl Vinylidene Total Example 1 0.1 0.04 0.05 0.02 0.2 0.20 Example 2 0.07 0.03 0.05 0.04 0.19 0.16 Example 3 0.12 0.07 0.07 0.01 0.27 0.26 Example 4 0.11 0.07 0.07 0.01 0.25 0.28 Example 5 0.11 0.06 0.08 0.01 0.25 0.24 Example 6 0.15 0.13 0.14 0.01 0.43 0.30 Example 7 0.13 0.08 0.09 0.02 0.31 0.26 Example 8 0.1 0.05 0.05 0.02 0.22 0.23 Example 9 0.09 0.03 0.03 0 0.15 0.20 Comparative Example 1 0.46 0.05 0.1 0.08 0.69 0.07 Comparative Example 2 0.01 0 0.03 0.01 0.05 0 Comparative Example 3 0.10 0.02 0.03 0.05 0.21 0.10 Comparative Example 4 0.08 0.02 0.03 0.04 0.18 0.11 Comparative Example 5 0.06 0.02 0.15 0.04 0.27 0.07 Comparative Example 6 0.1 0.03 0.12 0.05 0.3 0.1

As can be seen in Table 2, in the case of the ethylene / alpha -olefin copolymer of Examples 1 to 9 according to the present invention, compared to Comparative Example 1 (LC885X of LG Chem) and Comparative Example 2 (DF8200 of Mitsui) Trivinyl / total (%) values were found to be high. Also, in the case of Comparative Examples 3 and 4 using the catalyst of Synthesis Example 2, it was confirmed that the trivinyl / total (%) value was lower than that of the ethylene / alpha olefin copolymer of the present invention.

Furthermore, for Comparative Examples 5 and 6, the transition metal compound (1a) of Synthesis Example 1 was used in the same manner as in Example, but the desired trivinyl / It was found that a copolymer having a total (%) value could not be prepared.

In addition, the density, melt index, weight average molecular weight (Mw) and molecular weight distribution (MWD) of Examples 1 to 9 and Comparative Examples 1, 5 and 6 were measured and shown in Table 3 below.

① Density (g / cm3): Measured according to ASTM D-792.

② Melt Index (Melt Index, MI2.16): Measured by ASTM D-1238 (Condition E, 190 ° C, 2.16 Kg load).

③ Melt Index (Melt Index, MI10): Measured by ASTM D-1238 (Condition E, 190 ° C., 10 Kg load).

(4) The weight average molecular weight (Mw) and the number average molecular weight (Mn) were measured under the following gel permeation chromatography (GPC) analysis conditions of the resulting copolymer:

Column: Agilent Olexis

Solvent: Trichlorobenzene (TCB)

Flow rate: 1.0 ml / min

Sample concentration: 1.0 mg / ml

Injection volume: 200 μl

-Column temperature: 160 ℃

-Detector: Agilent High Temperature RI detector

-Standard: Polystyrene (corrected by 3rd order function)

Data processing: Cirrus

(5) The molecular weight distribution was calculated from the ratio of Mw / Mn.

density MI _2.16 MI ₁₀ MI ₁₀ / MI _2.16 Mw MWD g / cm ³ dg / min dg / min Da - Example 1 0.876 18 102.5 5.69 55,000 1.94 Example 2 0.876 12.8 82.4 6.44 54,000 1.9 Example 3 0.879 18.4 119.7 6.50 55,000 2.14 Example 4 0.879 2.24 16.3 7.29 89,000 2.04 Example 5 0.879 0.95 7.3 7.67 112,000 2.1 Example 6 0.874 33.7 217.8 6.46 47,000 2.06 Example 7 0.883 25.3 160.8 6.36 50,000 2.01 Example 8 0.893 11.9 83.3 7.00 58,000 2.12 Example 9 0.880 16.3 103.0 6.32 50,000 2.14 Comparative Example 1 0.881 22 151.8 6.9 54,000 2.4 Comparative Example 5 0.877 2.3 15.41 6.7 89,000 2.3 Comparative Example 6 0.875 1.8 12.6 7.0 94,000 2.26

From the results of Table 3, it was confirmed that the ethylene / alpha -olefin copolymers of Examples 1 to 9 of the present invention had a narrower molecular weight distribution than Comparative Example 1 (LC885X of LG Chem). In addition, in the case of Comparative Examples 5 and 6 prepared by not adding hydrogen or at 2 cc / min, the molecular weight distribution was increased, thereby adjusting the hydrogen input amount to 5 to 100 cc / min to narrow the molecular weight distribution as in the present invention. It was found that an ethylene / alpha-olefin copolymer having

Experimental Example 1 Crosslinking Degree and Behavior Characteristics

[Production of Resin Composition]

500 g of the sample of Example 1 was added to the crosslinking aid composition according to the recipe (a) as described below, and then aged for 15 hours after soaking at 40 ° C.

In addition, except that different recipes (a) to (f) were applied to each of the samples of Examples 3, 9 and Comparative Examples 1 to 4 as shown in Table 4 below, Resin compositions were prepared and applied, respectively.

(a) t-butyl 1- (2-ethylhexyl) monoperoxycarbonate (TBEC) 1 phr (parts per hundred rubber), triallyl isocyanurate (TAIC) 0.5 phr, methacryloxypropyltrimethoxy Silane (MEMO) 0.2 phr / Toluene (non-crosslinked polymer extraction solvent)

-(b) TBEC 0.6 phr, TAIC 0.8 phr, MEMO 0.2 phr / toluene

-(c) TBEC 0.6 phr, TAIC 0.93 phr, MEMO 0.21 phr / toluene

-(d) The same applies to (c) except that the soaking time is performed at 1.5 hours instead of 1 hour.

(e) TBEC 0.6 phr, TAIC 0.93 phr, MEMO 0.21 phr / xylene (non-crosslinked polymer extraction solvent)

-(f) TBEC 0.6 phr, TAIC 0.8 phr, MEMO 0.3 phr / xylene

[Manufacture of Film]

Using a micro extruder with soaked samples, a film having an average thickness of 450 μm was prepared at a low temperature (extruder barrel temperature of 90 ° C. or less) such that high temperature crosslinking was not possible.

In order to understand the crosslinking behavior, the film containing the crosslinking aid composition was manufactured in the form of a disc of 5 g diameter 4 cm, and the result including the maximum torque MH value until scorched for 1 hour at 150 ° C. The values are shown in Table 4.

This crosslinking behavior was measured using a Moving Die Rheometer called Premier MDR from Alpha Technologies.

[Crosslink Sheet Manufacturing]

Covering the top and bottom of the film sample prepared in the above [Production of the film] process with a Teflon sheet and put in a vacuum laminator, a crosslinked sheet was produced by laminating at 150 ℃ for 15 minutes. The crosslinked sheet is for measuring the degree of crosslinking and optical properties after crosslinking and is not attached to any substrate such as a glass substrate.

0.5 g of the crosslinked sheet was placed in toluene and aged at 60 ° C. for 15 hours. Toluene was washed and then dried at 80 ° C. for 6 hours. After drying, the weight of the sample was measured, and the degree of crosslinking was measured according to the following equation.

* Crosslinking degree = (weight after drying / weight before toluene treatment) * 100

Degree of crosslinking ML MH Final torque T10 T50 T90 T95 Max Rate % dNm min dNm / min ^(a) Example 1 67 0.02 2.77 2.75 1.64 4.49 13.26 18.48 0.45 ^(a) Comparative Example 1 57 0.04 2.54 2.53 2.14 5.87 16.17 20.26 0.30 ^(b) Comparative Example 1 44 0.03 1.88 1.87 2.08 6.11 17.03 23.32 0.20 ^(c) Example 3 56 0.02 2.79 2.78 3.03 6.78 17.00 22.90 0.33 ^(d) Example 3 60.2 0.02 2.97 2.96 2.95 6.52 16.58 20.58 0.37 ^(c) Comparative Example 2 49 0.01 2.80 2.79 3.09 6.07 15.07 18.95 0.41 ^(e) Example 9 55 0.02 2.41 2.40 3.26 7.12 17.17 22.66 0.27 ^(e) Comparative Example 2 51 0.02 2.10 2.09 3.19 6.59 15.93 19.53 0.27 ^(f) Example 9 56 0.01 2.51 2.49 3.08 6.62 16.82 21.45 0.30 ^(f) Comparative Example 3 41 0.02 1.62 1.60 3.87 7.42 18.44 26.12 0.18 ^(f) Comparative Example 4 39 0.01 1.59 1.56 3.94 7.57 18.62 26.35 0.17

In the crosslinking behavior characteristic results of Table 4, MH value and Final Torque value means that the higher the value, the higher the crosslinking degree. In addition, the T value is a factor related to the crosslinking rate. For example, T90 represents a time taken until the torque value is 90% saturation, and the smaller the value, the faster the crosslinking speed.

In addition, Figure 1 shows the crosslinking behavior of Example 1 and Comparative Example 1 according to the crosslinking recipe (a). Moreover, when the Example and the comparative example which applied the same crosslinking recipe were respectively compared from the result of Table 4, it can confirm that the resin composition of an Example has a high crosslinking degree compared with the comparative example. In particular, ^(a) the degree of crosslinking of the polymer of Example 1 ^{(a) (f} Comparative example 1, ^(b) comparison was higher than 10% as compared to Example 1, ^(f) carried out applying the same cross-linking Recipe for Example 9 ⁾ Comparative Example 3, ^(f) showed a much higher degree of crosslinking than Comparative Example 4.

In addition, ^(c) in the case of Example 3 gave ^(d) to increase the soaking time for the Example 3 was confirmed that the degree of crosslinking is further improved.

Experimental Example 2-Optical Properties

The yellow index (YI) and the total light transmittance (Tt) were measured for the crosslinked sheet according to the following method, and are shown in Table 5 below.

In addition, the yellow index (YI) and the total light transmittance (Tt) were measured in Table 5 below as 'pre-crosslinking' data before the cross-linking sheet was manufactured after the [manufacturing of the film] process.

① Yellow index (YI): Based on ASTM 1925, the reflectance of the 400 nm to 700 nm region was measured using Colorflex (Hunter lab), using this, to obtain a YI value according to the following formula (2).

[Equation 2]

YI = [100 (1.28XCIE-1.06ZCIE)] / YCIE

The YI is a value calculated using a color difference analysis program in a UV / VIS / NIR spectrometer (ASTM, D1925), and XCIE, YCIE, and ZCIE are relative values represented by red, green, and blue color coordinates, respectively.

② Total light transmittance (Tt): The total light transmittance with respect to the light of wavelength of 550 nm was measured using the hazemeter. The transmittance was measured three times after the specimen was placed in the specimen holder, and the average value thereof was obtained. The transmittance was measured under the standard condition of JIS K 7105.

After crosslinking Before crosslinking Tt @ 550nm YI Tt @ 550nm YI ^(a) Example 1 91 0.82 89.4 3.5 ^(c) Example 3 90.9 0.86 88.2 3.4 ^(e) Example 9 91.2 0.83 89.1 3.7 ^(f) Example 9 91.5 0.9 90.0 3.4 ^(a) Comparative Example 1 89.4 1.63 86 6.1 ^(c) Comparative Example 2 89.3 1.74 85.3 5.9 ^(f) Comparative Example 3 89.1 3.1 88.5 7.4 ^(f) Comparative Example 4 88.8 3.7 88.1 8.1

In Table 5, in the case of the film formed by including the ethylene / alpha -olefin copolymer of the present invention, it can be confirmed that the total light transmittance and the yellow index is superior to the comparative example. Specifically, in the case of the embodiment of the present invention, the yellow index value after crosslinking is very superior to 1.63 to 3.7 of the comparative example as the range of 0.82 to 0.9. In addition, the embodiment of the present invention can be seen that the total light transmittance after crosslinking is significantly improved compared to the comparative example showing a maximum value of 99.4 or more as 90.9. Therefore, it is expected that the ethylene / alpha-olefin copolymer of the present invention can be applied to the production of an optical film having excellent optical properties.

Claims (14)

Ethylene / alpha-olefin copolymers satisfying the following conditions (a) to (d):
(a) Density: 0.850 to 0.910 g / cc
(b) Melt Index (Melt Index, MI, 190 ° C., 2.16 kg loading conditions; MI _2.16 ): 0.1 to 100 dg / min
(c) molecular weight distribution (MWD): 1.5 to 3.0
(d) Rtv value according to Equation 1 below 0.12.

[Equation 1]

In Formula 1,
Nv, Ntv, Nvl, and Nvd refer to the number of vinyl, trivinyl, vinylene, and vinylidene functional groups per 1000 carbon atoms measured by nuclear magnetic spectroscopic analysis, respectively.
The method of claim 1,
The Rtv value is 0.12 to 0.30 ethylene / alpha-olefin copolymer.
The method of claim 1,
The density is 0.855 to 0.90 g / cc ethylene / alpha-olefin copolymer.
The method of claim 1,
The melt index (MI _2.16 ) is 12 to 35 dg / min ethylene / alpha -olefin copolymer.
The method of claim 1,
Ethylene / alpha-olefin copolymer having a melt index (190 ° C., 10 kg load condition; MI ₁₀ ) value for the melt index (190 ° C., 2.16 kg load condition; MI _2.16 ) of 8.5 or less.
The ethylene / alpha-olefin copolymer of claim 1, wherein the copolymer has a weight average molecular weight (Mw) of 40,000 to 150,000 g / mol.
The method of claim 1,
The copolymer is an ethylene / alpha-olefin copolymer having a molecular weight distribution of 1.5 to 2.4.
The method of claim 1,
The alpha-olefins are propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1 An ethylene / alpha-olefin copolymer comprising at least one member selected from the group consisting of tetradecene, 1-hexadecene and 1-eicosene.
The method of claim 1,
The alpha-olefin is an ethylene / alpha -olefin copolymer is contained in an amount of more than 0 99 mol% based on the total weight of the copolymer.
In the presence of a catalyst composition comprising a transition metal compound of Formula 1, the ethylene / alpha -olefin of claim 1 comprising the step of polymerizing ethylene and alpha-olefin-based monomers by introducing hydrogen at 5 to 100 cc / min Preparation of Copolymers:
[Formula 1]

In Chemical Formula 1,
R ₁ is hydrogen; C1-20 alkyl; C3-20 cycloalkyl; C2-20 alkenyl; C1-20 alkoxy; C6-20 aryl; C7-20 arylalkoxy; C7-20 alkylaryl; Or C7-20 arylalkyl,
R _2a to R _2e are each independently hydrogen; halogen; C1-20 alkyl; C3-20 cycloalkyl; C2-20 alkenyl; C1-20 alkoxy; Or C6-20 aryl,
R ₃ is hydrogen; halogen; C1-20 alkyl; C3-20 cycloalkyl; C2-20 alkenyl; C6-20 aryl; C6-20 alkylaryl; C7-20 arylalkyl; C1-20 alkyl amido; C6-20 aryl amido; C1-20 alkylidene; Or phenyl substituted with one or more selected from the group consisting of halogen, C1-20 alkyl, C3-20 cycloalkyl, C2-20 alkenyl, C1-20 alkoxy and C6-20 aryl,
R ₄ to R ₉ are each independently hydrogen; Silyl; C1-20 alkyl; C3-20 cycloalkyl; C2-20 alkenyl; C6-20 aryl; C7-20 alkylaryl; C7-20 arylalkyl; Or a metalloid radical of a Group 14 metal substituted with C 1-20 hydrocarbyl; Two or more adjacent to each other of the R ₆ to R ₉ may be connected to each other to form a ring,
Q is Si, C, N, P or S,
M is a Group 4 transition metal,
X ₁ and X ₂ are each independently hydrogen; halogen; C1-20 alkyl; C3-20 cycloalkyl; C2-20 alkenyl; C6-20 aryl; C7-20 alkylaryl; C7-20 arylalkyl; C1-20 alkylamino; C6-20 arylamino; Or C1-20 alkylidene.
The method of claim 10,
R ₁ is hydrogen; C1-12 alkyl; C3-12 cycloalkyl; C1-12 alkoxy; C6-12 aryl; C7-13 arylalkoxy; C7-13 alkylaryl; Or C7-13 arylalkyl,
R _2a to R _2e are each independently hydrogen; halogen; C1-12 alkyl; C3-12 cycloalkyl; C2-12 alkenyl; C1-12 alkoxy; Or phenyl,
R ₃ is hydrogen; halogen; C1-12 alkyl; C3-12 cycloalkyl; C2-12 alkenyl; C7-13 alkylaryl; C7-13 arylalkyl; Phenyl; Or phenyl substituted with one or more selected from the group consisting of halogen, C1-12 alkyl, C3-12 cycloalkyl, C2-12 alkenyl, C1-12 alkoxy and phenyl,
R ₄ to R ₉ are each independently hydrogen; C1-12 alkyl; C3-12 cycloalkyl; C6-12 aryl; C7-13 alkylaryl; Or C7-13 arylalkyl,
Two or more adjacent to each other of R ₆ to R ₉ may be connected to each other to form an aliphatic ring of C 5-12 or an aromatic ring of C 6-12;
The aliphatic ring or aromatic ring may be substituted with halogen, C1-12 alkyl, C2-12 alkenyl, or C6-12 aryl,
Q may be Si,
M may be Ti,
X ₁ and X ₂ are each independently hydrogen; halogen; C1-12 alkyl group; Or C2-12 alkenyl. A process for producing an ethylene / alpha-olefin copolymer.
The method of claim 10,
The transition metal compound is a method of producing an ethylene / alpha -olefin copolymer is selected from the group consisting of compounds of the formula 1-1 to 1-10:
[Formula 1-1] [Formula 1-2] [Formula 1-3] [Formula 1-4]

[Formula 1-5] [Formula 1-6] [Formula 1-7] [Formula 1-8]

[Formula 1-9] [Formula 1-10]

The method of claim 10,
The polymerization is carried out at 100 to 150 ° C, method for producing an ethylene / alpha-olefin copolymer.
A resin composition for an optical film, comprising the ethylene / alpha-olefin copolymer according to any one of claims 1 to 9.

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