KR102527751B1 - Resin Composition For Optical Film Comprising Ethylene/alpha-olefin Copolymer, And Optical Film Comprising The Same - Google Patents

Abstract

상기 식 1에서, N_vd, N_tv, N_vl 및 N_v는 각각 핵자기 분광 분석을 통해 측정된 탄소원자 1000개당 비닐리덴(vinylidene), 트라이비닐(trivinyl), 비닐렌(vinylene), 비닐(vinyl) 작용기의 개수를 의미한다.The present invention provides a resin composition for an optical film comprising an ethylene/alpha-olefin copolymer that satisfies the following conditions (a) to (d):
(a) Density: 0.850 to 0.910 g/cc
(b) Melt Index (MI, 190 ℃, 2.16 kg load conditions): 0.1 to 100 dg / min
(c) molecular weight distribution (MWD): 1.5 to 3.0
(d) R _v value according to Equation 1 below is 0.18 to 0.59.
[Equation 1]

In Equation 1, N _vd , N _tv , N _vl and N _v are vinylidene, trivinyl, vinylene, vinyl (vinylidene, trivinyl), vinylene, vinyl ( vinyl) means the number of functional groups.

Description

Resin composition for optical film comprising ethylene/alpha-olefin copolymer and optical film comprising same

The present invention relates to a resin composition for an optical film comprising an ethylene/alpha-olefin copolymer exhibiting excellent physical properties by having a narrow molecular weight distribution and controlling the content of vinyl groups in the polymer within a certain range, and to an optical film including the same.

Olefin polymerization catalyst systems can be classified into Ziegler-Natta and metallocene catalyst systems, and these two highly active catalyst systems have been developed according to their respective characteristics. Ziegler-Natta catalyst has been widely applied to existing commercial processes since its invention in the 1950s, but since it is a multi-site catalyst in which several active sites are mixed, it is characterized by a wide molecular weight distribution of the polymer and comonomer There is a problem that there is a limit to securing desired physical properties because the composition distribution of is not uniform.

On the other hand, the metallocene catalyst is composed of a combination of a main catalyst mainly composed of a transition metal compound and a cocatalyst composed of an organometallic compound mainly composed of aluminum. Such a catalyst is a single site catalyst as a homogeneous complex catalyst. A polymer with a narrow molecular weight distribution and a uniform comonomer composition distribution is obtained according to the characteristics of a single active point, and the tacticity of the polymer, copolymerization characteristics, molecular weight, It has properties that can change crystallinity, etc.

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 preparation time are required when preparing the supported catalyst. However, it was cumbersome to support each of the metallocene catalysts used on the carrier.

Korean Patent Application No. 10-2003-0012308 discloses a method for controlling the molecular weight distribution by carrying a dinuclear metallocene catalyst and a mononuclear metallocene catalyst together with an activator on a carrier to change the combination of catalysts in a reactor and polymerize them. is starting However, this method has limitations in simultaneously implementing the characteristics of each catalyst, and also has a disadvantage in that the metallocene catalyst part is released from the carrier component of the finished catalyst, causing fouling in the reactor.

On the other hand, linear low-density polyethylene is a resin prepared by copolymerizing ethylene and alpha olefin at low pressure using a polymerization catalyst, and has a narrow molecular weight distribution, short chain branches of a certain length, and no long chain branches. Linear low-density polyethylene film has high breaking strength, elongation, tear strength, and drop impact strength along with the characteristics of general polyethylene, so it is increasingly used in stretch films and overlap films, where conventional low-density polyethylene or high-density polyethylene are difficult to apply. are doing

However, linear low-density polyethylene using 1-butene or 1-hexene as a comonomer is mostly produced in a single gas phase reactor or single loop slurry reactor, and has higher productivity than a process using 1-octene comonomer, but these products are also used Due to the limitations of catalyst technology and process technology, physical properties are greatly inferior to those of the case of using 1-octene comonomer, and the molecular weight distribution is narrow, resulting in poor processability.

US Patent No. 4,935,474 reports a method for producing polyethylene having a wide molecular weight distribution by using two or more metallocene compounds. U.S. Patent No. 6,828,394 reports a method for producing polyethylene that has excellent processability and is particularly suitable for film by using a mixture of those having good comonomer binding properties and those not having good comonomer bonding properties. In addition, in U.S. Patent No. 6,841,631 and U.S. Patent No. 6,894,128, polyethylene having a bimodal or multimodal molecular weight distribution is prepared with a metallocene-based catalyst using at least two metal compounds, and is used for applications such as films, blow molding, and pipes. reported to be applicable. However, although these products have improved processability, they have a problem in that the extruded appearance is rough and the physical properties are not stable even under relatively good extrusion conditions because the dispersion state by molecular weight in the unit particle is not uniform.

Against this background, there is a constant demand for manufacturing better products with a balance between physical properties and processability, and in particular, there is a need for polyethylene copolymers with excellent processability and excellent optical properties.

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

Accordingly, the present invention is to provide a resin composition for an optical film exhibiting excellent physical properties, particularly excellent crosslinking properties, by including an ethylene/alpha-olefin copolymer having a narrow molecular weight distribution and a vinyl group content within a certain range. .

In addition, an object of the present invention is to provide a resin composition for an optical film having improved optical properties such as yellow index (YI) and total light transmittance (Tt), and an optical film manufactured using the resin composition.

One embodiment of the present invention provides a resin composition for an optical film comprising an ethylene/alpha-olefin copolymer that satisfies the following conditions (a) to (d):

(a) Density: 0.850 to 0.910 g/cc

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

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

(d) R _v value according to Equation 1 below is 0.18 to 0.59.

[Equation 1]

In Equation 1, N _vd , N _tv , N _vl and N _v are vinylidene, trivinyl, vinylene, vinyl (vinylidene, trivinyl), vinylene, vinyl ( vinyl) means the number of functional groups.

Another embodiment of the present invention provides an optical film including the resin composition.

The resin composition for an optical film of the present invention has excellent crosslinking properties by using an ethylene/alpha-olefin copolymer having a narrow molecular weight distribution compared to the prior art and having a vinyl content in the polymer that satisfies a specific ratio relative to total unsaturated functional groups.

In addition, the resin composition for an optical film of the present invention and an optical film using the same have excellent optical properties such as yellow index (YI) and total light transmittance (Tt).

Figure 1 shows the molecular weight distribution of Preparation Example 2 and Comparative Preparation Example 1 as an embodiment of the present invention.
Figure 2 shows the crosslinking behavior characteristics of Example 1 and Comparative Example 1 as an embodiment of the present invention.
Figure 3 shows the crosslinking behavior characteristics of Example 2 and Comparative Example 2 as an embodiment of the present invention.

Terms used in this specification are only used to describe exemplary embodiments, and are not intended to limit the present invention. Singular expressions include plural expressions unless the context clearly dictates otherwise. In this specification, terms such as "comprise", "comprise" or "having" are intended to indicate that there is an embodied feature, step, component, or combination thereof, but one or more other features or steps; It should be understood that the presence or addition of components, or combinations thereof, is not previously excluded.

Since the present invention can have various changes and various forms, specific embodiments will be exemplified and described in detail below. However, it should be understood that this is not intended to limit the present invention to the specific disclosed form, and includes all modifications, equivalents, and substitutes included in the spirit and scope of the present invention.

The term “composition” as used herein includes mixtures of materials comprising the composition as well as reaction products and decomposition products formed from the materials of the composition.

The term “polymer” as used herein refers to a polymeric compound prepared by polymerizing monomers, whether of the same or different types. The generic term polymer thus encompasses the term homopolymer, commonly used to refer to a polymer prepared from only one monomer, and the term interpolymer, as defined below.

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

1. Resin composition for optical film

One embodiment of the present invention provides a resin composition for an optical film comprising an ethylene/alpha-olefin copolymer that satisfies the following conditions (a) to (d):

(a) Density: 0.850 to 0.910 g/cc

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

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

(d) R _v value according to Equation 1 below is 0.18 to 0.59.

[Equation 1]

In Equation 1, R _v is the ratio of the number of vinyl groups to the number of functional groups per 1000 carbon atoms measured by nuclear magnetic spectroscopy.

Optionally, the ethylene/alpha-olefin copolymer of the present invention may have an R _vd value of 0.25 or less according to Equation 2 below.

[Equation 2]

In Equation 2, R _vd is the ratio of the number of vinylidene groups to the number of functional groups per 1000 carbon atoms measured by nuclear magnetic spectroscopy.

In Equations 1 and 2, N _vd , N _tv , N _vl and N _v are vinylidene, trivinyl, vinylene and N per 1000 carbon atoms measured by nuclear magnetic spectroscopy, respectively. It means the number of vinyl functional groups.

As an example, the R _v value may be 0.55 or less, or 0.50 or less, or 0.46 or less, or 0.40 or less, or 0.39 or less, or 0.35 or less, or 0.32 or less, or 0.30 or less, or 0.29 or less, 0.19 or more, or It may be 0.22 or more, or 0.24 or more.

The content of the vinyl group in the copolymer is possible through control of the polymerization temperature and the amount of hydrogen input during production. When the ethylene/alpha-olefin copolymer according to the present invention satisfies the vinyl group content, a resin composition for an optical film is obtained by using the vinyl group content. When applied to, it can exhibit excellent crosslinking degree and/or optical properties.

As an example, the R _vd value may be 0.25 or less, or 0.22 or less, or 0.20 or less, or 0.15 or less, or 0.10 or less, or 0.09 or less, or 0.08 or less, or 0.07 or less, or 0.06 or less, 0.02 or more, or It may be 0.03 or more, or 0.04 or more. When the vinylidene group content satisfies the above numerical range, a narrow molecular weight distribution, excellent cross-linking properties, and thus optical properties may be exhibited.

In addition, the ethylene/alpha-olefin copolymer preferably has the number of unsaturated functional groups including vinyl, trivinyl, vinylene, and vinylidene in the copolymer of 0.65 or less per 1000 carbon atoms while satisfying the R _v value. do. Specifically, it may be 0.6 or less, or 0.5 or less, or 0.45 or less, or 0.4 or less, and may be 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 above numerical range, a narrow molecular weight distribution, excellent crosslinking properties, and thus optical properties may be exhibited.

In addition, the number of vinyl functional groups in the copolymer may be 0.3 or less per 1000 carbon atoms. Specifically, it may be 0.29 or less, or 0.25 or less, or 0.2 or less, or 0.15 or less, or 0.1 or less, or 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 above numerical range, a narrow molecular weight distribution, excellent crosslinking properties, and thus optical properties may be exhibited.

In addition, the number of trivinyl functional groups in the copolymer may be 0.15 or less, 0.1 or less, or 0.08 or less, 0.01 or more, or 0.02 or more per 1000 carbon atoms. When the number of the unsaturated functional groups satisfies the above numerical range, a narrow molecular weight distribution, excellent crosslinking properties, and thus optical properties may be exhibited.

In addition, the number of vinylene functional groups in the copolymer may be 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 per 1000 carbon atoms, 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 above numerical range, a narrow molecular weight distribution, excellent crosslinking properties, and thus optical properties may be exhibited.

In addition, the number of vinylidene functional groups in the copolymer may be 0.07 or less, or 0.05 or less, or 0.01 or more, or 0.02 or more per 1000 carbon atoms. When the number of the unsaturated functional groups satisfies the above numerical range, a narrow molecular weight distribution, excellent crosslinking properties, and thus optical properties may be exhibited.

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 a structure of RCH=CHR' (E form) or RCH=CHR' (Z form) structure, and the vinylidene means a RR'C=CH ₂ structure. Here, R, R' and R" may each independently be a polymer chain or a branched chain according to a comonomer alpha-olefin.

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

The resin composition for an optical film of the present invention may exhibit an excellent degree of crosslinking. For example, the degree of crosslinking of the resin composition for an optical film of the present invention may be 55% or more, or 58% or more, or 63% or more, or 67% or more, or 69% or more.

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

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

Specifically, the yellowness index (YI) value of the resin composition for an optical film of the present invention 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 than or equal to 3.9, or less than or equal to 2.9, or less than or equal to 1.5, or less than or equal to 1.2. As the YI value is smaller, the quality stability of the optical film is corrected.

In particular, when the yellow index of the resin composition for an optical film according to the present invention is crosslinked and then measured, a higher value may be obtained. For example, after performing the crosslinking, the yellow index may be 0.5 or more, or 0.7 or more, or 0.9 or more, or 1.0 or more, and may be 1.5 or less, or 1.48 or less, or 1.3 or less, or 1.2 or less.

The yellow index is a value quantifying yellowing 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, the reflectance of the resin composition in a wavelength range of 400 nm to 700 nm may be measured using the UV/Vis spectrometer, and the yellow index value may be calculated by Equation 3 below.

[Equation 3]

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

In Equation 3, 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-like resin composition at a temperature of 150° C. may satisfy Equation 4 below.

[Equation 4]

Tt≥90.0%

The total light transmittance may be a value measured with a haze meter for wavelengths of light of 200 nm or more, for example, 300 nm, 350 nm, 400 nm, 450 nm, 500 nm, 550 nm or 600 nm, , Preferably it may be a value measured with a haze meter for light with a wavelength of 550 nm. The total light transmittance of the resin composition of the present invention measured above indicates 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 for an optical film of the present invention is 90% or more, or 90.2% or more, or 90.5% or more, or 90.9% or more, or 91% or higher, or 92% or higher. In addition, considering the photoelectric efficiency of the optical device, the total light transmittance may be adjusted to have a total light transmittance within the aforementioned range.

In addition, a modified resin composition, for example, a silane-modified resin composition or an amino-silane-modified resin composition, may be provided using the resin composition for an optical film of the present invention.

For 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.

The unsaturated silane compound may be grafted onto the main chain including the polymerization unit of the copolymer of the present invention in the presence of a radical initiator, etc., and included in a silane-modified resin composition or an amino silane-modified resin composition in a polymerized form.

As an example, the unsaturated silane compound is vinyltrimethoxy silane, vinyltriethoxy silane, vinyltripropoxy silane, vinyltriisopropoxy silane, vinyltributoxy silane, vinyltripentoxy silane, vinyltriphenoxy It may be silane, or vinyltriacetoxy silane, etc. As an example, vinyltrimethoxy silane or vinyltriethoxy silane may be used, but is not limited thereto.

In addition, the amino silane compound is an unsaturated silane compound grafted on the main chain of the copolymer of the present invention, for example, a reactive functional group such as an alkoxy group of vinyltriethoxysilane with a hydroxy group in the step of grafting modification of the ethylene/alpha-olefin copolymer. By acting as a catalyst that promotes the hydrolysis reaction for conversion, the adhesive strength with the upper and lower glass substrates or the backsheet made of fluororesin or the like can be further improved. At the same time, the amino silane compound may also participate as a reactant in the direct copolymerization reaction, thereby providing a moiety having an amine functional group to the amino silane-modified resin composition.

The amino silane compound is a silane compound containing an amine group, and is not particularly limited as long as it is a primary amine or a secondary amine. For example, as an amino silane compound, aminotrialkoxysilane, aminodialkoxysilane, etc. may be used. Examples 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, Aminoethylaminopropylmethyldimethine Toxysilane, aminoethylaminopropylmethyldiethoxysilane, aminoethylaminomethyltriethoxysilane, aminoethylaminomethylmethyldiethoxysilane, diethylenetriaminopropyltrimethoxysilane, diethylenetriaminopropyltriethoxysilane, Diethylenetriaminopropylmethyldimethoxysilane, diethyleneaminomethylmethyldiethoxysilane, (N-phenylamino)methyltrimethoxysilane, (N-phenylamino)methyltriethoxysilane, (N-phenylamino)methyl Methyldimethoxysilane, (N-phenylamino)methylmethyldiethoxysilane, 3-(N-phenylamino)propyltrimethoxysilane, 3-(N-phenylamino)propyltriethoxysilane, 3-(N- At least one selected from the group consisting of phenylamino) propylmethyldimethoxysilane, 3-(N-phenylamino)propylmethyldiethoxysilane, and N-(N-butyl)-3-aminopropyltrimethoxysilane can be heard These 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 is a radical initiator in the step of preparing the silane-modified resin composition, and may serve to initiate a reaction in which an unsaturated silane compound is grafted into the resin composition. In addition, by forming a cross-linking between the silane-modified resin composition or between the silane-modified resin composition and the non-modified resin composition in the step of lamination in the manufacture of an opto-electronic device, heat resistance and durability of a final product, such as an encapsulant sheet, can be improved. there is.

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

Specifically, t-buylcumyl 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-hexyne; hydroperoxides such as cumene hydroperoxide, diisopropylbenzene hydroperoxide, 2,5-dimethyl-2,5-di(hydroperoxy)hexane, and t-butyl hydroperoxide; 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 fibarate, 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-hexyne; and ketone peroxides such as methyl ethyl ketone peroxide and cyclohexanone peroxide, azo compounds such as lauryl peroxide, azobisisobutyronitrile, and azobis(2,4-dimethylvaleronitrile). It may include one or more selected from, but is not limited thereto.

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

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

In addition, the resin composition of the present invention may contain a crosslinking aid in addition to the crosslinking agent. By including the crosslinking assistant in the resin composition, the degree of crosslinking between the resin compositions by the above-described crosslinking agent may be increased, and thus heat resistance and durability of a final product, for example, an encapsulant sheet may be further improved.

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, and when the crosslinking aid is included in less than 0.01 parts by weight. , The effect of improving heat resistance properties is insignificant, and when included in an amount exceeding 0.5 parts by weight, a problem affecting the physical properties of a final product, such as an encapsulant sheet, may occur and the production cost may increase.

As the crosslinking aid, various crosslinking aids known in the art may be used. For example, as the crosslinking aid, a compound containing at least one unsaturated group such as an allyl group or a (meth)acryloxy group may be used.

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

In addition, the resin composition of the present invention, if necessary, may further include at least one additive selected from a light stabilizer, a UV absorber, and a heat stabilizer.

The light stabilizer may serve to prevent photooxidation by capturing active species at the onset of photodegradation of the resin, depending on the application to which the composition is applied. The type of light stabilizer that can be used is not particularly limited, and known compounds such as hindered amine-based compounds or hindered piperidine-based compounds can be used.

The UV absorber, depending on the use of the composition, absorbs ultraviolet rays from sunlight and the like, converts them into harmless thermal energy within the molecule, and serves to prevent the excitation of active species initiating photodegradation in the resin composition. . Specific types of UV absorbers that can be used are not particularly limited, and examples include inorganic UV absorbers such as benzophenone, benzotriazole, acrylonitrile, metal complex salts, hindered amines, ultrafine titanium oxide or ultrafine zinc oxide. One type or a mixture of two or more types of absorbents and the like can be used.

In addition, examples of the thermal stabilizer include tris (2,4-di-tert-butylphenyl) phosphite, bis [2,4-bis (1,1-dimethylethyl) -6-methylphenyl] ethyl ester phosphorous acid, tetra kiss(2,4-di-tert-butylphenyl)[1,1-biphenyl]-4,4'-diylbisphosphonate and bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, etc. a phosphorus-based heat stabilizer; and lactone-based heat stabilizers such as reaction products of 8-hydroxy-5,7-di-tert-butyl-furan-2-one and o-xylene. One or two or more of these may be used. there is.

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 may be appropriately selected in consideration of the use of the resin composition, the shape or density of the additive, and is usually appropriately within the range of 0.01 part by weight to 5 parts by weight based on 100 parts by weight of the total solid content of the resin composition. can be regulated.

In addition, the resin composition, in addition to the above components, may appropriately additionally include various additives known in the related art according to the application 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 for encapsulating a device in various optoelectronic devices, but is not limited thereto, and is, for example, an industrial material applied to an elevated temperature lamination process. can also be used as

2. Optical film

Another embodiment of the present invention provides an optical film including the resin composition.

The optical film of the present invention may be prepared by molding the resin composition into a film or sheet shape. Such a molding method is not particularly limited, and for example, it can be produced by sheeting or filming by a conventional process such as a T-die process or extrusion. For example, the manufacture of the optical film may be performed in an in situ process using a device in which the manufacture of a modified resin composition using the resin composition and the process of forming a film or sheet are connected to each other.

The thickness of the optical film may be adjusted to about 10 μm to 2,000 μm, or about 100 μm to 1250 μm in consideration of the support efficiency and breakability of the device in the optoelectronic device, the light weight or workability of the device, and the like. So it can be changed.

3. Ethylene/alpha-olefin copolymers

The ethylene/alpha-olefin copolymer used in the resin composition for an optical film of the present invention satisfies the conditions (a) to (d) at the same time by using a catalyst as described below and introducing an optimal amount of hydrogen during polymerization. By doing so, physical properties, particularly crosslinking properties, may be greatly improved.

Specifically, the ethylene/alpha-olefin copolymer 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 0.850 g/cc or more, or 0.855 g/cc or more, or 0.86 g/cc or more, or 0.865 or more, and 0.91 g/cc or less, or 0.90 g/cc or less, or 0.89 g/cc may be below.

In general, the density of olefin-based polymers is affected by the type and content of monomers used during polymerization, the degree of polymerization, etc. In the case of copolymers, the effect of the comonomer content is large. An olefin copolymer can be prepared, and the amount of comonomer that can be introduced into the copolymer can depend on the copolymerizability of the catalyst, i.e., 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 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, and in this case, the effect of maintaining mechanical properties and improving impact strength according to density control is more remarkable.

In addition, the ethylene/alpha-olefin copolymer has a narrow molecular weight distribution (MWD) ranging from 1.5 to 3.0. As an example, the molecular weight distribution may be 1.6 or more, or 1.7 or more, or 1.8 or more, and may be 2.7 or less, or 2.4 or less, or 2.2 or less.

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

Meanwhile, in the present invention, the weight average molecular weight (Mw) and number average molecular weight (Mn) are polystyrene equivalent molecular weights analyzed by gel permeation chromatography (GPC), and the molecular weight distribution is determined from the ratio of Mw/Mn can be calculated.

The ethylene/alpha-olefin copolymer 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 45,000 g/mol or more, or 49,000 g/mol or more, or 52,000 g/mol or more, and 130,000 g/mol or less, or 90,000 g/mol or less, or 65,000 g/mol or less. there is.

In addition, the ethylene/alpha-olefin copolymer has a melt index in the range of 0.1 to 100 dg/min (Melt Index, MI, measured under ASTM D1238 at 190 °C and a load of 2.16 kg). As an example, the ethylene/alpha-olefin copolymer has a melt index (MI) of 1 dg/min or more, or 1.5 dg/min or more, or 3 dg/min or more, or 5 dg/min or more, or 12 dg/min or more. min, or 16 dg/min or more, and may be 90 dg/min or less, or 70 dg/min or less, or 40 dg/min or less, or 37 dg/min or less, or 35 dg/min or less.

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

In addition, the ethylene/alpha-olefin copolymer has an MFR ₁₀ /MFR _2.16 value, which is a ratio between a melt index measured at 190 ° C under a load of 10 kg and a melt index measured at 190 ° C under a load of 2.16 kg, 8.5 or less, or 7.9 or less, or 7.5 or less, or 5.0 or more, or 5.5 or more, or 6.0 or more. MFR ₁₀ /MFR _2.16 is an indicator of the degree of long-chain branching of the copolymer, and an MFR ₁₀ /MFR _2.16 value of 8.5 or less means that there is little long-chain branching.

When the weight average molecular weight and the melt index satisfy the above ranges, it may be suitable for application to a 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 in the polymerization process together with the type of catalyst used, and by satisfying the above conditions, improvement while maintaining excellent mechanical properties processability can be shown.

In addition, the ethylene/alpha-olefin copolymer may have a crystallization temperature (Tc) of 35°C to 80°C. More specifically, the crystallization temperature may be 40 °C or higher, or 45 °C or higher, and may be 75 °C or lower, 70 °C or lower, or 65 °C or lower. This high crystallization temperature is due to the uniform distribution of the comonomer in the ethylene/alpha-olefin copolymer, and excellent structural stability can be exhibited by having the above temperature range.

In addition, the ethylene/alpha-olefin copolymer 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 within this temperature range, excellent thermal stability can be exhibited.

In the present invention, the crystallization temperature and 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, maintained for 5 minutes, lowered to 20°C, and the temperature is increased again. At this time, the rate of rise and fall of the temperature is adjusted to 10 ℃ / min, respectively, and the result measured in the second temperature rising section is the melting temperature, and the result measured in the section appearing while decreasing the temperature is the crystallization temperature.

In addition, in the ethylene/alpha-olefin copolymer, the alpha-olefin monomer, which is a comonomer, is C4-20 It may be an olefinic 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 them alone or a mixture of two or more may be used.

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

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 10 to 50 mole %.

4. Manufacturing method of ethylene/alpha-olefin copolymer

The ethylene/alpha-olefin copolymer comprises polymerizing ethylene and alpha-olefin monomers by introducing hydrogen at 5 to 100 cc/min in the presence of a catalyst composition comprising a transition metal compound represented by Formula 1 below. can be made:

[Formula 1]

In 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; Alkylidene of C1-20; Or a 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 C1-20 hydrocarbyl; Two or more of R ₆ to R ₉ adjacent to each other 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 example 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 it may be C7-20 arylalkyl,

The 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;

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

Two or more of R ₆ to R ₉ adjacent to each other may be connected to each other to form a C5-20 aliphatic ring or C6-20 aromatic ring; The aliphatic ring or aromatic ring may be substituted with halogen, C1-20 alkyl, C2-12 alkenyl, or C6-12 aryl,

The 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; C1-13 alkylamino; C6-12 arylamino; Or it may be C1-12 alkylidene.

In addition, in the transition metal compound of Formula 1 according to another example 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 it may be C7-13 arylalkyl,

The 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;

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

Two or more of R ₆ to R ₉ adjacent to each other may be connected to each other to form a C5-12 aliphatic ring or a C6-12 aromatic ring;

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

The Q may be Si,

M may be Ti,

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

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

The R ₁ may be hydrogen or C1-12 alkyl,

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

R ₃ is hydrogen; C1-12 alkyl; or phenyl;

The R ₄ and R ₅ are each independently hydrogen; Or it may be C1-12 alkyl,

The R ₆ to R ₉ may each independently be hydrogen or methyl;

The Q may be Si,

M may be Ti,

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

The transition metal compound of Formula 1 is stably bridged by cyclopentadiene in which benzothiophene is fused by a cyclic bond, and an amido group (NR ₁ ) by Q (Si, C, N or P), Group 4 transition metals form coordinated structures. When applied to olefin polymerization using the catalyst composition, it is possible to produce a polyolefin having characteristics such as high activity, high molecular weight, and high copolymerizability even at a high polymerization temperature.

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

In addition, since the phenyl group, which is a bulky substituent, is located around the central metal, β-hydrogen transfer is suppressed, so that olefin polymers with higher molecular weight can be prepared and have excellent copolymerizability.

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

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

[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, the catalyst composition may further include a cocatalyst to activate the transition metal compound of Chemical Formula 1.

The cocatalyst is an organometallic compound containing a Group 13 metal, and specifically, may include at least one of a compound represented by Chemical Formula 2, a compound represented by Chemical Formula 3, and a compound represented by Chemical Formula 4 below.

[Formula 2]

R ₄₁ -[Al(R ₄₂ )-O] _n -R ₄₃

In Formula 2,

R ₄₁ , R ₄₂ and R ₄₃ are each independently any one of 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 greater than or equal to 2;

[Formula 3]

D(R ₄₄ ) ₃

In Formula 3, D is aluminum or boron,

R ₄₄ is each independently any one of 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 Formula 4,

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

Z is a Group 13 element, A is each independently a hydrocarbyl group having 1 to 20 carbon atoms; Hydrocarbyloxy group having 1 to 20 carbon atoms; and substituents in which one or more hydrogen atoms of these substituents are substituted with one or more substituents selected from 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-based compound in which repeating units are bonded in a linear, circular, or network type, and specific examples include methyl aluminoxane (MAO), ethyl aluminoxane, isobutyl aluminoxane or tert-butyl aluminoxane, etc. are mentioned.

In addition, specific examples of the compound of Formula 3 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, and may be selected from trimethylaluminum, triethylaluminum, or triisobutylaluminum.

In addition, the compound represented by Chemical Formula 4 may include borate-based compounds in the form of trisubstituted ammonium salts, dialkyl ammonium salts, or trisubstituted phosphonium salts. More specific examples include trimethylammonium tetraphenylborate, methyldioctadecylammonium tetraphenylborate, triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tri(n-butyl)ammonium tetraphenylborate, and methyltetradecylborate. Octadecylammonium tetraphenylborate, N,N-dimethylaninium tetraphenylborate, N,N-diethylaninium tetraphenylborate, N,N-dimethyl(2,4,6-trimethylaninium)tetraphenylborate, Trimethylammonium Tetrakis(pentafluorophenyl)borate, Methylditetradecylammonium Tetrakis(pentaphenyl)borate, Methyldioctadecylammonium Tetrakis(pentafluorophenyl)borate, Triethylammonium, Tetrakis(pentafluorophenyl)borate Phenyl) borate, tripropylammoniumtetrakis(pentafluorophenyl)borate, tri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate, tri(sec-butyl)ammoniumtetrakis(pentafluorophenyl) ) borate, N,N-dimethylaninium tetrakis(pentafluorophenyl)borate, N,N-diethylaniniumtetrakis(pentafluorophenyl)borate, N,N-dimethyl(2,4,6- Trimethylaninium) tetrakis (pentafluorophenyl) borate, trimethylammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate, triethylammonium tetrakis (2,3,4,6-tetrafluoro Rophenyl)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)borate or N,N-dimethyl-(2,4,6-trimethylaninium)tetrakis-(2 borate-based compounds in the form of trisubstituted ammonium salts such as ,3,4,6-tetrafluorophenyl)borate; Dialkylammonium salt type borates 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) ) borate-based compounds in the form of trisubstituted phosphonium salts such as borate; and the like.

By using such a cocatalyst, the molecular weight distribution of the finally prepared ethylene/alpha-olefin copolymer may be more uniform, and polymerization activity may be improved.

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

In addition, the catalyst composition may include the transition metal compound of Chemical 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 a medium ratio within the above range, an optimal shape can be exhibited. In addition, when the cocatalyst is supported on the carrier together, the weight ratio of the cocatalyst to the carrier may be 1:1 to 1:100, more specifically 1:1 to 1:50. When the cocatalyst and the carrier are included in the above weight ratio, the catalytic activity can be improved and the microstructure of the polymer produced can be optimized.

On the other hand, as the carrier, silica, alumina, magnesia, or a mixture thereof may be used, or by drying these materials at a high temperature to remove moisture from the surface, a state containing a highly reactive hydroxyl group or siloxane group on the surface may be used In addition, the high-temperature dried supports 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 support is less than 200 ° C, the moisture on the surface is too high, and the moisture on the surface and the cocatalyst react, and when the drying temperature exceeds 800 ° C, the pores on the surface of the carrier are combined and the surface area is reduced. This is undesirable because only siloxane remains and the reaction site with the cocatalyst 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 manufacturing method and conditions of the carrier or drying conditions, such as temperature, time, vacuum or spray drying.

Meanwhile, the polymerization of the ethylene/alpha-olefin copolymer may be carried out by continuously polymerizing ethylene and alpha-olefin monomers while continuously introducing hydrogen in the presence of the catalyst composition.

At this time, the hydrogen gas serves to suppress the rapid reaction of the transition metal compound at the initial stage of polymerization and terminate the polymerization reaction. Accordingly, an ethylene/alpha-olefin copolymer having a narrow molecular weight distribution and a vinyl group content within a certain range can be effectively produced by using hydrogen gas and controlling the amount thereof.

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

In addition, the polymerization reaction may be carried out at 80 to 200 ° C., but the vinyl group content in the ethylene/alpha-olefin copolymer can be more easily controlled by controlling the polymerization temperature together with the amount of hydrogen added. 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 organic aluminum compound for removing moisture in the reactor may be further added, and the polymerization reaction may proceed in the presence of the organoaluminum compound. Specific examples of the organic aluminum compound include trialkyl aluminum, dialkyl aluminum halide, alkyl aluminum dihalide, aluminum dialkyl hydride, or alkyl aluminum sesqui halide. 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 or (C ₂ H ₅ ) ₃ Al ₂ Cl ₃ . These organoaluminum compounds may be continuously charged to the reactor and may be added at a rate of about 0.1 to 10 moles per kilogram of reaction medium charged to the reactor for adequate moisture 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 , and more preferably about 80 to about 93 Kgf/cm ² .

In addition, when a transition metal compound is used in a supported form on a carrier, the transition metal compound is an aliphatic hydrocarbon solvent having 5 to 12 carbon atoms, for example, pentane, hexane, heptane, nonane, decane, and isomers thereof and toluene, benzene It may be dissolved in an aromatic hydrocarbon solvent such as dichloromethane or a hydrocarbon solvent substituted with a chlorine atom such as chlorobenzene or added after dilution. The solvent used here 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 it is also possible to use a cocatalyst further.

Example

Hereinafter, a preferred embodiment is presented to aid understanding of the present invention. However, the following examples are only provided to more easily understand the present invention, and the content of the present invention is not limited thereby.

[Synthesis Example 1: Preparation of transition metal compound]

Step 1: Preparation of ligand compound (1a-1)

In a 250 mL Schlenk flask, add 10 g (1.0 eq, 49.925 mmol) of 1,2-dimethyl-3H-benzo[b]cyclopenta[d]thiophene and 100 mL of THF, and add 22 mL of n-BuLi (1.1 eq, 54.918 mmol, 2.5 M in hexane) was added dropwise at -30°C, and stirred at room temperature for 3 hours. The stirred Li-complex THF solution was cannulated into a Schlenk flask containing 8.1 mL (1.0 eq, 49.925 mmol) of dichloro(methyl)(phenyl)silane and 70 mL of THF at -78°C, followed by stirring at room temperature overnight. After stirring and vacuum drying, the mixture was extracted with 100 mL of hexane.

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

(1a-1)

1H NMR (CDCl3, 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 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. was added dropwise at -30 °C and then stirred overnight at room temperature. After stirring, 12.6 mL of MeMgBr (37.725 mmol, 3.0 eq, 3.0 M in diethyl ether) was added dropwise, followed by 13.2 mL of TiCl ₄ (13.204 mmol, 1.05 eq, 1.0 M in toluene) sequentially, and the mixture was stirred overnight at room temperature. . After stirring, vacuum drying, extraction with 150 mL of hexane, and after removing the solvent to 50 mL, 4 mL of DME (37.725 mmol, 3.0eq) was added dropwise, followed by stirring at room temperature overnight. After vacuum drying again, the mixture was extracted with 150 mL of hexane. After solvent drying, 2.23 g (38%, dr = 1:0.5) of a brown solid was obtained.

(1a)

^1H NMR (CDCl ₃ , 500 MHz): δ 7.98 (d, 1H), 7.94 (d, 1H), 7.71 (t, 6H), 7.50 to 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 shlenk 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 added by syringe under a nitrogen atmosphere, and a pale yellow slurry was formed. Then, after the flask was stirred for 2 hours, the temperature of the flask was raised to room temperature while removing the generated butane gas. After lowering the temperature by immersing the flask in a low-temperature bath again at -78°C, CO ₂ gas was introduced. As carbon dioxide gas was introduced, the slurry disappeared and became a transparent solution. The temperature was raised to room temperature while removing carbon dioxide gas by connecting the flask to a bubbler. After that, excess CO ₂ gas and solvent were removed under vacuum. After transferring the flask to a dry box, pentane was added, vigorously stirred, and filtered to obtain lithium carbamate as a white solid compound. The white solid compound is coordinated with diethyl ether. At this time, the yield is 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 sequentially added. After immersing the Schlenk flask in a -20°C low temperature bath made of acetone and a small amount of dry ice and stirring for 30 minutes, t-BuLi (25.1 mL, 1.7 M, 42.60 mmol) was added thereto. At this time, the color of the reaction mixture changed to red. The mixture was stirred for 6 hours while maintaining -20°C. CeCl ₃ 2LiCl solution (129 mL, 0.33 M, 42.60 mmol) and tetramethylcyclopentinone (5.89 g, 42.60 mmol) dissolved in tetrahydrofuran were mixed in a syringe, and then introduced into the flask under a nitrogen atmosphere. The temperature of the flask was slowly raised to room temperature, and after 1 hour, the thermostat was removed and the temperature was maintained at room temperature. Subsequently, after adding water (15 mL) to the flask, ethyl acetate was added and filtered to obtain a filtrate. After transferring the filtrate to a separatory funnel, hydrochloric acid (2 N, 80 mL) was added and shaken for 12 minutes. And, after neutralization by adding saturated sodium hydrogen carbonate aqueous solution (160 mL), the organic layer was extracted. Anhydrous magnesium sulfate was added to the organic layer to remove moisture, and after filtering, the filtrate was taken and the solvent was removed. The obtained filtrate was purified by column chromatography using hexane and ethyl acetate (v/v, 10:1) solvent to obtain a yellow oil. The yield was 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 compound

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 put into a round flask, the temperature was lowered to -30 ° C, and n-BuLi (17.7 g, 2.5 M, 64.0 mmol) was added slowly while stirring. It was reacted for 6 hours while raising the temperature to room temperature. Thereafter, the solid was obtained by filtration while washing with diethyl ether several times. A vacuum was applied to remove the remaining solvent to obtain dilithium compound (9.83 g) as a yellow solid. The yield was 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 Preparation of -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 put in a round flask, and MeLi (21.7 mL, 31.52 mmol, 1.4 M) was slowly added while 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) above ( 5.30 g, 15.76 mmol) was added to the flask. The mixture was stirred for 3 hours while raising the temperature to room temperature. After the reaction was completed, the solvent was removed by vacuum, and the mixture was dissolved in pentane and filtered to obtain a filtrate. Removal of the pentane under vacuum gave the compound (3.70 g) as a dark brown color. 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.

[Preparation of Ethylene/Alpha-Olefin Copolymer]

Preparation Example 1

After filling a 1.5L 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) (0.15μmol/min) prepared in Synthesis Example 1 as a catalyst, dimethylanilinium tetrakis (pentafluorophenyl) borate cocatalyst (0.15 μmol/min) was introduced into the reactor at the same time. Then, ethylene (0.87 kg / h) and hydrogen gas (25 cc / min) were introduced into the autoclave reactor, and the copolymerization reaction was continuously performed while maintaining the pressure of 89 bar and the polymerization temperature of 140 ° C. for more than 60 minutes to obtain a copolymer was manufactured.

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

Preparation Examples 2 to 14 and Comparative Preparation Examples 4 to 6

Polymers of Preparation Examples 2 to 14 were prepared in the same manner as in Preparation Example 1, except that the reactants were added in the amounts shown in Table 1 below.

In addition, the transition metal compound (2a) prepared in Synthesis Example 2 was used, except that the reactants were added in the amount shown in Table 1 below, in the same manner as in Preparation Example 1, Comparative Preparation Examples 4 to 6 A polymer was prepared.

C2 C6 1-C4 _H2 Cat. Co-cat. polymerization temperature Kg/h sccm µmol/min ℃ Preparation Example 1 0.87 5.5 0.8 25 0.15 0.15 140 Preparation Example 2 0.87 5.5 0.8 26 0.25 0.375 144 Preparation Example 3 0.87 5.5 0.9 15 0.3 0.45 160 Production Example 4 0.87 5.5 0.8 20 0.075 One 140 Preparation Example 5 0.87 5.5 0.8 20 0.25 0.04 140 Preparation Example 6 0.87 5.5 0.7 22 0.075 0.5 140 Preparation Example 7 0.87 5.5 0.7 22 0.25 0.04 140 Preparation Example 8 0.87 5.5 0.85 24 0.25 0.375 155 Preparation Example 9 0.87 5.5 0.8 10 0.25 0.375 148 Preparation Example 10 0.87 5.5 0.8 10 0.25 0.375 146 Preparation Example 11 0.87 5.5 0.85 24 0.25 0.375 152 Preparation Example 12 0.87 5.5 0.85 24 0.25 0.375 161 Preparation Example 13 0.87 5.5 0.85 24 0.25 0.375 172 Preparation Example 14 0.87 7.0 0.83 16 0.17 0.34 140 Comparative Preparation Example 4 0.87 5.5 0.45 6 0.30 0.90 160 Comparative Preparation Example 5 0.87 5.5 0.43 6 0.24 0.72 160 Comparative Preparation Example 6 0.87 5.0 0.62 0 0.32 0.96 145

Comparative Preparation Examples 1 to 3

On the other hand, as Comparative Manufacturing Example 1, LG Chem's LC885X product was purchased, as Comparative Manufacturing Example 2, Mitsui's DF8200 product was purchased, and as Comparative Manufacturing Example 3, Mitsui's DF610 product was purchased and used.

of Preparation Examples 1 to 14 and Comparative Preparation Examples 1 to 6 The number of functional groups of vinylene, trivinyl, vinyl and vinylidene per 1000 carbon atoms in the copolymer was measured by nuclear magnetic spectroscopy according to the following method and is shown in Table 2.

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

② In the 1H NMR spectrum, the TCE-d2 peak was corrected to 6.0 ppm, and the comonomer content ratio was calculated using the integral values of the 1.4 ppm and 0.96 ppm regions. The contents of each of vinyl group, vinylidene group, vinylene group and trivinylene group observed at 4.7 ppm to 5.6 ppm were calculated (analysis method: AMT-3863). Peak assignment was referred to [ Macromolecules 2014, 47, 3282-3790 ].

Relative content (piece/1000C) Vinyl/Total Vinylidene/Total vinylene trivinyl vinyl vinylidene Total Preparation Example 1 0.1 0.04 0.05 0.02 0.2 0.25 0.1 Preparation Example 2 0.16 0.02 0.06 0.02 0.26 0.23 0.08 Preparation Example 3 0.19 0.04 0.1 0.03 0.36 0.28 0.08 Production Example 4 0.1 0.02 0.07 0.06 0.25 0.28 0.24 Preparation Example 5 0.08 0.02 0.05 0.04 0.2 0.25 0.2 Preparation Example 6 0.07 0.03 0.05 0.04 0.19 0.26 0.21 Preparation Example 7 0.06 0.02 0.05 0.04 0.17 0.29 0.24 Preparation Example 8 0.12 0.07 0.07 0.01 0.27 0.26 0.04 Preparation Example 9 0.11 0.07 0.07 0.01 0.25 0.28 0.04 Preparation Example 10 0.11 0.06 0.08 0.01 0.25 0.32 0.04 Preparation Example 11 0.15 0.13 0.14 0.01 0.43 0.33 0.02 Preparation Example 12 0.13 0.08 0.09 0.02 0.31 0.29 0.06 Preparation Example 13 0.1 0.05 0.05 0.02 0.22 0.23 0.09 Preparation Example 14 0.09 0.03 0.03 0 0.15 0.20 0.00 Comparative Preparation Example 1 0.46 0.05 0.1 0.08 0.69 0.14 0.12 Comparative Preparation Example 2 0.01 0 0.03 0.01 0.05 0.60 0.2 Comparative Preparation Example 3 0.06 0.02 0.02 0.03 0.12 0.17 0.25 Comparative Preparation Example 4 0.10 0.02 0.03 0.05 0.21 0.14 0.24 Comparative Preparation Example 5 0.08 0.02 0.03 0.04 0.18 0.17 0.22 Comparative Preparation Example 6 0.4 0.09 0.09 0.07 0.65 0.14 0.11

In addition, the density, melt index, weight average molecular weight (Mw) and molecular weight distribution (MWD) of Preparation Examples 1 to 14 and Comparative Preparation Examples 1 to 6 were measured and shown in Table 3 below.

① Density (g/cm ³ ): Measured according to ASTM D-792.

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

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

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

- Column: Agilent Olexis

- Solvent: Trichlorobenzene (TCB)

- Flow rate: 1.0 ml/min

- Sample concentration: 1.0 mg/ml

- Injection amount: 200 μl

- Column temperature: 160 ℃

- Detector : Agilent High Temperature RI detector

- Standard: Polystyrene (correction with cubic function)

- Data processing : Cirrus

⑤ 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 - Preparation Example 1 0.876 18 102.5 5.69 55,000 1.94 Preparation Example 2 0.879 20 113.8 5.69 55,000 2.1 Preparation Example 3 0.877 14 103.2 7.37 55,000 1.9 Production Example 4 0.870 14.5 93.3 6.43 - - Preparation Example 5 0.871 13.5 84.1 6.23 - - Preparation Example 6 0.876 12.8 82.4 6.44 54,000 1.9 Preparation Example 7 0.876 14 85.2 6.08 52,000 1.9 Preparation Example 8 0.879 18.4 119.7 6.50 55,000 2.14 Preparation Example 9 0.879 2.24 16.3 7.29 89,000 2.04 Preparation Example 10 0.879 0.95 7.3 7.67 112,000 2.1 Preparation Example 11 0.874 33.7 217.8 6.46 47,000 2.06 Preparation Example 12 0.883 25.3 160.8 6.36 50,000 2.01 Preparation Example 13 0.893 11.9 83.3 7.00 58,000 2.12 Preparation Example 14 0.880 16.3 103.0 6.32 50,000 2.14 Comparative Preparation Example 1 0.881 22 151.8 6.9 54,000 2.4 Comparative Preparation Example 2 0.884 17 108.2 6.36 55,000 1.9 Comparative Preparation Example 3 0.863 1.32 8.6 6.52 107,000 1.98 Comparative Preparation Example 4 0.897 5.86 41.7 7.12 68,000 1.92 Comparative Preparation Example 5 0.900 2.80 20.4 7.30 77,000 2.02 Comparative Preparation Example 6 0.862 1.20 9.3 7.72 91,000 2.18

From the results of Table 3, it can be confirmed that the ethylene/alpha-olefin copolymers of Preparation Examples 1 to 14 of the present invention have a narrower molecular weight distribution than Comparative Preparation Examples 1 and 6.

In addition, the molecular weight distribution of Preparation Example 2 and Comparative Preparation Example 1 is shown in FIG. From this, it can also be confirmed that Preparation Example 2 has a narrower molecular weight distribution than Comparative Preparation Example 1.

Examples 1 to 6 and Comparative Examples 1 to 6

The resin composition of Example 1 was prepared by adding a crosslinking aid composition to 500 g of the sample of Preparation Example 1 according to the following recipe (a). After this, soaking for 1 hour at 40 ℃ was followed by aging for 15 hours.

In addition, as shown in Table 4 below, each sample of Preparation Examples 2, 8, and 14 and Comparative Preparation Examples 1, 2, 4, and 5, except for applying different recipes (a) to (f), respectively The resin compositions of Examples 2 to 6 and Comparative Examples 1 to 6 were prepared and applied in the same manner as in Example 1.

(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 as in (c) above was applied except that the soaking time was 1.5 hours instead of 1 hour.

(e) TBEC 0.6 phr, TAIC 0.93 phr, MEMO 0.21 phr / xylene

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

Experimental Example 1 - Crosslinking Behavior and Degree of Crosslinking

[Manufacture of film]

Films having an average thickness of 450 μm were prepared using a micro extruder with the soaked sample at a low temperature (extruder barrel temperature of 90 ° C or less) to the extent that high temperature crosslinking does not occur.

In order to determine the characteristics of crosslinking behavior, a film containing the crosslinking auxiliary composition was prepared in the form of a disc of 5 g and 4 cm in diameter, and results including maximum torque MH value until scorched at 150 ° C. for 1 hour Values are shown in Table 4.

These crosslinking behavior characteristics were measured using a moving die rheometer called Premier MDR from Alpha Technologies.

[Production of cross-linked sheet]

After covering the top/bottom of each film sample prepared in the above [film production] process with a Teflon sheet, it was placed in a vacuum laminator and laminated at 150 ° C. for 15 minutes to prepare a crosslinked sheet. The cross-linked sheet is for measuring the degree of cross-linking and optical properties after cross-linking, and is not attached to any substrate such as a glass substrate.

0.5 g of the crosslinked sheet was put into toluene (a non-crosslinked polymer extraction solvent) and aged at 60° C. for 15 hours. After washing with toluene, it was 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 formula and shown in Table 4.

* Degree of crosslinking = (Weight after drying / Weight before toluene treatment) * 100

manufacturing example degree of crosslinking ML MH Final Torque T10 T50 T90 T95 Max Rate % dNm min dNm/min Example 1 ^(a) Preparation Example 1 67 0.02 2.77 2.75 1.64 4.49 13.26 18.48 0.45 Comparative Example 1 ^(a) Comparative Preparation Example 1 57 0.04 2.54 2.53 2.14 5.87 16.17 20.26 0.30 Example 2 ^(b) Preparation Example 2 58 0.01 2.54 2.51 2.94 6.26 15.63 20.07 0.34 Comparative Example 2 ^(b) Comparative Preparation Example 1 44 0.03 1.88 1.87 2.08 6.11 17.03 23.32 0.20 Example 3 ^(c) Preparation Example 8 56 0.02 2.79 2.78 3.03 6.78 17.00 22.90 0.33 Example 4 ^(d) Preparation Example 8 60.2 0.02 2.97 2.96 2.95 6.52 16.58 20.58 0.37 Comparative Example 3 ^(c) Comparative Preparation Example 2 49 0.01 2.80 2.79 3.09 6.07 15.07 18.95 0.41 Example 5 ^(e) Preparation Example 14 55 0.02 2.41 2.40 3.26 7.12 17.17 22.66 0.27 Comparative Example 4 ^(e) Comparative Preparation Example 2 51 0.02 2.10 2.09 3.19 6.59 15.93 19.53 0.27 Example 6 ^(f) Production Example 14 56 0.01 2.51 2.49 3.08 6.62 16.82 21.45 0.30 Comparative Example 5 ^(f) Comparative Preparation Example 4 41 0.02 1.62 1.60 3.87 7.42 18.44 26.12 0.18 Comparative Example 6 ^(f) Comparative Preparation Example 5 39 0.01 1.59 1.56 3.94 7.57 18.62 26.35 0.17

(a) TBEC 1 phr, TAIC 0.5 phr, MEMO 0.2 phr / toluene (non-crosslinked polymer extraction solvent)

(b) TBEC 0.6 phr, TAIC 0.8 phr, MEMO 0.2 phr / toluene (non-crosslinked polymer extraction solvent)

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

(d) The same as in (c) above was applied except that the soaking time was 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 (non-crosslinked polymer extraction solvent)

In the crosslinking behavior characteristic results of Table 4, the higher the MH value and the Final Torque value, the higher the degree of crosslinking. In addition, the T value is a factor related to the crosslinking speed. For example, T90 indicates the time required for the torque value to reach 90% saturation, and the smaller the value, the faster the crosslinking speed.

2 shows the crosslinking behavior characteristics of Example 1 and Comparative Example 1 according to the crosslinking recipe (a), and FIG. 3 shows the crosslinking behavior characteristics of Example 2 and Comparative Example 2 according to the crosslinking recipe (b), respectively. .

In addition, from the results of Table 4, when comparing Examples and Comparative Examples to which the same crosslinking recipe was applied, it can be confirmed that the resin composition of Example has a higher degree of crosslinking than that of Comparative Example. In particular, the degree of crosslinking of the polymers of Examples 1 and 2 was 10% higher than that of Comparative Examples 1 and 2, respectively, and Example 6 showed a much higher degree of crosslinking than Comparative Examples 5 and 6 using the same crosslinking recipe.

In addition, in the case of Example 4 in which the soaking time was increased, it was confirmed that the degree of crosslinking was further improved compared to Example 3.

Experimental Example 2 - Optical Properties

The yellow index (YI) and total light transmittance (Tt) of the cross-linked sheet were measured according to the following methods, and are shown in Table 5 below.

In addition, the yellow index (YI) and total light transmittance (Tt) measured after the [film production] process and before preparing the crosslinked sheet are shown in Table 5 below as 'before crosslinking' data.

① Yellow index (YI): In accordance with ASTM 1925, the reflectance in the 400 nm to 700 nm region was measured using Colorflex (Hunter lab), and the YI value was obtained according to Equation 3 below.

[Equation 3]

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 for light having a wavelength of 550 nm was measured using a hazemeter. For the transmittance, the specimen was placed in a specimen holder and measured three times, and the average value thereof was obtained, and the transmittance was measured under the standard conditions of JIS K 7105.

manufacturing example after bridge before bridge Tt@550nm YI Tt@550nm YI Example 1 ^(a) Preparation Example 1 91 0.82 89.4 3.5 Example 2 ^(b) Preparation Example 2 90.9 1.34 88.7 3.9 Example 3 ^(c) Preparation Example 8 90.9 0.86 88.2 3.4 Example 5 ^(e) Preparation Example 14 91.2 0.83 89.1 3.7 Example 6 ^(f) Production Example 14 91.5 0.9 90.0 3.4 Comparative Example 1 ^(a) Comparative Preparation Example 1 89.4 1.63 86 6.1 Comparative Example 3 ^(c) Comparative Preparation Example 2 89.3 1.74 85.3 5.9 Comparative Example 5 ^(f) Comparative Preparation Example 4 89.1 3.1 88.5 7.4 Comparative Example 6 ^(f) Comparative Preparation Example 5 88.8 3.7 88.1 8.1

In Table 5, in the case of the film formed using the resin composition for an optical film of the present invention, it can be seen that the total light transmittance and yellow index are very excellent compared to the comparative example.

Specifically, in the case of the embodiment of the present invention, the yellow index value after crosslinking is in the range of 0.82 to 1.34, which is very excellent compared to 1.63 to 3.7 of the comparative example. In addition, it can be seen that the embodiment of the present invention has a total light transmittance of 90.9 or more after crosslinking, which is greatly improved compared to the comparative example showing a maximum value of 89.4. Therefore, it is expected that an optical film having excellent optical properties can be manufactured using the resin composition for an optical film of the present invention.

Claims (17)

An ethylene/alpha-olefin copolymer that satisfies the following conditions (a) to (e), wherein the yellow index value measured after crosslinking is 1.5 or less, and the total light transmittance (Tt) measured after crosslinking is 90.0% or more. Resin composition for optical film:
(a) Density: 0.850 to 0.910 g/cc
(b) Melt Index (MI, 190 ℃, 2.16 kg load conditions): 0.1 to 100 dg / min
(c) molecular weight distribution (MWD): 1.5 to 3.0
(d) an R _v value of 0.18 to 0.59 according to Equation 1 below
[Equation 1]

In Equation 1, N _vd , N _tv , N _vl and N _v are vinylidene, trivinyl, vinylene and vinyl per 1000 carbon atoms measured by nuclear magnetic spectroscopy, respectively. vinyl) means the number of functional groups,
(e) R _vd value according to Equation 2 below is 0.02 to 0.10
[Equation 2]

In Equation 2 above,
N _vd , N _tv , N _vl and N _v are the number of vinylidene, trivinyl, vinylene, and vinyl functional groups per 1000 carbon atoms measured by nuclear magnetic spectroscopy, respectively. means
delete According to claim 1,
R _v value of the ethylene / alpha-olefin copolymer is 0.19 to 0.46 resin composition for an optical film.
delete delete delete According to claim 1,
The density of the ethylene / alpha-olefin copolymer is 0.855 to 0.90 g / cc resin composition for an optical film.
According to claim 1,
The melt index (190 ℃, 2.16 kg load conditions) of the ethylene / alpha-olefin copolymer is 1.5 to 37 dg / min of the resin composition for an optical film.
According to claim 1,
The ethylene/alpha-olefin copolymer has a number of vinyl functional groups per 1000 carbon atoms measured by nuclear magnetic spectroscopy of 0.01 to 0.3;
A resin composition for an optical film having MFR ₁₀ /MFR 2.16, which is a ratio of a melt index measured at 190 ° C under a load of 10 kg and a melt index measured at 190 ° C under a load of _2.16 kg, of 8.5 or less.
According to claim 1,
A resin composition for an optical film wherein the ethylene/alpha-olefin copolymer has a weight average molecular weight (Mw) of 40,000 to 150,000 g/mol.
According to claim 1,
The ethylene / alpha-olefin copolymer has a molecular weight distribution of 1.5 to 2.2 resin composition for an optical film.
According to claim 1,
The alpha-olefin is propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1 - A resin composition for an optical film comprising at least one selected from the group consisting of tetradecene, 1-hexadecene and 1-eicosene.
According to claim 1,
The alpha-olefin is a resin composition for an optical film included in an amount of more than 0 and less than 99 mol% based on the total weight of the copolymer.
According to claim 1,
The ethylene/alpha-olefin copolymer comprises polymerizing ethylene and alpha-olefin monomers by introducing hydrogen at 5 to 100 cc/min in the presence of a catalyst composition comprising a transition metal compound represented by Formula 1 below. The prepared resin composition for an optical film:
[Formula 1]

In 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; Alkylidene of C1-20; Or a 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 C1-20 hydrocarbyl; Two or more of R ₆ to R ₉ adjacent to each other 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.
According to claim 14,
R ₁ is hydrogen; C1-12 alkyl; C3-12 cycloalkyl; C1-12 alkoxy; C6-12 aryl; C7-13 arylalkoxy; C7-13 alkylaryl; Or it may be C7-13 arylalkyl,
The 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;
The R ₄ to R ₉ are each independently hydrogen; C1-12 alkyl; C3-12 cycloalkyl; C6-12 aryl; C7-13 alkylaryl; Or it may be C7-13 arylalkyl,
Two or more of R ₆ to R ₉ adjacent to each other may be connected to each other to form a C5-12 aliphatic ring or a C6-12 aromatic ring;
The aliphatic ring or aromatic ring may be substituted with halogen, C1-12 alkyl, C2-12 alkenyl, or C6-12 aryl,
The Q may be Si,
M may be Ti,
X ₁ and X ₂ are each independently hydrogen; halogen; C1-12 alkyl group; Or a C2-12 alkenyl, a resin composition for an optical film.
According to claim 1,
A resin composition for an optical film further comprising at least one selected from the group consisting of an unsaturated silane compound, an amino silane compound, a crosslinking agent, a crosslinking aid, a light stabilizer, a UV absorber, and a heat stabilizer.
An optical film comprising the resin composition of any one of claims 1, 3, and 7 to 16.

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