KR102215369B1 - blown film - Google Patents

Abstract

The present invention relates to a blown film comprising an ethylene/1-hexene copolymer and an ethylene/1-octene copolymer, and the blown film according to the present invention has excellent sealing properties and can be usefully used for liquid filling and packaging. I can.

Description

Blown film

The present invention relates to a blown film which is excellent in sealing properties and is useful as a liquid filling and packaging material.

In the production and application fields of polyolefins using Ziegler Natta catalysts, along with the development of metallocene catalysts, various production processes and product uses have been developed. In particular, the development of a catalyst system consisting of a combination of a main catalyst composed of a transition metal compound and a cocatalyst composed of an aluminum metal compound through the aluminum metal compound invented by the Kaminsky Group in 1980 was achieved, and interest in metallocene catalysts and This is a situation where research is continuously being conducted.

These metallocene catalysts have characteristics capable of controlling particle order, copolymerization characteristics, molecular weight, crystallinity, and structure of a polymer by altering the ligand structure and changing polymerization conditions. Until now, various transition metal compound catalysts have been developed for olefin polymerization, but when applied as an actual coating film, high strength and excellent processability are required.

On the other hand, linear low-density polyethylene prepared with a metallocene catalyst has excellent physical properties as a coating film, and among them, ethylene/1-hexene copolymer is widely used. However, there is a need to further improve each physical property depending on the intended use, and for this purpose, there is a limit to changing the structure of the metallocene catalyst or limiting the conditions for polymerization.

Accordingly, the present invention uses an ethylene/1-hexene copolymer and an ethylene/1-octene copolymer together and has a low sealing initiation temperature and excellent hot-tack sealing strength, which is useful for filling liquids and packaging materials. It aims to provide a fresh film.

In order to solve the above problems, the present invention includes an ethylene/1-hexene copolymer and an ethylene/1-octene copolymer; According to ASTM F 1921, the sealing start temperature when reaching 2N when measured under hot-tack conditions is 75 to 92°C, and the maximum value of hot-tack sealing strength at 80 to 130°C is 3.16 to 4.00N. It provides a phosphorus, blown film.

The blown film according to the present invention has improved sealing properties, is excellent in mechanical properties such as transparency and impact strength, and can be usefully used for filling liquids and packaging materials.

1 is a graph showing the relationship between sealing temperature and strength for films of Examples and Comparative Examples of the present invention.

The terms used in the present 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 indicates otherwise. In the present specification, terms such as "comprises", "includes" or "have" are intended to designate the existence of a feature, step, component, or combination of the implemented features, one or more other features or steps, It is to be understood that the possibility of the presence or addition of components, or combinations thereof, is not excluded in advance.

The present invention will be described in detail below and exemplify specific embodiments, as various changes can be made and various forms can be obtained. However, this is not intended to limit the present invention to a specific form of disclosure, it is to be understood as including all changes, equivalents, and substitutes included in the spirit and scope of the present invention.

Hereinafter, the blown film of the present invention will be described in detail.

The blown film of the present invention comprises an ethylene/1-hexene copolymer and an ethylene/1-octene copolymer; According to ASTM F 1921, the sealing start temperature when reaching 2N when measured under hot-tack conditions is 75 to 92°C, and the maximum value of hot-tack sealing strength at 80 to 130°C is 3.16 to 4.00N. It has the characteristic of being.

More specifically, the hot-tack condition is for a film having a width of 25 mm and a thickness of 55 μm, a sealing pressure of 0.275 MPa, a sealing time of 0.5 seconds, and a cooling time. time) 0.1 seconds, measured at a peeling speed of 300 m/s, and the sealing (heat sealing) start temperature until reaching a sealing strength of 2N under these conditions is 75 to 92°C, or 77 to 92°C. , Or may be 80 to 92°C.

In addition, the maximum value of the hot-tack sealing strength in the temperature range of 80 to 130°C under the same hot-tack condition as described above may be 3.16 to 4.00N, or 3.18 to 4.00N, or 3.20 to 4.00N.

As described above, the blown film of the present invention has a low sealing initiation temperature, excellent low-temperature sealing properties, and high sealing strength. Accordingly, the sealing property is good even during high-speed packaging, so that it can be suitably used for packaging materials for filling liquids such as foods, especially sauces and liquid soups.

In the blown film according to the present invention, the ethylene/1-hexene copolymer is used as the first component, and is prepared by polymerizing ethylene and 1-hexene in the presence of a catalyst to be described later.

The ethylene/1-hexene copolymer has a relatively high density compared to the ethylene/1-octene copolymer, has excellent film processability and transparency, and has excellent mechanical properties such as drop impact strength and tear strength, so that agricultural films, laminates It can be suitably used for the production of film for use and blown film for general industrial use. However, there is a need to further improve the above properties depending on the intended use. For this purpose, in addition to the ethylene/1-hexene copolymer, in the present invention, a relatively low density ethylene/1-octene copolymer is used together.

According to an embodiment of the present invention, the density of the ethylene/1-hexene copolymer is 0.915 to 0.940 g/cm 3, preferably 0.920 to 0.930 g/cm 3.

Also preferably, the ethylene/1-hexene copolymer has a flowability of 0.2 to 1.1 g/10 min, more preferably 0.3 to 1.0 g/10 min, as measured according to ASTM D1238 (190° C., 2.16 kg condition) to be.

Also preferably, the weight average molecular weight of the ethylene/1-hexene copolymer is 100,000 to 130,000 g/mol.

The ethylene/1-hexene copolymer may be prepared by polymerizing ethylene and 1-hexene in the presence of a mixed supported metallocene catalyst in which at least two different metallocene compounds are supported on one carrier. At this time, the first metallocene compound, which is one kind of the metallocene compounds, is a compound represented by the following Formula 1, and the second metallocene compound, which is the other one of the metallocene compounds, is a compound represented by the following formula 2. .

[Formula 1]

(L ¹ ) _p (L ² )MQ _{3 -p}

In Formula 1,

M is a transition metal of Group 4 of the periodic table,

L ¹ and L ² are each independently hydrogen, C _{1 to 20} alkyl, C _{2 to 20} alkenyl, C _{6 to 30} aryl, C _{7 to 30} alkylaryl, C _{7 to 30} arylalkyl, C _{1 to 20} hydrocarbyl A metalloid radical of a Group 14 metal substituted with or a ligand in which two neighboring carbon atoms are connected by hydrocarbyl to form a 4 to 8 ring,

Q is halogen, C _{1 ~ 20} alkyl, C _{2 ~ 20} alkenyl, C _{6 ~ 30} aryl group, C _{7 ~ 30} alkylaryl, or C _{7 ~} of ₃₀ arylalkyl, hydrocarbons, two Q is C _{1 ~ 20} with Can form a ring,

p is 1 or 0,

[Formula 2]

In Chemical Formula 2,

M is a transition metal of Group 4 of the periodic table;

R ₁ and R ₂ are each independently hydrogen, C _{1 to 20} alkyl, C _{6 to 30} aryl, silyl, C _{2 to 20} alkenyl, C _{7 to 30} alkylaryl, C _{7 to 30} arylalkyl, or hydrocarbyl A metalloid radical of a Group 14 metal substituted with, wherein R1 and R2 may be linked to each other by an alkylidine radical including C _1-20 alkyl or C _6-30 aryl to form a ring;

R ₃ are each independently hydrogen, halogen, C _{1 ~ 20} alkyl, C _{6 ~ 30} aryl group, C _{2 ~ 20} alkenyl, C _{7 ~ 30} alkylaryl, C _{7 ~ 30} arylalkyl, C _{1 ~ 20} alkoxy, C _6-30 aryloxy, or amido radical, and also, the R ₃ in at least two R ₃ are connected to each other may form an aliphatic or aromatic ring;

CY1 is a substituted or unsubstituted aliphatic or aromatic ring,

Q ₁ and Q ₂ are each independently halogen; C _{1 ~ 20} alkyl amido, C _{6 ~ 30} aryl amido, C _{1 ~ 20} alkyl, C _{2 ~ 20} alkenyl, C _{6 ~ 30} aryl group, C _{7 ~ 30} alkylaryl, C _{7 ~ 30} arylalkyl, or It is a C _1-20 alkylidene.

Preferably, the second metallocene compound may be a compound represented by Formula 3 below.

[Formula 3]

In Chemical Formula 3,

M is a transition metal of Group 4 of the periodic table;

R4 and R5 are each the same as or different from each other, and are independently hydrogen, C _1-20 alkyl, C _6-30 aryl, or silyl;

R6 is, each the same as or different from each other, independently represent a C _{1 ~ 20} alkyl, C _{6 ~ 30} aryl group, C _{2 ~ 20} alkenyl, C _{7 ~ 30} alkylaryl, C _{7 ~ 30} arylalkyl, C _{1 ~ 20} alkoxy, _{6 ~} C ₃₀ aryloxy group, or an amido, wherein R ₆ in at least two R ₆ are connected to each other can form a aliphatic or aromatic ring;

Q ₃ and Q ₄ are halogen, C _1-20 alkylamido, C _6-30 arylamido, or C _1-20 alkyl.

A specific example of the second metallocene compound may be a compound represented by one of the following structural formulas, but is not limited thereto.

In the above structural formula,

R ₇ is hydrogen or methyl,

Each of Q ₅ and Q ₆ may be independently selected from methyl, dimethylamido, or chloro.

In the hybrid supported catalyst, as the carrier, a carrier containing a hydroxy group on the surface may be used, and preferably, a carrier having a highly reactive hydroxyl group and a siloxane group may be used after drying to remove moisture from the surface. have.

For example, silica dried at high temperature, silica-alumina, and silica-magnesia may be used, and these are usually oxides, carbonates, such as Na ₂ O, K ₂ CO ₃ , BaSO ₄ , and Mg(NO ₃ ) ₂ , It may contain sulfate and nitrate components.

In the hybrid supported catalyst, the mass ratio of the catalyst to the carrier is preferably 1:1 to 1:1000. When the carrier and the catalyst are included in the mass ratio, it may exhibit an appropriate supported catalytic activity, which may be advantageous in terms of maintaining the activity of the catalyst and economical efficiency.

In addition, the hybrid supported catalyst may further include a cocatalyst. The cocatalyst may further include at least one of the cocatalyst compounds represented by the following Formula 4, Formula 5, or Formula 6.

[Formula 4]

-[Al(R ₃₀ )-O] _m-

In Chemical Formula 4,

R ₃₀ may be the same as or different from each other, and each independently halogen; Hydrocarbons having 1 to 20 carbon atoms; Or a halogen-substituted C 1 to C 20 hydrocarbon;

m is an integer of 2 or more;

[Formula 5]

J(R ₃₁ ) ₃

In Chemical Formula 5,

R ₃₁ is as defined in Chemical Formula 4;

J is aluminum or boron;

[Formula 6]

_{^{[EH] + [ZA 4]}} - or _{^{[E] + [ZA 4]}} -

In Formula 6,

E is a neutral or cationic Lewis base;

H is a hydrogen atom;

Z is a group 13 element;

A may be the same as or different from each other, and each independently one or more hydrogen atoms is an aryl group having 6 to 20 carbon atoms or an alkyl group having 1 to 20 carbon atoms substituted or unsubstituted with halogen, hydrocarbon having 1 to 20 carbon atoms, alkoxy or phenoxy. .

Examples of the compound represented by Chemical Formula 4 include methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, butylaluminoxane, and the like, and a more preferable compound is methylaluminoxane.

Examples of the compound represented by Formula 5 include trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tripropyl aluminum, tributyl aluminum, dimethyl chloro aluminum, triisopropyl aluminum, tri-s-butyl aluminum, tricyclopentyl 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, trimethyl Boron, triethyl boron, triisobutyl boron, tripropyl boron, tributyl boron, etc. are included, and more preferable compounds are selected from trimethyl aluminum, triethyl aluminum, and triisobutyl aluminum.

Examples of the compound represented by Formula 6 include triethyl ammonium tetraphenyl boron, tributyl ammonium tetraphenyl boron, trimethyl ammonium tetraphenyl boron, tripropyl ammonium tetraphenyl boron, trimethyl ammonium tetra (p-tolyl) Boron, trimethylammonium tetra (o,p-dimethylphenyl) boron, tributyl ammonium tetra (p-trifluoromethylphenyl) boron, trimethyl ammonium tetra (p-trifluoromethylphenyl) boron, tributyl ammonium tetra Pentafluorophenyl boron, N,N-diethylanilinium tetraphenyl boron, N,N-diethylanilinium tetrapentafluorophenyl boron, diethylammonium tetrapentafluorophenyl boron, triphenylphosphonium Tetraphenyl boron, trimethylphosphonium tetraphenyl boron, triethyl ammonium tetraphenyl aluminum, tributyl ammonium tetraphenyl aluminum, trimethyl ammonium tetraphenyl aluminum, tripropyl ammonium tetraphenyl aluminum, trimethyl ammonium tetra (p-tolyl ) Aluminum, tripropyl ammonium tetra (p-tolyl) aluminum, triethyl ammonium tetra (o,p-dimethylphenyl) aluminum, tributyl ammonium tetra (p-trifluoromethylphenyl) aluminum, trimethyl ammonium tetra ( p-trifluoromethylphenyl)aluminum, tributylammonium tetrapentafluorophenylaluminum, N,N-diethylanilinium tetraphenylaluminum, N,N-diethylanilinium tetrapentafluorophenylaluminum, di Ethyl ammonium tetrapenta tetraphenyl aluminum, triphenyl phosphonium tetraphenyl aluminum, trimethyl phosphonium tetraphenyl aluminum, tripropyl ammonium tetra (p-tolyl) boron, triethyl ammonium tetra (o,p-dimethylphenyl) boron , Tributylammonium tetra (p-trifluoromethylphenyl) boron, triphenylcarbonium tetra (p-trifluoromethylphenyl) boron, triphenylcarbonium tetrapentafluorophenyl boron, and the like.

The hybrid supported catalyst according to the present invention is prepared by supporting a cocatalyst compound on a carrier, supporting the first metallocene compound on the carrier, and supporting the second metallocene compound on the carrier. And the order of catalyst loading may be changed as necessary.

When preparing the hybrid supported metallocene catalyst, a hydrocarbon-based solvent such as pentane, hexane, or heptane, or an aromatic solvent such as benzene or toluene may be used as a reaction solvent. In addition, the metallocene compound and the cocatalyst compound may be used in a form supported on silica or alumina.

During polymerization of the ethylene and 1-hexene, the content of ethylene may be 55 to 99.9% by weight, preferably 90 to 99.9% by weight, based on the total weight of ethylene and 1-hexene.

The polymerization reaction may be carried out by copolymerization using one continuous slurry polymerization reactor, a loop slurry reactor, a gas phase reactor, or a solution reactor.

The hybrid supported catalyst is an aliphatic hydrocarbon solvent having 5 to 12 carbon atoms, such as pentane, hexane, heptane, nonane, decane, and isomers thereof, and an aromatic hydrocarbon solvent such as toluene and benzene, and a chlorine atom such as dichloromethane and chlorobenzene. It can be dissolved or diluted in a substituted hydrocarbon solvent and injected. The solvent used here is preferably used after removing a small amount of water or air, which acts as a catalyst poison, by treating a small amount of alkyl aluminum, and it is possible to further use a cocatalyst.

In the blown film according to the present invention, the ethylene/1-octene copolymer is used as a second component, and is prepared by polymerizing ethylene and 1-octene in the presence of a catalyst to be described later. By using the ethylene/1-octene copolymer together with the ethylene/1-hexene copolymer, which is the main component of the polymer composition according to the present invention, physical properties such as transparency, drop impact strength, and tear strength can be further improved.

According to an embodiment of the present invention, the density of the ethylene/1-octene copolymer is 0.885 to 0.920 g/cm 3, preferably 0.885 to 0.910 g/cm 3.

Also preferably, the ethylene/1-octene copolymer has a flowability of 1.0 to 1.5 g/10 min, more preferably 1.1 to 1.3 g/10 min, as measured according to ASTM D1238 (190° C., 2.16 kg condition) to be.

Also preferably, the weight average molecular weight of the ethylene/1-octene copolymer is 90,000 to 100,000 g/mol.

The ethylene/1-octene copolymer may be prepared by polymerizing ethylene and 1-octene in the presence of a supported metallocene catalyst on which a metallocene compound is supported. In this case, the metallocene compound may be a compound represented by Formula 2 described above. Therefore, the method for preparing the supported metallocene catalyst, the carrier, the cocatalyst, and the supported metallocene catalyst is the same as described above for the ethylene/1-hexene copolymer, except that the compound represented by Formula 2 is used. .

During the polymerization of ethylene and 1-octene, the content of ethylene may be 55 to 99.9% by weight, preferably 90 to 99.9% by weight, based on the total weight of ethylene and 1-octene.

The polymerization reaction may be carried out by copolymerization using one continuous slurry polymerization reactor, a loop slurry reactor, a gas phase reactor, or a solution reactor.

The supported catalyst is substituted with an aliphatic hydrocarbon solvent having 5 to 12 carbon atoms, such as pentane, hexane, heptane, nonane, decane, and isomers thereof, and an aromatic hydrocarbon solvent such as toluene and benzene, and a chlorine atom such as dichloromethane and chlorobenzene. It can be dissolved or diluted in a hydrocarbon solvent and injected. The solvent used here is preferably used after removing a small amount of water or air, which acts as a catalyst poison, by treating a small amount of alkyl aluminum, and it is possible to further use a cocatalyst.

The blown film according to the present invention includes the ethylene/1-hexene copolymer and the ethylene/1-octene copolymer described above, and the weight ratio of the ethylene/1-hexene copolymer and the ethylene/1-octene copolymer is 20 :80 to 80:20, or 20:80 to 70:30, or 30:70 to 70:30 is preferred.

The blown film of the present invention includes an ethylene/1-hexene copolymer and an ethylene/1-octene copolymer, and exhibits excellent sealing properties. More specifically, according to ASTM F 1921, the sealing start temperature when reaching 2N when measured under hot-tack conditions is 75 to 92°C, and the maximum value of the hot-tack sealing strength at 80 to 130°C is It has a characteristic of 3.16 to 4.00N.

The blown film has a low sealing initiation temperature, excellent low-temperature sealing property, and high sealing strength. Therefore, the sealing property is good even during high-speed packaging, and is suitable for packaging materials for filling food, especially liquids such as sauces and liquid soups.

The blown film according to the present invention may contain other additives as needed in addition to the above components. Specifically, such additives include heat stabilizers, antioxidants, UV absorbers, light stabilizers, metal deactivators, fillers, reinforcing agents, plasticizers, lubricants, emulsifiers, pigments, optical bleaching agents, flame retardants, antistatic agents, foaming agents, and the like. The type of the additive is not particularly limited, and general additives known in the art may be used.

The blown film according to the present invention may be prepared by mixing the above components to prepare a polymer composition, and then prepared according to what is widely known in the art, and is not particularly limited.

For example, it is prepared according to the method of inflation molding so that the pellets of the polymer composition containing the above components are put into an extruder to have a thickness of about 10 to about 100 μm, preferably about 50 to about 60 μm. It is not limited.

It was confirmed that the blown film according to the present invention not only has excellent sealing properties, but also improves mechanical properties such as transparency, drop impact strength, and tear strength.

According to an embodiment of the present invention, the blown film according to the present invention has a drop impact strength measured according to ASTM D1709 (Method A) of 500 g or more, 600 g or more, 700 g or more, 800 g or more, 900 g or more, 1000 g or more, 1100 g or more, or 1200 g or more. The fall impact strength is excellent as the value increases, and there is no upper limit, but may be, for example, 2000 g or less, 1900 g or less, 1800 g or less, 1700 g or less, 1600 g or less, 1500 g or less, or 1400 g or less. .

In addition, according to an embodiment of the present invention, the blown film according to the present invention has an MD tear strength of 11 g/µm or more, 12 g/µm or more, 13 g/µm or more, and 14 g/µm, measured according to ASTM D1922. Or more, 15 g/µm or more, 16 g/µm or more, or 17 g/µm or more. The MD tear strength is excellent as the value increases, and thus there is no upper limit, but may be, for example, 20 g/µm or less, 19 g/µm or less, or 18 g/µm or less.

In addition, according to an embodiment of the present invention, the blown film according to the present invention has a TD tear strength measured according to ASTM D1922 of 19 g/µm or more, 20 g/µm or more, 21 g/µm or more, and 22 g/µm. Or more, or 23 g/µm or more. The TD tear strength is excellent as the value increases, and there is no upper limit, but may be, for example, 26 g/µm or less, 25 g/µm or less, or 24 g/µm or less.

Hereinafter, the present invention will be described in more detail based on the following examples. However, the following examples are intended to aid understanding of the present invention, and the scope of the present invention is not limited thereto.

< Example >

< Metallocene Preparation of catalyst Example >

Manufacturing example 1: first Metallocene Preparation of catalyst-[(CH ₂ ) ₄ - C ₅ H ₄ ] ₂ ZrCl ₂ of synthesis

n-butylchloride was reacted with NaCp to obtain n-BuCp. Thereafter, n-BuCp was dissolved in THF at -78°C, and normal butyllithium (n-BuLi) was slowly added, and the temperature was raised to room temperature again, followed by reaction for 8 hours. The lithium salt solution thus prepared was slowly added to a suspension solution of ZrCl ₄ (THF) ₂ (1.70g, 4.50mmol)/THF (30ml) at -78°C, and further reacted at room temperature for 6 hours. . All volatile substances were vacuum-dried, and hexane solvent was added to the obtained oily liquid substance to filter it out. After vacuum drying the filtered solution, hexane was added to induce a precipitate at low temperature (-20°C). The obtained precipitate was filtered at low temperature to obtain a white solid [(CH ₂ ) ₄ -C ₅ H ₄ ] ₂ ZrCl ₂ compound. (Yield 92%)

Manufacturing example 2: second Metallocene Preparation of catalyst-[(6-methyl-1,2,3,4- tetrahydro quinolin-8-yl) trimethylcyclopentadienyl - η ⁵ ,κ Synthesis of -N] titanium dichloride compound

A solution of 6-methyl-1,2,3,4-tetrahydroquinoline (1.16 g, 7.90 mmol) in carbon tetrachloride (4 mL) was cooled to -20 °C. N-bromo succinimide (1.41 g, 7.90 mml) solid was slowly added thereto, and the reaction temperature was raised to room temperature and further reacted for 5 hours. The resulting compound was separated by column chromatography using MC and hexane (v:v = 1:1) solvent to obtain a pale yellow oil (0.71g, 40%).

2,3-dimethyl-5-oxocyclopent-1-enylboronic acid (1.27 g, 8.26 mmol), Na ₂ CO ₃ (1.25 g, 11.8 mmol), Pd(PPh ₃ ) ₄ (0.182 g, 0.157 mmol) and a mixture of 8-bromo-1,2,3,4-tetrahydro-6-methylquinoline (7.87 mmol) synthesized above A solution obtained by adding degassed DME (dimethyl ether) (21 mL) and distilled water (7 mL) was heated at 95°C overnight. The reaction solution was lowered to room temperature and extracted twice with ethyl acetate solvent (50 mL). The obtained compound was separated by column chromatography using hexane and ethyl acetate (2:1) solvent to obtain a pale yellow solid. (90%)

Anhydrous La(OTf) ₃ (21.4 mmol) and TFH (24 mL) solution was cooled to -78 °C, and then MeLi (13.4 mL, 21.4 mmol) was added and reacted for about 1 hour. To this, 5-(3,4-dimethyl-2-cyclopenten-1-one)-7-methyl-1,2,3,4-tetrahydroquinoline (7.13 mmol) compound synthesized above was added thereto at -78 °C. After reacting for 2 hours, extraction was performed using water and an acetate solvent. The obtained organic layer was shaken with HCl (2 N, 20 mL) for 2 minutes, neutralized with NaHCO ₃ aqueous solution (20 mL), and dried over MgSO ₄ . The obtained compound was separated by column chromatography using hexane and ethyl acetate solvent (10:1) to obtain a pale yellow solid. (40%)

The obtained 1,2,3,4-tetrahydro-6-methyl-8-(2,3,5-trimethylcyclopenta-1,3-dienyl)quinoline ligand (0.696 mmol) and Ti(NMe ₂ ) ₄ compound (0.156 g, 0.696 mmol) was dissolved in toluene (2 mL), and the reaction solution was reacted at 80° C. for 2 days, and all solvents were removed to obtain a red solid compound. (100%)

Toluene (2 mL) was again added to the red solid compound obtained above, and Me ₂ SiCl ₂ (0.269 g, 2.09 mmol) was added at room temperature, and the reaction solution was reacted for about 4 hours. The obtained compound was recrystallized under hexane at -30°C to obtain a pure red solid. (0.183 g, 66%)

Manufacturing example 3: supported Metallocene Preparation of catalyst

Silica (SYLOPOL 948 manufactured by Grace Davison) was dehydrated at a temperature of 400° C. for 15 hours under vacuum. 1.0 kg of the silica is put into a reactor, and 10 L of toluene is added thereto. Add 5 L of 10 wt% methylaluminoxane (MAO)/toluene solution, and react slowly while stirring at 40°C. Thereafter, the aluminum compound was washed with a sufficient amount of toluene to remove unreacted aluminum compounds, and the remaining toluene was removed under reduced pressure at 50°C. After adding 10 L of toluene again, 50 g of the metallocene catalyst synthesized in Preparation Example 1 was dissolved in toluene and added together to react for 1 hour. After the reaction is over, the stirring is stopped, toluene is separated and removed, and then washed once with 20 L of toluene solution. Thereafter, 50 g of the metallocene catalyst synthesized in Preparation Example 2 was dissolved in toluene, and then added again and reacted for 1 hour. Thereafter, the solution was removed through filtering, washed twice with toluene, and dried under reduced pressure to obtain a solid powder.

<Ethylene/1- Hexene Copolymer and ethylene/1- Octen Preparation of copolymer Example >

Manufacturing example 4: ethylene/1- Hexene Copolymer production

The mixed supported metallocene catalyst prepared in Preparation Example 3 was added to a single loop slurry polymerization process to prepare a linear low-density polyethylene according to the conventional method. 1-hexene was used as the comonomer.

Manufacturing example 5: ethylene/1- Hexene Copolymer production

The mixed supported metallocene catalyst prepared in Preparation Example 3 was added to a single loop slurry polymerization process to prepare a linear low-density polyethylene according to the conventional method. 1-hexene was used as the comonomer.

Manufacturing example 6: ethylene/1- Octen Copolymer production

Hexane solvent (4.5 kg/h), 1-octene (0.3 kg/h) and ethylene (1.12 kg/h) were supplied to a 1.5 L continuous stirred reactor preheated to 120° C. at a high pressure of 90 to 100 bar, and 89 bar Solution polymerization was carried out at a reactor pressure of. Specifically, ethylene (1.12 kg/h) mixed with hydrogen (2.9 L/h) was supplied to a hexane solvent (4.5 kg/h) mixed with 1-octene (0.3 kg/h). It was fed continuously to the reactor as a stream. Triisobutylaluminium (TIBAL) used as a scavenger was supplied to a single stream in front of the reactor. The catalyst (0.5 umol/min) and cocatalyst (dimethylanilinium tetrakis (pentafluorophenyl) borate, 1.5 umol/min) prepared in Preparation Example 2 were continuously injected directly into the reactor. After polymerization, the molten polymer from the reactor through an outlet stream was passed through a separator and then separated into unreacted comonomer, unreacted ethylene, unreacted hydrogen and a stream of diluted mixture. The molten polymer was continuously pelleted and then the solid pellet was collected.

Manufacturing example 7: ethylene/1- Hexene Copolymer production

LLDPE was prepared Primepolymer's a Evolue ^® SP2020.

Each of the physical properties of the copolymers prepared in Preparation Examples 4 to 7 were measured as follows, and are shown in Table 1 below.

1) Melt Index (MI): It was measured according to ASTM D1238 (190°C, 2.16 Kg load).

2) Density: It was measured according to ASTM 1505.

Manufacturing Example 4 Manufacturing Example 5 Manufacturing Example 6 Manufacturing Example 7 Kinds Ethylene/1-hexene copolymer Ethylene/1-hexene copolymer Ethylene/1-octene copolymer Ethylene/1-hexene copolymer MI(g/10min) 1.0 0.3 1.2 2.1 Density (g/cm ³ ) 0.921 0.927 0.902 0.915 Weight average molecular weight (g/mol) About 110,000 About 110,000 About 90,000 About 110,000

< Blown Production of film Example >

Example One

Mixing the ethylene/1-hexene copolymer prepared in Preparation Example 4 and the ethylene/1-octene copolymer prepared in Preparation Example 6 at a weight ratio of 70:30 and dry blending without a separate extrusion process Thus, a polymer composition pellet was prepared.

Using a single screw extruder (Shinwha Industrial Single Screw Extruder, Blown Film M/C, 50 pie, L/D=20) for the manufactured pellet, inflation molding to a thickness of 0.06 mm at an extrusion temperature of 130 ~ 170℃ and blown The film was prepared. At this time, the die gap (Die Gap) was set to 2.0 mm, and the expansion ratio (Blown-Up Ratio) was set to 2.3.

Example 2

The ethylene/1-hexene copolymer prepared in Preparation Example 4 and the ethylene/1-octene copolymer prepared in Preparation Example 6 were mixed in a weight ratio of 50:50, A fresh film was prepared.

Example 3

The ethylene/1-hexene copolymer prepared in Preparation Example 4 and the ethylene/1-octene copolymer prepared in Preparation Example 6 were mixed in a weight ratio of 30:70, A fresh film was prepared.

Example 4

Mixing the ethylene/1-hexene copolymer prepared in Preparation Example 5 and the ethylene/1-octene copolymer prepared in Preparation Example 6 at a weight ratio of 30:70 and dry blending without a separate extrusion process Thus, a polymer composition pellet was prepared.

Using a single screw extruder (Shinwha Industrial Single Screw Extruder, Blown Film M/C, 50 pie, L/D=20) for the manufactured pellet, inflation molding to a thickness of 0.06 mm at an extrusion temperature of 130 ~ 170℃ and blown The film was prepared. At this time, the die gap (Die Gap) was set to 2.0 mm, and the expansion ratio (Blown-Up Ratio) was set to 2.3.

Comparative example One

A blown film was prepared in the same manner as in Example 1, except that only the ethylene/1-hexene copolymer prepared in Preparation Example 4 was used.

Comparative example 2

A blown film was prepared in the same manner as in Example 1, except that only the ethylene/1-hexene copolymer prepared in Preparation Example 5 was used.

Comparative example 3

A blown film was prepared in the same manner as in Example 1, except that only the ethylene/1-hexene copolymer prepared in Preparation Example 7 was used.

For the blown films obtained in the Examples and Comparative Examples, the sealing initiation temperature and sealing strength were measured by the following method, and are shown in Table 2 below.

In addition, the relationship between the sealing temperature and the sealing strength of the films of the Examples and Comparative Examples is shown in the graph of FIG.

1) Sealing start temperature: A sample film was prepared with a width of 25 mm and a thickness of 55 μm, and the temperature until reaching the sealing strength of 2N was measured according to ASTM F 1921 (measurement device: J&B, sealing pressure: 0.275 MPa, sealing time: 0.5 sec, cooling time: 0.1 sec, peeling speed: 300 m/s)

2) Sealing strength: The maximum sealing strength in the temperature range of 80 ~ 130 ℃ was measured under the same conditions as when the sealing start temperature was measured.

Sealing start temperature
(Unit: ℃) Sealing strength (unit: N) Example 1 92 3.20 Example 2 88 3.25 Example 3 82 3.91 Example 4 92 3.50 Comparative Example 1 108 2.77 Comparative Example 2 115 2.58 Comparative Example 3 93 3.15

As shown in FIGS. 1 and 2, compared to Comparative Examples 1 to 3 containing only ethylene/1-hexene copolymer, Examples 1 to 4 including ethylene/1-octene copolymer together have a lower sealing initiation temperature. And high hot-tack sealing strength.

< Experimental example >

For the blown films prepared in Examples and Comparative Examples, each physical property was measured by the following method.

1) Tear strength (Elmendorf tear): A film having a certain thickness was cut into a test piece with a die cutter, and then measured according to ASTM D 1922. At this time, the test speed was 500 mm/min, and the average value was taken by measuring 10 times per specimen.

2) Drop impact strength: The drop impact strength was obtained by measuring 20 or more times per film sample based on ASTM D 1709 [Method A].

3) Haze: It was measured based on ASTM D 1003. At this time, the average value was taken by measuring 10 times per specimen.

Tear strength (MD/TD, g/um) Falling impact strength (g) Cloudiness (%) Example 1 12.1/20.3 565 10.7 Example 2 12.0/19.9 946 8.6 Example 3 12.5/19.6 1177 6.8 Example 4 13.3/21.8 1235 8.4 Comparative Example 1 9.9/18.6 449 11.4 Comparative Example 2 9.4/22.7 328 17.8 Comparative Example 3 12.3/18.4 175 9.1

As shown in Table 3, compared to Comparative Examples 1 to 3 containing only the ethylene/1-hexene copolymer, Examples 1 to 4 including the ethylene/1-octene copolymer together have transparency, drop impact strength, and phosphorus It was confirmed that physical properties such as thermal strength were improved.

Claims (7)

Including an ethylene/1-hexene copolymer and an ethylene/1-octene copolymer, the ethylene/1-octene copolymer has a flowability measured according to ASTM D1238 (190°C, 2.16 kg condition) of 1.0 to 1.3 g/ 10 min;
According to ASTM F 1921, the sealing start temperature when reaching 2N when measured under hot-tack conditions is 75 to 92°C, and the maximum value of hot-tack sealing strength at 80 to 130°C is 3.16 to 4.00N. sign,
Blown film.
The method of claim 1,
The density of the ethylene/1-hexene copolymer is 0.915 to 0.940 g/cm 3;
The ethylene/1-octene copolymer has a density of 0.885 to 0.920 g/cm 3, a blown film.
The method of claim 1,
The ethylene/1-hexene copolymer has a flowability of 0.2 to 1.1 g/10 min as measured according to ASTM D1238 (190° C., 2.16 kg condition), a blown film.
The method of claim 1,
The weight average molecular weight of the ethylene/1-hexene copolymer is 100,000 to 130,000 g/mol, a blown film.
delete The method of claim 1,
The weight average molecular weight of the ethylene/1-octene copolymer is 90,000 to 100,000 g/mol, a blown film.
The method of claim 1,
The weight ratio of the ethylene/1-hexene copolymer and the ethylene/1-octene copolymer is 20:80 to 80:20, a blown film.

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