KR20040110113A - Linear low density polyethylene resin composition with high impact strength - Google Patents

Abstract

PURPOSE: Provided is a linear low density polyethylene resin composition for films, which has high impact strength and good film processability, while maintaining overall physical properties. CONSTITUTION: The linear low density polyethylene resin composition comprises: 75-99.9 wt% of high-strength linear low density polyethylene, obtained by the copolymerization of ethylene with CH2=CHR, wherein R is a C2-C8 alkyl group, in the presence of a magnesium-supported type non-metallocene catalyst; and 0.1-25 wt% of conventional low density polyethylene. The comonomer forming the high-strength linear low density polyethylene includes 1-butene or 1-hexene.

Description

LINEAR LOW DENSITY POLYETHYLENE RESIN COMPOSITION WITH HIGH IMPACT STRENGTH}

The present invention relates to a high impact linear low density polyethylene resin composition, more specifically, in the presence of a magnesium-supported non-metallocene catalyst, ethylene and CH ₂ = CHR (where R is a C ₂ ~ C ₈ alkyl group) The present invention relates to a high-impact linear low-density polyethylene resin composition composed of high strength linear low-density polyethylene and general low-density polyethylene synthesized by copolymerization, which satisfies film formability while satisfying film processability.

In general, linear low density polyethylene (LLDPE) is a copolymer of ethylene and CH ₂ = CHR (where R is an alkyl group having _{2 to 8} carbon atoms) and contains a short chain branch. It has excellent mechanical properties and has been widely applied to films.

In the case of resin for film, a material having excellent impact strength is required compared to the existing material, and this trend is more remarkable especially for heavy packaging film having a film thickness of 100 μm or more.

Magnesium-supported non-metallocene (Non-Metallocene) recently reported in domestic and foreign patents (Korean Patent No. 218,046; Korean Patent No. 223,105; US Patent No. 5,798,424; US Patent No. 6,114,276; Japanese Patent No. 2,999,162, etc.). The new catalyst for the olefin polymerization is known to be able to synthesize so-called "Super Strength LLDPE" because it has excellent control of molecular structure such as comonomer distribution and molecular weight distribution in the polymer chain during olefin copolymerization. High-strength LLDPE has high impact properties that show excellent mechanical properties such as Falling Dart Impact Strength, which is more than twice as high as the film made with general-purpose LLDPE polymerized under Ziegler-Natta catalyst. It is a new material. Such high-strength LLDPEs include conventional metallocene LLDPE and LLDPE polymerized with magnesium-supported nonmetallocene catalysts.

In general, general-purpose LLDPE manufactured under the existing Ziegler-Natta catalysts is known to have excellent film processability due to its low molecular weight distribution but wide molecular weight distribution, compared to specialized products such as high-strength LLDPE, and low density polyethylene (Low Density Polyethylene). LDPE), which contains an intramolecular long chain branch, is known to have excellent processability.

Therefore, by applying these material properties it is possible to produce a new film material that exhibits excellent high impact properties while excellent film processability.

An object of the present invention is a film made of a high strength LLDPE and a general LDPE synthesized by copolymerizing ethylene and CH ₂ = CHR (where R is a C ₂ -C ₈ alkyl group) in the presence of a magnesium-supported nonmetallocene catalyst. It is to provide a high impact LLDPE resin composition that is excellent in overall physical properties and also satisfies film processability.

The high-impact LLDPE resin composition of the present invention is a high-strength LLDPE 75 to 99.9 synthesized by copolymerizing ethylene and CH ₂ = CHR (wherein R is a C ₂ -C ₈ alkyl group) in the presence of a magnesium-supported nonmetallocene catalyst. It consists of wt% and 0.1-25 wt% of normal LDPE.

LLDPE used in the high-impact LLDPE resin composition of the present invention is a high-strength LLDPE synthesized by copolymerizing ethylene and butene-1 or hexene-1 in the presence of a magnesium-supported nonmetallocene-based catalyst. It is preferable that 75 to 99.9 weight% is included. When the high-strength LLDPE is included in less than 75% by weight, the improvement effect of physical properties such as high impact characteristics is insignificant, and when it is contained in excess of 99.9% by weight, it is not preferable because the processability of the resin composition can be reduced.

High-strength LLDPE used in the high impact LLDPE resin composition of the present invention preferably has a melt flow rate (Melt Flow Rate) of 0.2 to 20 g / 10 minutes as measured by ASTM D-1238 (190 ℃, 2.16 kg), density Is 0.910 to 0.930 g / cm ³ . If the melt flow index of the high-strength LLDPE is less than 0.2 g / 10 min, the flowability of the resin is very low, and if the melt flow index is more than 20 g / 10 min, the mechanical properties of the resin are not preferable.

The magnesium-supported nonmetallocene catalyst used in the preparation of the high strength LLDPE is not particularly limited in its kind, and those known in the art may be used.

General LDPE to be mixed with the high strength LLDPE is a resin containing a long chain branch that can improve the resin processability, it is preferably contained 0.1 to 25% by weight relative to 100% by weight of the total resin. When the general LDPE is included in less than 0.1% by weight, the effect of improving the processability of the film due to the reduction of the melt pressure of the resin during film forming is insignificant, and when included in excess of 25% by weight, the fall of the impact impact strength, the main physical properties of the resin composition is reduced It is not preferable because it becomes large.

The high impact characteristic LLDPE resin composition of the present invention has a melt flow index of 0.9 to 20 g / 10 minutes as measured by ASTM D-1238 (190 ° C, 2.16 kg), and a general LDPE having a density of 0.910 to 0.930 g / cm ³ is preferable. Is used. If the melt flow index of the general LDPE is less than 0.9g / 10 minutes, the flow-improving effect of the high-strength LLDPE is reduced, and if the mechanical properties of the resin is sharply lowered when more than 20g / 10 minutes is not preferable.

The high impact LLDPE resin composition of the present invention can be produced in a film form through the following process.

High-strength LLDPE and general LDPE resin, which are used as a substrate of the high-impact LLDPE resin composition of the present invention, are first dry blended using a tumbler mixer or the like, followed by a single-screw or twin screw extruder. (Twin-Screw Extruder) using the melt blending (Melt Blending) above the melting point of the resin to prepare a pellet-like sample.

The pelletized kneaded material thus mixed is introduced into an extruder hopper attached to a blown film machine, melted using an extruder above the melting point of the resin, and then bubbled in the blown film machine. ) It is manufactured into a film through expansion, cooling, pressing and winding processes.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the following Examples are not intended to limit the present invention.

Example

According to the mixing ratio of the resin composition of Table 1, the resin of high-strength LLDPE and general LDPE was first dry blended in a tumbler mixer, and then melt blended in a single screw extruder to prepare pellet samples. This pellet-shaped sample was molded in a blown film machine under the following processing conditions to form a film having a thickness of about 170 μm.

As can be seen from Table 1, Examples 1 to 5 are mixed resin compositions of high strength LLDPE and general LDPE, Comparative Example 1 is a high strength LLDPE single resin, and Comparative Example 2 is a general C ₆ -LLDPE single resin.

(Unit: weight%) Suzy High strength LLDPE ¹⁾ LDPE ²⁾ C ₆ -LLDPE ³⁾ Example 1 98 2 - Example 2 95 5 - Example 3 90 10 - Example 4 85 15 - Example 5 75 25 - Comparative Example 1 100 - - Comparative Example 2 - - 100

¹⁾ comonomer: hexene-1; Melt flow index = 0.9 g / 10 min; Density = 0.921 g / cm ³

²⁾ melt flow index = 2.8 g / 10 min; Density = 0.925 g / cm ³

³⁾ Comonomer: hexene-1, melt flow index = 0.9 g / 10 min, density = 0.921 g / cm ³

Blown Film Processing Conditions

※ Blown film machine temperature profile: 170/180/190/200/200/195 ℃

※ Die gap: 2.5 mm

※ Blow-Up Ratio: 2.5

After the film sample thus formed was sufficiently cooled at room temperature, the physical properties of the film were measured by the following physical property measurement method, and the results are shown in Table 2.

Property measurement method

The physical properties of the films molded by the above Examples and Comparative Examples were measured in the following manner.

① Falling Dart Impact Strength

The fall impact strength was determined after 20 or more measurements per film sample according to ASTM D-1709.

② Tensile Strength at Break

The tensile strength at break and the elongation at break were measured according to ASTM D-882 after the film having a predetermined thickness was cut out in the form of a test piece with a die cutter. At this time, the tensile speed was 500 mm / min, and the average value was taken 10 times per specimen.

③ Haze and Gloss

After cutting the specimen from the film formed, the haze and gloss of the film were measured according to ASTM D-1003 and ASTM D-2457, respectively.

④ Resin Melt Pressure

The melt melt pressure generated at the extrusion portion during film formation under the blown film processing conditions was measured.

Properties Resin Melting Pressure (kgf / cm ² ) Fall impact strength (g) Tensile Strength at Break (kgf / cm ² ) Cloudiness (%) Glossiness (45 °,%) MD ^a) TD ^b) Example 1 293 1,539 427 399 37.1 42.6 Example 2 291 1,402 414 393 34.1 44.3 Example 3 284 1,257 405 390 32.5 44.3 Example 4 276 1,106 393 386 32.1 45.4 Example 5 265 1,011 381 376 31.5 46.7 Comparative Example 1 301 1,560 441 405 38.0 41.1 Comparative Example 2 297 624 377 372 37.3 41.5

^a) Machine Direction.

^b) Transverse Direction.

As can be seen in Comparative Example 1 and Examples 1 to 5, high strength LLDPE / general LDPE blend films have a progressive decrease in resin melt pressure during film molding as the LDPE content in the blend increases, resulting in improved film formability. In addition, the high-strength LLDPE / general LDPE blend film, it can be seen that as the LDPE content in the blend is increased, the film's haze decreases and the glossiness increases, resulting in excellent film optical properties.

On the other hand, as can be seen in Comparative Example 2 and Examples 1 to 5, the mechanical properties such as fall impact strength, tensile strength at break, etc. of the high-strength LLDPE / LDLD blends gradually decrease as the LDPE content in the blend increases. In comparison with the general C ₆ -LLDPE of Comparative Example 2, until the LDPE content is 25% by weight or less, it can be seen that it maintains a high value. In addition, when comparing the physical properties of the high-strength LLDPE / general LDPE blend film with that of general C ₆ -LLDPE, the impact impact strength is excellent until the LDPE content of the blend is 25 wt% or less, and the film processability and other film properties are good. It can be seen that it exhibits characteristics.

As can be seen from the above, according to the present invention, in the presence of a magnesium-supported non-metallocene catalyst, high-strength LLDPE synthesized by copolymerizing ethylene and CH ₂ = CHR (wherein R is a C ₂ -C ₈ alkyl group); By mixing general LDPE, it is possible to provide an LLDPE resin composition having excellent impact properties and good film processing properties and film processability in comparison with high strength LLDPE single resin or general C ₆ -LLDPE single resin.

Claims (4)

75-99.9% by weight of high-strength linear low density polyethylene synthesized by copolymerizing ethylene and CH ₂ = CHR (where R is a C ₂ -C ₈ alkyl group) in the presence of a magnesium-supported nonmetallocene-based catalyst, and 0.1 to general low density polyethylene Linear low density polyethylene resin composition comprising 25% by weight. The method of claim 1, wherein the high-strength linear low density polyethylene has a melt flow index of 0.2 to 20 g / 10 minutes, as measured by ASTM D-1238 (190 ℃, 2.16 kg), characterized in that the density is 0.910 ~ 0.930 g / cm ³ Linear low density polyethylene resin composition. The method of claim 1, wherein the general low density polyethylene has a melt flow index of 0.9 to 20 g / 10 minutes, as measured by ASTM D-1238 (190 ℃, 2.16 kg), characterized in that the density is 0.910 ~ 0.930 g / cm ³ Linear low density polyethylene resin composition. The linear low density polyethylene resin composition according to claim 1, wherein the comonomer constituting the high strength linear low density polyethylene is butene-1 or hexene-1.