KR100255272B1 - Resin laminate for recyclable pe pouch bag composition - Google Patents

Abstract

PURPOSE: A resin laminated product for a polyethylene packaging material is provided, which is recyclable and is improved in the low temperature impact strength, the charging property to the quality of materials, the transparency and the gloss. CONSTITUTION: The resin laminated product is prepared by co-extruding the HDPE outer layer film with the MFR190T value of 0.1-3.0 g/10 in and the density of 0.93-0.97 g/cm¬3, and the inner layer film comprising VLDPE resin with the MFR190T value of 0.1-3.0 g/10 in and the density of 0.86-0.91 g/cm¬3. Also the resin laminated product is prepared by co-extruding the HDPE outer layer film with the MFR190T value of 0.1-3.0 g/10 in and the density of 0.93-0.97 g/cm¬3, the middle film comprising a LLDPE resin containing alpha-olefin of C4-C8, and the inner layer film comprising VLDPE resin with the MFR190T value of 0.1-3.0 g/10 in and the density of 0.86-0.90 g/cm¬3. Also the resin laminated product is prepared by blown molding the HDPE outer layer film with the MFR190T value of 0.1-3.0 g/10 in and the density of 0.93-0.97 g/cm¬3, and the inner layer film comprising VLDPE resin with the MFR190T value of 0.1-3.0 g/10 in and the density of 0.86-0.91 g/cm¬3.

Description

Resin laminate for recyclable polyethylene packaging

The present invention relates to a resin laminate with a recyclable polyethylene packaging. In particular, it is excellent in impact resistance, printing property, gloss property and cryogenic heat sealing property, and excellent in low temperature and low temperature impact strength, and can be recycled and reused by using a single polyethylene (PE) material. It is related with the resin laminated body for packaging materials. More specifically, the present invention relates to a polyethylene resin composition and moldings thereof, which are impact resistant, environmentally friendly, and recyclable and easy to use as a resin laminate for kitchen detergent detergent filling.

Recently, as interest in resource conservation and environmental preservation has increased rapidly, re-fills are increasingly sold for products that can continue to be used after the contents have been used, such as synthetic detergents.

As such, when the liquid filling product is sold separately, the packing material of the filling product is determined in consideration of the nature of the contents and the distribution environment. For example, the synthetic resin in use as a packaging container (pouch) for a conventional disposable detergent detergent is determined. The material is a laminate made of PET / Nylon / LLDPE triple material or nylon / LLDPE double material. After each layer is extruded, dry lamination is carried out using an adhesive or adhesive resin, followed by additional heat sealing. After aging under temperature and constant pressure, the contents are filled and used.

Liquid packaging materials, such as synthetic detergents using different materials, have a high manufacturing cost and can not be recycled due to the use of different kinds of resin films. This causes a problem in recycling, such as a separate waste disposal cost.

Therefore, the object of the present invention is to eliminate the above-mentioned disadvantages of the prior art, it is possible to recycle (recycle) using a single polyolefin material without high manufacturing costs, and the room temperature and low temperature impact strength, the content filling properties for the material, transparency and An object of the present invention is to provide a multilayer film for pouches that can be used as a material for packaging synthetic detergents having excellent gloss.

The packaging laminate of the present invention may be a laminate of an outer layer and an inner layer, or a laminate of an outer layer, an intermediate layer, and an inner layer of three layers, and an appropriate protective layer and a printing layer may be added as necessary. It can be included as.

That is, the multilayer film may be commercialized into double and triple films depending on the use and properties.

As an outer layer of the multilayer film laminate of the present invention, the MFR _190T is 0.1-3.0 g / 10 min, the density is 0.93-0.97 g / cm ² , the MI _21.6 / MI _5.0 is 40 or less, and measured by a differential scanning calorimeter. Low pressure high density polyethylene (HDPE) with one endothermic peak at melting point alone, or high density polyethylene with MFR _190T 0.01 to 0.1 g / 10 min, density 0.930-0.970 g / cm ² and MI _21.6 / MI _5.0 less than 40 HDPE) can be used as a suitable blend.

Melt Flow Rate (MFR) is the melt flow rate and MFR _190T represents the MFR value measured at a temperature of 190 ° C, the method of measurement of which is described in ASTM D 1230 (D) or KSM 3012, It is a method of measuring the weight of polyethylene resin flowing out through a die for 10 minutes by a die having a diameter of 2.0955 mm with a load of 2.16 kg.

As the outer layer of the multilayer film laminate of the present invention, in addition to the two kinds of HDPE resins mentioned above, a copolymer resin of ethylene and propylene may be used to improve the rigidity and gloss of the product. Ethylene propylene random copolymer resin having a Bikat softening point of 70-160 ° C. and a melt index of 3-15 is preferred.

MFR _190T is 0.1-3.0g / 10min and has a density of 0.930-0.970g / cm ² , and MFR _190T 0.01-0.1g / 10min and a density of 0.930-0.970g / cm ² is 10: It can be used by blending in a ratio of 90 to 90:10. In addition, a polypropylene resin having an MFR _230T of 2-20 g / 10 minutes, a density of 0.88-0.92 g / cm ^3, and a Vicat softening point of 70-160 ° C. may be used as an outer layer material.

In the packaging layer of the present invention, the inner layer is a low-density polyethylene (VLDPE) using a metallocene catalyst having an extremely low melting temperature of resin, or a linear low-density polyethylene containing α-olefin having 4 or more carbon atoms. (LLDPE) can be used by blending to a certain amount.

In other words, as the inner layer of the multilayer film laminate of the present invention, MFR _190T is 0.5-3.0 g / 10 min, has a density of 0.89-0.930, and is a comonomer, a linear low density polyethylene (LLDPE) containing α-olefin having 4 or more carbon atoms. ) the product or MFR _190T is 0.1-3.0g / 10 minutes and a density of 0.86-0.91g / cm ² and a melting point of 50-100 ℃ the peak of the melting point measured by a differential scanning calorimeter will appear as one and Water 150 ℃ GPC Ultra low density polyethylene (VLDPE) resin using a mecarlocene catalyst may be used as the molecular weight distribution measured by 2-3, or they may be used by blending up to 10-90%. The method of blending the resin is a conventional blending method, in which resins used in each layer of the laminate of the present invention are simply mixed in a hopper in a pellet form, which is commonly referred to as a dry blend.

When the laminate of the present invention is applied as a triple film, a linear low density polyethylene product including α-olefin having 4 to 8 carbon atoms as comonomer can be used as an intermediate layer between the inner layer and the outermost layer.

When the multilayer film laminate of the present invention is implemented as a double film, the thickness ratio of the outer layer and the inner layer may be 10:90 to 90:10, and the thickness of the entire film may be in the range of 50-200 μm.

In the case where the laminate of the present invention is a triple film, a ratio of 30:35:35 for the thickness ratio of the inner layer of the outer layer is appropriate, and the application ratio of 2-40: 20-96: 2-40 is possible. The overall thickness of the triple film is also applicable over the 50-200㎛ range.

Polyethylene multilayer film produced by the above method has a tensile strength of 250kg / cm ² or more, the drop impact strength of the film is 870g or more, elongation of 600% or more, the strength, stiffness and gloss is in harmony, and the room temperature after filling the liquid contents And when the three times repeated drop impact test at a height of 1.5m at low temperature (-10 ℃) there was no generation of the band, it can exhibit features such as excellent standing properties of the material (Recycle) possible.

The present invention is described in detail by the following examples, but the scope of the present invention is not limited to these examples.

Example 1

Low-pressure high-density polyethylene (HDPE) products for use in the outer layer films include LG Petrochemical BE0400 products with MI 0.2 g / 10 min and density 0.957 g / cm ² and LG Petrochemical MI 0.05 g / 10 min with density 0.957. The product was blended at a ratio of 10 to 90 to 90 to 10%, extruded into a top-down water cooled film, and used as an outer layer.

The thickness of the outermost layer was extruded to 50-100㎛.

In addition, Hyundai Octene LLDPE with MI (2.16Kg) 1.0g / 10min, density 0.919g / cm ² and MI0 0.80g / 10min Density 0.80g / cm ² metallocene PE with inner layer film The product was blended at a ratio of 10-90% to 90-10% and extruded into a top-down water-cooled film together with the outermost layer. The film was extruded to a thickness of 50-100 μm. The top-down water-cooled film extrusion manufacturing method is a molten resin is extruded through a circular die in the extruder barrel into a tube state, the air is put into this tube to expand the film to have a desired width, and at the same time the film formed by putting the coolant outside the die After solidifying to produce a hollow cylinder called a bubble, the bubble is wound on a nip roll and wound through a plurality of guide rolls to a double layer on a winder, where the width of the film is determined by the bubble size and the amount of extrusion When constant the film thickness is adjusted at the nip roll speed. The physical properties of the thus obtained film having a thickness of 150 μm were measured and the results are shown in Table 1.

The physical property was measured by the following method.

(1) MFR _190T : measured by ASTM D 1230 (D) at 190 ° C

(2) Density: measured by ASTM D 1505

(3) MI ₂₀ / MI ₂ : MI ₂₀ is the MFR value measured by ASTM D 1238 at a load of 21.6 kg, MI is the MFR value at its similar 21.6 kg load and represents the ratio of these two values.

(4) Melting point (T _m ): 4 to 5 mg of the sample is weighed and heated to 20 ° C. at a rate of temperature rise of 10 ° C./minute for 10 minutes, and then cooled to 47 ° C. at a rate of temperature decrease of 20 ° C./minute , And then the endothermic peak was recorded in a chart while heating up by 10 ° C. per minute and heating. At this time, when one of the heat-absorption peak appeared, it showed a heat absorbing T _m1 H of the highest melting point, indicating a second Ron endothermic peak of the high temperature side as T _m1 H. Measured with a differential scanning calorimeter (Perkin Elmer).

(5) Melt tension: measured by the melt tension tester manufactured by Toyo Seki

Nozzle: L = 8,000 Temperature Condition: 190 ℃

Extrusion Speed: 150mm / min Blow Out Speed: 2m / min

(6) Transparency: The measured value according to ASTM D 1790 B was divided by the thickness.

Daart measurement value (kg) / sheet thickness (cm)

(8) Young's modulus: measured with a crosshead traveling speed fixed per person tester (manufactured by Instron)

Sample: JIS K 6781 (Mull Type) Ambient Temperature: 23 ℃

Tensile Speed: 500mm / min Sheet Temperature: 200mm / min

The Young's modulus (E) was calculated by the following equation from the calculated chart under the above conditions and measured in the MD and TD directions. E ₀ = R ₀ (L ₀ / A)

Where E ₀ is the Young's modulus in several directions, R ₀ is the initial gradient, L ₀ is the Chunk price, and A is the minimum area for sample preparation. At this time, R ₀ is obtained by the following formula.

R ₀ = E ₀ / L ₀

(E ₀ is the one point load on the initial tangent, and L ₀ is the elongation by F ₁ for this tangent.)

(9) Dropping Impact Strength: Injecting a liquid detergent such as 800 ml of surfactant into an elliptical PE blow bottle and repeating it three times at 1.5m height at room temperature (23 ℃) and low temperature (-10 ℃). Drop test was performed to determine the number of bags.

(10) Standing property: After testing a certain amount of contents into each material, the standing property was tested.

Example 2

R150L (MI 8.0 g / 10 min, density 0.900 g / cm ² ) was used alone as a porous random PP product of propylene-ethylene random copolymer copolymer used as the outer layer in Example 1, and was top-down as in Example 1. The film thickness was extruded to 50-100 mu m for the water cooled film. For the inner layer film of the multilayer film was prepared in the same manner as in Example 1. The physical properties of the laminate thus obtained are shown in Table 1.

Example 3

As in Example 1, LG Petrochemical BE0400 product with a MI value of 0.2 g / 10 min and a density of 0.959 g / cm ² was used as a low pressure high density polyethylene (HDPE) product, and a linear low density polyethylene product (Hyundai SF318 or Perforated FN810) was used as the intermediate layer. Product) alone.

The inner layer of the product is the same as in Example 1.

Triple film extrusion was carried out in an extruder equipped with an inter bubble cooling (IBC) system.

The thickness ratio of the triple film was 50:50:50 μm, and the physical properties of the film thus obtained are shown in Table 1.

[Comparative Example]

A triple film laminate was prepared, but PET was used as the outer layer, Nylon was used as the intermediate layer, and LLDPE was used as the inner layer.

Unlike the products of Examples 1, 2, and 3, the comparative example was manufactured by dry lamination on the LLDPE after extrusion of PET and Nylon.

The properties of the film having a thickness of 150 µm thus obtained are shown in Table 1, and the film had low temperature, heat sealability, recyclability, and the like, as compared with the product of Examples.

Claims (16)

A laminate for liquid packaging comprising: a) a high density polyethylene (HDPE) product outer layer film having an MFR _190T value of 0.1-3.0 g / 10 min and a density of 0.93-0.97 g / cm ² ; And b) a multi-layer film laminate formed by co-extrusion of an inner layer film comprising an ultra low density polyethylene (VLDPE) resin having an MFR _190T value of 0.1-3.0 g / 10 min and a density of 0.86-0.91 g / cm ² . The outer layer film is a high density polyethylene resin having a MFR _190T value of 0.01 to 0.1 g / 10 minutes, 0.1 to 3.0 g / 10 minutes, and a density of 0.93 to 0.97 g / cm ² , respectively. A multilayer film laminate comprising a resin obtained by blending at a ratio of 10. The resin of claim 1 or 2, wherein the outer layer film is obtained by blending the high density polyethylene (HDPE) resin with a polypropylene resin having an MFR _230T value of 2 to 20 g / 10 minutes and a density of 0.88 to 0.92 g / cm ³ . Multilayer film laminate comprising a. The multilayer film lamination according to claim 1 or 2, wherein the inner layer film is a copolymer of the ultra low density polyethylene resin and a linear polyethylene (LLDPE) resin having an MFR _190T 0.5-3.0 g / 10 min and a density of 0.89-0.93 g / cm. sieve. The multilayer film laminate according to claim 1 or 2, wherein the ultra-low density polyethylene resin has a molecular weight distribution of 1 to 4 and a weight average molecular weight of the group IV B of the periodic table of 80,000 to 120,000. The multilayer film laminate according to claim 1 or 2, wherein the multilayer film has a thickness of 50 to 200 µm. The multilayer film laminate according to claim 1 or 2, wherein the thickness ratio of the outer layer film to the inner layer film is from 2:98 to 98: 2. A laminate for liquid packaging comprising: a) a high density polyethylene (HDPE) product outer layer film having an MFR _190T value of 0.1-3.0 g / 10 min and a density of 0.93-0.97 g / cm ² ; b) an interlayer film comprising a linear low density polyethylene (LLDPE) resin comprising an α-olefin having 4 to 8 carbon atoms; And c) a multilayer film laminate formed by co-extruding an inner layer film comprising an ultra low density polyethylene (VLDPE) resin having an MFR _190T value of 0.1-3.0 g / 10 min and a density of 0.86-0.90 g / cm ² . The outer layer film of the present invention comprises a high density polyethylene resin having a MFR _190T value of 0.01 to 0.1 g / 10 minutes and 0.1 to 3.0 g / 10 minutes and a density of 0.93 to 0.97 g / cm ² , respectively. A multilayer film laminate comprising a resin obtained by blending at a ratio of 10. The outer layer film is obtained by blending the high density polyethylene (HDPE) resin with a polypropylene resin having an MFR _230T value of 2 to 20 g / 10 minutes and a density of 0.88 to 0.92 g / cm ³ . Multilayer film laminated body containing resin. The multilayer film lamination according to claim 8 or 9, wherein the inner layer film is a copolymer of the ultra low density polyethylene resin and a linear polyethylene (LLDPE) resin having an MFR _190T 0.5-3.0 g / 10 min and a density of 0.89-0.93 g / cm. sieve. The multilayer film laminate according to claim 8 or 9, wherein the ultra low density polyethylene resin has a molecular weight distribution of 1 to 4 and a weight average molecular weight of Group IV of the periodic table of 80,000 to 120,000. The multilayer film laminate according to claim 8 or 9, having a thickness of 50 to 200 µm. The multilayer film laminate according to claim 13, wherein the thickness ratio of the outer layer film: the middle layer film: the inner layer film is 2 to 40: 20 to 96: 2 to 40. In a polyethylene multilayer film laminate extruded by blow molding, a) an outer layer of a high density polyethylene (HDPE) product having an MFR _190T value of 0.1-3.0 g / 10 min and a density of 0.93-0.97 g / cm ² film; And b) an inner layer film comprising an ultra low density polyethylene (VLDPE) resin having an MFR _190T value of 0.1-3.0 g / 10 min and a density of 0.86-0.91 g / cm ² . The multilayer film laminate of claim 15, further comprising an inner layer film comprising an ultra low density polyethylene (VLDPE) resin having an MFR _190T value of 0.1-3.0 g / 10 min and a density of 0.86-0.91 g / cm ² . .