KR19990061856A - Resin laminate for recyclable polyethylene packaging material - Google Patents

Abstract

The present invention can be recycled using a single polyolefin material without a high manufacturing cost, and can be used as a material for synthetic detergent packaging excellent in room temperature and low temperature impact strength, content charging property for a material, transparency and gloss To provide a multilayer film laminate.

The packaging laminate of the present invention can be a laminate having a two-layer structure of an outer layer and an inner layer or a three-layer structure of an outer layer, an intermediate layer and an inner layer, As shown in FIG.

Description

Resin laminate for recyclable polyethylene packaging material

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin laminate having a recyclable polyethylene package. In particular, it is excellent in impact resistance, printing characteristics, gloss characteristics and cryogenic heat sealing properties of materials, excellent in low temperature resistance and low temperature impact strength, and can be recycled and reused as a single material of polyethylene (PE) To a resin laminate for packaging material. More specifically, the present invention relates to a polyethylene resin composition and a molded product thereof, which are shockproof, environmentally friendly, recyclable, and easy to use as a resin laminate for filling a detergent for kitchen use.

In recent years, interest in conserving resources and preserving the environment has been rapidly increasing, and in the case of a product such as a synthetic detergent that can be used continuously after using all the contents, re-fill is increasingly sold separately.

When the liquid filling article is sold separately, the packing material of the filling article is determined in consideration of the properties of the contents and the circulation environment. For example, in the case of using a synthetic resin as a packaging container (pouch) for filling a disposable synthetic detergent The material is made of PET / Nylon / LLDPE triple material or Nylon / LLDPE double material. After each layer is extruded, dry lamination is performed using adhesive or adhesive resin, It is aged at a temperature and a constant pressure and then used after filling the contents.

Liquid packaging materials such as synthetic detergents using different materials are very expensive to manufacture and at the same time have a disadvantage in that they can not be recycled because resins having different properties are stacked due to the use of different kinds of resin films Thereby causing a problem in recycling such as a separate waste disposal cost.

Accordingly, it is an object of the present invention to provide a polyolefin material which can be recycled by using a single polyolefin material without eliminating the above-mentioned disadvantages of the prior art, and can be used at room temperature and low temperature impact strength, And which can be used as a material for synthetic detergent packaging excellent in glossiness and the like.

The packaging laminate of the present invention can be a laminate having a two-layer structure of an outer layer and an inner layer or a three-layer structure of an outer layer, an intermediate layer and an inner layer, As shown in FIG.

That is, the multi-layer film can be commercialized as a double or triple film depending on its use and properties.

The outer layer of the multilayered film laminate of the present invention has an MFR _190T of 0.1-3.0 g / 10 min, a density of 0.93-0.97 g / cm ² , an MI of _21.6 / MI _5.0 of 40 or less, the endothermic peaks of the melting point one by itself a low pressure process high density polyethylene (HDPE) or MFR appears _190T is 0.01~0.1 g / 10 min and a density of a _{^{0.930-0970 g / cm 2 MI 21.6 /}} MI 5.0 40 less than or equal to the high-density polyethylene ( HDPE).

As the outer layer of the multilayered film laminate of the present invention, a copolymer resin of ethylene and propylene may be used in addition to the two kinds of HDPE resins mentioned above in order to improve rigidity and gloss of the product. As the copolymer resin used in the present invention, Is an ethylene-propylene random copolymer resin having a Bycaff's softening point of 70-160 DEG C and a melt index of 3-15.

MFR _190T is 0.1-3.0 g / 10 min, and a density having with the physical properties of 0.930-0.970 g / cm ² and of MFR _190T 0.01-0.1 g / 10 minutes and a density of 0.930-0.970 g / cm ² in 10: 90 to 90: 10. A polypropylene resin having an MFR _{230T of 2} to 20 g / 10 min and a density of 0.88 to 0.92 g / cm ³ and a Bycal softening point of 70 to 160 ° C can be used as an outer layer material.

As the inner layer in the packaging laminate of the present invention, ultra low density polyethylene (VLDPE) using a metallocene catalyst having an extremely low melting point of the resin may be used alone or as a linear low density polyethylene containing an alpha -olefin having 4 or more carbon atoms (LLDPE) may be blended in a certain amount.

That is, the inner layer of the multilayered film laminate of the present invention is a linear low density polyethylene (MFL _190T) having a density of 0.5 to 3.0 g / 10 min, a density of 0.89 to 0.930, and an alpha -olefin having 4 or more carbon atoms as a comonomer ) Or a MFR _190T of 0.1-3.0 g / 10 min, a density of 0.86-0.91 g / cm ^2, and a melting point of 50-100 ° C as measured by a differential scanning calorimeter and a water 150 ° C GPC Density polyethylene (VLDPE) resin using a metallocene catalyst, or they may be blended to 10-90%.

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

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

When the laminate of the present invention is a triple film, the ratio of the thickness of the inner layer of the outer layer to the thickness of the inner layer of the outer layer is suitably in the range of 30: 35: 35, the application ratio of 2: 40: 20 to 96: The overall thickness of the triple film is also applicable over the range of 50-200 μm.

The polyethylene multi-layer film produced by the above method has a tensile strength of 250 kg / cm ² or more, a falling impact strength of the film of 870 g or more, a elongation of 600% or more and a balance of strength, rigidity and gloss, After 3 successive drops at 1.5 m height at normal temperature and low temperature (-10 ℃), there was no occurrence of wave in the impact test, and excellent standing of material and recycle possibility can be shown.

The present invention will be described in detail with reference to 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 outer layer films include LG Petrochemical BE0400 with an MI of 0.2 g / 10 min and a density of 0.957 g / cm ² , LG Petrochemical FE0070 with an MI of 0.05 g / 10 min and a density of 0.957 The product was blended at a ratio of 10 to 90 to 90 to 10% and extruded into a top-down water-cooled film to be used as an outer layer.

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

In addition, the inner layer pireum MI (2.16 Kg) 1.0 g / 10 min, density 0.919 g / cm ² in a modern octene LLDPE with MI 0.80 g / 10 bun density 0.80 g / cm ² of US exon (Exon) four metallocene PE with The product was extruded into a top-down water-cooled film together with the outermost layer by blending in a ratio of 10-90% to 90-10%. The film was extruded to have a thickness of 50-100 [mu] m. The physical properties of the thus-obtained 150 μm-thick film were measured, and the results are shown in Table 1.

The physical properties were measured by the following methods.

(1) MFR _190T : Measured at 190 캜 according to ASTM D 1230 (D)

(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, and MI is the MFR value at a similar load of 21.6 kg.

(4) Melting point (T _m ): 4 to 5 mg of the sample was weighed and heated to 20 ° C at a temperature raising rate of 10 ° C / min for 10 minutes, cooled to 47 ° C at a temperature lowering rate of 20 ° C / , And then recorded at a rate of 10 DEG C per minute and heated while being recorded on the chart. In this case, when one peak is observed, the peak T _m1 H of the highest melting point is shown, and the endothermic peak of the second highest temperature is T _m1 H. Measured with a differential scanning calorimeter (Perkin Elmer).

(5) Melting Tension: Measured by a melt tension tester manufactured by Toyo Seiki Co., Ltd.

Used nozzle: L = 8,000 Temperature condition: 190 ℃

Extrusion speed: 150 mm / min Feed rate: 2 m / min

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

Da art measurement (kg) / sheet thickness (cm)

(8) Young's modulus: Measured by crosshead moving speed fixed type per person tester (manufactured by Instron)

Sample: JIS K 6781 (dumbbell type) Ambient temperature: 23 ° C

Tensile speed: 500 mm / min Sheet temperature: 200 mm / min

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

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

R ₀ = E ₀ / L ₀

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

(9) Dropping Impact Strength: A liquid detergent such as 800 ml of a surfactant is injected into an elliptical type PE blow bottle, and then, at a room temperature (23 ° C) and a low temperature (-10 ° C) The number of bands was measured by repeated drop test.

(10) Standing property: Each material was tested for standability after injecting a certain amount of contents.

Table 1 Physical property measurement results of the laminate film

division Configuration Example 1 Example 2 Example 3 Comparative Example 1 Outermost layer MI (g / 10 min) Density (g / cm ² ) Resin 0.2 0.050.957 0.957 BE0400 + FE0070 = 50 + 50 = 50 μm 8.00.900R150L = 75um 0.20.957BE040050um --PET 15um Middle layer MI (g / 10 min) Density (g / cm ² ) Resin 1.00.918SF318 = 50um - 1.00.918SF318 = 50um Nylon15um Inner layer MI (g / 10 min) Density (g / cm ² ) Resin 1.0 0.80.918 0.880SF318 + EXACT4033 = 50 + 50 = 50um Same as left 1.0 0.80.918 0.880SF318 + EXACT4033 = 50 + 50 = 50um 1.00.918SF318120um Overall Thickness um 150 150 150 150 Film Properties Young's modulus (kg / cm ² ₎ Tear strength (kg / mm) Tensile strength (kg / cm ² ) Drop impact strength (g) 3,30013033090085 3,80015046090095 3,50012338095090 3,300110280870120

Example 2

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

Example 3

A low-pressure high-density polyethylene (HDPE) product of LG Petrochemical BE0400 having an MI value of 0.2 g / 10 min and a density of 0.959 g / cm ² was used as in Example ¹ , and a linear low density polyethylene product (Hyundai SF318 or FN810 Product) was extruded alone.

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

Triple film extrusion was performed in an extruder equipped with an IBC (Inter bubble cooling) system.

The thickness ratio of the triple film was set to 50: 50: 50 [mu] m. Physical properties of the film thus obtained are shown in Table 1.

Comparative Example

A triple film laminate was prepared using PET as the outer layer, Nylon as the middle layer and LLDPE as the inner layer.

Unlike the products of Examples 1, 2 and 3, the comparative products were produced by extruding PET and nylon, and dry laminated to LLDPE, respectively.

The properties of the thus obtained 150 μm thick film are shown in Table 1. The characteristics of the film such as low temperature, heat sealability, and recyclability were poor compared with the products of the Examples.

Claims (16)

In the laminate for liquid packaging material, a) a high density polyethylene (HDPE) product outer layer film having an MRF _190T value of 0.1-3.0 g / 10 min and a density of 0.93-0.97 g / cm ² ; And b) an inner layer film comprising an ultra low density polyethylene (VLDPE) resin having a MRF _190T value of 0.1-3.0 g / 10 min and a density of 0.86-0.91 g / cm ² Layered film laminate. The method according to claim 1, The outer layer film was prepared by blending a high-density polyethylene resin having an MRF _190T value of 0.01 to 0.1 g / 10 min and 0.1 to 3.0 g / 10 min and a density of 0.93 to 0.97 g / cm ² at a ratio of 10:90 to 90:10 A multilayer film laminate comprising the obtained resin. 3. The method according to claim 1 or 2, The outer layer film comprises a resin obtained by blending a polypropylene resin having a density of 0.88 to 0.92 g / cm < ³ > with an HDPE resin and an MRF _230T value of 2 to 20 g / . 3. The method 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 MRF _190T 0.5-3.0 g / 10 min and a density of 0.89-0.93 g / cm. 3. The method according to claim 1 or 2, The ultra low density polyethylene resin has a molecular weight distribution of 1 to 4 and a weight average molecular weight of Group IVB of the Periodic Table of the Elements of 80,000 to 120,000. 3. The method according to claim 1 or 2, A multilayer film laminate having a thickness of 50 to 200 m. 3. The method according to claim 1 or 2, Wherein the thickness ratio of the outer layer film and the inner layer film is from 2: 98 to 98: 2. In the laminate for liquid packaging material, a) a high density polyethylene (HDPE) outer layer film having an MRF _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 alpha -olefin having 4 to 8 carbon atoms; And c) an inner layer film comprising an ultra low density polyethylene (VLDPE) resin having an MRF _190T value of 0.1-3.0 g / 10 min and a density of 0.86-0.90 g / cm ² Layered film laminate. 9. The method of claim 8, The outer layer film was prepared by blending a high-density polyethylene resin having an MRF _190T value of 0.01 to 0.1 g / 10 min and 0.1 to 3.0 g / 10 min and a density of 0.93 to 0.97 g / cm ² at a ratio of 10:90 to 90:10 A multilayer film laminate comprising the obtained resin. 10. The method according to claim 8 or 9, The outer layer film comprises a resin obtained by blending a polypropylene resin having a density of 0.88 to 0.92 g / cm < ³ > with an HDPE resin and an MRF _230T value of 2 to 20 g / . 10. The method 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 MRF _190T 0.5-3.0 g / 10 min and a density of 0.89-0.93 g / cm. 10. The method according to claim 8 or 9, 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 the Elements of 80,000 to 120,000. 10. The method according to claim 8 or 9, A multilayer film laminate having a thickness of 50 to 200 m. 14. The method of claim 13, Outer layer film: interlayer film: inner layer film A multilayer film laminate having a thickness ratio of 2: 40: 20 to 96: 2: 40. In a multilayer polyethylene film multilayer film extruded by a blown molding method, a) a high density polyethylene (HDPE) product outer layer film having an MRF _190T value of 0.1-3.0 g / 10 min and a density of 0.93-0.97 g / cm ² ; And b) an inner layer film comprising an ultra low density polyethylene (VLDPE) resin having a MRF _190T value of 0.1-3.0 g / 10 min and a density of 0.86-0.91 g / cm ² ≪ / RTI > 16. The method of claim 15, MRF _190T value of the multi-layer film laminate comprising 0.1-3.0 g / 10 min, and add an interlayer film for a density of including ultra low density polyethylene (VLDPE) resins 0.86-0.91 g / cm ^2.