Polyolefin resin composition and article produced therefrom

Abstract

A polyolefin resin composition according to the present invention is characterised by comprising: about 35-55 wt % of an arbitrary polypropylene resin; about 10-35 wt % of a propylene-ethylene-1-butene copolymer; about 1-15 wt % of an ethylene-propylene elastomer; about 5-25 wt % of a propylene-ethylene elastomer; and about 1-15 wt % of maleic anhydride grafted polypropylene. The polyolefin resin composition has, for example, excellent adhesive strength with respect to a polar substrate and excellent adhesive strength with respect to a polar substrate after a high-temperature thermal history.

Description

Polyolefin resin composition and molded article made therefrom

[0001] The present invention relates to a polyolefin resin composition and a molded article manufactured therefrom. More specifically, the present invention relates to a polyolefin resin composition having excellent adhesion strength to a polar substrate, adhesion strength to a polar substrate after high-temperature thermal history, and a molded article manufactured therefrom.

[0002]

[0003] Multilayer laminated packaging materials are widely used for packaging contents where quality preservation is critical, such as food, pharmaceuticals, and electronic devices. Laminates used for this purpose are generally composed of a polar substrate layer with excellent barrier properties (blocking gases such as oxygen) and a non-polar polyolefin-based resin layer with excellent moisture resistance and chemical resistance.

[0004] Among polyolefin resins, polypropylene resin is widely used as a thermoplastic molding material due to its excellent heat resistance, chemical resistance, and rigidity. However, it is common practice to use acid modification to achieve adhesion to polar substrate layers. Additionally, elastomers are typically blended with polypropylene resin to impart flexibility and wettability, thereby achieving improved adhesion. Furthermore, since polypropylene resin is a material with insufficient gas barrier properties, it is common practice to use it in a multilayer laminate form with polar materials to compensate for this. However, because polypropylene resin is a non-polar material, it has a lack of adhesion to polar materials with excellent gas barrier properties, such as polyamide resins, ethylene-vinyl alcohol copolymers, and metals.

[0005] To address these issues, acid-modified polypropylene, manufactured using a technique that modifies polypropylene resin with unsaturated carboxylic acids or their derivatives, has been widely used in the past. However, since using such acid-modified polypropylene alone results in insufficient flexibility and wettability, it is typically used in combination with polypropylene resin, acid-modified polypropylene, and an elastomer component when applied as an adhesive resin. Nevertheless, even when using an elastomer, there is a risk that adhesion properties may deteriorate under heating conditions, such as those using hot air ovens or microwave ovens.

[0006] Therefore, there is a need to develop polyolefin resin compositions that exhibit excellent adhesion strength to polar substrates and adhesion strength to polar substrates after high-temperature thermal history.

[0007] The background technology of the present invention is disclosed in Japanese Patent Publication No. 2004-269688, Korean Registered Patent No. 10-1200658, etc.

[0008]

[0009] The objective of the present invention is to provide a polyolefin resin composition having excellent adhesion strength to a polar substrate, adhesion strength to a polar substrate after high-temperature thermal history, etc.

[0010] Another objective of the present invention is to provide a molded article formed from the polyolefin resin composition.

[0011] The above and other objectives of the present invention can all be achieved by the present invention described below.

[0012]

[0013] 1. One aspect of the present invention relates to a polyolefin resin composition. The polyolefin resin composition comprises about 35 to about 55 weight% of random polypropylene resin; about 10 to about 35 weight% of propylene-ethylene-1-butene copolymer; about 1 to about 15 weight% of ethylene-propylene elastomer; about 5 to about 25 weight% of propylene-ethylene elastomer; and about 1 to about 15 weight% of maleic anhydride grafted polypropylene.

[0014] 2. In the above embodiment 1, the random polypropylene resin is a propylene-ethylene random copolymer having a propylene-derived component content of about 90 to about 99 mol% and an ethylene-derived component content of about 1 to about 10 mol%, and the melt-flow index measured at 230°C and 2.16 kg according to ASTM D1238 may be about 0.1 to about 4.5 g / 10 min.

[0015] 3. In the above 1 or 2 embodiments, the propylene-ethylene-1-butene copolymer is a random copolymer having a propylene-derived component content of about 85 to about 98 mol%, an ethylene-derived component content of about 1 to about 7 mol%, and a 1-butene-derived component content of about 1 to about 8 mol%, and may have a melt flow index of about 0.1 to about 20 g / 10 min measured at 230°C and 2.16 kg according to ASTM D1238.

[0016] 4. In the above 1 to 3 embodiments, the weight ratio of the random polypropylene resin and the propylene-ethylene-1-butene copolymer may be about 1:0.2 to about 1:0.7.

[0017] 5. In the above 1 to 4 embodiments, the ethylene-propylene elastomer may have an ethylene-derived component content of about 65 to about 85 weight% and a propylene-derived component content of about 15 to about 35 weight%, and may have a melt flow index of about 0.1 to about 3 g / 10 min measured at 190°C and 2.16 kg according to ASTM D1238.

[0018] 6. In the above 1 to 5 embodiments, the propylene-ethylene elastomer may have a propylene-derived component content of about 75 to about 95 weight% and an ethylene-derived component content of about 5 to about 25 weight%, and may have a melt flow index of about 5 to about 15 g / 10 min measured at 230°C and 2.16 kg according to ASTM D1238.

[0019] 7. In the above 1 to 6 embodiments, the maleic anhydride grafted polypropylene may have a maleic anhydride-derived component content of about 0.5 to about 5 weight%.

[0020] 8. In the above 1 to 7 embodiments, the polyolefin resin composition may further comprise about 0.5 to about 10 weight percent of homopolypropylene resin.

[0021] 9. In the above 1 to 8 embodiments, the polyolefin resin composition may further comprise about 1 to about 15 weight percent of polyethylene resin.

[0022] 10. In the above embodiments 1 to 9, 2 g of the polyolefin resin composition is placed between aluminum sheets with a thickness of 200 μm, and the temperature is 190°C and the pressure is 100 kgf / cm² 2After preparing a specimen with a length of 100 mm and a width of 20 mm by heat pressing for 60 seconds under conditions, the adhesive strength (peel strength) measured by peeling the aluminum sheet layer and the polyolefin resin composition layer at a speed of 100 mm / min according to ASTM D1876 (T-Peel test) may be about 8 to about 10 kgf / 20 mm.

[0023] 11. In the above 1 to 10 embodiments, the polyolefin resin composition uses polypropylene resin as the outer and inner layers, uses an ethylene-vinyl alcohol copolymer as the barrier layer, and uses the polyolefin resin composition as the adhesive layer. A five-layer film specimen is prepared using a co-extrusion multilayer film molding machine, consisting of an inner layer with a thickness of 360 μm, an adhesive layer with a thickness of 20 μm, a barrier layer with a thickness of 40 μm, an adhesive layer with a thickness of 20 μm, and an outer layer with a thickness of 360 μm. After cutting the specimen to a length of 100 mm and a width of 15 mm, the adhesive strength (peel strength) measured by peeling the barrier layer and the adhesive layer at a speed of 50 mm / min according to ASTM D1876 (T-Peel test) may be about 2.5 to about 4 kgf / 15 mm.

[0024] 12. In the above 1 to 11 embodiments, the polyolefin resin composition uses polypropylene resin as the outer and inner layers, uses an ethylene-vinyl alcohol copolymer as the barrier layer, and uses the polyolefin resin composition as the adhesive layer. A five-layer film specimen is prepared using a co-extrusion multilayer film molding machine, consisting of an inner layer with a thickness of 360 μm, an adhesive layer with a thickness of 20 μm, a barrier layer with a thickness of 40 μm, an adhesive layer with a thickness of 20 μm, and an outer layer with a thickness of 360 μm. The specimen is cut to a length of 100 mm and a width of 15 mm, stored in a hot air oven at 150°C for 30 minutes, and then the adhesive strength (peel strength) measured by peeling the barrier layer and the adhesive layer at a speed of 50 mm / min according to ASTM D1876 (T-Peel test) may be about 2 to about 4 kgf / 15 mm.

[0025] 13. In the above 1 to 12 embodiments, the polyolefin resin composition uses polypropylene resin as the outer and inner layers, uses an ethylene-vinyl alcohol copolymer as the barrier layer, and uses the polyolefin resin composition as the adhesive layer. A five-layer film specimen is prepared using a co-extrusion multilayer film molding machine, consisting of an inner layer with a thickness of 360 μm, an adhesive layer with a thickness of 20 μm, a barrier layer with a thickness of 40 μm, an adhesive layer with a thickness of 20 μm, and an outer layer with a thickness of 360 μm. The specimen is cut to a length of 100 mm and a width of 15 mm, placed in a 1,000 W microwave oven, and exposed to microwaves for 1 minute and 30 seconds. Then, the adhesive strength (peel strength) measured by peeling the barrier layer and the adhesive layer at a speed of 50 mm / min according to ASTM D1876 (T-Peel test) may be about 2 to about 4 kgf / 15 mm.

[0026] 14. In the above 1 to 13 embodiments, the polyolefin resin composition may have a melt flow index of about 0.1 to about 15 g / 10 min measured at 230°C and 2.16 kg in accordance with ASTM D1238.

[0027] 15. Another aspect of the present invention relates to a molded article. The molded article is characterized by being formed from a polyolefin resin composition according to any one of 1 to 14.

[0028]

[0029] The present invention has the effect of providing a polyolefin resin composition having excellent adhesion strength to a polar substrate, adhesion strength to a polar substrate after high-temperature thermal history, and a molded article formed therefrom.

[0030]

[0031] The present invention will be described in detail below.

[0032] The polyolefin resin composition according to the present invention comprises (A) random polypropylene resin; (B) propylene-ethylene-1-butene copolymer; (C) ethylene-propylene elastomer; (D) propylene-ethylene elastomer; and (E) maleic anhydride grafted polypropylene.

[0033] In this specification, "a to b" indicating a numerical range is defined as "≥a and ≤b".

[0034]

[0035] (A) Random polypropylene resin

[0036] A random polypropylene resin according to one embodiment of the present invention can be applied together with propylene-ethylene-1-butene copolymer, ethylene-propylene elastomer, propylene-ethylene elastomer, maleic anhydride graft polypropylene, etc., to improve the adhesion strength to a polar substrate (polyamide resin, ethylene-vinyl alcohol copolymer, metal, etc.) of a polyolefin resin composition, the adhesion strength to a polar substrate after high-temperature thermal history, moldability, etc., and a random polypropylene resin used in a conventional thermoplastic resin composition can be used.

[0037] In a specific example, the random polypropylene resin may be a propylene-ethylene random copolymer having a propylene-derived component content of about 90 to about 99 mol%, for example, about 94 to about 98 mol%, and an ethylene-derived component content of about 1 to about 10 mol%, for example, about 2 to about 6 mol%. Within the above range, the mechanical properties, moldability, etc. of the polyolefin resin composition may be excellent.

[0038] In a specific example, the random polypropylene resin may have a melting point (Tm) measured by a differential scanning calorimeter of about 135 to about 155°C, for example, about 140 to about 150°C, but is not limited thereto. Within the above range, the mechanical properties, moldability, etc. of the polyolefin resin composition may be excellent.

[0039] In a specific example, the random polypropylene resin may have a melt flow index of about 0.1 to about 4.5 g / 10 min, for example, about 1 to about 3 g / 10 min, measured at 230°C and 2.16 kg in accordance with ASTM D1238. Within this range, the mechanical properties and moldability of the polyolefin resin composition may be excellent.

[0040] In a specific example, the random polypropylene resin may be included in an amount of about 35 to about 55 weight%, for example, about 40 to about 50 weight%, of the total polyolefin resin composition. If the content of the random polypropylene resin is less than about 35 weight%, there is a risk that the adhesive strength to a polar substrate and mechanical properties of the polyolefin resin composition after high-temperature thermal history will be reduced, and if it exceeds about 55 weight%, there is a risk that the adhesive strength to a polar substrate, the adhesive strength to a polar substrate after high-temperature thermal history, moldability, wettability, etc. of the polyolefin resin composition will be reduced.

[0041]

[0042] (B) Propylene-ethylene-1-butene copolymer

[0043] A propylene-ethylene-1-butene copolymer according to one embodiment of the present invention can be applied together with random polypropylene resin, ethylene-propylene elastomer, propylene-ethylene elastomer, maleic anhydride graft polypropylene, etc., to improve the adhesion strength to polar substrates (polyamide resin, ethylene-vinyl alcohol copolymer, metal, etc.) of a polyolefin resin composition, the adhesion strength to polar substrates after high-temperature thermal history, moldability, etc., and a propylene-ethylene-1-butene copolymer used in conventional thermoplastic resin compositions can be used.

[0044] In a specific example, the propylene-ethylene-1-butene copolymer may be a random copolymer having a propylene-derived component content of about 85 to about 98 mol%, for example, about 90 to about 95 mol%, an ethylene-derived component content of about 1 to about 7 mol%, for example, about 2 to about 5 mol%, and a 1-butene-derived component content of about 1 to about 8 mol%, for example, about 3 to about 5 mol%. Within the above range, the mechanical properties, moldability, etc. of the polyolefin resin composition may be excellent.

[0045] In a specific example, the propylene-ethylene-1-butene copolymer may have a melting point (Tm) measured by a differential scanning calorimeter of about 125 to about 155°C, for example, about 130 to about 150°C, but is not limited thereto. Within the above range, the mechanical properties, moldability, etc. of the polyolefin resin composition may be excellent.

[0046] In a specific example, the propylene-ethylene-1-butene copolymer may have a melt flow index of about 0.1 to about 20 g / 10 min, for example, about 1 to about 15 g / 10 min, measured at 230°C and 2.16 kg according to ASTM D1238. Within this range, the mechanical properties and moldability of the polyolefin resin composition may be excellent.

[0047] In a specific example, the propylene-ethylene-1-butene copolymer may be included in an amount of about 10 to about 35 weight%, for example, about 15 to about 30 weight%, of the total polyolefin resin composition. If the content of the propylene-ethylene-1-butene copolymer is less than about 10 weight%, there is a risk that the adhesion strength to a polar substrate, the adhesion strength to a polar substrate after high-temperature thermal history, moldability, wettability, etc. of the polyolefin resin composition may be reduced, and if it exceeds about 35 weight%, there is a risk that the adhesion strength to a polar substrate after high-temperature thermal history and mechanical properties of the polyolefin resin composition may be reduced.

[0048] In a specific example, the weight ratio of the random polypropylene resin and the propylene-ethylene-1-butene copolymer may be about 1:0.2 to about 1:0.7, for example, about 1:0.3 to about 1:0.6. Within this range, the adhesion strength of the polyolefin resin composition to a polar substrate, the adhesion strength to a polar substrate after high-temperature thermal history, moldability, etc., may be superior.

[0049]

[0050] (C) Ethylene-propylene elastomer

[0051] An ethylene-propylene elastomer according to one embodiment of the present invention can be applied together with a random polypropylene resin, a propylene-ethylene-1-butene copolymer, a propylene-ethylene elastomer, and maleic anhydride graft polypropylene, etc., to improve the adhesion strength to a polar substrate (polyamide resin, ethylene-vinyl alcohol copolymer, metal, etc.) of a polyolefin resin composition, the adhesion strength to a polar substrate after high-temperature thermal history, moldability, etc., and an ethylene-propylene elastomer used in conventional thermoplastic resin compositions can be used.

[0052] In a specific example, the ethylene-propylene elastomer may have an ethylene-derived component content of about 65 to about 85 weight%, for example, about 70 to about 80 weight%, and a propylene-derived component content of about 15 to about 35 weight%, for example, about 20 to about 30 weight%. Within the above range, the mechanical properties, moldability, and adhesion strength to a polar substrate of the polyolefin resin composition may be excellent.

[0053] In a specific example, the ethylene-propylene elastomer may have a melt flow index of about 0.1 to about 3 g / 10 min, for example, about 0.5 to about 2 g / 10 min, measured at 190°C and 2.16 kg according to ASTM D1238. Within this range, the mechanical properties, moldability, and adhesion strength to polar substrates of the polyolefin resin composition may be excellent.

[0054] In a specific example, the ethylene-propylene elastomer may be included in an amount of about 1 to about 15 weight%, for example, about 5 to about 10 weight%, of the total polyolefin resin composition. If the content of the ethylene-propylene elastomer is less than about 1 weight%, there is a risk that the adhesion strength to the polar substrate of the polyolefin resin composition, the adhesion strength to the polar substrate after high-temperature thermal history, and wettability may be reduced, and if it exceeds about 15 weight%, there is a risk that the adhesion strength to the polar substrate of the polyolefin resin composition, the adhesion strength to the polar substrate after high-temperature thermal history, mechanical properties, and moldability may be reduced.

[0055]

[0056] (D) Propylene-ethylene elastomer

[0057] A propylene-ethylene elastomer according to one embodiment of the present invention can be applied together with a random polypropylene resin, a propylene-ethylene-1-butene copolymer, an ethylene-propylene elastomer, and maleic anhydride graft polypropylene, etc., to improve the adhesion strength to a polar substrate (polyamide resin, ethylene-vinyl alcohol copolymer, metal, etc.) of a polyolefin resin composition, the adhesion strength to a polar substrate after high-temperature thermal history, and moldability, and a propylene-ethylene elastomer used in a conventional thermoplastic resin composition can be used.

[0058] In a specific example, the propylene-ethylene elastomer may have a propylene-derived component content of about 75 to about 95 weight%, for example, about 85 to about 95 weight%, and an ethylene-derived component content of about 5 to about 25 weight%, for example, about 5 to about 15 weight%. Within the above range, the adhesion strength, etc. to the polar substrate of the polyolefin resin composition may be excellent.

[0059] In a specific example, the propylene-ethylene elastomer may have a melt flow index of about 5 to about 15 g / 10 min, for example, about 6 to about 10 g / 10 min, measured at 230°C and 2.16 kg in accordance with ASTM D1238. Within this range, the adhesion strength and moldability of the polyolefin resin composition to a polar substrate may be excellent.

[0060] In a specific example, the propylene-ethylene elastomer may be included in an amount of about 5 to about 25 weight%, for example, about 10 to about 20 weight%, of the total polyolefin resin composition. If the content of the propylene-ethylene elastomer is less than about 5 weight%, there is a risk that the adhesion strength to the polar substrate of the polyolefin resin composition, the adhesion strength to the polar substrate after high-temperature thermal history, mechanical properties, moldability, etc., may be reduced, and if it exceeds about 20 weight%, there is a risk that the adhesion strength to the polar substrate of the polyolefin resin composition, the adhesion strength to the polar substrate after high-temperature thermal history, mechanical properties, etc., may be reduced.

[0061] In a specific example, the weight ratio of the ethylene-propylene elastomer and the propylene-ethylene elastomer may be about 1:0.9 to about 1:2, for example, about 1:1 to about 1:1.9. Within this range, the adhesion strength of the polyolefin resin composition to a polar substrate, the adhesion strength to a polar substrate after high-temperature thermal history, etc., may be superior.

[0062]

[0063] (E) Maleic anhydride grafted polypropylene

[0064] Maleic anhydride grafted polypropylene according to one embodiment of the present invention is applied together with random polypropylene resin, propylene-ethylene-1-butene copolymer, ethylene-propylene elastomer, propylene-ethylene elastomer, etc., and can improve the adhesion strength to polar substrates (polyamide resin, ethylene-vinyl alcohol copolymer, metal, etc.) of the polyolefin resin composition, the adhesion strength to polar substrates after high-temperature thermal history, moldability, etc. For example, the maleic anhydride grafted polypropylene may be a random polypropylene resin in which maleic anhydride is graft-polymerized.

[0065] In a specific example, the maleic anhydride grafted polypropylene may have a maleic anhydride-derived component content of about 0.5 to about 5 weight%, for example, about 1 to about 3 weight%. Within this range, the adhesion strength to a polar substrate of the polyolefin resin composition may be excellent.

[0066] In a specific example, the maleic anhydride grafted polypropylene may have a weight-average molecular weight of about 30,000 to about 80,000 g / mol, for example, about 40,000 to about 70,000 g / mol, as measured by gel permeation chromatography (GPC). Within this range, contamination of the adhesive surface can be prevented, and the adhesive strength to polar substrates can be excellent.

[0067] In a specific example, the maleic anhydride grafted polypropylene may be included in an amount of about 1 to about 15 weight%, for example, about 5 to about 10 weight%, of the total polyolefin resin composition. If the content of the maleic anhydride grafted polypropylene is less than about 1 weight%, there is a risk that the adhesion strength of the polyolefin resin composition to a polar substrate will be significantly reduced, and if it exceeds about 15 weight%, there is a risk that the mechanical properties, moldability, etc. of the polyolefin resin composition will be reduced.

[0068]

[0069] (F) Homopolypropylene resin

[0070] A polyolefin resin composition according to one embodiment of the present invention may further include a homopolypropylene resin to improve adhesion strength, moldability, mechanical properties, etc., to a polar substrate after high-temperature thermal history. The homopolypropylene resin may be an isotactic homopolypropylene resin, such as that used in conventional thermoplastic resin compositions.

[0071] In a specific example, the homopolypropylene resin may have a melting point (Tm) measured by a differential scanning calorimeter of about 150 to about 170°C, for example, about 155 to about 165°C, but is not limited thereto. Within this range, the mechanical properties, moldability, etc. of the polyolefin resin composition may be excellent.

[0072] In a specific example, the homopolypropylene resin may have a melt flow index of about 1 to about 20 g / 10 min, for example, about 5 to about 15 g / 10 min, measured under conditions of 230°C and 2.16 kg according to ASTM D1238. Within this range, the retention of adhesive strength of the polyolefin resin composition (adhesion strength to a polar substrate after high-temperature thermal history), moldability, etc., may be excellent.

[0073] In a specific example, when the homopolypropylene resin is applied, its content may be about 0.5 to about 10 weight%, for example, about 1 to about 8 weight%, of the total polyolefin resin composition. Within this range, the retention of adhesive strength of the polyolefin resin composition (adhesion strength to a polar substrate after high-temperature thermal history), moldability, etc., may be superior.

[0074]

[0075] (G) Polyethylene resin

[0076] A polyolefin resin composition according to one embodiment of the present invention may further include a polyethylene resin to improve moldability by reducing the neck-in phenomenon when forming a sheet or film. As the polyethylene resin, a polyethylene resin used in conventional thermoplastic resin compositions may be used. For example, the polyethylene resin may include one or more selected from low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), medium-density polyethylene (MDPE), and high-density polyethylene (HDPE).

[0077] In a specific example, the polyethylene resin may have a melt flow index of about 1 to about 10 g / 10 min, for example, about 2 to about 9 g / 10 min, measured at 190°C and 2.16 kg according to ASTM D1238. Within this range, the film or sheet moldability of the polyolefin resin composition may be excellent.

[0078] In a specific example, when the polyethylene resin is applied, its content may be about 1 to about 15 weight%, for example, about 5 to about 10 weight%, of the total polyolefin resin composition. Within this range, the moldability of the polyolefin resin composition may be excellent when molding films, sheets, etc.

[0079]

[0080] A polyolefin resin composition according to one embodiment of the present invention may further include additives included in a conventional polyolefin resin composition. Examples of such additives include, but are not limited to, antioxidants, heat stabilizers, UV stabilizers, flame retardants, anti-dripping agents, lubricants, release agents, nucleating agents, antistatic agents, pigments, dyes, and mixtures thereof. When using such additives, the content thereof may be about 0.001 to about 10 parts by weight, for example, about 0.1 to about 5 parts by weight, based on 100 parts by weight of the total of components (A) to (G), but is not limited thereto.

[0081]

[0082] A polyolefin resin composition according to one embodiment of the present invention may be in the form of pellets, which are formed by mixing the above components and melt-extruding them using a conventional twin-screw extruder at about 170 to about 240°C, for example, about 190 to about 230°C.

[0083] In a specific example, 2 g of the polyolefin resin composition is placed between aluminum sheets with a thickness of 200 μm, and the polyolefin resin composition is subjected to a temperature of 190°C and a pressure of 100 kgf / cm².2 After preparing a specimen with a length of 100 mm and a width of 20 mm by heat pressing for 60 seconds under conditions, the adhesive strength (peel strength) measured by peeling the aluminum sheet layer and the polyolefin resin composition layer at a speed of 100 mm / min according to ASTM D1876 (T-Peel test) may be about 8 to about 10 kgf / 20 mm, for example, about 8.5 to about 9.6 kgf / 20 mm.

[0084] In a specific example, the polyolefin resin composition uses polypropylene resin as the outer and inner layers, uses an ethylene-vinyl alcohol copolymer as the barrier layer, and uses the polyolefin resin composition as the adhesive layer, and a five-layer film specimen consisting of an inner layer with a thickness of 360 μm, an adhesive layer with a thickness of 20 μm, a barrier layer with a thickness of 40 μm, an adhesive layer with a thickness of 20 μm, and an outer layer with a thickness of 360 μm is manufactured using a co-extrusion multilayer film molding machine, and after cutting the specimen to a length of 100 mm and a width of 15 mm, the adhesive strength (peel strength) measured by peeling the barrier layer and the adhesive layer at a speed of 50 mm / min according to ASTM D1876 (T-Peel test) may be about 2.5 to about 4 kgf / 15 mm, for example, about 2.7 to about 3.8 kgf / 15 mm.

[0085] In a specific example, the polyolefin resin composition uses polypropylene resin as the outer and inner layers, uses an ethylene-vinyl alcohol copolymer as the barrier layer, and uses the polyolefin resin composition as the adhesive layer, and a 5-layer film specimen consisting of an inner layer with a thickness of 360 μm, an adhesive layer with a thickness of 20 μm, a barrier layer with a thickness of 40 μm, an adhesive layer with a thickness of 20 μm, and an outer layer with a thickness of 360 μm is manufactured using a co-extrusion multilayer film molding machine, the specimen is cut to a length of 100 mm and a width of 15 mm, and stored in a hot air oven at 150°C for 30 minutes, and then the adhesive strength (peel strength) measured by peeling the barrier layer and the adhesive layer at a speed of 50 mm / min according to ASTM D1876 (T-Peel test) may be about 2 to about 4 kgf / 15 mm, for example, about 2.5 to about 3.5 kgf / 15 mm.

[0086] In a specific example, the polyolefin resin composition uses polypropylene resin for the outer and inner layers, uses an ethylene-vinyl alcohol copolymer for the barrier layer, and uses the polyolefin resin composition for the adhesive layer; a five-layer film specimen is manufactured using a co-extrusion multilayer film forming machine, comprising an inner layer with a thickness of 360 μm, an adhesive layer with a thickness of 20 μm, a barrier layer with a thickness of 40 μm, an adhesive layer with a thickness of 20 μm, and an outer layer with a thickness of 360 μm; the specimen is cut to a length of 100 mm and a width of 15 mm, placed in a 1,000 W microwave oven, and exposed to microwaves for 1 minute and 30 seconds; and then, according to ASTM D1876 (T-Peel test), the barrier layer and the adhesive layer are peeled off at a speed of 50 mm / min, and the adhesive strength (peel strength) measured is approximately 2 to approximately 4 kgf / 15 mm, for example, approximately It can be 2.6 to about 3.5 kgf / 15 mm.

[0087] In a specific example, the polyolefin resin composition may have a melt flow index of about 0.1 to about 15 g / 10 min, for example, about 1 to about 10 g / 10 min, measured at 230°C and 2.16 kg in accordance with ASTM D1238.

[0088]

[0089] The molded article according to the present invention is formed from the polyolefin resin composition. The polyolefin resin composition may be manufactured in the form of pellets, and the manufactured pellets may be manufactured into various molded articles (products) through various molding methods such as film molding, injection molding, extrusion molding, vacuum molding, and casting molding. Such molding methods are well known to those skilled in the art to which the present invention belongs. The molded article has excellent adhesion strength to a polar substrate, adhesion strength to a polar substrate after high-temperature thermal history of 100°C or higher using a hot air oven, microwave oven, etc., and moldability, and is useful as an adhesive film or sheet for adhesion to a polar substrate.

[0090]

[0091] The present invention is to be explained more specifically through the following examples, but these examples are for illustrative purposes only and should not be interpreted as limiting the invention.

[0092]

[0093] Examples

[0094] The specifications of each component used in the examples and comparative examples below are as follows.

[0095] (A) Random polypropylene resin (propylene-ethylene random copolymer, manufacturer: Lotte Chemical, propylene-derived component content: approx. 97.2 mol%, ethylene-derived component content: approx. 2.8 mol%, melt flow index (230℃ / 2.16 kg): approx. 1.8 g / 10 min) was used.

[0096] (B) A propylene-ethylene-1-butene random copolymer (manufacturer: Lotte Chemical, propylene-derived component content: approximately 92 mol%, ethylene-derived component content: approximately 3.5 mol%, 1-butene-derived component content: approximately 4.5 mol%, melt flow index (230℃ / 2.16 kg): approximately 7 g / 10 min) was used.

[0097] (C) Ethylene-propylene elastomer

[0098] Ethylene-propylene elastomer (ethylene-derived component content: about 75 wt%, melt flow index (190℃ / 2.16 kg): about 1 g / 10 min) was used.

[0099] (D) Propylene-ethylene elastomer

[0100] Propylene-ethylene elastomer (propylene-derived component content: about 91 wt%, melt flow index (230℃ / 2.16 kg): about 8 g / 10 min) was used.

[0101] (E) Maleic anhydride grafted polypropylene

[0102] Maleic anhydride grafted polypropylene (content of maleic anhydride-derived components: approx. 1.2 wt%, weight-average molecular weight: approx. 66,200 g / mol, density: approx. 0.90 g / cm³ 3 ) was used.

[0103] (F) Homopolypropylene resin (isotactic homopolypropylene, manufacturer: Lotte Chemical, melt flow index (230℃ / 2.16 kg): approximately 12 g / 10 min) was used.

[0104] (G) Polyethylene resin

[0105] Low-density polyethylene (LDPE, manufacturer: Lotte Chemical, melt flow index (190℃ / 2.16 kg): approximately 7 g / 10 min) was used.

[0106]

[0107] Examples 1 to 5 and Comparative Examples 1 to 5

[0108] After adding each of the above components in the amounts listed in Tables 1 and 2 below, pellets were prepared by extrusion at approximately 190°C. A twin-screw extruder with L / D=40 and a diameter of 19 mm was used for extrusion. The prepared pellets were dried at approximately 80°C for at least 2 hours, and then specimens were prepared using a film forming machine. The physical properties of the prepared specimens were evaluated by the following method, and the results are shown in Tables 1 and 2 below.

[0109]

[0110] Methods for measuring physical properties

[0111] (1) Evaluation of adhesion strength to a polar substrate (aluminum): 2 g of the polyolefin resin composition was placed between aluminum sheets 200 μm thick, and the temperature was 190°C and the pressure was 100 kgf / cm² 2 After preparing a specimen with a length of 100 mm and a width of 20 mm by heating and pressing for 60 seconds under conditions, the adhesive strength (peel strength, unit: kgf / 20 mm) was measured by peeling the aluminum sheet layer and the polyolefin resin composition layer at a speed of 100 mm / min using a universal testing machine (UTM, manufacturer: ZwickRoell, device name: Z020) in accordance with ASTM D1876 (T-Peel test).

[0112] (2) Evaluation of adhesion strength on a polar substrate (ethylene-vinyl alcohol copolymer): Polypropylene resin (Manufacturer: Lotte Chemical, Product Name: B-310) was used as the outer and inner layers, ethylene-vinyl alcohol copolymer (melt flow index (230℃ / 2.16 kg): approx. 4.1 g / 10 min) was used as the barrier layer, and the above polyolefin resin composition was used as the adhesive layer. A 5-layer film specimen consisting of an inner layer 360 μm thick, an adhesive layer 20 μm thick, a barrier layer 40 μm thick, an adhesive layer 20 μm thick, and an outer layer 360 μm thick was manufactured using a co-extrusion multilayer film forming machine. After cutting the specimen to a length of 100 mm and a width of 15 mm, a universal testing machine (UTM, Manufacturer: ZwickRoell, Device Name: Z020) was used in accordance with ASTM D1876 (T-Peel test). The adhesive strength (peel strength, unit: kgf / 15 mm) was measured while peeling the barrier layer and the adhesive layer at a speed of 50 mm / min.

[0113] (3) Evaluation of adhesion strength on a polar substrate (ethylene-vinyl alcohol copolymer) after high-temperature thermal history using a hot air oven: Polypropylene resin (Manufacturer: Lotte Chemical, Product Name: B-310) was used as the outer and inner layers, ethylene-vinyl alcohol copolymer (melt flow index (230℃ / 2.16 kg): approx. 4.1 g / 10 min) was used as the barrier layer, and the above polyolefin resin composition was used as the adhesive layer. A 5-layer film specimen consisting of an inner layer 360 μm thick, an adhesive layer 20 μm thick, a barrier layer 40 μm thick, an adhesive layer 20 μm thick, and an outer layer 360 μm thick was manufactured using a co-extrusion multilayer film forming machine. The specimen was cut to a length of 100 mm and a width of 15 mm, stored in a hot air oven at 150℃ for 30 minutes, and then tested against ASTM D1876 (T-Peel test). Based on this, the adhesive strength (peel strength, unit: kgf / 15 mm) was measured by peeling the barrier layer and the adhesive layer at a speed of 50 mm / min using a universal testing machine (UTM, manufacturer: ZwickRoell, device name: Z020).

[0114] (4) Evaluation of adhesion strength on a polar substrate (ethylene-vinyl alcohol copolymer) after high-temperature thermal history using a microwave oven: Polypropylene resin (Manufacturer: Lotte Chemical, Product Name: B-310) was used as the outer and inner layers, ethylene-vinyl alcohol copolymer (melt flow index (230℃ / 2.16 kg): approx. 4.1 g / 10 min) was used as the barrier layer, and the above polyolefin resin composition was used as the adhesive layer; a 5-layer film specimen consisting of an inner layer 360 μm thick, an adhesive layer 20 μm thick, a barrier layer 40 μm thick, an adhesive layer 20 μm thick, and an outer layer 360 μm thick was manufactured using a co-extrusion multilayer film forming machine; the specimen was cut to a length of 100 mm and a width of 15 mm, placed in a 1,000 W microwave oven, and exposed to microwaves for 1 minute and 30 seconds, after which ASTM Based on D1876 (T-Peel test), the adhesive strength (peel strength, unit: kgf / 15 mm) was measured by peeling the barrier layer and the adhesive layer at a speed of 50 mm / min using a universal testing machine (UTM, manufacturer: ZwickRoell, device name: Z020).

[0115] (5) Evaluation of moldability: The melt flow index (unit: g / 10 min) of the pellet sample was measured according to ASTM D1238 at 230°C and 2.16 kg.

[0116]

[0117] Example 1 2345(A) (WH) 4645444544(B) (WH) 2625202520(C) (WH) 88888(D) (WH) 1212151212(E) (WH) 85555(F) (WH) -5--3(G) (WH) --858 Adhesion strength to aluminum (kgf / 20 mm) 9.3 8.9 9.1 8.6 9.5 Adhesion strength to ethylene-vinyl alcohol copolymer (kgf / 15 mm) 3.2 2.9 3.1 2.8 3.2 Adhesion strength after thermal hysteresis (kgf / 15 mm, hot air oven) 3.0 2.9 2.9 2.7 3.3 Adhesion strength after thermal hysteresis (kgf / 15 mm, microwave oven) 3.2 3.0 3.0 2.8 3.3 Melt flow index (g / 10 min)3.43.74.53.03.1

[0118]

[0119] Comparative Example 1 2345(A) (WH) 3065444664(B) (WH) 42720260(C) (WH) 880.5178(D) (WH) 121227.5315(E) (WH) 88885(F) (WH) -----(G) (WH) ----8 Adhesion strength to aluminum (kgf / 20 mm) 9.5 6.8 6.5 7.5 7.9 Adhesion strength to ethylene-vinyl alcohol copolymer (kgf / 15 mm) 3.4 2.1 1.9 2.3 2.1 Adhesion strength after thermal hysteresis (kgf / 15 mm, hot air oven) 1.8 1.4 1.1 1.7 1.3 Adhesion strength after thermal hysteresis (kgf / 15 mm, microwave oven) 1.6 1.3 1.1 1.6 1.4 Melt flow index (g / 10 min)3.6 2.9 3.1 2.7 2.8

[0120]

[0121] From the above results, it can be seen that the polyolefin resin composition of the present invention has excellent adhesion strength to polar substrates (aluminum, ethylene-vinyl alcohol copolymer, etc.), adhesion strength to polar substrates after high-temperature thermal history (using a hot air oven, microwave oven, etc.), and moldability (melt flow index).

[0122] On the other hand, in Comparative Example 1, in which a small amount of random polypropylene resin was applied and an excess amount of propylene-ethylene-1-butene copolymer was applied, it can be seen that the adhesive strength to the polar substrate after high-temperature thermal history is reduced, and in Comparative Example 2, in which an excess amount of random polypropylene resin was applied and a small amount of propylene-ethylene-1-butene copolymer was applied, it can be seen that the adhesive strength to the polar substrate and the adhesive strength to the polar substrate after high-temperature thermal history are reduced. In Comparative Example 3, in which a small amount of ethylene-propylene elastomer is applied and an excess amount of propylene-ethylene elastomer is applied, it can be seen that the adhesion strength to the polar substrate and the adhesion strength to the polar substrate after high-temperature thermal history are reduced. In Comparative Example 4, in which an excess amount of ethylene-propylene elastomer is applied and a small amount of propylene-ethylene elastomer is applied, it can be seen that the adhesion strength to the polar substrate and the adhesion strength to the polar substrate after high-temperature thermal history are reduced. Additionally, in Comparative Example 5, in which an excess amount of random polypropylene resin is applied and a propylene-ethylene-1-butene random copolymer is not applied, it can be seen that the adhesion strength to the polar substrate and the adhesion strength to the polar substrate after high-temperature thermal history are reduced.

[0123]

[0124] The present invention has been described above with reference to embodiments. Those skilled in the art will understand that the present invention may be embodied in modified forms without departing from the essential characteristics of the invention. Therefore, the disclosed embodiments should be considered in an illustrative rather than a restrictive sense. The scope of the invention is defined by the claims, not by the foregoing description, and all variations within the scope of equivalents should be interpreted as being included in the invention.

Claims

1. Random polypropylene resin about 35 to about 55 weight%; Propylene-ethylene-1-butene copolymer about 10 to about 35 weight%; About 1 to about 15 weight% of ethylene-propylene elastomer; Propylene-ethylene elastomer about 5 to about 25 weight%; and A polyolefin resin composition characterized by comprising about 1 to about 15 weight% of maleic anhydride grafted polypropylene.

2. A polyolefin resin composition according to claim 1, wherein the random polypropylene resin is a propylene-ethylene random copolymer having a propylene-derived component content of about 90 to about 99 mol% and an ethylene-derived component content of about 1 to about 10 mol%, and has a melt flow index of about 0.1 to about 4.5 g / 10 min measured at 230°C and 2.16 kg in accordance with ASTM D1238.

3. A polyolefin resin composition according to claim 1 or 2, wherein the propylene-ethylene-1-butene copolymer is a random copolymer having a propylene-derived component content of about 85 to about 98 mol%, an ethylene-derived component content of about 1 to about 7 mol%, and a 1-butene-derived component content of about 1 to about 8 mol%, and a melt flow index of about 0.1 to about 20 g / 10 min measured at 230°C and 2.16 kg in accordance with ASTM D1238.

4. A polyolefin resin composition characterized in that, in any one of claims 1 to 3, the weight ratio of the random polypropylene resin and the propylene-ethylene-1-butene copolymer is about 1:0.2 to about 1:0.

7.

5. A polyolefin resin composition according to any one of claims 1 to 4, wherein the ethylene-propylene elastomer has an ethylene-derived component content of about 65 to about 85 weight% and a propylene-derived component content of about 15 to about 35 weight%, and a melt flow index of about 0.1 to about 3 g / 10 min measured at 190°C and 2.16 kg in accordance with ASTM D1238.

6. A polyolefin resin composition according to any one of claims 1 to 5, wherein the propylene-ethylene elastomer has a propylene-derived component content of about 75 to about 95 weight% and an ethylene-derived component content of about 5 to about 25 weight%, and a melt flow index of about 5 to about 15 g / 10 min measured at 230°C and 2.16 kg in accordance with ASTM D1238.

7. A polyolefin resin composition according to any one of claims 1 to 6, wherein the maleic anhydride grafted polypropylene has a maleic anhydride-derived component content of about 0.5 to about 5 weight%.

8. A polyolefin resin composition according to any one of claims 1 to 7, characterized in that the polyolefin resin composition further comprises about 0.5 to about 10 weight percent of homopolypropylene resin.

9. A polyolefin resin composition according to any one of claims 1 to 8, characterized in that the polyolefin resin composition further comprises about 1 to about 15 weight percent of polyethylene resin.

10. In any one of claims 1 to 9, the polyolefin resin composition is prepared by placing 2 g of the polyolefin resin composition between aluminum sheets with a thickness of 200 μm, at a temperature of 190°C and a pressure of 100 kgf / cm² 2 A polyolefin resin composition characterized by an adhesive strength (peel strength) of about 8 to about 10 kgf / 20 mm, measured by preparing a specimen of 100 mm in length and 20 mm in width by heat pressing for 60 seconds under conditions, and then peeling an aluminum sheet layer and a polyolefin resin composition layer at a speed of 100 mm / min according to ASTM D1876 (T-Peel test).

11. A polyolefin resin composition according to any one of claims 1 to 10, wherein the polyolefin resin composition uses polypropylene resin as the outer layer and inner layer, uses an ethylene-vinyl alcohol copolymer as the barrier layer, and uses the polyolefin resin composition as the adhesive layer, and a 5-layer film specimen composed of an inner layer with a thickness of 360 μm, an adhesive layer with a thickness of 20 μm, a barrier layer with a thickness of 40 μm, an adhesive layer with a thickness of 20 μm, and an outer layer with a thickness of 360 μm is manufactured using a co-extrusion multilayer film molding machine, and the specimen is cut to a length of 100 mm and a width of 15 mm, and the adhesive strength (peel strength) measured by peeling the barrier layer and the adhesive layer at a speed of 50 mm / min according to ASTM D1876 (T-Peel test) is about 2.5 to about 4 kgf / 15 mm.

12. A polyolefin resin composition according to any one of claims 1 to 11, wherein the polyolefin resin composition uses polypropylene resin as the outer and inner layers, uses an ethylene-vinyl alcohol copolymer as the barrier layer, and uses the polyolefin resin composition as the adhesive layer, and a 5-layer film specimen composed of an inner layer with a thickness of 360 μm, an adhesive layer with a thickness of 20 μm, a barrier layer with a thickness of 40 μm, an adhesive layer with a thickness of 20 μm, and an outer layer with a thickness of 360 μm is manufactured using a co-extrusion multilayer film molding machine, the specimen is cut to a length of 100 mm and a width of 15 mm, stored in a hot air oven at 150°C for 30 minutes, and then the adhesive strength (peel strength) measured by peeling the barrier layer and the adhesive layer at a speed of 50 mm / min according to ASTM D1876 (T-Peel test) is about 2 to about 4 kgf / 15 mm.

13. In any one of claims 1 to 12, the polyolefin resin composition uses polypropylene resin for the outer and inner layers, uses an ethylene-vinyl alcohol copolymer for the barrier layer, and uses the polyolefin resin composition for the adhesive layer; a five-layer film specimen is manufactured using a co-extrusion multilayer film forming machine, comprising an inner layer 360 μm thick, an adhesive layer 20 μm thick, a barrier layer 40 μm thick, an adhesive layer 20 μm thick, and an outer layer 360 μm thick; the specimen is cut to a length of 100 mm and a width of 15 mm, placed in a 1,000 W microwave oven, and exposed to microwaves for 1 minute and 30 seconds; and then, according to ASTM D1876 (T-Peel test), the barrier layer and the adhesive layer are peeled off at a speed of 50 mm / min, and the adhesive strength (peel strength) measured is approximately 2 to approximately 4 kgf / 15 Polyolefin resin composition characterized by being mm.

14. A polyolefin resin composition according to any one of claims 1 to 13, wherein the polyolefin resin composition has a melt flow index of about 0.1 to about 15 g / 10 min as measured at 230°C and 2.16 kg in accordance with ASTM D1238.

15. A molded article characterized by being formed from a polyolefin resin composition according to any one of claims 1 to 14.