Patent Application
20250178310
The present application claims priority under 35 U.S.C. § 119(a) to Korean patent application number 10-2023-0171124 filed on Nov. 30, 2023, the entire disclosure of which is incorporated by reference herein.
The embodiments of the present disclosure generally relate to a biodegradable resin composition and a film formed from the biodegradable resin composition.
Metal or a synthetic resin is applied to various industrial materials such as a disposable product and a packaging material, etc. For example, a plastic film formed from a metal foil or a synthetic resin may be used as the packaging material. However, the metal foil has no recyclability. Also, plastic films which are made from non-degradable resins which do not decompose naturally. Hence, disposing such type of plastic films releases harmful substances into the environment.
Recently, biodegradable resins have been proposed as a substitute for non-degradable resins. The biodegradable resin is a resin that can be decomposed naturally by natural organic organisms such as bacteria and microorganisms, etc. In recent years, as environmental issues due to the non-degradable resin have increased, demand for biodegradable resins is increasing.
For example, biodegradable resins may be utilized in various industrial fields such as a packaging material industry, electronic product industry, automobile industry, building material industry, marine industry, stationery industry, pulp and paper industry, etc.
A biodegradable resin generally has higher biodegradability than a synthetic resin, but flexibility, mechanical properties, workability, and gas barrier properties of films formed from the biodegradable resin may be lower than those made with a synthetic resin. Therefore, it is necessary to develop a biodegradable resin having improved gas barrier properties, durability, and film workability, while improving biodegradability.
An embodiment of the present disclosure provides a biodegradable resin composition capable of providing improved biodegradability and barrier properties.
In addition, another embodiment of the present disclosure provides a biodegradable film having improved biodegradability and barrier properties.
Further, another embodiment of the present disclosure provides a multilayer barrier film having improved biodegradability and barrier properties.
According to embodiments of the present disclosure, there is provided a biodegradable resin composition including: thermoplastic starch (TPS); a biodegradable polymer having a melt flow index of greater than 30 g/10 min under conditions of 19° C. and a load of 2.16 kg, and a plasticizer, wherein a content of the biodegradable polymer is 30% by weight or less based on a total weight of the biodegradable resin composition, and the melt flow index measured under conditions of 190° C. and a load of 2.16 kg is 2.5 g/10 min to 20 g/10 min.
In some embodiments, the biodegradable polymer may include an aliphatic polyester resin.
In an embodiment, the biodegradable polymer may include polybutylene adipate terephthalate (PBAT).
In some embodiments, the content of the biodegradable polymer may be 10% by weight to 30% by weight based on the total weight of the biodegradable resin composition.
In some embodiments, the melt flow index of the biodegradable polymer measured under conditions of 190° C. and a load of 2.16 kg may be greater than 30 g/10 min and 75 g/10 min or less.
In some embodiments, a content of the plasticizer may be less than 20% by weight based on the total weight of the biodegradable resin composition.
In an embodiment, the content of the plasticizer may be 1% by weight to 10% by weight based on the total weight of the biodegradable resin composition.
In some embodiments, the plasticizer may include a first plasticizer including a dihydric alcohol or a trihydric alcohol, and a second plasticizer including a tetrahydric or higher polyhydric alcohol.
In an embodiment, a content of the second plasticizer may be greater than a content of the first plasticizer based on the weight.
In some embodiments, a content of the thermoplastic starch may be 50% by weight or more based on the total weight of the biodegradable resin composition.
In an embodiment, the content of the thermoplastic starch may be 50% by weight to 90% by weight based on the total weight of the biodegradable resin composition.
In some embodiments, a ratio of the content of the thermoplastic starch to the content of the biodegradable polymer may be 2 or more based on weight.
In addition, there is provided a biodegradable film formed from the biodegradable resin composition according to the above-described embodiments.
In some embodiments, the biodegradable film may have an oxygen gas permeability of 50 g/m2·day or less, which is measured under conditions of a relative humidity of 0% and a temperature of 25° C. at a thickness of 100 μm to 200 μm
Further, there is provided a multilayer barrier film including a first resin layer, a barrier layer disposed on the first resin layer, and formed from the biodegradable resin composition according to the above-described embodiments; and a second resin layer disposed on the barrier layer.
In some embodiments, each of the first resin layer and the second resin layer may have a lower water vapor transmission rate than the barrier layer.
In some embodiments, each of the first resin layer and the second resin layer may include a polyolefin polymer or a polyester polymer.
The biodegradable resin composition according to exemplary embodiments includes thermoplastic starch and a biodegradable polymer. Thereby, the biodegradability and gas barrier properties of a film formed from the biodegradable resin composition may be improved.
The biodegradable polymer may have a melt flow index within a predetermined range. Thereby, workability of the film of the biodegradable resin composition may be improved. The biodegradable polymer may include a polyester resin. Thus, the moldability, workability, and productivity may be improved, while further increasing gas barrier properties of the biodegradable film.
The melt flow index of the biodegradable resin composition may be adjusted within a predetermined range. Accordingly, the workability of the film may be improved while improving the mechanical properties.
The above and other objects, features and other advantages of the embodiments of the present disclosure will be more clearly understood from the following detailed description taken in conjunction with the accompanying drawing, in which:
According to embodiments of the present disclosure, a biodegradable resin composition including thermoplastic starch and a biodegradable polymer is provided. In addition, a multilayer barrier film including a biodegradable film formed from the biodegradable resin composition and a barrier layer formed from the biodegradable resin composition are provided.
The terms “first,” “second,” “upper surface,” “lower surface,” etc. as used herein indicate relative positions of each component and do not mean an absolute upper-lower relationship therebetween.
The term “biodegradability” as used herein may mean that a substance is decomposed by natural organic organisms such as bacteria, germs, and microorganisms, etc., or natural environmental factors such as heat, moisture, and sunlight, etc. For example, the biodegradability may refer to biodegradability certified according to ISO 14851 or ISO 14855 standards.
Hereinafter, a biodegradable resin composition according to embodiments of the present disclosure will be described in detail. However, the embodiments are merely illustrative and the present disclosure is not limited to the specific embodiments described by way of example.
The biodegradable resin composition may include thermoplastic starch (TPS). The thermoplastic starch may refer to a starch-derived compound having thermoplasticity.
The biodegradable resin composition may include thermoplastic starch, thereby improving biodegradability and enhancing workability and moldability into a film. For example, when the resin composition includes starch with no thermoplasticity, film processing and molding may be substantially impossible.
In an embodiment, thermoplastic starch may be prepared by adding a polar compound as a plasticizer to starch derived from plants such as wheat, rice, corn, potato, sweet potato, cassava, tapioca, etc., and performing physical or chemical treatment thereon. For example, a mixture of starch and the polar compound may be kneaded while applying a predetermined shear pressure to transform the starch into thermoplastic starch.
In an embodiment, a polyhydric alcohol compound such as glycerol, sorbitol, ethylene glycol, or mannitol, etc. may be used as the polar compound. A content of the polar compound in a total weight of the mixture of starch and the polar compound may be 20% by weight (“wt %”) to 30 wt %. Within the above range, a melt flow index and biodegradability of the thermoplastic starch, and gas barrier properties of the film may be improved.
In an embodiment, the melt flow index (MFI), i.e., melt index (MI) of the thermoplastic starch may be greater than about 0 g/10 min and about 0.2 g/10 min or less. The melt flow index of the thermoplastic starch may be measured under conditions of 190° C. and a load of 2.16 kg. Within the above range, the gas barrier properties, workability, and mechanical properties of the thermoplastic resin composition may be further improved.
In addition, the thermoplastic starch has high miscibility with other resins. Therefore, dispersibility of the resin or polymer components in the biodegradable resin composition may be enhanced.
In some embodiments, a content of the thermoplastic starch may be 50 wt % or more based on a total weight of the biodegradable resin composition. The thermoplastic starch may be included in the biodegradable resin composition as a main component thereof, thereby improving the biodegradability and gas barrier properties of the film formed from the biodegradable resin composition.
In an embodiment, the content of the thermoplastic starch may be about 50 wt % to 98 wt %, 50 wt % to 90 wt %, 55 wt % to 85 wt %, or 60 wt % to 80 wt % based on the total weight of the biodegradable resin composition.
The biodegradable resin composition may include a biodegradable polymer. The biodegradable polymer may refer to a resin or polymer having biodegradability.
The melt flow index of the biodegradable polymer may be greater than 30 g/10 min. The melt flow index of the biodegradable polymer may be measured under conditions of 190° C. and a load of 2.16 kg.
The workability of the biodegradable resin composition may be improved by the biodegradable polymer having the melt flow index in the above range. For example, when the resin composition includes only thermoplastic starch or includes a biodegradable polymer having a melt flow index of 30 g/10 min or less, the melt flowability of the resin composition may be deteriorated. Accordingly, the moldability and mechanical properties of the film may be decreased.
According to exemplary embodiments, processing of the film may be facilitated while having a level of biodegradability that can be naturally degradable by the biodegradable polymer having a melt flow index of greater than 30 g/10 min.
In some embodiments, the melt flow index of the biodegradable polymer may be greater than about 30 g/10 min and about 75 g/10 min or less, greater than about 30 g/10 min and about 70 g/10 min or less, greater than about 30 g/10 min and about 60 g/10 min or less, or about 40 g/10 min to about 60 g/10 min. Within the above range, the workability and moldability of the biodegradable resin composition may be further improved without causing a decrease in the gas barrier properties and mechanical properties of the film.
The content of the biodegradable polymer may be 30 wt % or less based on the total weight of the biodegradable resin composition. Accordingly, the mechanical properties, gas barrier properties, and hygroscopicity of the film formed from the biodegradable resin composition may be further improved.
For example, when the content of the biodegradable polymer exceeds 30 wt %, the dispersibility between the biodegradable polymer and the thermoplastic starch may be decreased, and the melt flowability may be excessively increased, thereby decreasing the strength and durability of the film. In addition, the melt strength of the biodegradable resin composition may be excessively reduced, thereby decreasing the film moldability, and a microcrystal structure of the thermoplastic starch may be destroyed by the biodegradable polymer, thereby increasing gas permeability and hygroscopicity.
In some embodiments, the content of the biodegradable polymer may be about 1 wt % to about 30 wt %, about 10 wt % to about 30 wt %, or about 15 wt % to about 30 wt % based on the total weight of the biodegradable resin composition. Within the above range, the workability and moldability of the biodegradable resin composition may be improved, as well as the mechanical properties and barrier properties of the film may be further improved.
In some embodiments, a ratio of the content of the thermoplastic starch to the content of the biodegradable polymer may be 2 or more based on the weight, and about 2 to 10, or about 2 to 8. Within the above range, the melt flowability and workability of the thermoplastic resin composition may be improved, as well as the barrier properties of the film may be further improved. For example, as the content of the biodegradable polymer is increased, an inherent crystal structure of the thermoplastic starch may be destroyed, thereby increasing a penetration path of oxygen.
In some embodiments, the biodegradable polymer may include an aliphatic polyester resin. The term “aliphatic” as used herein may refer to a structure that does not include aromaticity such as a benzene ring, etc. When including an aliphatic polyester resin as the biodegradable polymer, the compatibility of the biodegradable polymer and thermoplastic starch may be further enhanced.
In some embodiments, the aliphatic polyester resin may include at least one of polybutylene adipate terephthalate (PBAT), polybutylenes succinate (PBS), polylactic acid (PLA), polyglycolic acid (PGA) and polycaprolactone (PCL).
In some embodiments, the biodegradable polymer may include polybutylene adipate terephthalate. The polybutylene adipate terephthalate has high affinity with the thermoplastic starch, such that the dispersibility and kneading uniformity of the biodegradable resin composition may be further improved. Accordingly, the film may be easily formed and processed, as well as the mechanical properties and barrier properties may be further improved.
The biodegradable resin composition may include a plasticizer. Thereby, the melt flowability of the biodegradable resin composition may be improved by the plasticizer, and the stiffness and brittleness of the film may be improved.
According to exemplary embodiments, a content of the plasticizer may be less than 20 wt %. Accordingly, the melt flowability of the biodegradable resin composition, the stiffness and brittleness of the film may be adjusted to an appropriate range, such that the workability and moldability may be improved.
For example, when the content of the plasticizer is 20 wt % or more, the plasticizer may move to the surface of the film and leach out of the film, and the mechanical properties and gas barrier properties may be decreased. In addition, the melt strength of the resin composition may be excessively reduced, thereby causing a decrease the moldability of the film, and an increase in the moisture absorbing properties of the film due to the polar plasticizer.
In some embodiments, the content of the plasticizer may be about 1 wt % or more and less than about 20 wt %, about 1 wt % to about 15 wt %, about 1 wt % to about 10 wt %, or about 5 wt % to about 10 wt % based on the total weight of the biodegradable resin composition.
In an embodiment, the content of the biodegradable polymer may be greater than the content of the plasticizer.
In some embodiments, the plasticizer may include a compound having a polar functional group. In an embodiment, the plasticizer may include a polyhydric alcohol compound.
The polyhydric alcohol compound may include a sugar compound such as glucose, sucrose, fructose, galactose, xylose, maltose, lactose, etc., a sugar alcohol compound such as erythritol, xylitol, malitol, mannitol, sorbitol, polyglycitol, glycerol, etc., a glycol compound such as ethylene glycol, propylene glycol, etc.
In some embodiments, the plasticizer may include a first plasticizer including a dihydric alcohol or a trihydric alcohol, and a second plasticizer including a tetrahydric or higher polyhydric alcohol. When including heterogeneous alcohols having the specific functional number together, a decrease in the mechanical properties and barrier properties of the film may be suppressed, as well as the melt flowability of the resin composition may be further improved.
For example, the first plasticizer may include ethylene glycol, propylene glycol, glycerol and the like. For example, the second plasticizer may include erythritol, xylitol, malitol, polyglycitol, sorbitol and the like.
In an embodiment, the content of the second plasticizer may be greater than the content of the first plasticizer. For example, a ratio of the content of the second plasticizer to the content of the first plasticizer may be greater than 1 and 10 or less, 2 to 5, or 3 to 5 based on the weight. Within the above range, the moldability, barrier properties, and strength of the film may be further enhanced.
The melt flow index of the biodegradable resin composition may be about 2.5 g/10 min to 20 g/10 min. The melt flow index of the biodegradable resin composition may be measured under conditions of 190° C. and a load of 2.16 kg.
When the melt flow index of the biodegradable resin composition is less than 2.5 g/10 min, the melt flow rate is low, such that the workability of the film may be decreased, a surface roughness of the film may be increased, and the film may be easily broken, thereby making it difficult to form a film having a desired shape. When the melt flow index of the biodegradable resin composition is greater than 20 g/10 min, the film may not be substantially formed, and even if the film is formed, the melt strength and mechanical properties of the film may be decreased.
In some embodiments, the melt flow index of the biodegradable resin composition may be about 3 g/10 min to 20 g/10 min, about 5 g/10 min to 16 g/10 min, or about 7 g/10 min to 15 g/10 min. Within the above range, the workability, moldability, flexibility, and strength of the film may be further improved.
In some embodiments, the biodegradable resin composition may further include other additives. For example, the additive may include antioxidants, thermal stabilizers, UV protectors, electrostatic endowing agents, antistatic agents, antiblocking agents, etc.
According to exemplary embodiments, the biodegradable resin composition may be formed by kneading thermoplastic starch, a biodegradable polymer and a plasticizer.
In some embodiments, the thermoplastic starch and the biodegradable polymer may be added into a hopper dryer and dried. The dried thermoplastic starch and biodegradable polymer may be dry kneaded along with the plasticizer.
The dry kneaded mixture may be added into an internal mixer and kneaded. A temperature of the internal mixer may be maintained at, for example, about 120° C. to about 200° C., about 130° C. to about 180° C., or about 150° C. to about 180° C.
A rotation speed of the internal mixer rotor may be, for example, about 30 rpm to 120 rpm, about 40 rpm to 100 rpm, or about 60 rpm to 90 rpm. The kneading process may be performed for about 5 to 20 minutes or about 5 to 15 minutes, for example.
The kneaded product may be collected to obtain the biodegradable resin composition.
In an embodiment, the kneading process may be performed through an extruder other than the internal mixer. For example, the thermoplastic starch, the biodegradable polymer, and the plasticizer may be added into a single-screw extruder or a twin-screw extruder, then melted and kneaded.
In an embodiment, an inlet temperature of the extruder may be about 100° C. to 160° C., or about 120° C. to 150° C. In an embodiment, a barrel temperature of the extruder may be about 120° C. to 200° C., or about 140° C. to 180° C. In an embodiment, an outlet temperature of the extruder may be about 120° C. to 200° C., or about 140° C. to 180° C.
In some embodiments, the inlet temperature of the extruder may be lower than the barrel temperature and the outlet temperature. In an embodiment, the inlet temperature of the extruder may be about 15° C. to 25° C. lower than the barrel temperature and the outlet temperature.
In an embodiment, the rotation speed of the extruder may be about 100 rpm to 300 rpm.
The kneaded product discharged from the outlet of the extruder is obtained and then added into a pelletizer where it is cut to obtain a biodegradable resin composition in the shape of pellets.
In an embodiment, the biodegradable resin composition may be processed/prepared by foaming-expansion molding, injection molding, compression molding, casting film molding process, inflation film molding process and the like.
biodegradable films according to embodiments of the present disclosure may be formed from the biodegradable resin composition.
In some embodiments, the biodegradable film may be manufactured by pressing the biodegradable resin composition. The biodegradable resin composition may be pressed through a press.
In an embodiment, the pressing temperature may be maintained at about 100° C. to about 200° C., about 120° C. to about 180° C., or about 130° C. to about 170° C.
In an embodiment, the biodegradable resin composition may be compressed at a pressure of 10 MPa to 30 MPa, 15 MPa to 25 MPa, or 18 MPa to 22 MPa for 1 minute to 3 minutes.
In some embodiments, the biodegradable resin composition may be extruded to manufacture a biodegradable film.
In an embodiment, the biodegradable resin composition may be dried at a temperature of 50° C. to 120° C. for 30 minutes to 5 hours. Accordingly, the workability of the biodegradable resin composition may be further improved.
The biodegradable resin composition may be added into the extruder and extruded. In an embodiment, the extruder may be the single-screw extruder or the twin-screw extruder.
In an embodiment, the melt extrusion temperature of the biodegradable resin composition may be about 120° C. to 200° C., about 130° C. to 180° C., or about 140° C. to 160° C. In an embodiment, the rotation speed of the extruder may be about 20 rpm to 80 rpm.
The molten material, i.e., molten resin discharged from the extruder may be cooled to manufacture a biodegradable film.
In an embodiment, the biodegradable resin composition melted in the extruder may be extruded from a t-die to a chill roll and cooled (for example, a casting film manufacturing method). In an embodiment, the biodegradable resin composition melted in the extruder may be cooled by contact with air through an air ring in a ring-shaped die (e.g., a spiral die, etc.) (e.g., a blown film manufacturing method).
In an embodiment, the biodegradable film may have a thickness of about 50 μm to 250 μm, about 100 μm to 200 μm, or about 120 μm to 180 μm. Within the above range, the gas permeability to the film may be sufficiently reduced.
In an embodiment, the biodegradable film may have an oxygen gas permeability of 50 g/m2·day or less, 30 g/m2·day or less, or 10 g/m2·day or less. For example, the oxygen gas permeability of the biodegradable film may be 0.1 g/m2·day to 10 g/m2·day. The oxygen gas permeability of the biodegradable film may be measured under a relative humidity condition of 0% and a temperature condition of 25° C. at a thickness of 100 μm to 200 μm.
Hereinafter, the embodiments of the present disclosure will be described in detail with reference to the drawing.
Referring to
The barrier layer 111 may be formed from the biodegradable resin composition according to the above-described embodiments. For example, the barrier layer 111 may be the above-described biodegradable film. Accordingly, the gas barrier property and biodegradability of the multilayer barrier film may be improved.
In some embodiments, the first resin layer 112 and the second resin layer 113 may have a lower water vapor transmission rate (WVTR) than the barrier layer 111. Therefore, the first resin layer 112 and the second resin layer 113 may substantially function as a moisture barrier layer, thereby suppressing deformation and damage of the barrier layer 111 due to moisture.
In some embodiments, the multilayer barrier film may have a water vapor transmission rate (WVTR) of 20 g/m2·day or less. For example, the water vapor transmission rate (WVTR) of the multilayer barrier film may be about 10 g/m2·day to 13 g/m2·day.
In some embodiments, the first resin layer 112 and the second resin layer 113 may have a higher strength than the barrier layer 111. Therefore, the impact resistance and mechanical properties of the multilayer barrier film may be further improved.
In some embodiments, the first resin layer 112 and the second resin layer 113 may include a polyolefin resin or a polyester resin.
The polyolefin resin may include polyethylene or polypropylene. The polyethylene may include high-density polyethylene (HDPE), low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), medium-density polyethylene (MDPE), etc.
The polyester resin may include polybutylene adipate terephthalate, polylactic acid, polycaprolactone, polybutylene succinate, polyglycolic acid, etc.
In an embodiment, the first resin layer 112 and the second resin layer 113 may include low-density polyethylene. Accordingly, the water resistance, mechanical properties, and impact resistance of the multilayer barrier film may be further improved.
In an embodiment, the first resin layer 112 and the second resin layer 113 may include polybutylene adipate terephthalate. Accordingly, the multilayer barrier film may have complete biodegradability certified according to the ISO 14851 standard or the ISO 14855 standard, and may suppress deformation and decrease in the properties due to moisture.
In an embodiment, the first resin layer 112, the second resin layer 113 and the barrier layer 111 may be manufactured by the same method as the method for manufacturing the above-described biodegradable film. For example, the resin layers or the barrier layer 111 may be formed by pressing or extruding the resin composition.
In some embodiments, the first resin layer 112 and the second resin layer 113 may be laminated with the barrier layer 111 through adhesive layers. For example, a first adhesive layer 114 may be disposed between the first resin layer 112 and the barrier layer 111, and a second adhesive layer 115 may be disposed between the barrier layer 111 and the second resin layer 113.
In an embodiment, the number of laminated layers of the multilayer barrier film may be 3 or more, 5 or more, or 7 or more. For example, a laminated structure of the first resin layer, the multilayer barrier film, and the second resin layer may be repeatedly laminated to form the multilayer barrier film, or the multilayer barrier film may further include another resin layer.
The multilayer barrier film may be provided as a barrier film for packaging materials of various products, such as packaging materials for food packaging and packaging materials for battery packaging, for example.
Hereinafter, experimental examples including specific examples and comparative examples are proposed to facilitate understanding of the embodiments of the present disclosure. However, the following examples are only given for illustrating the embodiments and are not intended to limit the appended claims. It will be apparent to those skilled in the art that various alterations and modifications are possible within the scope and technical concepts of the present disclosure, and such alterations and modifications are duly included in the appended claims. Furthermore, the embodiments may be combined to from additional embodiments.
Thermoplastic starch (TPS) and a polymer were injected into an internal mixer (Brabender Measuring Mixer W50), with the types and contents described in Table 1 below. A kneaded product of about 73 wt % of tapioca starch and about 27 wt % of glycerol was used as the TPS. The melt flow index of TPS measured under conditions of 190° C. and a load of 2.16 kg according to ASTM D1238 was 0.1 g/10 min or less.
The mixture was kneaded for 10 minutes by setting the temperature of the internal mixer to 160° C. and the kneading speed to 80 rpm, then a resin composition of the kneaded product was collected.
The resin composition was placed in a press which was heated to 150° C., and pressed at about 20 MPa for 2 minutes to manufacture a film having a thickness of about 100 μm to 150 μm.
The film was mounted on an oxygen permeability meter (MOCON OX TRANS model 2/61) to measure an oxygen permeability. The oxygen permeability was measured at a point where the permeability is stabilized after measuring for 12 hours under a relative humidity condition of 0% and a temperature condition of 25° C. Measurement results are shown in Table 1 below.
The specific components of the compounds described in Table 1 above are as follows.
Referring to Table 1 above, in Samples No. 1, No. 2 and No. 3 including a biodegradable polymer (aliphatic ester resin) as a polymer mixed with thermoplastic starch, the film had a low oxygen permeability of 3.5 g/m2·day or less.
However, in Samples No. 4 to No. 8, a polyolefin-based copolymer was kneaded along with the thermoplastic starch, and the gas barrier property was greatly increased to 120 g/m2·day or more.
A resin composition and a film were manufactured in the same manner as in Experimental Example (1) by changing the contents of TPS and PBAT as shown in Table 2 below, and the oxygen permeability of the film was measured in the same manner as in Experimental Example (1). Measurement results are shown in Table 2 below.
Referring to Table 2 above, in the case of samples having a PBAT content greater than 30 wt %, the oxygen permeability of the film was increased to 27 g/m2·day or more. Referring to the samples, as the PBAT content of the resin composition was increased, the oxygen barrier property of the film was decreased.
Thermoplastic starch (TPS), PBAT, and a plasticizer were injected into an internal mixer (Brabander Measuring Mixer W50). The polymer types and contents used are described in the Table 3 below. A kneaded product of about 73 wt % of tapioca starch and about 27 wt % of glycerol was used as the TPS. The melt flow index of the TPS measured under conditions of 190° C. and a load of 2.16 kg according to ASTM D1238 was 0.1 g/10 min or less. The melt flow index of the PBAT was measured under conditions of 190° C. and a load of 2.16 kg according to ASTM D1238.
The mixture was kneaded for 10 minutes using the internal mixer. The temperature of the internal mixer was at 160° C. and the kneading speed was 80 rpm After 10 minutes of kneading the biodegradable resin composition of the kneaded product was collected and placed in a press set to a temperature of 150° C. and, pressed at about 20 MPa for 2 minutes to manufacture a biodegradable film having a thickness of about 100 μm to 200 μm.
The melt flow index (MFI) of the biodegradable resin composition was measured under a temperature condition of 190° C. and a load condition of 2.16 kg according to ASTM D1238.
The biodegradable film was mounted on an oxygen transmission rate meter (MOCON, OX TRANS model 2/61) to measure the oxygen permeability (OTR) of the film. The oxygen permeability was measured at a point where the permeability is stabilized after measuring for 12 hours under a relative humidity condition of 0% and a temperature condition of 25° C.
Measurement results are shown in Table 3 below.
The specific components of the compounds described in Table 3 are as follows.
Referring to Table 3 above, in the case of the examples, the melt flow index was adjusted to an appropriate range by including PBAT having a melt flow index greater than 30 g/10 min of the biodegradable resin composition, and the film had a low oxygen permeability.
In the case of Comparative Examples 1 to 6, the content of PBAT was greater than 30 wt %, and the oxygen permeability of the film was increased greatly to 27 g/m2·day or more.
In the case of Comparative Examples 7 to 10, the melt flow index of the biodegradable resin composition was less than 2.5 g/10 min, and the workability and moldability were decreased.
In the case of Comparative Example 11, the PBAT that was used had a melt flow index of less than 30 g/10 min, and the melt flow index of the biodegradable resin composition was less than 5 g/10 min. The melt flow index was significantly decreased compared to Examples 4 and 5 which included the same plasticizer and PBAT having a melt flow index of more than 30 g/10 min.
In the case of Comparative Examples 12 and 13, the melt flow index of the biodegradable resin composition was significantly increased to 27.7 g/10 min and 32.2 g/10 min, respectively.
Thermoplastic starch (TPS), PBAT, and a plasticizer were dry kneaded to prepare a sample of 6 kg. The material types and their contents are described in Table 4 below.
The dry kneaded sample was added into a co-rotating twin-screw extruder and kneaded. The length to diameter (L/D) ratio of the twin-screw extruder was about 45. The inlet temperature of the extruder was maintained at 130° C., and the temperatures of the barrel and outlet of the extruder were maintained at 150° C., respectively. The rotation speed of the extruder was adjusted within 100 rpm to 300 rpm.
The kneaded product discharged from the outlet of the extruder was transported to a cooling belt and to a pelletizer where it was cut to obtain a pelletized biodegradable resin composition.
The melt flow index (MFI) of the biodegradable resin composition was measured under a temperature condition of 190° C. and a load condition of 2.16 kg according to ASTM D1238.
The biodegradable resin composition was processed into a film in an inflation film processing machine. Specifically, the pellet-shaped biodegradable resin composition was added into the inflation film processing machine, and melt-extruded through an inflation die in an extrusion section. A circular die having a diameter of 50 nm was used as the inflation die. The temperature of the extrusion section was maintained at about 145° C., and the speed of the extrusion section was adjusted to 20 rpm to 80 rpm. The molten resin extruded from the extrusion section was discharged to a film manufacturing section, and the molten film discharged from the film manufacturing section was cooled by bubbling to manufacture a film. The bubble-up ratio (BUR) was adjusted to 2 to 4 so that the diameter of the molten film was 100 mm to 200 mm.
In the film manufacturing section, the cooled film was transported and wound into a roll shape using a nip roll and a winder roll. The speed of the nip roll was adjusted to 2 m/min to 6 m/min, the speed of the winder roll was adjusted to 3 m/min to 7 m/min, and the speed of the winder roll was set to be higher than the speed of the nip roll. The film was formed to have a thickness of about 100 μm to 200 μm.
The film was mounted on an oxygen permeability meter (MOCON, OX TRANS model 2/61) to measure an oxygen permeability (OTR). The oxygen permeability was measured at a point where the permeability is stabilized after measuring for 12 hours under a relative humidity condition of 0% and a temperature condition of 25° C.
The upper limit of the oxygen permeability measuring device is 1,200 g/m2·day, and when the oxygen permeability is greater than 1,200 g/m2·day, the oxygen permeability is indicated as ‘Over’ in Table 4.
Measurement results are shown in Table 4 below.
Referring to Table 4 above, in the case of Comparative Examples 14 and 15, the moldability of the film was decreased in the inflation processing method due to the low melt flowability of the biodegradable resin composition. Specifically, when forming bubbles by air injection, the film was tom, or the surface roughness of the film was increased, and thus the oxygen barrier property was decreased.
In the case of Examples 9 and 10, the biodegradable resin composition had a high melt flow index, and the film had a low oxygen permeability. The biodegradable resin compositions according to the examples had high film workability and moldability in both the pressing method (Examples 1 to 8) and the continuous film processing method (Examples 9 and 10).
A barrier layer was prepared using the biodegradable resin composition used in Example 9. Specifically, the pellet-shaped biodegradable resin composition was added into the inflation film processing machine, and melt-extruded using the inflation die in the extrusion section. A circular die having a diameter of 50 nm was used as the inflation die. The temperature of the extrusion section was maintained at about 145° C., and the speed of the extrusion section was adjusted to the speed shown in Table 6 below. The molten resin extruded from the extrusion section was discharged to the film manufacturing section, and the molten film discharged from the film manufacturing section was cooled by bubbling. The bubble-up ratio (BUR) was adjusted to 2 to 4 so that the diameter of the melt was 100 mm to 200 mm.
The cooled molten film was manufactured into a barrier layer using a nip roll and a winder roll in the film manufacturing section. The speed of the nip roll was adjusted to 2.9 m/min, and the speed of the winder roll was adjusted to 3 m/min to 4 m/min.
A first resin layer and a second resin layer were manufactured using the resins described in Table 5 below. The first resin layer and the second resin layer were manufactured in the same manner as the barrier layer manufacturing method, except that the resin composition, the temperature of the extrusion section, and the speed of the extrusion section were changed as shown in Table 5 below. The first resin layer, the barrier layer and the second resin layer were sequentially laminated to manufacture a multilayer barrier film. The total thickness of the multilayer barrier film was adjusted as shown in Table 5 below.
When manufacturing the barrier layer, the speed of the extrusion section was changed as shown in Table 6 below, and the barrier layer was adjusted to have the thickness shown in Table 6 below.
Each manufactured multilayer barrier film was mounted on an oxygen transmission rate measuring device (MOCON, OX TRANS model 2/61) to measure an oxygen permeability (OTR). The oxygen permeability was measured at a point where the permeability is stabilized after measuring for 12 hours under a relative humidity condition of 0% and a temperature condition of 25° C.
Measurement results are shown in Table 6 below.
Referring to Table 6 above, in Examples 11 and 12, the resin layers were disposed on upper and lower surfaces of the barrier layer, respectively, to manufacture a multilayer barrier film. The barrier layers of Examples 11 and 12 had a thinner thickness than the biodegradable film of Example 9, but the oxygen barrier property was further improved by the resin layer.
In the case of the multilayer barrier film of Example 11, the moisture permeability measured based on ASTM F1249 using a moisture permeability meter (MOCON, PERMATRAN_W 3/33 MA) under conditions of a temperature of 37.6° C. and a permeation area of 50 cm2 was about 10 g/m2·day to 13 g/m2·day. The resin layers are disposed on the upper and lower surfaces of the barrier layer, such that moisture permeability may be additionally suppressed.
Although the invention has been described with reference to specific embodiments it should be understood that many other embodiments and variations thereof may be envisioned by those with ordinary skill in the art of the invention without departing from the scope of the present disclosure.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10-2023-0171124 | Nov 2023 | KR | national |
