WO2007027027A1 - Biodegradable polyester composition having barrier property - Google Patents
Biodegradable polyester composition having barrier property Download PDFInfo
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- WO2007027027A1 WO2007027027A1 PCT/KR2006/003378 KR2006003378W WO2007027027A1 WO 2007027027 A1 WO2007027027 A1 WO 2007027027A1 KR 2006003378 W KR2006003378 W KR 2006003378W WO 2007027027 A1 WO2007027027 A1 WO 2007027027A1
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- barrier properties
- polyester resin
- biodegradable
- polylactic acid
- composition according
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/013—Fillers, pigments or reinforcing additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/346—Clay
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
- C08L101/16—Compositions of unspecified macromolecular compounds the macromolecular compounds being biodegradable
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
Abstract
Provided is a biodegradable polyester resin composition having barrier properties, comprising a nanocomposite of polylactic acid and layered clay in a biodegradable polyester resin. Articles manufactured from the biodegradable polyester resin composition of the present invention exhibit superior biodegradability, barrier properties and tear strength.
Description
Description
BIODEGRADABLE POLYESTER COMPOSITION HAVING
BARRIER PROPERTY
Technical Field
[1] The present invention relates to a biodegradable polyester resin composition having barrier properties, comprising a biodegradable polyester resin and a nanocomposite of polylactic acid and layered clay. Background Art
[2] Plastic is inexpensive and has excellent physical properties such as lightweightness and the like, and therefore is commonly and widely used as a packaging material which is indispensable for modern life. However, rush production of large numbers of plastic products throughout the world has increasingly raised environmental pollution concerns which are getting severe. As plastic materials for general packaging, polyethylene, polypropylene, polyethylene terephthalate and the like are predominantly used, but they may lead to the high risk of damage to incinerators, due to a high- calorific value upon combustion thereof. In addition, plastic products are highly recalcitrant to degradation even with landfill treatment, due to chemical and biological stability thereof, and consequently the residual wastes pose problems such as shortened life of landfill sites. In order to solve these problems, biodegradable plastic, which has a low heat value of combustion, is degradable in soil and is also capable of achieving the rapid waste landfill stabilization due to degradability thereof even under landfill treatment, has been developed and is widely used for various applications.
[3] Aliphatic polyester resins have been known to be biodegradable for a long period of time, but they have suffered from limitations in use thereof due to low crystallinity and low molecular weight which result in significantly low tear strength, tensile strength and elongation, as compared to general-purpose poly olefin resins. For example, aliphatic polyester films, which are composed of succinic acid, adipic acid or both of them and a diol component as main structural units, exhibit flexibility, high elongation and impact resistance and excellent heat sealability, and can thus be shaped in the form of bags. However, such aliphatic polyester films exhibit glass transition temperature and crystallization temperature lower than room temperature, due to structural characteristics of the backbone, and have significantly poor physical properties such as low tear strength and inferior barrier properties, as compared to general-purpose polyethylene resins.
[4] As an attempt to improve tear strength and mechanical properties of biodegradable aliphatic polyester resins, biodegradable polyester resin compositions are known in
which polylactic acid is added to biodegradable aliphatic polyester resins. European Patent Application No. 0 980 894 discloses significant improvement in mechanical properties and rupture resistance and flexibility of a film fabricated from a mixture of polylactic acid and polybutylene succinate in the presence of a biodegradable plasticizer.
[5] US Patent No. 5,883,199 discloses a binary mixture of polylactic acid and polyester, wherein the content of polylactic acid is in a range of 10 to 90% and polyester is present as a continuous or co-continuous phase.
[6] Korean Patent Application No. 2003-70009722 discloses a mixture of biodegradable polyesters comprising a polyhydroxy acid, polyester of the diacid/diol type and a polymer of polylactic acid. According to this patent, it is described that the use of the above polyester mixture can provide a biodegradable film having excellent transparency and biaxial strength.
[7] However, prior art conventional biodegradable polyester compositions suffer from limitations in applications thereof for food packaging that requires oxygen-barrier properties, or for agrochemical containers that require chemical-barrier properties.
[8] Meanwhile, when a nano-sized, layered clay is mixed with a polymer matrix to form a fully exfoliated, partially exfoliated, intercalated or partially intercalated nanocomposite, such characteristic morphology of the nanocomposite results in improved barrier properties. Thus, articles having improved barrier properties via the use of such a nanocomposite receive a great deal of attention.
[9] In the foregoing, the most important thing is to maintain certain morphology selected from the fully exfoliated, partially exfoliated, intercalated and partially intercalated forms of the nanocomposite even after completion of molding processes. Preferably, the fully exfoliated structure is advantageous to improve barrier properties. In particular, when it is desired to prepare a molded article from a composition of such a nanocomposite and a polymer matrix, the dispersed form of the nanocomposite in the polymer matrix is also important to improve barrier properties. Disclosure of Invention Technical Problem
[10] Therefore, the present invention has been made in view of the above problems, and it is an object of the present invention to provide a biodegradable polyester resin composition having barrier properties, which has excellent biodegradability, mechanical strength, oxygen-barrier properties, organic solvent-barrier properties and moisture-barrier properties as well as enables a nanocomposite to maintain exfoliated morphology thereof even after completion of molding processes, thereby being capable of manufacturing a biodegradable article having desired barrier properties which is
dispersed in a specific form in a polymer matrix. Technical Solution
[11] In accordance with an aspect of the present invention, the above and other objects can be accomplished by the provision of a biodegradable polyester resin composition having barrier properties, comprising a dry mixture of 1 to 60 parts by weight of a nanocomposite of polylactic acid and layered clay, based on 100 parts by weight of a biodegradable polyester resin composed of an aliphatic polyester resin and an aliphatic/aromatic polyester resin.
[12] In an embodiment of the present invention, the aliphatic polyester resin may be at least one selected from the group consisting of polycaprolactone, polylactic acid and diol/dicarboxylic acid-based aliphatic polyester.
[13] In another embodiment of the present invention, the diol/dicarboxylic acid-based aliphatic polyester may be a polycondensation product of a C -C diol with a C -C di- carboxylic acid.
[14] In a further embodiment of the present invention, the biodegradable aliphatic/ aromatic polyester may be at least one selected from polycondensation products of a C -C diol, dimethylterephthalate or dimethylisophthalate, and a C -C dicarboxylic acid.
[15] In a further embodiment of the present invention, the layered clay may be at least one selected from the group consisting of montmorillonite, bentonite, kaolinite, mica, hectorite, fluorohectorite, saponite, beidelite, nontronite, stevensite, vermiculite, hallosite, volkonskoite, suconite, magadite and kenyalite.
[16] In accordance with another aspect of the present invention, there is provided a biodegradable article having barrier properties, which is manufactured by molding the above-mentioned biodegradable polyester resin composition having barrier properties.
[17] In an embodiment of the present invention, the biodegradable article having barrier properties may be a pipe, container, sheet or film.
[18] In another embodiment of the present invention, the nanocomposites of polylactic acid and layered clay may be dispersed in the form of multiple lamellae in the biodegradable polyester resin, wherein 2 to 300 nanocomposites are present per unit length of resin (mm), and each lamella has a thickness of 0.001 to 200 D and an average aspect ratio of 10 to 1000. Brief Description of the Drawings
[19] FIGS. 1 and 2 are schematic views showing a cross-sectional shape of a biodegradable article having barrier properties, manufactured according to one embodiment of the present invention. FlG. 1: MD (Machine Direction) and FlG. 2: TD (Transverse Direction). Mode for the Invention
[20] Hereinafter, the present invention will be described in more detail.
[21] A biodegradable nanocomposite composition having barrier properties according to the present invention comprises a dry mixture of 1 to 60 parts by weight of a nanocomposite of polylactic acid and layered clay, relative to 100 parts by weight of a biodegradable polyester resin composed of an aliphatic polyester resin and an aliphatic/aromatic polyester resin. [22] The aliphatic polyester resin may be at least one selected from the group consisting of polycaprolactone, polylactic acid and diol/dicarboxylic acid-based aliphatic polyester. [23] The diol/dicarboxylic acid-based aliphatic polyester may be a polycondensation product of a C -C diol with a C -C dicarboxylic acid.
1 6 4 10
[24] The biodegradable aliphatic/aromatic polyester may be at least one selected from polycondensation products of a C -C diol, dimethylterephthalate or dimethylisophthalate and a C -C dicarboxylic acid.
[25] The diol that can be used in the present invention may include, for example ethylene glycol, 1,3-propanediol, 1,4-butanediol and 1,6-hexanediol, which may be used alone or in any combination thereof.
[26] The biodegradable nanocomposite having barrier properties according to the present invention can be prepared by mixing the layered clay with polylactic acid.
[27] In biodegradable nanocomposite having barrier properties, the weight ratio of polylactic acid : layered clay is in a range of 58.0 : 42.0 to 99.9 : 0.1, preferably 85.0 : 15.0 to 99.0 : 1.0. If the weight ratio of polylactic acid is less than 58.0, conglomeration of the layered clay occurs and therefore suitable dispersion thereof is not achieved. If the weight ratio of polylactic acid is higher than 99.9, improvement of barrier properties is undesirably insignificant.
[28] The layered clay is preferably organically modified, layered clay in which an organic modifying agent is intercalated into the interlayers of the clay. The content of the organic modifying agent in the layered clay is preferably in a range of 1 to 45% by weight. If the content of the organic modifying agent is less than 1% by weight, the compatibility between the layered clay and polyamide/polyolefin mixture is lowered. If the content of the organic modifying agent is higher than 45% by weight, it is not easy to intercalate chains of the resin having barrier properties into the interlayers of the clay.
[29] The layered clay is preferably at least one selected from the group consisting of montmorillonite, bentonite, kaolinite, mica, hectorite, fluorohectorite, saponite, beidelite, nontronite, stevensite, vermiculite, hallosite, volkonskoite, suconite, magadite and kenyalite, and the organic modifying agent is preferably an organic material containing a functional group selected from the group consisting of primary,
secondary, tertiary and quaternary ammonium, phosphonium, maleate, succinate, acrylate, benzylic hydrogens, oxazoline and distearyldimethyl ammonium.
[30] Upon preparing the biodegradable nanocomposite having barrier properties, additives such as a thermal stabilizer, a plasticizer and the like may be further added in addition to polylactic acid and layered clay.
[31] The biodegradable nanocomposite having barrier properties may be preferably included in an amount of 1 to 60 parts by weight, more preferably 3 to 40 parts by weight, relative to 100 parts by weight of the biodegradable polyester resin. If the content of the biodegradable nanocomposite is less than 1 part by weight, improvement of barrier properties and mechanical properties is insufficient. If the content of the biodegradable nanocomposite is higher than 60 parts by weight, processability is undesirably poor.
[32] When the layered clay in the nanocomposite having barrier properties is more finely exfoliated inside polylactic acid which is present as a discontinuous phase, superior barrier properties of the nanocomposite can be exerted. That is, the layered clay, which was finely exfoliated inside polylactic acid, forms a barrier film and therefore serves to improve barrier properties and mechanical properties of the nanocomposite itself, which ultimately also leads to improvement in barrier properties and mechanical properties of a molded article. As such, in the present invention, polylactic acid and layered clay are blended to disperse a nano-sized layered clay in polylactic acid, thereby maximizing a contact area between polymer chains and layered clay to prevent permeation of gas and liquid.
[33] Preparation of the composition of the present invention involves dry-blending which refers to simultaneous mixing of a pelletized biodegradable nanocomposite having barrier properties and a biodegradable polyester resin in a predetermined ratio using a pellet mixer.
[34] The biodegradable polyester resin composition having barrier properties may further include, if necessary, other additives such as a stabilizer, a slip agent, a dispersant, a filler, a coupling agent, an antioxidant, a UV stabilizer and the like.
[35] Examples of the stabilizer that can be used in the present invention may include trimethyl phosphate, triphenyl phosphate and the like. The stabilizer may be added in an amount of 0.1 to 5 parts by weight, relative to 100 parts by weight of the biodegradable polyester resin.
[36] The antioxidant that can be used in the present invention may include, for example
Irganox series, Ultranox series, and TEP series. The antioxidant may be added in an amount of 0.1 to 6 parts by weight, relative to 100 parts by weight of the biodegradable polyester resin.
[37] The UV stabilizer that can be used in the present invention may include, for
example hindered amine light stabilizers (abbreviated as HALS) which are added in an amount of 0.1 to 5 parts by weight, relative to 100 parts by weight of the biodegradable polyester resin.
[38] The slip agent that can be used in the present invention may include, for example calcium stearate, zinc stearate, PE wax, general wax and the like. The slip agent may be added in an amount of 0.1 to 10 parts by weight, relative to 100 parts by weight of the biodegradable polyester resin.
[39] The filler that can be used in the present invention may include, for example talc, calcium carbonate, limestone, titanium dioxide (TiO ), carbon black and the like. The filler may be added in an amount of 0.1 to 35 parts by weight, relative to 100 parts by weight of the biodegradable polyester resin.
[40] The dispersant that can be used in the present invention may include, for example carboxylated polyethylene, phthalic acid, stearic acid and the like. The dispersant may be added in an amount of 0.1 to 10 parts by weight, relative to 100 parts by weight of the biodegradable polyester resin.
[41] The thus dry-blended, pelletized biodegradable polyester resin composition having barrier properties is melt-mixed in a molding machine, and is then molded while maintaining a structure thereof capable of exerting barrier properties, thereby obtaining a biodegradable article having barrier properties according to the present invention. That is, the biodegradable article having barrier properties, which was molded from the biodegradable polyester resin composition having barrier properties according to the present invention, is characterized in that at least one morphology of fully exfoliated, partially exfoliated, intercalated and partially intercalated structures of the nanocomposite having barrier properties is maintained intact even after being molded.
[42] In connection with the biodegradable article having barrier properties, the dispersed form of the nanocomposite having barrier properties in the biodegradable polyester resin matrix is particularly important to improve barrier properties. Specifically, the nanocomposite having barrier properties takes a multiple lamellar structure which in turn lengthens permeation paths of gases and organic solvents, thereby decreasing a permeation rate thereof and consequently highly improving barrier properties.
[43] The structure of the biodegradable article having barrier properties according to the present invention is schematically shown in FIGS. 1 and 2. FIGS. 1 and 2 are schematic cross-sectional views of the biodegradable article having barrier properties which was manufactured by melting and molding the nanocomposite having barrier properties in an extruder, wherein the biodegradable nanocomposite having barrier properties (2) takes a multiple lamellar structure in a polyester continuous phase (1).
[44] FIG. 1 : Cross-sectional view of the article as viewed from MD (Machine Direction)
and FlG. 2: Cross-sectional view of the article as viewed from TD (Transverse Direction).
[45] In the biodegradable article having barrier properties according to the present invention, the polylactic acid nanocomposite dispersed in the biodegradable polyester matrix resin takes a multiple lamellar structure, wherein 2 to 300 nanocomposites are present per mm of resin (unit length), each lamella has a thickness of 0.001 to 200 D and an average aspect ratio (Φn) of 10 to 1000. Herein, the average aspect ratio (Φn) is a value calculated from the observed unit length (1 mm) region, using the following equation:
[46] Φn=ΣNiΦi/ΣNi
[47] wherein Ni represents the number of dispersed lamellae to be observed and Φi represents an aspect ratio of individual lamellae to be observed.
[48] For manufacturing the biodegradable article having barrier properties according to the present invention, the polylactic acid nanocomposite is prepared by performing plasticizing and kneading processes at a temperature higher than a melting point, using appropriate equipment such as a single-screw extruder, co-rotating twin-screw extruder, counter-rotating twin-screw extruder, continuous kneader, planetary gear extruder or batch kneader. Manufacturing of the biodegradable article having barrier properties from the thus-prepared polylactic acid nanocomposite and biodegradable polyester resin may be carried out using conventional molding methods known in the art, such as blow molding, extrusion molding, pressure forming and injection molding. Examples of the molded articles having barrier properties, manufactured by the above method, may include pipes, containers, sheets and films.
[49] The biodegradable article having barrier properties according to the present invention forms a multi-layered barrier film via alignment of the layered clay in the biodegradable nanocomposite having barrier properties during molding processes, thereby further improving barrier properties of the molded article.
[50]
[51] EXAMPLES
[52] Now, the present invention will be described in more detail with reference to the following examples. These examples are provided only for illustrating the present invention and should not be construed as limiting the scope and spirit of the present invention.
[53] Materials
[54] The materials used in the following examples are as follows:
[55] - Aliphatic/aromatic polyester: EnPoI G8000 (IRe Chemical Ltd, Korea)
[56] - Aliphatic polyester: EnPoI G4600 (IRe Chemical Ltd, Korea)
[57] - Polylactic acid: LACTY 9030 (Shimadzu Corporation, Japan)
[58] - Thermal stabilizer/Coupling agent: IR 1010 (Songwon Industrial Co., Ltd.,
Korea)
[59]
[60] [Preparative Example 1] Preparation of polylactic acid nanocomposite
[61] 97% by weight of polylactic acid (PLA) (LACTY 9030, Shimadzu Corporation,
Japan) was introduced into a main hopper of a twin screw extruder (co-rotating twin screw extruder, Φ40, SM Platek Co., Ltd., Korea). Then, 3% by weight of organically modified montmorillonite (Cloisite 2OA, Southern Clay Products, USA) as layered clay, and 0.1 part by weight of IR 1010 as a thermal stabilizer based on total 100 parts by weight of ethylene- vinyl alcohol copolymer and the organically modified montmorillonite were separately introduced into the side feeder of the twin screw extruder, thereby preparing a PLA/layered clay nanocomposite in the form of a pellet. Extrusion was carried out under the following conditions: extrusion temperature of 105- 125- 125- 125- 125-120- 120°C, screw rotation speed of 300 rpm, and discharge rate of 40 kg/hr.
[62]
[63] [Example 1]
[64] 100 parts by weight of aliphatic/aromatic polyester, 10 parts by weight of polylactic acid nanocomposite prepared in Preparative Example 1, 1.5 parts by weight of calcium stearate and 1.5 parts by weight of a thermal stabilizer/coupling agent were dry-blended and the resulting mixture was extruded in a blown film extruder (extruder size: 30 mm, HANKOOK EM Co., Ltd., Korea) at an extrusion temperature of 105-125- 125°C, thereby preparing a film having a thickness of 30 D.
[65]
[66] [Example 2]
[67] A film was prepared in the same manner as in Example 1, except that aliphatic polyester was used instead of aliphatic/aromatic polyester.
[68]
[69] [Examples 3 through 7]
[70] A film was prepared in the same manner as in Example 1, except that contents of aliphatic/aromatic polyester, aliphatic polyester, polylactic acid nanocomposite, calcium stearate and thermal stabilizer/coupling agent were set as in Table 1 below.
[71]
[72] [Comparative Example 1]
[73] A film was prepared in the same manner as in Example 1, except that no polylactic acid nanocomposite was added.
[74]
[75] [Comparative Example 2]
[76] A film was prepared in the same manner as in Example 2, except that no polylactic acid nanocomposite was added. [77]
[78] [Comparative Example 3]
[79] A film was prepared in the same manner as in Example 4, except that no polylactic acid nanocomposite was added. [80]
[81] [Comparative Example 4]
[82] A film was prepared in the same manner as in Example 1, except that polylactic acid was added instead of a polylactic acid nanocomposite. [83] [Comparative Example 5]
[84] A film was prepared in the same manner as in Example 2, except that polylactic acid was added instead of a polylactic acid nanocomposite. [85]
[86] [Comparative Example 6]
[87] A film was prepared in the same manner as in Example 4, except that polylactic acid was added instead of a polylactic acid nanocomposite. [88] [Comparative Example 7]
[89] A film was prepared in the same manner as in Example 5, except that polylactic acid was added instead of a polylactic acid nanocomposite. [90]
[91] [Comparative Example 8]
[92] A film was prepared in the same manner as in Example 3, except that polylactic acid was added instead of a polylactic acid nanocomposite. [93]
[94] [Comparative Example 9]
[95] A film was prepared in the same manner as in Example 6, except that polylactic acid was added instead of a polylactic acid nanocomposite. [96] <Table 1>
Composition of film
[98] [99] Oxygen-Barrier Property Test [100] Films having a thickness of 30 D, which were respectively prepared in Examples 1 through 7 and Comparative Examples 1 through 9, were left at a temperature of 23°C under 50% relative humidity for 1 day, and the oxygen permeability of films was measured using an oxygen permeability tester (Model OX-TRAN 2/20, Mocon, USA). The results thus obtained are given in Table 2 below.
[101] <Table 2>
Gas-barrier properties of films
[103] Tear strength of films, which were respectively prepared in Examples 1 through 7 and Comparative Examples 1 through 9, was measured using a tensile tester (Model 4204 UTM, Instron, USA), according to the test method specified in ASTM 1004. The results thus obtained are given in Table 3 below.
[104] <Table 3> [105]
Tear sirength of films
* MD: Machine Direction and TD: Transverse Direction
[106] As can be seen from the results of Tables 2 and 3, films of Examples 1 through 7 exhibited superior tear strength and gas-barrier properties without a decrease of biodegradability, as compared to films of Comparative Examples 1 through 9, at approximately the same composition therebetween.
[107] As show in the drawing, it can be seen that the article having barrier properties according to the present invention exhibits superior barrier properties via dispersion of the biodegradable polylactic acid nanocomposite having barrier properties in the continuous phase of the biodegradable polyester resin, in the form of a multiple lamellar structure. Industrial Applicability
[108] As apparent from the above description, articles having barrier properties, manufactured from a biodegradable nanocomposite composition having barrier properties according to the present invention, have superior biodegradability, mechanical strength and gas-barrier properties.
[109] Although the preferred embodiments of the present invention have been disclosed for illustrative purposes, those skilled in the art will appreciate that various modifications, additions and substitutions are possible, without departing from the scope and spirit of the invention as disclosed in the accompanying claims.
Claims
Claims
[I] A biodegradable polyester resin composition having barrier properties, comprising a dry mixture of 1 to 60 parts by weight of a nanocomposite of polylactic acid and layered clay, relative to 100 parts by weight of a biodegrad able polyester resin composed of an aliphatic polyester resin and an aliphatic/ aromatic polyester resin.
[2] The composition according to claim 1, wherein the aliphatic polyester resin is at least one selected from the group consisting of polycaprolactone, polylactic acid and diol/dicarboxylic acid-based aliphatic polyester. [3] The composition according to claim 2, wherein the diol/dicarboxylic acid-based aliphatic polyester is a polycondensation product of a C -C diol with a C -C di- carboxylic acid. [4] The composition according to claim 1, wherein the aliphatic/aromatic polyester is at least one selected from polycondensation products of a C -C diol, dimethyl- terephthalate or dimethylisophthalate, and a C -C dicarboxylic acid. [5] The composition according to claim 1, wherein the layered clay is at least one selected from the group consisting of montmorillonite, bentonite, kaolinite, mica, hectorite, fluorohectorite, saponite, beidelite, nontronite, stevensite, vermiculite, hallosite, volkonskoite, suconite, magadite and kenyalite. [6] The composition according to claim 1, wherein the weight ratio of polylactic acid
: layered clay in the nanocomposite is in the range of 58.0 : 42.0 to 99.9 : 0.1. [7] The composition according to claim 1, wherein the layered clay contains 1 to
45% by weight of an organic modifying agent. [8] The composition according to claim 7, wherein the organic modifying agent is an organic material containing a functional group selected from the group consisting of primary, secondary, tertiary and quaternary ammonium, phosphonium, maleate, succinate, acrylate, benzylic hydrogens, oxazoline and distearyldimethyl ammonium. [9] The composition according to claim 1, further comprising at least one additive selected from the group consisting of a stabilizer, a slip agent, a dispersant, a filler, a coupling agent, an antioxidant and a UV stabilizer. [10] The composition according to claim 9, wherein the filler is at least one selected from the group consisting of talc, calcium carbonate, limestone, titanium dioxide
(TiO ) and carbon black.
[II] A biodegradable article having barrier properties, which is manufactured by molding a composition of any one of Claims 1 through 10.
[12] The article according to claim 11, wherein the nanocomposites of polylactic acid
and layered clay are dispersed in the form of multiple lamellae in the biodegradable polyester resin, wherein 2 to 300 nanocomposites are present per mm of resin, and each lamella has a thickness of 0.001 to 200 D and an average aspect ratio of 10 to 1000.
[13] The article according to claim 12, wherein the article is a film, sheet, container or pipe.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-2005-0080025 | 2005-08-30 | ||
| KR1020050080025A KR100843593B1 (en) | 2005-08-30 | 2005-08-30 | Biodegradable polyester compositon having barrier property |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2007027027A1 true WO2007027027A1 (en) | 2007-03-08 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/KR2006/003378 WO2007027027A1 (en) | 2005-08-30 | 2006-08-28 | Biodegradable polyester composition having barrier property |
Country Status (2)
| Country | Link |
|---|---|
| KR (1) | KR100843593B1 (en) |
| WO (1) | WO2007027027A1 (en) |
Cited By (13)
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| US20110126497A1 (en) * | 2006-05-23 | 2011-06-02 | Huhtamaki Forchheim Zweigniederlassung Der Huhtamaki Deutschland Gmbh & Co | Method for the production of a biodegradable plastic film, and film |
| GB2477733A (en) * | 2010-02-10 | 2011-08-17 | Michael John Flaherty | Biodegradable packaging material |
| US20110226789A1 (en) * | 2010-03-22 | 2011-09-22 | Clear Lam Packaging, Inc | Additive for performance enhancement of biopolymer articles |
| WO2014111665A2 (en) * | 2013-01-18 | 2014-07-24 | Vegetal And Mineral Water | Composition for producing biodegradable bottles |
| US20140329039A1 (en) * | 2011-12-15 | 2014-11-06 | Tipa Corp. Ltd. | Biodegradable sheet |
| WO2015092257A1 (en) * | 2013-12-17 | 2015-06-25 | Université De Reims Champagne-Ardenne | Composition based on agro-based biodegradable polymers |
| US10294343B2 (en) | 2014-09-24 | 2019-05-21 | The Chemours Company Fc, Llc | Materials with enhanced protection of light sensitive entities |
| CN114249970A (en) * | 2022-01-06 | 2022-03-29 | 苏州瀚海新材料有限公司 | Bio-based polyester for food paper-plastic packaging material and preparation method thereof |
| CN114891251A (en) * | 2022-06-09 | 2022-08-12 | 王新华 | High-barrier degradable agricultural water-retaining mulching film and preparation method thereof |
| US11821142B2 (en) | 2020-10-09 | 2023-11-21 | The Procter & Gamble Company | Methods of producing biodegradable and recyclable barrier paper laminate |
| CN117511159A (en) * | 2024-01-05 | 2024-02-06 | 湖南大道新材料有限公司 | Cosmetic dry-wet separation packaging bag |
| US11913173B2 (en) | 2020-10-09 | 2024-02-27 | The Procter & Gamble Company | Biodegradable and recyclable barrier paper laminate |
| US11913174B2 (en) | 2020-07-30 | 2024-02-27 | The Procter & Gamble Company | Recyclable paper barrier laminate |
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| KR100833583B1 (en) * | 2008-02-19 | 2008-05-30 | 에콜그린 주식회사 | Nature-friendly biodegradable sheet |
| KR101030231B1 (en) * | 2010-10-06 | 2011-04-22 | 주식회사 폴리사이언텍 | Low carbon environment-friendly polylactic acid freshness-keeping film |
| KR102137535B1 (en) * | 2019-10-31 | 2020-08-21 | 남양에코텍 주식회사 | Food packaging comprising biodegradable barrier film |
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| KR100566397B1 (en) * | 2004-09-15 | 2006-03-31 | 호남석유화학 주식회사 | Novel Clay/Polylactide Nanocomposite with Improved Shear Thining Property and Preparation Thereof |
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| GB2477733A (en) * | 2010-02-10 | 2011-08-17 | Michael John Flaherty | Biodegradable packaging material |
| US20110226789A1 (en) * | 2010-03-22 | 2011-09-22 | Clear Lam Packaging, Inc | Additive for performance enhancement of biopolymer articles |
| US10377896B2 (en) | 2010-03-22 | 2019-08-13 | Sonoco Development Inc. | Biopolymer roll stock for form-fill-sealed article |
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| US20140329039A1 (en) * | 2011-12-15 | 2014-11-06 | Tipa Corp. Ltd. | Biodegradable sheet |
| FR3001224A1 (en) * | 2013-01-18 | 2014-07-25 | Vegetal And Mineral Water | COMPOSITION FOR THE PRODUCTION OF BIODEGRADABLE BOTTLES |
| WO2014111665A2 (en) * | 2013-01-18 | 2014-07-24 | Vegetal And Mineral Water | Composition for producing biodegradable bottles |
| WO2014111665A3 (en) * | 2013-01-18 | 2014-11-13 | Vegetal And Mineral Water | Composition for producing biodegradable bottles |
| WO2015092257A1 (en) * | 2013-12-17 | 2015-06-25 | Université De Reims Champagne-Ardenne | Composition based on agro-based biodegradable polymers |
| US10294343B2 (en) | 2014-09-24 | 2019-05-21 | The Chemours Company Fc, Llc | Materials with enhanced protection of light sensitive entities |
| US11913174B2 (en) | 2020-07-30 | 2024-02-27 | The Procter & Gamble Company | Recyclable paper barrier laminate |
| US11913173B2 (en) | 2020-10-09 | 2024-02-27 | The Procter & Gamble Company | Biodegradable and recyclable barrier paper laminate |
| US11821142B2 (en) | 2020-10-09 | 2023-11-21 | The Procter & Gamble Company | Methods of producing biodegradable and recyclable barrier paper laminate |
| CN114249970A (en) * | 2022-01-06 | 2022-03-29 | 苏州瀚海新材料有限公司 | Bio-based polyester for food paper-plastic packaging material and preparation method thereof |
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| CN114891251A (en) * | 2022-06-09 | 2022-08-12 | 王新华 | High-barrier degradable agricultural water-retaining mulching film and preparation method thereof |
| CN114891251B (en) * | 2022-06-09 | 2023-12-22 | 未来超级生物环保科技(北京)有限公司 | High-barrier degradable agricultural water-retaining mulching film and preparation method thereof |
| CN117511159A (en) * | 2024-01-05 | 2024-02-06 | 湖南大道新材料有限公司 | Cosmetic dry-wet separation packaging bag |
| CN117511159B (en) * | 2024-01-05 | 2024-03-22 | 湖南大道新材料有限公司 | Cosmetic dry-wet separation packaging bag |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20070027994A (en) | 2007-03-12 |
| KR100843593B1 (en) | 2008-07-03 |
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