KR20150068364A

KR20150068364A - Extrudable composition derived from renewable resources

Info

Publication number: KR20150068364A
Application number: KR1020157007253A
Authority: KR
Inventors: 리차드 피터 스칼조; 제임스 엣슨 브란덴버그; 마빈 린 미첼; 파울라 하인즈 미첼; 멜빈 글렌 미첼; 신시아 가일 미첼; 토마스 제이슨 울프; 앰버 레인 울프
Original assignee: 어스 리뉴어블 테크놀로지스
Priority date: 2012-09-26
Filing date: 2013-09-24
Publication date: 2015-06-19
Also published as: MX2015003766A; CA2881018A1; WO2014052300A1; AU2013323753A1; EP2900754A4; BR112015005600A2; EP2900754A1; AU2013323753A2; JP2015533186A; CN104781330A

Abstract

The extrudable composition may be an extrudable composition having a thermal deformation temperature greater than about 50 캜 and a melting point of between about 80 캜 and about 190 캜 and the extrudable composition comprises about 60% to about 99.8% of partially crystalline or crystalline polylactic acid, From about 0.05 to about 8% dextrin, from about 0.1 to about 8% natural oil, fatty acid, fatty acid ester, wax or wax ester, from about 0.01 to about 5% nanofiber, from about 0 to about 10% crystallizer, From about 0% to about 1% modifier, from about 0% to about 5% pigment, from about 0% to about 1% plasticizer, from about 0% to about 1% polish and from about 0% to about 1%

Description

[0001] EXTRUDABLE COMPOSITION DERIVED FROM RENEWABLE RESOURCES [0002]

The present application is a continuation-in-part of U. S. Patent Application No. Provisional Application No. 61 / 705,683 filed November 14, 2012; 61 / 726,188, filed July 9, 2013; 61 / 844,155 filed Mar. 8, 2013, the entirety of which is incorporated herein by reference. In part of U.S. Serial No. 13 / 790,889, the contents of which are incorporated herein by reference in their entirety.

The present invention relates to an extrudable composition and a method of making a molded article therefrom. The extrudable composition comprises a polylactic acid polymer derived from renewable resources and the composition is biodegradable.

Molded articles are typically formed from a variety of extrudable polymer compositions, and representative products include bottles and other food containers, films, packages, and the like. In the past, these molded articles were generally formed from petroleum-based polymers not derived from renewable resources nor biodegradable. Representative petroleum-based polymers include polypropylene (PP), polyethylene terephthalate (PET), polystyrene (PS), and polyvinyl chloride (PVC). These petroleum-based polymers are not only naturally friendly, but also solvents and methods for making these polymers are not environmentally friendly. Moreover, although some of these polymers are recyclable, they are not biodegradable and cause problems such as landfill disposal.

The solution to this problem is to make a molded article using a polymer derived from renewable resources. An example of such a polymer derived from renewable resources is polylactic acid (PLA). PLA is derived from a variety of natural renewable resource materials such as corn, plant starches (e.g., potato), and stem (e.g., sorghum). Such efforts to utilize PLAs are described, for example, in U.S. Pat. Open Publication Nos. 2011 / 005847A1 and 2010 / 0105835A1, PCT Publication No. WO 2007 / 047999A1, U.S. Pat. Patent Publications 5,744,510, 6,150,438, 6,756,428, and 6,869,985, the contents of which are incorporated by reference in their entirety. For the purposes of this disclosure, the term " lactide-based polymer " is intended to have the same meaning as the term polylactide, polylactic acid (PLA) and polylactide polymer, Or all of the polymers formed through the ring-opening polymerization of a mixture of a copolymer or of a monomer with another monomer. The term is also intended to include those where the coordination and arrangement of the constituent monomers are different (e.g., syndiotactic, isotactic, amorphous, crystalline, partially crystalline, etc.). The lactide-based polymer may or may not originate from renewable resources.

PLA is formed through ring-opening polymerization of lactide. PLA is a crystalline polymer and thus has problems with respect to melt viscosity, temperature stability, tensile strength, and impact resistance during molding. There is therefore a continuing need for improved extrudable compositions that can overcome the problems associated with molded articles made from compositions that are biodegradable and more naturally-friendly, i.e., renewable, especially compositions comprising PLA.

To this end, the invention provides extrudable compositions comprising polylactic acid (PLA) coated with cyclodextrin and natural oils (e.g. vegetable oils), fatty acids, waxes or wax esters. The present invention also relates to a process for preparing PLA by coating PLA with a natural oil, fatty acid, wax or wax ester, mixing the PLA with the cyclodextrin, drying the mixture to remove substantially all of the water, And molding the extruded composition into a product. &Lt; Desc / Clms Page number 5 >

Thus, in one aspect of the invention, the heat distortion temperature is higher than about 50 캜 and the melting point is about 80 캜 to about 190 캜,

a) about 60 to about 99.8% of partially crystalline or crystalline polylactic acid;

b) about 0.05 to about 8% cyclodextrin;

c) from about 0.1 to about 8% natural oil, natural wax;

d) from about 0.01 to about 5% nanofibers;

e) from about 0% to about 10% crystallizer;

f) from about 0% to about 1% of a melt rheology modifier based on starch;

g) about 0% to about 5% pigment;

h) from about 0 to about 1% plasticizer;

i) from about 0% to about 1% of a polish agent; And

and j) from about 0% to about 1% of the barrier.

In another aspect of the invention there is provided a process for the production of extrudable articles comprising PLA and cyclodextrins, nanofibers, crystallizing agents, melt flow modifiers based on starches and pigments derived from renewable resources and coated with natural oils, fatty acid esters, waxes or wax esters A container formed from the composition is provided.

In another aspect of the invention there is provided a container stopper formed from an extrudable composition comprising a cyclodextrin coated with PLA, a natural oil, a fatty acid ester, a wax or a wax ester, a crystallizing agent, a crystallization retarder and a dye.

In another aspect of the invention, a lid or cover formed from an extrudable composition comprising PLA coated with a natural oil, fatty acid ester, wax or wax ester and an extrudable composition comprising cyclodextrin, crystallizing agent, crystallization retardant, pigment and optionally nanofibers to provide.

In another aspect of the invention, there is provided a process for preparing a PLA comprising coating PLA with natural oils, fatty acids, fatty acid esters, waxes and / or wax esters, mixing the PLA with the cyclodextrin, , Extruding the dried mixture, and molding the extruded composition into a product.

1 is a DSC chart corresponding to Example 1. Fig.
2 is a DSC chart corresponding to the second embodiment.
3 is a DSC chart corresponding to the third embodiment.
4 is a DSC chart corresponding to Comparative Example 1. Fig.
5 is a DSC chart corresponding to Comparative Example 2. Fig.
6 is a DSC chart corresponding to Comparative Example 3. Fig.
7 is a DSC chart corresponding to Comparative Example 4. Fig.
8 is a DSC chart corresponding to Example 4-6 and Comparative Example 7;
9 is a DSC chart corresponding to Examples 10-13.
10 shows a DSC chart corresponding to Examples 14 and 16 and Comparative Example 6 and Comparative Example 8. Fig.

The foregoing aspects and other aspects of the present invention will be described in more detail as follows, by way of representation and methodology as set forth herein. It is to be understood that the invention may be embodied in other forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art.

The terms used in the description of the present invention are intended to illustrate specific embodiments and are not intended to limit the invention. As used in the detailed description of the embodiments of the invention and the appended claims, the singular forms "a", "one" and "the" include plural unless the context clearly dictates otherwise. Also, "and / or" as used herein refers to and includes any and all possible combinations of one or more items in the associated list. Further, the term "about" as used herein in reference to measurable values such as the total amount, dose, time, temperature, etc. of a compound refers to the amount of the compound in the range of 20%, 10%, 5%, 1%, 0.5% 0.1%. &Lt; / RTI > When a range is used (for example, a range of x to y), it means that the measurable value corresponds to a range of about x to about y, or about ₁ to about y ₁ , and so on. Furthermore, the terms "comprises" and / or "comprising ", as used in this specification, specify the presence of stated features, integers, steps, acts, components and / , Steps, acts, elements, components, and / or groups thereof. Unless otherwise defined, all terms including technical and scientific terms used in the description of the present invention have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.

The terms "first", "second", "third", "a", "b", and "c" may be used herein to describe various elements of the present invention, It is to be understood that the invention is not limited by the terms. These terms are only used to distinguish certain elements of the present invention from others. Thus, the first component referred to below may be said to be component-wise, and similarly, it may be the third component without departing from the spirit of the present invention. Thus, terms such as "first", "second", "third", "a", "b", and "c" are not necessarily intended to refer to sequences or other sequences of related components And is used only for the purpose of distinction. The order of actions (or steps) is not necessarily limited to the order presented in the claims and / or drawings unless otherwise specified.

All patents, patent applications and publications mentioned herein are incorporated by reference in their entirety. Where the terms conflict, they are in accordance with the present disclosure.

The embodiments described in one aspect of the present invention are not limited to the aspects described. The embodiments may be applied to other aspects of the invention as long as they do not prevent these aspects of the invention from operating for the intended purpose of the invention.

As described above, the present invention provides an extrudable composition comprising a cyclodextrin and a polylactic acid (PLA) coated with natural oils, fatty acids or waxes. In one embodiment, the extrudable composition may further comprise a carboxylic acid or alkyl ester plasticizer. In another embodiment, the extrudable composition may comprise nanofibers. In another embodiment, the extrudable composition may comprise a crystallizing agent or a crystallization retarding agent. In another embodiment, the extrudable composition may comprise a flow modifier. In another embodiment, the extrudable composition may include pigments, and often naturally occurring pigments. In another embodiment, the extrudable composition may comprise a polish. In another embodiment, the extrudable composition may comprise a barrier agent. Various combinations of these embodiments are also contemplated by the present invention.

The extrudable composition of the present invention is useful as a non-biodegradable, conventional polymer derived from non-renewable resources such as polyethylene terephthalate (PET), high density polyethylene (HDPE), polyethylene (PE), and polypropylene Can be compounded so that they can be sufficiently followed. In particular, the present invention provides an extrudable composition having heat distortion or heat distortion (HDT) melt viscosity, temperature stability and impact resistance corresponding to conventional polymers.

Generally, PLA can be derived from lactic acid. Lactic acid can be produced commercially by fermentation of agricultural products such as whey, corn starch, potato, molasses, sugarcane, and the like. Typically, the PLA polymer is formed by first forming a lactide monomer through depolymerization of the lactic acid oligomer. This monomer can then undergo a ring opening polymerization of monomers. For the purposes of this application, the term " lactide-based polymer " is intended to have the same meaning as polylactide, polylactic acid (PLA) and polylactide polymer, and includes lactide monomers alone Or all polymers formed through ring-opening polymerization of a copolymer with other monomers. The term also includes where the configuration and arrangement of the constituent monomers are different (e.g., syndiotactic, isotactic, etc.). The lactide-based polymer may or may not originate from renewable resources.

The lactide monomer may be polymerized in the presence of a suitable polymerization catalyst under elevated temperature elevation conditions as is generally known in the art. The catalyst may be any compound or composition known to catalyze the polymerization of lactide. Such catalysts are well known, and U.S. Pat. Patent No. And alkyl lithium salts such as those disclosed in U.S. Pat. No. 5,028,667, stannous octoate, aluminum isopropoxide, and certain rare earth metal compounds. The particular amount of catalyst used will generally vary depending on the process temperature and the desired polymerization rate as well as the catalytic activity of the material. Typical catalyst concentrations include from about 10: 1 to about 100,000: 1 by molar ratio of lactide to catalyst, and in one embodiment from about 2,000: 1 to about 10,000: 1. According to one exemplary process, the catalyst can be distributed to the lactide monomer starting material. If it is a solid, the catalyst may have a relatively small particle size. In one embodiment, the catalyst may be added to the monomer solution with a dilute solution dissolved in an inert solvent, such that the catalyst can be easily handled and homogeneously mixed with the monomer solution. In embodiments where the catalyst is a toxic agent, the process may include removing the catalyst from the mixture after the polymerization, for example, through one or more leaching steps.

In one embodiment, the polymerization process can be carried out at elevated temperature, for example from about 95 ° C to about 200 ° C, or in another embodiment from about 110 ° C to about 170 ° C, and in another embodiment from about 140 ° C to about 160 ° C have. The temperature can be selected so as to obtain an appropriate polymerization rate for the particular catalyst used while maintaining a sufficiently low temperature to avoid polymer degradation in general. In one embodiment, the polymerization can occur at elevated pressures as is generally known in the art. The process typically takes about 1 to about 72 hours, such as about 1 to about 4 hours.

The molecular weight of the degradable polymer must be high enough to allow entanglement between the polymer molecules and sufficiently low to be melt processed. For melt processing, the PLA polymer or copolymer has a weight average molecular weight of from about 10,000 g / mol to about 600,000 g / mol, preferably less than about 500,000 g / mol or less than about 400,000 g / mol, more preferably from about 50,000 g / A weight average molecular weight of from about 300,000 g / mol or from about 30,000 g / mol to about 400,000 g / mol, and most preferably from about 100,000 g / mol to about 250,000 g / mol or from about 50,000 g / mol to about 200,000 g / mol Respectively. When PLA is used, PLA is preferably in the semi-crystalline or partially crystalline form. In order to form the semi-crystalline PLA, it is preferred that at least about 90 mole percent, more preferably at least about 95 mole percent, of the repeat units of the polylactide is L- or D-lactide. The process can be carried out by a method that facilitates crystal formation, for example, a method of sufficiently orienting the crystal. Alternatively, amorphous PLA may be blended with PLA having a higher crystallinity. Alternatively, the crystallizing agent described below may be added to make the amorphous PLA more crystalline and / or to adjust the ratio of amorphous PLA and crystalline PLA when both are used.

Polylactide homopolymers obtainable from commercial sources can also be used to make the disclosed polymeric composites. For example, Polysciences, Inc., NatureWorks, LLC, Cargill, Inc., Mitsui (Japan), Shimadzu (Japan) Poly (L-lactic acid) available from Chronopol (Japan), Chronopol or Synbra Technologies (Netherlands). The PLA polymer is low enough for processability, but may have a melting point sufficiently high for thermal stability. The melting point may therefore be from about 80 캜 to about 190 캜, and in one embodiment from about 150 캜 to about 180 캜.

PLA can be copolymerized with one or more other polymeric materials. In one embodiment, the lactide based copolymer may be copolymerized with monomers or oligomers derived from one or more other renewable resources. Thus, in one embodiment, the lactide-based copolymer may be a PLA polymer or a PLA copolymer and a polyhydroxyalkanoate (PHA). PHAs are rapidly degradable, but often do not have the processability of PLA. PHA can be obtained by bacterial fermentation of sugars or lipids. Representative PHAs are U.S. It is introduced in patent 6,808,795 B2. Commercially available PHAs include Procter & Gamble's Nodax (TM).

In another embodiment, the PLA can be copolymerized with other polymers or copolymers that may or may not be biodegradable. Such polymers or copolymers include, but are not limited to, biodegradable or non-biodegradable polypropylene (PP), aromatic / aliphatic polyesters, aliphatic polyester amide polymers, polycaprolactones, polyesters, polyurethanes derived from aliphatic polyols, polyamides, Terephthalate (PET), polystyrene (PS), polyvinyl chloride (PVC), and cellulose esters.

In addition to the PLA described above, the extrudable composition comprises cyclodextrin. Cyclodextrins (CDs) are cyclic oligomers of glucose, typically containing 6, 7, or 8 glucose monomers linked by? -1,4 linkages. These oligomers are generally referred to as? -Cyclodextrin (? -CD),? -Cyclodextrin (? -CD or BCD), and? -Cyclodextrin (? -CD), respectively. Advanced oligomers containing up to 12 glucose monomers are known, but their preparation is more difficult. Each glucose unit has three hydroxy groups available at positions 2, 3, and 6. Thus, a-CD has 18 possible hydroxy groups or 18 substitutable positions and can have a degree of substitution (DS) of up to 18. Similarly, β-CD and γ-CD have a maximum of 21 and 24 DS, respectively. DS is often expressed as the average DS, which is the number of substituents in the cyclodextrin divided by the number of glucose monomers. For example, a fully acylated β-CD has a DS of 21 or an average DS of 3. According to the nomenclature, this derivative is termed heptakis (2,3,6-tri-O-acetyl) -? - cyclodextrin and is commonly abbreviated to triacetyl-? - cyclodextrin.

CD is produced by first treating starch with? -Amylase to partially reduce the molecular weight of the starch and then treating it with an enzyme known as cyclodextrin glucosyltransferase to form a cyclic structure. Topologically, CD can be depicted as a toroid in which the first hydroxy group is located in a small circumference and the second hydroxy group is located in a large circumference. Because of this arrangement, the exterior of the torus is hydrophilic enough to allow the CD to be soluble in water, while the interior is hydrophobic. This difference between the inner and outer surfaces allows the CD or selected CD derivative to act as a host molecule so that the guest molecule can form an inclusion complex with the hydrophobic guest molecule if it has an appropriate size for the cavity.

Thus, PLA can be a guest molecule. However, cyclodextrins, particularly BCD, are not soluble in PLA and may be poorly dispersed. One known solution to this is the use of organic solvents to aid dispersion. However, the use of such organic solvents is undesirable in that such solvents, such as toluene, methylene chloride, etc., are not environmentally friendly.

It has been found that dispersions can be unexpectedly improved by adding natural oils, fatty acids, fatty acid esters, waxes or wax esters to PLA prior to blending or blending PLA and CD. In one embodiment, natural oils, fatty acids, fatty acid esters, waxes or wax esters are coated onto PLA (e.g., PLA pellets) pellets via agitation. Without wishing to be bound by any particular theory, it is believed that the hydrophobic coating of natural oil, fatty acid, wax or wax ester is first incorporated into the center of the CD, and that the oil, fatty acid, wax or wax ester, . Mixtures or blends of natural oils, fatty acids, waxes or wax esters may be used.

In one embodiment, the extrudable composition may comprise a natural oil. Suitable natural oils include, but are not limited to, lard, tallow, fish oil, coffee oil, soybean oil, safflower oil, tung oil, tall oil, marigold, rapeseed oil, peanut oil, linseed oil, sesame oil, grape seed oil, , Sunflower oil, cotton seed oil, corn oil, canola oil, orange oil, and mixtures thereof. During operation, the shaped particles or additives to be introduced into the PLA polymer are preferably coated with at least one of the oils and heated to about 160 ℉ to about 180 동안 for a period of about 4 to about 12 hours. This will saturate the particles or additive sufficiently with oil. In this way, after the particles or additives are saturated with oil in the presence of heat, the particles can be substantially contained in the PLA polymer matrix.

Suitable waxes include naturally occurring waxes and wax esters include, without limitation, waxes, plant-derived waxes, bird waxes, non-waxy insect waxes, and microbial waxes. Wax esters can also be used. As used herein, the term 'wax ester' generally refers to esters of long chain fatty acids and long chain fatty alcohols. The chain length of the fatty alcohol and fatty acid constituent of the wax ester may vary, but generally the wax ester may have a total carbon number of about 20 or more. Wax esters generally have melting points higher than the melting point of fats and oils. For example, wax esters generally have melting points greater than about 45 < 0 > C. Additionally, wax esters encompassed herein include all wax esters, such as saturated or unsaturated, branched, or straight chain. It has also been found that the wax also promotes an increase in the heat distortion temperature of the PLA film and imparts barrier properties such as low oxygen permeability and water vapor permeability.

Suitable fatty esters or fatty acid esters are polymeric products in which the unsaturated higher fatty acids are reacted with alcohols. Representative higher fatty esters include oleic acid esters, linoleic acid esters, resinoleic esters, lauric acid esters, myristic acid esters, stearic acid esters, palmitic acid esters, eicosic acid esters, &Lt; / RTI >

Such esters can be combined with suitable oils and various esters derived from carboxylic acids can be included to function as plasticizers for PLA. Representative carboxylic acids include acetic acid, citric acid, tartaric acid, lactic acid, formic acid, oxalic acid, and benzoic acid. Furthermore, these acids can react with ethanol to form acid ethyl esters such as ethyl acetate, ethyl lactate, monoethyl citrate, diethyl citrate, and triethyl citrate (TEC). Most naturally occurring fats and oils are fatty acid esters of glycerol.

In another embodiment, the extrudable composition may comprise nanofibers. Suitable nanofibers include silica derived fibers and have a diameter of about 1 mu m or less using SEM measurements and typically have a length of from about 65 to about 650 nm. Suitable nanofibers are available from Johns Manville under the name Micro-Stand ™ 106-475. Alternatively, treated (purified) cellulose-derived nanofibers can be used. For example, wood pulp can be treated with natural oil to make pulp and oil mechanically refined in pulp-type refiner to produce a fibril that gels the solution. Biodegradable wood fibers such as bleached or unbleached hardwood and softwood kraft pulp may be used as pulp. Especially preferred are tropical hardwoods such as northern hardwood and eucalyptus with high fiber counts such as aspen. Non-wood fibers such as flax, hemp, espalato, cotton, kenaf, bamboo, abaca, rice straw, or other plant derived fibers may also be used. Alternatively, renewable and biodegradable cellulosic fiber materials, especially those with microfiber structures, such as switchgrass, may be used. Applicants do not wish to be bound to any one theory, but nanofibers contribute to the crystallization of PLA thereby facilitating the use of amorphous PLA and also contributing to the improvement of the properties of the extrudable composition when amorphous and / or partially crystalline PLA is used .

In another embodiment, the extrudable composition may comprise a crystallizing agent and in this case the polymer may have a crystalline form such as platelet. Examples of crystallizing agents include, but are not limited to, talc, kaolin, mica, bentonite clay, calcium carbonate, titanium dioxide and aluminum oxide.

In another embodiment, the extrudable composition may comprise a melt flow modifier based on starch. Suitable starches are those produced by plants, including cereals (corn, rice, sorghum), potatoes, lobster, tapioca and sweet potato. During operation, these plant-based starches tend to gel when combined with PLA and can be used to impart a smooth surface to the molded article.

In another embodiment, the extrudable composition may comprise one or more crystallization retarders. Examples of crystallization retarders include, but are not limited to, xanthan gum, guar gum, and locust bean gum.

Other embodiments may include pharmaceutical containers and pigments for imparting common colors associated with functional food containers, such as white, brown, and green. In embodiments where a white container is required, titanium dioxide may preferably be included with safflower oil as natural oil. The amount of pigment typically added is from 0 to 67%, depending on the type of extruder used, preferably from about 0.1 to 3%, based on the total weight of the extrudable composition. In embodiments where green vessels are required, sodium copperchlorohelin or edible aniline powder sold by the DDW The Color House may be used as the pigment. In embodiments where a brown container is required, a blend of 0.019% to 0.021% edible black, 0.008% to 0.010% blue, 0.104% to 0.106% red and 0.063% to 0.065% yellow dye blend sold by Keystone (Chicago, IL) have.

Agents for imparting additional moisture and oxygen barrier properties may be included. Representative moisture and oxygen barrier agents include candelilla lead, beeswax, and other waxes. Preferably, such barrier agents are derived from renewable resources.

A polish to impart aesthetically pleasing gloss to the container may be included. Representative brighteners include nourishing oils such as shea butter and Brazil nut oil. Preferably such polishes are derived from renewable resources.

Other additives may include other natural or synthetic plasticizers such as lignin, impact modifiers, fiber reinforcements other than nanofibers, antioxidants, antimicrobials, fillers, UV stabilizers, glass transition temperature modifiers, melt point modifiers and heat distortion temperature modifiers . Particularly preferred fillers are biodegradable non-wood fibers such as those used in nanofibers and include kenaf, cotton, flax, esparto, hemp, abaca, or various fiber hubs.

Generally, the extrudable composition may comprise an extrudable composition having a thermal deformation temperature greater than about 50 DEG C and a melting point between about 80 DEG C and about 190 DEG C, the extrudable composition comprising: a) from about 0 to about 100% amorphous PLA, ; b) from about 0% to about 100% of partially crystalline PLA or crystalline PLA; c) from about 0.1 to about 8% of a natural oil or natural wax; d) from about 0.01 to about 5% nanofibers; e) from about 0.05 to about 8% BCD; e) from about 0% to about 10% crystallizer; f) from about 0% to about 1% of a melt flow modifier based on starch; g) from about 0 to about 1% of a polysaccharide crystallization retarding agent; h) from about 0% to about 5% pigment; i) from about 0 to about 1% plasticizer; j) about 0 to about 1% of a polish; And k) from about 0% to about 1% of the barrier. In one embodiment of the invention, the extrudable composition comprises about 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95% %, 98%, or greater than about 99% amorphous or crystalline PLA. In another embodiment of the present invention, the extrudable composition may comprise a mixture of amorphous and crystalline PLA. In yet another embodiment, the BCD is added to the extrudable composition in an amount of BCD of about 0.05%, 0.4%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, or about 8% exist. In yet another embodiment, natural oils or natural waxes may be added to the extrudable composition at about 0.1%, 0.25%, 0.5%, 0.75%, 1%, 1.5%, 2%, 3%, 4%, 5% 7%, or up to about 8% natural oil. In yet another embodiment, the nanofibers comprise nanofibers of up to about 0.1%, 0.2%, 0.25%, 0.3%, 0.4%, 0.5%, 0.75%, 1%, 2%, 3%, 4% &Lt; / RTI > In yet another embodiment, the crystallizing agent is selected from the group consisting of crystals of up to about 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, or up to about 10% It exists in the amount of topic. In another embodiment, the starch-based melt flow modifier is optionally present in an extrudable composition in an amount of from about 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9% % Of starch based melt flow modifier. In yet another embodiment, the polysaccharide crystallization retarder may optionally comprise up to about 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, or up to about 1% Lt; / RTI > In another embodiment, the dye may be present in the selectively extrudable composition in an amount of up to about 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, or up to about 1% Lt; / RTI > In yet another embodiment, a plasticizer is present in the selectively extrudable composition in an amount of from about 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, or up to about 1% Lt; / RTI > In another embodiment, the polish may be applied to the selectively extrudable composition at a level of from about 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, or up to about 1% Lt; / RTI > In yet another embodiment, the barrier can be selectively applied to the extrudable composition at a rate of about 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, or up to about 1% &Lt; / RTI >

Prior to extrusion, the extrudable composition is dried to remove substantially all of the moisture, i. E., To a moisture content of less than about 0.02%, and often less than about 0.01%. Typically, drying with a desiccant is used.

In one embodiment, a master batch is used. By using a master batch, often more expensive additives can be first added to a master batch in large percentage amounts and then added to 100% PLA. The use of such masterbatches can be used to incorporate additives, such as those that improve properties such as barrier properties, flexibility, HDT properties, etc., more cost-effectively. Another example is that the master batch can be formulated so that the consumer can make the color of the product as desired. For example, a certain amount of basic dye (e.g., green dye) is added to pure PLA and then a master batch containing the dye / PLA composition and a small amount of green dye (s) An extrudable composition is produced. A small amount of green pigment (s) in the master batch can be selected to achieve the desired color or tint of the desired color.

For purposes of illustration, extrudable compositions for caps or lids having properties similar to HPDE caps or lids can be made. A master batch comprising crystalline PLA, natural oil coated on PLA, nanofibers, cyclodextrin, crystallizing agent, pigment and crystallization retardant is prepared by coating PLA with oil, adding a crystallizing agent, blending with BCD, .

The extrudable composition can then be made into a product. For example, the process may include extrusion, injection molding, or blow molding the composition in molten form. For purposes of this disclosure, the injection molding process includes any molding process in which the polymer melt or the monomer or oligomer solution is injected into a mold that is molded and cured under pressure, for example, with a ram injector or reciprocating screw. The blow molding process can include any method by which a polymer can be molded and cured using a fluid to form an article. The blow molding process may include extrusion blow molding, injection blow molding, and stretch blow molding, if desired. Extrusion molding methods include extrusion of the melt from the die under pressure and curing to make the final article, e.g., a film or fiber. The uniaxial screw or twin screw extruder can be used, and the choice of extruder and the amount of each component varying with the extruder are within the knowledge of those skilled in the art.

In one embodiment, the molded article is a container. As used in this specification and the appended claims, the term "container" refers to any container or article of merchandise used to store, deliver, package, distribute, or transport various types of goods or objects Including, but not limited to, articles, utensils, or containers. Specific examples of such containers include, but are not limited to, a box, a cup, a shell, a jar, a plate, a dish, a cutlery, a tray, a crate, a case, a cuff, a cereal box, , A bowl, an egg shell, a cover, a straw, an envelope, a pile, a basket, a bag, or any other kind of support. Containers and other articles used with containers are also intended to be included in the term "container ".

In another embodiment, the extrudable composition disclosed herein can be made into a container, and in a particular embodiment, a container suitable for storing and protecting an environmentally sensitive material, such as a bioactive material, including drug and functional food Can be made. For purposes herein, the term "about" is defined herein to encompass materials regulated by the US government, including, for example, drugs and other biological agents. For purposes herein, "functional food" is defined herein to refer to a bioactive material that is not necessarily regulated by the US government, including, for example, vitamins, health supplements,

In another embodiment, the molded article is a hermetically sealed container. The term "stopper" as used herein and in the appended claims is intended to cover, store, transport, distribute, serve, or provide a lid, cover, rug, compartment, wrapper, film, cushioning material, kitchen utensil, But is not limited to, any containment such as any other article used in the art. Exemplary stoppers include, but are not limited to, screw caps, snap lids, tamper resistant, tamper resistant, and child resistant stoppers or lids.

For purposes of illustration, extrudable compositions for containers having properties similar to PET containers can be made. A masterbatch comprising a partially crystalline or crystalline PLA, a natural oil, a nanofiber, a cyclodextrin, a pigment, and a crystallizing agent may be prepared by mixing the oil with the nanofiber, adding the oil and the nanofiber together with the other components to the PLA, Followed by mixing with a mixture of cyclodextrin and starch crystallization retarder, adding a crystallizing agent, stirring and drying. Pigments / pigments may be added to the master batch. Alternatively, a separate arrangement of crystalline PLA and pigment can be made and then this separate arrangement with the master match is combined.

Exemplary formulations for the container comprise about 70 to about 95% crystalline polylactic acid, about 0.05 to about 8% cyclodextrin, about 0.1 to about 8% natural oil or wax, about 0.01 to about 5% nanofibers, about 0.01 To about 10%, a starch based flow modifier about 0.01% to about 1%, and a colorant from about 0.01% to about 8%.

Another illustrative example is an extrudable composition for a bottle or container stopper or lid having properties similar to HDPE. An exemplary formulation for the lid comprises about 70% to about 95% crystalline polylactic acid, about 0.05% to about 8% cyclodextrin, about 0.1% to about 8% natural oil or wax, about 0.01% to about 10% crystallizer, 0.01 to about 1%, a dye of about 0.01 to about 8%, and optionally nanofibers.

Formed articles and structures comprising an extrudable composition may comprise a laminate comprising a composite material disclosed as one or more layers of the laminate. For example, the laminate structure may include one or more layers formed of the composite material described herein to provide specific inhibitors at defined locations within the laminate structure. Barrier properties can also be increased by wax coating the interior or exterior of the vessel used for spraying or dipping.

Alternatively, various extrusion, blow molding, injection molding, casting or melting processes known to those skilled in the art may be used in the manufacture of films or sheets. Exemplary products include articles used to wrap or otherwise wrap food or various other solid objects. The film or sheet may have a variety of thicknesses and physical properties that may vary depending upon the desired end product and the article to be packaged, such as stiffness, breathability, temperature stability, and the like. Exemplary techniques for providing films or sheets are described, for example, in U.S. Pat. Patent disclosure Nos. 2005/0112352, 2005/0182196, and 2007/0116909, and U.S. Pat. Patent No. 6,291,597, the contents of which are incorporated by reference in their entirety.

As an exemplary embodiment, the laminate may comprise a layer of impermeable polymer on the surface of the structure, for example, a container (e.g., a bottle or jar) or an inner surface of a package (e.g., a blister pack of a pill) . In one particular embodiment, the extruded film formed from the extrudable composition may form one or more layers of such a laminate structure. For example, impermeable PLA-based films can form an inner layer of the container, for example, to prevent leakage, decomposition or evaporation of liquid that can be stored in the container. Such an embodiment may be particularly useful when considering storage of functional foods, especially in the form of alcoholic liquids, such as alcoholic extracts or tinctures.

The following examples are intended to further illustrate the nature of the invention and should not be construed as limiting the scope of the invention as defined by the appended claims.

Examples 1-3 were performed to show improved properties when PLA was coated with natural oil before mixing with BCD.

Example 1

An extrudable composition comprising 91.5% PLA, 7% BCD, and 1.5% jojoba oil was prepared. If the BDC and PLA are merely blended, the BCD will not be well dispersed and will not dissolve in the molten PLA during extrusion. Therefore, jojoba oil is stirred and PLA coated, then BCD is added to the coated PLA and stirred again. The composition is heated to 160 to 180 DEG F for a period of 4 to 12 hours to fully saturate the BCD with oil so that the BCD particles are completely contained in the PLA polymer matrix. The resulting composition is then extruded into a uniform film without flakes.

Example 2

The extrudable composition comprising 90.5% crystalline PLA, 7% BCD, 1.5% jojoba oil, and plasticizer 0.1% triethyl citrate (TEC) is prepared, wherein the jojoba oil and TEC are coated on the PLA by stirring, Add to PLA and stir again. The composition is heated to 160 내지 to 180 동안 for a period of 4 to 12 hours to fully saturate the BCD with oil and TEC so that the BCD particles are completely contained in the PLA polymer matrix. The resulting composition is then extruded into a film.

Example 3

To prepare an extrudable composition comprising 91.5% crystalline PLA, 7% BCD, and 1.5% olive oil, wherein the olive oil is coated on the PLA by agitation and the BCD is then added to the PLA and stirred again. The composition is heated to 160 to 180 DEG F for a period of 4 to 12 hours to fully saturate the BCD with oil so that the BCD particles are completely contained in the PLA polymer matrix. The resulting composition is then extruded into a film.

Comparative Example 1

A 100% polyester (PE) composition is made and extruded into film.

Comparative Example 2

A 100% polypropylene (PP) composition is made and extruded into a film.

Comparative Example 3

A PLA composition comprising amorphous PLA, jojoba oil, turmeric, and cotton wool is made and extruded into a film.

Comparative Example 4

Amorphous PLA, jojoba oil, turmeric, and cotton wool, and extruded into a film.

The results of the stress / strain data of Examples 1-3 and Comparative Examples 1-4 are shown in Table 1, the results of DSC data of Example 1-3 are shown in Figs. 1-3, the results of DSC of Comparative Example 1-4 are shown in Fig. 4 -7. Table 1 and Figures 1-7 illustrate that the extrudable compositions of the present invention (Example 1-3) comprising PLA, BCD, and natural oils, fatty acids, waxes or waxes esters were PE (Comparative Example 1) and PP 2) and an improved PLA formulation that does not include BCD and PLA coated natural oils, fatty acids, waxes or wax esters (Comparative Examples 3 and 4),% elongation at break and% stiffness And breaking point energy and heat resistance; They also do not require toxic solvents without adverse effects on physical properties.

Example 4

An extrudable composition comprising 95.6% of amorphous PLA, 0.4% of nano-silica fiber, and 4.0% of white pigment is appropriately combined, dried, prepared and extruded into a film.

Example 5

An extrudable composition comprising 91.0% crystalline PLA, 4.0% mica, 1.0% jojoba oil applied to PLA, and 4.1% white pigment is suitably combined, dried, prepared and extruded into a film.

Example 6

Example 4 Extrudable compositions comprising a mixture of 50% and 50% of Example 5 are appropriately combined, dried, prepared and extruded into a film.

Comparative Example 5

100% amorphous PLA is extruded into the film.

Comparative Example 6

100% crystalline PLA is extruded into the film.

Comparative Example 7

100% polyester is extruded into a film.

The results of the stress / strain data of Example 4-6 and Comparative Example 5-7 are shown in Table 2, and the results of DSC data of Example 4-6 and Comparative Example 7 are shown in FIG. The results show that the extrudable compositions of the present invention (Examples 4-6) comprising PLA, BCD, nanofibers and / or natural oils are 100% PLA (Comparative Examples 5 and 6) or conventional polyester (Comparative Example 7) % Breakthrough stress and breaking point energy and heat resistance compared to the prior art.

The use of small amounts of nanofibers is shown in Examples 7 and 10.

Example 7

An extrudable composition comprising a blend of 95.5% of PLA and 3% of BCD and 1.5% of jojoba oil was prepared as described above, i.e. blended with an equivalent portion of 99.5% amorphous PLA and 0.5% of nanosilica fibers, , Dried and extruded into a film.

Example 8

An extrudable composition comprising 98.4% crystalline PLA, 1.5% jojoba oil and 0.1% nano-silica fiber is appropriately combined, dried, prepared as described above and extruded into a film.

Example 9

An extrudable composition comprising 99.9% amorphous PLA and 0.1% nano-silica fiber is suitably combined, dried, prepared and extruded into a film.

Example 10

Extrudable compositions comprising a mixture of 95.5% of crystalline PLA, 3% of BCD and 1.5% of jojoba oil, and 95.75% of crystalline PLA and 0.25% of nanosilica fibers and 4% of white pigment, And then extruded into a film.

The results of the stress / strain data of Examples 7-10 are shown in Table 3.

The use of small amounts of nanofibers is shown in Examples 11-13.

Example 11

Extrudable compositions comprising 97.8% amorphous PLA, 0.2% nano-silica fibers, and 2% white pigment are appropriately combined, dried, prepared and extruded into a film.

Example 12

An extrudable composition comprising 94.7% of amorphous PLA, 0.3% of nano-silica fiber, 1.0% of mica, and 4.0% of white pigment is appropriately combined, dried, manufactured and extruded into a film.

Example 13

An extrudable composition comprising 92.15% of amorphous PLA, 0.75% of jojoba oil, 0.1% of nano-silica fiber, 3.0% of mica, and 4.0% of white pigment is appropriately combined, dried, prepared and extruded into a film.

The stress / strain data results of Examples 11-13 are shown in Table 4 and the DSC data results are shown in FIG.

Example 14

To test an extrudable composition following the PET for containers, a master batch was prepared by adding a jojoba oil to crystalline PLA and stirring to 0.5% nano silica, 2.0% BCD, 1.0% mica and 20.0% mica and drying, &Lt; / RTI > 20% and 80% of the green pigments of PolyOne are added to the masterbatch in a ribbon-type mixer. To this is added 100% crystalline PLA. The final overall composition is as follows.

89.7% Crystalline PLA

0.4% BCD

1.6% Jojoba oil

0.1% Nanosilica fiber

4.0% mica

0.2% 칡

4.0% Green pigment

Example 15

The final total composition is prepared as described above to test one extrudable composition following HDPE for bottle caps.

88.5% Crystalline PLA

1.0% BCD

3.0% Safflower oil

0.1% Nanosilica fiber

2.0% mica

0.2% Xanthan gum

5.0% White pigment

0.2% TEC

Stress / strain data for Examples 14 and 15 compared to Comparative Example 6 (100% PLA) and Comparative Example 8 (100% HDPE) DSC data of Example 14 (Earth Bottle EB-PET) compared with Comparative Example 6 and DSC data of Example 15 (Earth Bottle EB-HDPE) compared with Comparative Example 8 are shown in FIG. 10 Respectively.

Example 16

To test the extrudable composition with the container white, a master batch was prepared by adding 0.4% of safflower oil and 0.4% of shea butter polish, followed by 0.4% of nano silica to prepare an extrudable composition. This is followed by agitation over 59.6% of crystalline PLA and stirring with BCD 1.6%, TiO ₂ dye 24%, 칡 0.8%, mica 8%, and candelilla wax (Barrier) 0.4% and dried. The master batch is combined with 50% of TiO ₂ dye and 50% of 100% crystalline PLA. The final overall composition is as follows.

92.9% Crystalline PLA

0.4% BCD

1.2% Safflower oil

0.1% Nanosilica fiber

2.0% mica

0.2% 칡

3.0% TiO ₂ pigment

0.1% Shea Butter Polish

0.1% Candelilla Barry

Example 17

To test the extrudable composition having a brown color for the container, a master batch was prepared by adding together 6.0% of jojoba oil and 0.5% of shea butter polish and then adding 0.5% of nano silica to prepare an extrudable composition. This was followed by stirring over 78.7% of crystalline PLA and a solution containing 2.0% of BCD, 1.0% of brown pigment (0.040 g of black, 0.018 g of blue, 0.210 g of red and 0.160 of red), 1.0% of manganese, 10.0% of mica, 0.5%, and dried. It binds with 24% of brown pigment and 76% of 100% crystalline PLA. The final overall composition is as follows.

95.7% Crystalline PLA

0.4% BCD

1.2% Jojoba oil

0.1% Nanosilica fiber

2.0% mica

0.2% 칡

0.2% Brown pigment

0.1% Shea Butter Polish

0.1% Candelilla Barry

Example 18

To test the extrudable composition with green for the container, a master batch was prepared by adding together 6.0% of jojoba oil and 0.5% of shea butter polish and then adding 0.5% of nano silica to prepare an extrudable composition. It is then stirred on 78.0% of 100% crystalline PLA and stirred with 2.0% BCD, 1.5% chlorophyllin dye, 1.0% urea, 10.0% mica, 0.5% candelilla wax barley and dried. This master batch is combined with 24% of chlorophyllin pigment and 76% of 100% crystalline PLA. The final overall composition is as follows.

95.6% Crystalline PLA

1.2% Jojoba oil

0.1% Nanosilica fiber

0.4% BCD

2.0% mica

0.2% 칡

0.3% Chlorophyllin pigment

0.1% Shea Butter Polish

0.1% Candelilla Barry

Examples 14a and 14b

To evaluate the barrier properties of extrudable compositions, the same compositions (14a and 14b) as in Example 14 were extruded into bottles with varying mica content, with the exception of% mica. Oxygen Permeation Rate (OTR) and water vapor transmission rate (WVTR) were measured. The results are shown in Tables 6 and 7.

The observed oxygen permeation rates exhibited by bottles made with the compositions of Examples 19-22 are comparable to PET and HDPE.

The observed water vapor transmission rates exhibited by the bottles made with the compositions of Examples 23-26 are comparable to PET.

To evaluate the barrier properties of the extrudable composition, the pure PLA composition is compared to Example 14 comprising 2% mica and Example 18 comprising 2% mica and cantelilla wax. The water vapor transmission rate (WVTR) was measured. The results are shown in Table 8.

Having described some embodiments of the invention, various obvious changes can be made therein without departing from the spirit or scope of the invention as hereinafter claimed, and the invention as defined by the appended claims is not limited by the specific details set forth in the above specification .

Claims

The heat distortion temperature is higher than about 50 캜 and the melting point is about 80 캜 to 190 캜,
a) about 60 to about 99.8% of partially crystalline or crystalline polylactic acid;
b) about 0.05 to about 8% cyclodextrin;
c) from about 0.1 to about 8% of a natural oil, fatty acid, fatty acid ester, wax or wax ester;
d) from about 0.01 to about 5% nanofibers;
e) from about 0% to about 10% crystallizer;
f) from about 0% to about 1% of a melt rheology modifier based on starch;
g) about 0% to about 5% pigment;
h) from about 0 to about 1% plasticizer;
i) from about 0% to about 1% of a polish agent; And
j) from about 0% to about 1% of the barrier.

The composition according to claim 1, wherein the cyclodextrin is? -Cyclodextrin.

The method according to claim 1, wherein the natural oil is selected from the group consisting of lard, tallow, fish oil, coffee oil, coconut oil, soybean oil, safflower oil, tung oil, tall oil, marigold, rapeseed oil, peanut oil, linseed oil, sesame oil, , Dehydrated castor oil, tallow oil, sunflower oil, cottonseed oil, corn oil, canola oil, orange oil, and mixtures thereof.

2. The composition of claim 1, wherein the fatty acid ester is a polymerization product of an unsaturated higher fatty acid.

5. The composition of claim 4 wherein said unsaturated higher fatty acid ester is selected from the group consisting of oleic acid, linoleic acid, resinoleic acid, lauric acid, myristic acid, stearic acid, palmitic acid, eicosanoic acid, eleostearic acid, glycerol, &Lt; / RTI > and mixtures thereof.

The method according to claim 1, further comprising adding additives selected from the group consisting of a plasticizer, an impact modifier, an additional fiber reinforcement, an antioxidant, an antimicrobial agent, a filler, a UV stabilizer, a pigment, a glass transition temperature modifier, a melting point modifier, &Lt; / RTI >

The extrudable composition of claim 1, wherein the nanofibers are derived from silica or cellulosic fibers.

The extrudable composition of claim 1, wherein the crystallizing agent is selected from the group consisting of mica, kaolin, clay, talc, calcium carbonate, aluminum oxide, and mixtures thereof.

2. The composition of claim 1 wherein the moisture content is less than about 0.02% water.

The composition according to claim 1, wherein the starch-based melt flow modifier is gum.

The composition of claim 1, wherein the plasticizer is an acid ethyl ester.

12. The extrudable composition of claim 11, wherein the acid ethyl ester is triethyl citrate.

A product formed from the extrudable composition of claim 1.

14. The article of manufacture of claim 13, wherein said article of manufacture is selected from the group consisting of a bottle, a lid, a lid, a stopper, a container, a package and a barrel.

14. The article of manufacture of claim 13, wherein said article is a container.

16. The container of claim 15, wherein the cyclodextrin is beta -cyclodextrin.

The method according to claim 15, wherein the natural oil is selected from the group consisting of lard, tallow, fish oil, coffee oil, coconut oil, soybean oil, safflower oil, tung oil, tall oil, marigold, rapeseed oil, peanut oil, linseed oil, sesame oil, grape seed oil, , Dehydrated castor oil, tallow oil, sunflower oil, cottonseed oil, corn oil, canola oil, orange oil, and mixtures thereof.

a) about 70 to 95% crystalline polylactic acid;
b) about 0.05 to 8% cyclodextrin;
c) about 0.1 to 8% of a natural oil, fatty acid, fatty acid ester, wax or wax ester;
d) about 0.01 to 5% of nanofibers;
e) from about 0.01 to 10% crystallizer;
f) about 0.01 to 1% of a melt flow modifier based on starch; or
g) a container formed from an extrudable composition derived from a renewable resource comprising from about 0.01 to 8% of a pigment.

19. The container of claim 18, wherein the cyclodextrin is beta-cyclodextrin.

The method according to claim 18, wherein the natural oil is selected from the group consisting of lard, tallow, fish oil, coffee oil, coconut oil, soybean oil, safflower oil, tung oil, tall oil, marigold, rapeseed oil, peanut oil, linseed oil, sesame oil, grape seed oil, , Dehydrated castor oil, tallow oil, sunflower oil, cottonseed oil, corn oil, canola oil, orange oil, and mixtures thereof.

19. The container of claim 18, wherein the fatty acid ester is a polymerized product of an unsaturated higher fatty acid.

22. The composition of claim 21, wherein the unsaturated higher fatty acid ester is selected from the group consisting of oleic acid, linoleic acid, regenoric acid, lauric acid, myristic acid, stearic acid, palmitic acid, eicosanoic acid, eleostearic acid, glycerol, Lt; RTI ID = 0.0 > of: < / RTI >

19. The composition of claim 18, further comprising additives selected from the group consisting of a plasticizer, an impact modifier, an additional fiber reinforcement, an antioxidant, an antimicrobial agent, a filler, a UV stabilizer, a pigment, a glass transition temperature modifier, a melting point modifier, Containers containing.

19. The container of claim 18, wherein the nanofiber is derived from silica or cellulosic fibers.

19. The container of claim 18, wherein the crystallizing agent is selected from the group consisting of mica, kaolin, clay, talc, calcium carbonate, aluminum oxide, and mixtures thereof.

19. The container of claim 18 wherein the moisture content is less than about 0.02% water.

19. The container of claim 18, wherein the starch-based melt flow modifier is a melt.

19. The container of claim 18, wherein the plasticizer is an acid ethyl ester.

29. The container of claim 28, wherein the acid ethyl ester is triethyl citrate.

19. The container of claim 18, wherein the extrudable composition further comprises candelilla wax or shea butter or both.

The container and the stopper are both formed from an extrudable composition derived from a renewable resource,
a) about 70 to 95% crystalline polylactic acid;
b) about 0.05 to 8% cyclodextrin;
c) about 0.1 to 8% of a natural oil, fatty acid, fatty acid ester, wax or wax ester;
d) from about 0.01 to 10% crystallizer;
e) about 0.01 to 1% of a crystallization retarding agent; And
f) about 0.01 to 8% pigment.

32. The closure of claim 31, wherein the cyclodextrin is? -Cyclodextrin.

The method of claim 31, wherein the natural oil is selected from the group consisting of lard, tallow, fish oil, coffee oil, coconut oil, soybean oil, safflower oil, tung oil, tall oil, marigold, rapeseed oil, peanut oil, linseed oil, sesame oil, , Dehydrated castor oil, tallow oil, sunflower oil, cottonseed oil, corn oil, canola oil, orange oil, and mixtures thereof.

32. The closure of claim 31, wherein the fatty acid ester is a polymerization product of an unsaturated higher fatty acid.

35. The composition of claim 34, wherein the unsaturated higher fatty acid ester is selected from the group consisting of oleic acid, linoleic acid, regenoric acid, lauric acid, myristic acid, stearic acid, palmitic acid, eicosanoic acid, eleostearic acid, glycerol, Wherein the stopper is selected from the group consisting of:

32. The closure of claim 31, wherein the cyclodextrin is? -Cyclodextrin.

32. The composition of claim 31, further comprising additives selected from the group consisting of a plasticizer, an impact modifier, an additional fiber reinforcement, an antioxidant, an antimicrobial agent, a filler, a UV stabilizer, a pigment, a glass transition temperature modifier, a melting point modifier, Stopper included.

32. The closure of claim 31, wherein the nanofibers are derived from silica or cellulosic fibers.

32. The closure of claim 31, wherein the crystallizing agent is selected from the group consisting of mica, kaolin, clay, talc, calcium carbonate, aluminum oxide, and mixtures thereof.

No content

32. The closure of claim 31 wherein the moisture content is less than about 0.02% water.

32. The closure of claim 31, wherein the starch based melt flow modifier is a starch.

32. The closure of claim 31, wherein the crystallization retarder is selected from the group consisting of xanthan gum, guar gum, and locust bean gum.

32. The closure of claim 31, wherein the extrudable composition further comprises candelilla wax or shea butter or both.

A bottle cap or lid made from an extrudable composition comprising a PLA and a polysaccharide crystallization retarder derived from a renewable resource and coated with cyclodextrin, natural oils, fatty acid esters, waxes or wax esters and / or alkyl ester plasticizers.

48. The method of claim 48 wherein said natural oil is selected from the group consisting of lard, tallow, fish oil, coffee oil, coconut oil, soybean oil, safflower oil, tung oil, tall oil, marigold, rapeseed oil, peanut oil, linseed oil, sesame oil, grape seed oil, , Dehydrated castor oil, tallow oil, sunflower oil, cottonseed oil, corn oil, canola oil, orange oil, and mixtures thereof.

49. The bottle cap or cap of claim 48, further comprising nanosilica fibers having a diameter of less than 1 占 퐉.

49. The bottle lid or lid of claim 48, further comprising a crystallizing agent.

49. The bottle cap or cap of claim 48, wherein said cyclodextrin is beta-cyclodextrin.

49. The bottle cap or lid of claim 48, wherein the polysaccharide crystallization control agent is a xanthan gum.

Coating PLA with natural oils, fatty acids, fatty acid esters, waxes or wax esters and / or alkyl ester plasticizers;
Mixing the coated PLA with cyclodextrin;
Drying the mixture so that the moisture content is less than 0.2% of water;
Extruding the dried mixture; And
And molding the extruded composition into a product.

55. The method of claim 54, wherein the PLA and inclusion particles are coated with a natural oil, fatty acid, fatty acid ester, wax or wax ester and / or alkyl ester plasticizer through agitation.

55. The method of claim 54, wherein the nanofiber, cyclodextrin, crystallizing agent, melt flow modifier based on starch and the polysaccharide crystallization retarder are substantially saturated with oil so that the cyclodextrin is substantially comprised in the PLA polymer matrix. To about 160 < 0 > F to about 180 < 0 > F for a period of from about 4 to about 12 hours.

55. The method of claim 54, wherein the molded article is molded by extrusion, injection molding or blow molding.

55. The method of claim 54, wherein the cyclodextrin is? -Cyclodextrin.

54. The method of claim 54, wherein said PLA is selected from the group consisting of rod, tallow, fish oil, coffee oil, coconut oil, soybean oil, safflower oil, tung oil, tall oil, marigold, rapeseed oil, peanut oil, linseed oil, sesame oil, grape seed oil, Dehydrated castor oil, tallow oil, sunflower oil, cottonseed oil, corn oil, canola oil, orange oil, and mixtures thereof.

55. The method of claim 54, wherein the alkyl ester plasticizer is triethyl citrate.

55. The method of claim 54, wherein the mixture further comprises a nanofiber, a crystallizing agent, a melt flow modifier based on starch, a polysaccharide crystallization retarder, and / or a pigment.

55. The method of claim 53, wherein the product is selected from the group consisting of a bottle, a lid, a lid, a container, a package, and a barrel.