JP2015533186A - Composition for extrusion molding from renewable resources - Google Patents

Abstract

The extrusion composition has a heat deflection temperature of about 50 ° C. or higher and a melting point of about 80 ° C. to about 180 ° C., and the extrusion composition has about 60 to about 99.8% partial crystals. Crystalline polylactic acid, about 0.05 to about 8% cyclodextrin, about 0.1 to about 8% natural oil, fatty acid, fatty acid ester, wax or wax ester, about 0.01 to about About 0% to about 10% crystallization agent; about 0 to about 1% starch-based melt rheology modifier; about 0 to about 5% colorant; About 1% plasticizer, about 0 to about 1% brightener, and about 0 to about 1% blocking agent.

Description

[Cross-reference of related applications]
No. 61/705683 (filed on Sep. 26, 2012), U.S. Provisional Application No. 61/726188 (Nov. 14, 2012), U.S. Provisional Patent Application No. 61/844155. (July 9, 2013), and US Patent Application No. 13/790889, a continuation-in-part application (March 8, 2013). All of these disclosures are hereby incorporated by reference herein.

  The present invention relates to a composition for extrusion and a method for producing a molded article therefrom. The composition for extrusion includes a polylactic acid polymer derived from renewable resources, and the composition is biodegradable.

  Molded articles are typically formed from various extrusion polymer compositions, examples of such products include bottles and other food containers, films, packaging, and the like. In the past, such molded articles have typically been formed from petroleum-based polymers that are not derived from renewable resources and are not biodegradable. Examples of such petroleum-based polymers are polypropylene (PP), polyethylene terephthalate (PET), polystyrene (PS), and polyvinyl chloride (PVC). Not only are these petroleum-based polymers themselves environmentally friendly, but the solvents and methods for producing the polymers are not environmentally friendly. Furthermore, some of these polymers can be recycled, but they are not biodegradable and cause problems in landfills.

  A solution to this problem is to form molded articles from polymers derived from renewable resources. An example of such a renewable resource-derived polymer is polylactic acid (PLA). PLA is derived from a variety of natural renewable resources such as corn, plant starch (eg, potato), and stem (eg, sugarcane). Such efforts utilizing PLA are described, for example, in US Patent Application Publication No. 2011/005847, US Patent Application Publication No. 2010/0105835, International Publication No. 2007/047999, and US Pat. No. 5,744,510. , US Pat. No. 6,150,438, US Pat. No. 6,756,428, and US Pat. No. 6,869,985. All of these disclosures are hereby incorporated by reference. As used herein, “lactide-based polymer” is intended to be synonymous with terms such as polylactide, polylactic acid (PLA), polylactide polymer, etc., and any of those formed by ring-opening polymerization of lactide monomers. Are also intended to be included, which may be alone (ie, a homopolymer) or a mixture or copolymer with another monomer. This term is intended to include both the form and arrangement of the monomers that make up the polymer (syndiotactic, isotactic, amorphous, crystalline, partially crystalline, etc.). Lactide based polymers may or may not be derived from renewable resources.

  PLA is produced by ring-opening polymerization of lactide. PLA is a crystalline polymer and thus faces difficulties with respect to melt viscosity, temperature stability, tensile force, and impact resistance when molded. Therefore, an improved extrusion that is more environmentally friendly, i.e. derived from renewable resources and biodegradable, to overcome the difficulties that arise when molding products from such compositions, particularly those comprising PLA. There is still a need for compositions for this purpose.

  In view of such circumstances, the present invention provides a composition for extrusion molding comprising cyclodextrin and polylactic acid (PLA) coated with natural oil (for example, plant-based oil), fatty acid, wax or wax ester. It is to provide. The present invention also provides a method of forming a molded article from an extrusion composition comprising coating PLA with natural oil, fatty acid, fatty acid ester, wax or wax ester; Mixing the coated PLA with cyclodextrin, drying the mixture to remove substantially all of the moisture, extruding the dried mixture, and the extruded composition Molding the product into the shape of the product.

Furthermore, the present invention provides, as one aspect thereof, an extrusion composition having a heat deflection temperature of about 50 ° C. or higher and a melting point of about 80 ° C. to about 190 ° C. The composition for
(A) about 60 to about 99.8% partially crystalline or crystalline polylactic acid;
(B) about 0.05 to about 8% cyclodextrin;
(C) about 0.1 to about 8% natural oil, fatty acid, fatty acid ester, wax or wax ester;
(D) about 0.01 to about 5% nanofibers;
(E) about 0 to about 10% crystallinity agent;
(F) about 0 to about 1% starch-based melt rheology modifier;
(G) from about 0 to about 5% colorant;
(H) from about 0 to about 1% plasticizer;
(I) about 0 to about 1% gloss agent;
(J) about 0 to about 1% of a barrier agent.

  The present invention, as another aspect, provides a container formed from a composition for extrusion from renewable resources, the composition for extrusion comprising natural oil, fatty acid ester, wax or Includes PLA and cyclodextrin coated with wax ester, nanofibers, crystallization agent, starch-based rheology modifier, and colorant.

  In another aspect, the present invention provides a closure for a container formed from an extrusion composition, the extrusion composition comprising a natural oil, a fatty acid ester. PLA and cyclodextrin coated with wax or wax ester, crystallization agent, crystallinity retarder, and colorant.

  In yet another aspect, the present invention provides a cap or lid formed from an extrusion composition, the extrusion composition comprising a natural oil, fatty acid ester, wax or wax ester. PLA and cyclodextrin coated with, a crystallization agent, a crystal retarder, a colorant, and optionally nanofibers.

  The present invention, as yet another aspect, provides a method of forming a molded article, the method comprising coating PLA with natural oil, fatty acid, fatty acid ester, wax and / or wax ester; Mixing the coated PLA with cyclodextrin, drying the mixture to a moisture level such that it contains no more than 0.2% water, and extruding the dried mixture. Forming the extruded composition into a product shape.

It is a DSC chart corresponding to a 1st Example. It is a DSC chart corresponding to a 2nd Example. It is a DSC chart corresponding to a 3rd Example. It is a DSC chart corresponding to the 1st comparative example. It is a DSC chart corresponding to the 2nd comparative example. It is a DSC chart corresponding to the 3rd comparative example. It is a DSC chart corresponding to the 4th comparative example. It is a DSC chart corresponding to the 4th-6th Example and the 7th comparative example. It is a DSC chart corresponding to 10th-13th Example. It is a DSC chart corresponding to the 14th and 16th examples and the 6th and 8th comparative examples.

  Each aspect of the present invention described above will be described in more detail with reference to the following description of the present specification and the accompanying drawings. The present invention can be implemented in a wide variety of forms and should not be construed as limited to the embodiments set forth herein, but rather, these embodiments encompass the present disclosure. And is intended to fully convey the scope of the invention to those skilled in the art.

The terminology used in the description of the invention herein is for the purpose of describing particular embodiments and is not intended to be limiting of the invention. In the description of the embodiments of the invention and in the appended claims, the singular forms “a,” “an,” “the,” and the like include the plural unless specifically stated otherwise. As used herein, “and / or” refers to any and all combinations of one or more of the associated listed items and are intended to include combinations thereof. Further, as used herein, the term “about” when referring to measurable values such as compound content, application amount, time, temperature, etc., is 20%, 10%, 5%, 0% of the specified amount. Including a variation of .5%, or even 0.1%. When ranges (eg, x to y ranges) are used, the measured value shall mean a range of about x to about y or any other range, such as about x ₁ to about y ₁ . As used herein, the term “comprising” identifies the presence of a described feature, integer, step, operation, element, and / or component, but one or more other features, integer, step, operation, The presence or addition of elements, components and / or groups thereof shall not be excluded. Unless defined otherwise, all terms including technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.

  Terms such as “first”, “second”, “third”, “(a)”, “(b)”, and “(c)” describe various elements of the present invention herein. However, the present invention is not intended to be limited by these terms. These terms are only used to distinguish one element of the invention from another. In this way, the first element described below can also be named an element aspect without departing from the teaching of the present invention, and the same applies to the third. In this way, “first”, “second”, “third”, “(a)”, “(b)”, “(c)”, etc. are sequences of related elements or other hierarchies. Is not necessarily communicated, but only for identification purposes. The sequence of operations (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 hereby incorporated by reference in their entirety. If there is a conflict in terminology, this specification is correct.

  An embodiment described for one aspect of the invention does not correspond to only one aspect. Any embodiment can be applied to any aspect of the invention, provided that the embodiment does not prevent that aspect of the invention from achieving its objectives.

  As mentioned above, the present invention provides an extrusion composition comprising cyclodextrin and polylactic acid (PLA) coated with natural oil, fatty acid or wax. In one embodiment, the composition for extrusion may include a carboxylic acid or alkyl ester plasticizer. In another embodiment, the composition for extrusion may include nanofibers. In yet another embodiment, the composition for extrusion may include a crystallization agent or a crystal retardant. In yet another embodiment, the extrusion composition may include a rheology modifier. In yet another embodiment, the composition for extrusion may include a colorant, which is often a naturally occurring colorant. In yet another embodiment, the extrusion composition may include a brightener. In yet another embodiment, the composition for extrusion may include a blocking agent. Various combinations of these embodiments also belong to the technical scope of the present invention.

  The composition for extrusion molding according to the present invention is a non-biodegradable conventional polymer derived from non-renewable resources such as polyethylene terephthalate (PET), high density polyethylene (HDPE), polyethylene (PE), and polypropylene (PP). Sometimes formulated to substantially mimic properties. In particular, the present invention provides a composition for extrusion having the same heat deflection or heat distortion (HDT), melt viscosity, temperature stability, and impact resistance as conventional polymers.

  PLA is usually derived from lactic acid. Lactic acid can be produced commercially by fermentation of agricultural products such as whey, corn, corn starch, potato, molasses and sugar cane. Typically, PLA polymer formation first forms lactide monomers by depolymerization of lactic acid oligomers. The monomer is then ring-opening polymerized. As used herein, the term “lactide-based polymer” is intended to be synonymous with terms such as polylactide, polylactic acid (PLA), and polylactide polymer, and is formed by ring-opening polymerization of lactide monomers. Any polymer is intended to be included, and this polymer may be alone (ie, a homopolymer) or may be a mixture or copolymer with another monomer. This term is intended to include both the form and arrangement of the monomers that make up the polymer (syndiotactic, isotactic, etc.). Lactide based polymers may or may not be derived from renewable resources.

  Lactide monomers can be polymerized in the presence of a suitable polymerization catalyst at high temperature and pressure 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 include stannous octoate, aluminum isopropoxide, and certain rare earth metal compounds described in US Pat. No. 5,028,667, such as alkyl lithium salts. The amount of catalyst used will generally vary depending on the catalytic activity of the material, as well as the temperature of the process and the desired polymerization rate. Typical catalyst concentrations are from about 10: 1 to about 100,000: 1 molar ratio of lactide to catalyst, and in one embodiment, the molar ratio is from about 2000: 1 to about 10,000: 1. As an example of the process, the catalyst can be dispersed within the starting lactide monomer material. When solid, the catalyst has a relatively small particle size. In one embodiment, the catalyst may be added to the monomer solution as a diluted solution in an inert solvent, which facilitates handling of the catalyst and facilitates uniform mixing of the entire monomer solution. become. In embodiments where the catalyst is toxic, the process may be followed by a polymerization reaction followed by a step of removing the catalyst from the mixture, for example, performing one or more leaching steps. it can.

  In one embodiment, the polymerization process is performed at an elevated temperature, such as from about 95 ° C to about 200 ° C, in one embodiment from about 110 ° C to about 170 ° C, and in another embodiment from about 140 ° C to about 160 ° C. ° C. The temperature is usually selected to obtain an appropriate polymerization rate for the particular catalyst used while maintaining a temperature low enough to avoid polymer degradation. In one embodiment, the polymerization is performed under high pressure as is generally known in the art. Typically, this process takes from about 1 to about 72 hours, such as from about 1 hour to about 4 hours.

  The molecular weight of the degradable polymer must be high enough to allow entanglement of the polymer molecules, while low enough to allow melt processing. For melt processing, the average molecular weight of the PLA polymer or copolymer is from about 10,000 g / mol to about 600,000 g / mol, preferably about 500,000 g / mol or less or about 400,000 g / mol or less. More preferably from about 50,000 g / mol to about 300,000 g / mol or from about 30,000 g / mol to about 400,000 g / mol, most preferably from about 100,000 g / mol to about 250,000 g. / Mol or about 50,000 g / mol to about 200,000 g / mol. When using PLA, the PLA is preferably in the form of a semi-crystal or a partial crystal. To form a semicrystalline PLA, it is preferred that at least about 90 mole percent of the repeating units in the polylactide is one of L-lactide and D-lactide, even more preferably at least about 95 mole percent. That's right. Processing is performed in a way that facilitates crystal formation, for example using a wide range of orientations. Alternatively, amorphous PLA may be blended with PLA having higher crystallinity. Alternatively, the crystallization agents described below may be added to make amorphous PLA more crystalline and / or to adjust both levels when both amorphous and crystalline PLA are used.

  Polylactide homopolymers available from commercial sources may be disclosed and utilized to form polymer composites. For example, poly (L-lactic acid) available from Polyscience, Inc, Natureworks, LLC, Cargill, Inc, Mitsui (Japan), Shimadzu (Japan), Chronopol or Synbra Technolpogies (Netherlands) is utilized in the disclosed method. Sometimes. PLA polymers may have melting points that are low enough for processability but high enough for thermal stability. As such, the melting point is about 80 ° C. to about 190 ° C., and in some embodiments about 150 ° C. to 180 ° C.

  The PLA may be copolymerized with one or more other polymeric materials. In one embodiment, the lactide-based copolymer may be copolymerized with one or more other monomers or oligomers derived from non-renewable resources. Thus, in one embodiment, the lactide-based copolymer may be a PLA polymer or copolymer and polyhydroxyalkanoate (PHA). PHA has rapid environmental degradability but does not have the processability of PLA. PHA may be induced by bacterial fermentation of sugar or lipid. Examples of PHA are described in US Pat. No. 6,808,795. A commercially available PHA is Nodax (registered trademark) manufactured by Proctor & Gamble.

  In another embodiment, the PLA may be copolymerized with another polymer or copolymer that may or may not be biodegradable. Examples of such polymers or copolymers include polypropylene (PP), aromatic / aliphatic polyesters, aliphatic polyesteramide polymers, polycaprolactones, polyesters, polyurethanes derived from aliphatic polyols, polyamides, polyethylene terephthalate (PET), polystyrene ( PS), polyvinyl chloride (PVC), and cellulose esters that are or are not biodegradable.

  In addition to the PLA described above, the composition for extrusion includes cyclodextrin. Cyclodextrins (CDs) are cyclic oligomers of glucose that typically contain 6, 7, or 8 glucose monomers joined by α-1,4 linkages. These oligomers are typically α-cyclodextrin (α-CD), β-cyclodextrin (β-CD or BCD), and γ-cyclodextrin (γ-CD), respectively. Higher oligomers containing up to 12 glucose monomers are known, but their production is more difficult. Each glucose unit has three hydroxyls in the 2, 3, and 6 positions. Thus, α-CD has 18 hydroxyls or 18 substitution sites, and α-CD may have a maximum degree of substitution (DS) of 18. Similarly, β-CD and γ-CD have a maximum DS of 21 or 24, respectively. DS is often expressed as an average DS. Average DS is the number of substitutions divided by the number of glucose monomers in cyclodextrin. For example, fully acylated β-CD will have a DS of 21 or an average DS of 3. In terms of terminology, this derivative is referred to as heptakis (2,3,6-tri-O-acetyl) -β, cyclodextrin, typically abbreviated as triacetyl-β-cyclodextrin.

  The production of CD is first treated with an enzyme known as cyclodextrin glucosyltransferase, which treats starch with α-amylase to partially reduce the molecular weight of starch and then forms a cyclic structure. Topologically, CD is represented as a toroid, where the primary hydroxyl is located on the smaller periphery and the secondary hydroxyl is located on the larger periphery. Due to this arrangement, the interior of the torus is hydrophobic, while the exterior is sufficiently hydrophilic that the CD can dissolve in water. This difference between the inner and outer surfaces is that the CD or selected CD derivative acts as a host molecule and that if the hydrophobic guest molecule is properly dimensioned to fit within the cavity, the hydrophobic guest molecule Makes it possible to form inclusion complexes.

  Therefore, PLA becomes a guest molecule. However, cyclodextrins, especially BCD, do not dissolve in PLA resins and are therefore poorly dispersed. One known solution is to use an organic solvent to aid dispersion. However, such organic solvents are not desirable. This is because organic solvents such as toluene and methylene chloride are not environmentally friendly.

  We have found the surprising fact that the dispersion is improved by adding natural oils, fatty acids, fatty acid esters, waxes or wax esters to the PLA before mixing or blending the PLA and CD together. In one embodiment, a natural oil, fatty acid, fatty acid ester, wax or wax ester is coated on PLA (eg, PLA pellets) using agitation. Without being bound by one theory, hydrophilic coatings of natural oils, fatty acids, waxes and wax esters first enter the center of the CD, which natural oils, fatty acids, waxes or wax esters CD PLA. It is assumed that the composition can be easily extruded by pulling it into the center of the film. Natural oils, fatty acids, waxes or wax esters may use blends or mixtures thereof.

  In one embodiment, the composition for extrusion may comprise natural oil. Suitable oils are lard, beef tallow, fish oil, coffee oil, soybean oil, safflower oil, oilseed oil, tall oil, calendula oil, rapeseed oil, peanut oil, linseed oil, sesame oil, grape seed oil, olive oil, jojoba oil, dehydrated castor oil Beef tallow oil, sunflower oil, cottonseed oil, corn oil, canola oil, orange oil, and mixtures thereof. In the practice of the present invention, the shaped particles or additives introduced into the PLA polymer are preferably coated with at least one of the above oils and from about 160 ° F. to about 180 over about 4 to about 12 hours. Should be heated to ° F. This will substantially saturate the particles or additives with oil. In this way, after the particles or additives are saturated in the presence of heat, the particles substantially enter the PLA polymer matrix.

  Suitable waxes include naturally occurring waxes and wax esters, including but not limited to bee waxes, plant-based waxes, bird waxes, non-beebee insect waxes, and microbial waxes. Wax esters can also be used. As used herein, “wax ester” refers to an ester of a long-chain aliphatic alcohol having a long-chain fatty acid. The chain lengths of the fatty alcohol and fatty acid components of the wax ester vary, but in general, the wax ester may contain a total of about 20 or more carbon atoms. Wax esters may generally have a melting point of about 45 ° C. or higher. In addition, the wax ester herein includes wax esters such as saturated or unsaturated, branched or straight chain. It has been found that the wax facilitates increasing the thermal deflection temperature of the PLA film and provides barrier properties such as reducing oxygen migration and water vapor migration.

  Suitable fatty acid esters are the polymerization products of unsaturated higher fatty acids reacted with alcohol. Examples of higher fatty acid esters include oleic acid esters, linoleic acid esters, lauric acid esters, myristic acid esters, stearic acid esters, palmitic acid esters, eicosanoic acid esters, eleostearic acid esters, and the like, and mixtures thereof.

  These esters may be combined with a suitable oil, and various esters derived from carboxylic acids may be included as acting as plasticizers for PLA. Exemplary carboxylic acids include acetic acid, citric acid, tartaric acid, lactic acid, formic acid, oxalic acid and benzoic acid. Further, these acids may be reacted with ethanol to produce carboxylic acid ethyl esters such as ethyl acetate, ethyl lactate, monoethyl citrate, diethyl citrate and triethyl citrate (TEC). Most naturally derived fats and oils are fatty acid esters of glycerol.

  In another embodiment, the extrusion composition may include nanofibers. Suitable nanofibers include silica-derived fibers, have a diameter of about 1 μm or less using SEM measurements, and typically have a length of about 65 μm to 650 μm. A suitable nanofiber is available from John Manville as Micro-Stand® 106-475. Alternatively, nanofibers derived from treated (purified) cellulose may be used. For example, wood pulp is treated with natural oil, and the pulp and oil are mechanically disaggregated with a pulp-type disaggregator to produce fibrils, which cause the solution to form a gel. Biodegradable wood fibers such as bleached or unbleached hardwood or softwood kraft pulp may be used as the pulp. Northern hardwoods with high fiber counts such as aspen and tropical hardwoods such as eucalyptus are particularly advantageous. Non-wood fibers may also be used, such as flux, Asa, African hanega, cotton, kenaf, bamboo, Manila Asa, rice straw, or other fibers of plant origin. Alternatively, renewable and biodegradable resource cellulose fibers, particularly cellulose fibers having a microfibrous structure such as switchgrass may be used. Although applicants do not wish to be bound by any theory, nanofibers contribute to the crystallinity of PLA, thus facilitating the use of amorphous PLA and utilizing amorphous and / or partially crystalline PLA Then, it is estimated that it contributes to the improvement of the physical characteristic of the composition for extrusion molding.

  In another embodiment, the composition for extrusion may include a crystallization agent and the polymer may be in the form of platelet-like crystals. Examples of crystallization agents include but are not limited to kaolin, mica, bentonite clay, calcium carbonate, titanium dioxide and aluminum oxide.

  In another embodiment, the composition for extrusion may include a starch-based melt rheology modifier. Suitable starch is starch produced by plants, such plants include cereals (corn, rice, sorghum, etc.), potatoes, kuzukon, tapioca and sweet potatoes. In the practice of this invention, these plant-based starches can gel when combined with PLA, providing a smooth surface to the molded article.

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

  Another embodiment may include colorants that provide common colors associated with pharmaceutical and functional food containers, ie, white, amber, and green. In embodiments where a white container is desired, titanium dioxide can be used, preferably with safflower oil as a natural oil. Typically, the amount of colorant present is 0-67% depending on the type of extruder used, and preferably about 0.1-3 based on the total weight of the composition for extrusion. %. In embodiments where a green container is desired, copper chlorophyllin sodium or food grade aniline powder available from DDW The Color House can be used as a colorant. In embodiments where an amber color is desired, 0.019-0.021% food grade black, 0.008-0.010% blue, 0.104-0.0.0 available from Keystone (Chicago, Ill.). A blend of 106% red and 0.063-0.065% yellow colorant can be used.

  Agents that provide additional water and oxygen barrier properties may be included. Examples of water and oxygen barriers are canderia wax, beeswax, and other waxes. Preferably such blocking agents are derived from renewable resources.

  A brightener may be included to provide an aesthetically pleasing gloss to the container. Examples of brighteners are nut oils such as shea butter and brazil nut oil. Preferably such brighteners are derived from renewable resources.

  Other additives include natural or synthetic plasticizers such as lignin, impact modifiers, fiber reinforcements other than nanofibers, antioxidants, antibacterial agents, fillers, UV stabilizers, glass transition temperature modifiers. , Melting point modifiers and thermal deflection temperature modifiers. Of particular importance as fillers are renewable non-wood fibers, such as those used for nanofibers, such non-wood fibers include kenaf, cotton, flux, African hanegaya, There are Asa, Manila Asa or various fibrous herbs.

  Generally, the extrusion composition is preferably an extrusion composition having a heat deflection temperature of about 50 ° C. or higher and a melting point of about 80 ° C. to about 190 ° C. The product comprises (a) about 0 to about 100% amorphous PLA, (b) about 0 to about 100% partially crystalline or crystalline PLA, (c) about 0.1 to about 8% natural oil or Natural wax, (d) about 0.01 to about 5% nanofibers, (e) about 0.05 to about 8% BCD, (e) about 0 to 10% crystallization agent, (f) about 0 ~ About 1% starch-based melt rheology modifier, (g) about 0 to about 1% polysaccharide crystal retarder, (h) about 0 to about 5% colorant, (i) about 0 to about 1% plasticizer, (j) about 0 to about 1% brightener, and (k) about 0 to about 1% blocking agent. In one embodiment of the invention, the composition for extrusion is about 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, Amorphous or crystalline PLA may be included in a proportion greater than 96%, 97%, 98% or about 99%. In another embodiment of the invention, the extrusion composition may comprise a mixture of amorphous and crystalline PLA. In another embodiment, the BCD is 0.05%, 0.4%, 1%, 2%, 3%, 4%, 5%, 6%, 7% or about 8% in the composition for extrusion. Present as BCD in amounts as low as%. In another embodiment, the natural oil or natural wax is about 0.1%, 0.25%, 0.5%, 0.75%, 1%, 1.5% in the composition for extrusion. Present as natural oil in proportions up to 2%, 3%, 4%, 5%, 6%, 7% or about 8%. In another embodiment, the nanofibers are about 0.1%, 0.2%, 0.25%, 0.3%, 0.4%, 0.5%, 0.75%, 1%, 2% %, 3%, 4% or up to about 5% as nanofibers. In another embodiment, the optional crystallization agent is about 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9% in the composition for extrusion. Present as a crystallization agent in proportions up to about 10%. In another embodiment, the optional starch-based melt rheology modifier is about 0.1%, 0.2%, 0.3%, 0.4%, 0.00% in the composition for extrusion. It is present in proportions up to 5%, 0.6%, 0.7%, 0.8%, 0.9% or about 1%. In another embodiment, the optional polysaccharide crystal retarder is about 0.1%, 0.2%, 0.3%, 0.4%, 0.5% in the composition for extrusion. , 0.6%, 0.7%, 0.8%, 0.9% or up to about 1%. In another embodiment, the optional colorant is about 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6% in the composition for extrusion. %, 0.7%, 0.8%, 0.9% or up to about 1%. In another embodiment, the optional plasticizer is about 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6% in the composition for extrusion. %, 0.7%, 0.8%, 0.9% or up to about 1%. In another embodiment, the optional brightener is about 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6% in the composition for extrusion. %, 0.7%, 0.8%, 0.9% or up to about 1%. In another embodiment, the optional blocking agent is about 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6 in the composition for extrusion. %, 0.7%, 0.8%, 0.9% or up to about 1%.

  Prior to extrusion, the extrusion composition is dried to remove substantially all moisture. That is, there is no more than about 0.02% water and often no more than about 0.01% water. Typically drying with a desiccant is utilized.

  In one embodiment, a master batch is used. By utilizing a masterbatch, expensive additives are pre-mixed in high proportions to form a masterbatch and then added to 100% PLA. Such use of the masterbatch can be used to cost-effectively incorporate additives that improve barrier properties, flexibility properties, HDT properties, and the like. In another embodiment, the masterbatch can also be formulated so that the color of the consumer product can be customized. For example, a small amount of base colorant (eg, green colorant) is added to pure PLA, and then the colorant / PLA composition is combined with the final extrusion composition with a small amount of colorant to produce the desired A final extrusion composition having the following color is obtained. A small amount of green in the masterbatch may be selected to reach the desired shade of the desired color.

  For illustrative purposes, it is also possible to make an extrusion composition for a closure or cap that has properties comparable to the HPDE closure or cap. A masterbatch comprising crystalline PLA, natural oil coated on this PLA, nanofibers, cyclodextrin, crystallization agent, pigment and crystal retarder can be formed, and the formation of this masterbatch This is done by coating, adding a crystallizing agent, blending the BCD, and combining the remaining ingredients.

  The extrusion composition is then formed into a product. For example, the process may include extruding, injection molding or blow molding the composition in the molten state. As used herein, an injection molding process includes any molding process in which a polymer melt or oligomer solution is pressed into a mold under pressure, for example, by a ram injector or a reciprocating screw, shaped and cured. The blow molding process may include any method in which the polymer is shaped by use of a fluid and then cured to form a product. The blow molding process may include any of extrusion blow molding, injection blow molding, and stretch blow molding. Extrusion methods include extrusion methods in which the melt is extruded from a die under pressure and cured to form a final product, such as a film or fiber. Single screw or twin screw extruders may be used, and it is within the ability of one skilled in the art to select the extruder and vary the amount of each component depending on the extruder.

  In one embodiment, the molded article is a container. The term “container” is used in this specification and the appended claims to store, distribute, package, divide or transport various types of products (including but not limited to food and beverage products) or objects. Including, but not limited to, any product, container, or vessel utilized to do. Specific examples of such containers are boxes, cups, “clamshells”, jars, bottles, plates, bowls, cutlery, trays, cartons, cases, frame boxes, cereal paper boxes, frozen boxes, milk cartons Includes beverage container carriers, dishes, egg cartons, lids, straws, envelopes, book shelves, bags, buggies, or other types of holders. Containment products and other products used in connection with containers are also intended to be included in the term “container”.

  In another embodiment, the composition for extrusion disclosed herein may be formed as a container, and in certain embodiments, environmentally sensitive, such as bioactive materials including drugs and functional foods. It is a suitable container for holding and protecting various materials. As used herein, the term “drug” is defined to include materials defined by the US government, including, for example, drugs and other biologics. As used herein, the term “functional food” is defined to refer to bioactive agents not necessarily prescribed by the US government, including, for example, vitamins, dietary supplements, and the like.

  In another embodiment, the molded article is a containment product, which is a closure. In this specification and the appended claims, the term “sealing device” refers to caps, lids, liners, dividers, packages, films, cushioning materials, household items, and any other product used in packaging. Including, but not limited to. Examples of seals include, but are not limited to, screw caps, snaps on the caps, tamper-evident mechanisms, tamper evident mechanisms, seals or caps with pediatric safety mechanisms.

  For purposes of illustration, it is also possible to make an extrusion composition for containers that has properties comparable to PET containers. Master batches containing partially crystalline or crystalline PLA, natural oils, nanofibers, cyclodextrins, pigments, crystallizing agents can be formed. Natural oil and nanofibers are added to the PLA along with other ingredients, combined with a mixture of cyclodextrin and starch crystal retarder, the crystallizing agent is added, and then stirred and dried. Colorants / pigments may be added to the masterbatch. Alternatively, a separate batch of crystalline PLA and pigment may be made and then the master batch and this separate batch are fed together.

  Examples of container formulations include about 70 to about 95% crystalline polylactic acid, about 0.05 to about 5% nanofibers, about 0.01 to about 10% crystallization agent, about 0.01 to about 1% starch-based rheology modifier, and from about 0.01 to about 8% colorant.

  As another illustrative example, it is possible to make an extrusion composition for a closure or cap for containers or bottles having properties equivalent to HDPE. Exemplary formulations for the cap include 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 Can comprise about ~ 10% crystallization agent, about 0.01 to about 1% crystal retarder, and about 0.01 to about 8% colorant, and can optionally include nanofibers. it can.

  Molded products and structures containing the composition for extrusion may include a laminate with the composite material disclosed as a laminate of one or more layers. For example, a laminate structure may include one or more layers formed from a composite material as described herein, thereby providing a specific inhibitor at a predetermined location in the laminate structure. can do. The barrier properties can be improved by using a wax coating inside or outside the vessel used as a spray and dip.

  Alternatively, various extrusion, blow molding, injection molding, casting or melting processes known to those skilled in the art may be used to form the film or sheet. Examples of such products are products used to wrap or otherwise package food or various other solid products. The film or sheet can have a wide variety of thicknesses, and other properties such as stiffness, breathability, temperature stability, etc. can be varied based on the desired end product and end product to be packaged. . Examples of techniques for providing a film or sheet include, for example, US Patent Application Publication No. 2005/0112352, US Patent Application Publication No. 2005/0182196, and US Patent Application Publication No. 2007/0116909. And U.S. Pat. No. 6,291,597, the disclosures of all of which are hereby incorporated by reference.

  As an example of an embodiment, the laminate may include an impermeable polymer layer that adheres to the surface of a structure, such as the inner surface of a container (eg, a bottle or jar) or a package (eg, a blister pack for tablets). Good. In a specific embodiment, an extruded film formed from an extrusion composition may form one or more layers of such a laminate structure. For example, an impermeable PLA-based film may form the inner layer of a container and thus prevent leakage, deterioration or evaporation of liquids that may be stored, for example, in the container. Such an embodiment is particularly useful when considering storage of alcohol-based liquids, such as alcohol-based extracts or functional foods in the form of tinctures. .

  The following examples are used 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 demonstrate that the properties were improved by coating PLA with natural oil prior to mixing with BCD.

[Example 1]
An extrusion composition was formed containing 91.5% PLA, 7% BCD, and 1.5% jojoba oil. If BCD and PLA are simply mixed, BCD is not well dispersed and does not dissolve in molten PLA during extrusion. In this way, jojoba oil is first applied on the PLA with stirring, then BCD is added to the coated PLA and stirred again. The composition is heated to 160 ° F. to 180 ° F. for 4-12 hours, thereby fully saturating the BCD with oil, thereby allowing the BCD particles to fully penetrate into the PLA polymer matrix. The resulting composition was then extruded as a film, which was uniform with no flakes.

[Example 2]
An extrusion composition was formed containing 90.5% crystalline PLA, 7% BCD, 1.5% jojoba oil, and 0.1% triethyl citrate (TEC) as a plasticizer. This was when jojoba oil and TEC were applied over the PLA with stirring, then BCD was added to the PLA and then stirred again. The composition is heated to 160 ° F. to 180 ° F. for 4-12 hours, which fully saturates the BCD with oil and TEC, thereby allowing the BCD particles to fully penetrate into the PLA polymer matrix. The resulting composition was then extruded as a film.

[Example 3]
An extrusion composition was formed containing 90.5% crystalline PLA, 7% BCD, 1.5% olive oil. This was the olive oil applied on the PLA with stirring, then BCD was added to the PLA and then stirred again. The composition is heated to 160 ° F. to 180 ° F. for 4-12 hours, which allows the BCD particles to fully penetrate into the PLA polymer matrix. The resulting composition was then extruded as a film.

[Comparative Example 1]
A 100% polyester (PE) composition was formed and extruded as a film.

[Comparative Example 2]
100% polypropylene (PP) was formed and extruded as a film.

[Comparative Example 3]
A PLA composition comprising amorphous PLA, jojoba oil, turmeric, and cotton floc was formed and extruded as a film.

[Comparative Example 4]
A PLA composition comprising amorphous PLA, jojoba oil, turmeric, and cotton floc was formed using a desiccant dryer and extruded as a film.

  Table 1 shows the results of the stress / strain data of Examples 1 to 3 and Comparative Examples 1 to 4. The results of the DSC data of Examples 1 to 3 are shown in FIGS. The results of the DSC data of Comparative Examples 1 to 4 are shown in FIGS. Table 1 and FIGS. 1-7 show the composition for extrusion of the present invention comprising PLA, BCD, and natural oils, fatty acids, waxes or wax esters (Examples 1-3), PE (Comparative Example 1) and Elongation compared to PP (Comparative Example 2) and compared to known PLA formulations without BCD and natural oils, fatty acids, waxes or wax esters coated on PLA (Comparative Examples 3 and 4) And toughness,% strain, breaking energy and heat resistance were improved. Furthermore, a strong solvent that adversely affects physical properties was not necessary.

[Example 4]
Extruded compositions containing 95.6% amorphous PLA, 0.4% nanosilica fibers, and 4.0% white pigment, combined in an appropriate combination, dried and extruded as a film .

[Example 5]
Proper combination of an extrusion composition comprising 91.0% crystalline PLA, 4.0% mica, 1.0% jojoba oil applied to PLA, or 4.1% white pigment And dried to form a film.

[Example 6]
Extrusion compositions containing a mixture of 50% of Example 4 and 50% of Example 5 were suitably combined, dried and formed as a film.

[Comparative Example 5]
100% amorphous PLA was extruded as a film.

[Comparative Example 6]
100% crystalline PLA was extruded as a film.

[Comparative Example 7]
100% polyester was extruded as a film.

  Table 2 shows the results of the stress / strain data of Examples 4 to 6 and Comparative Examples 5 to 7. Results of DSC data of Examples 4 to 6 are shown in FIGS. The DSC data results of Examples 4 to 6 and Comparative Example 7 are shown in FIG. The results show that the composition for extrusion of the present invention comprising PLA, BCD, nanofibers and / or natural oils (Examples 4-6) is 100% PLA (Comparative Examples 5 and 6) or conventional polyester ( Compared with Comparative Example 7), the elongation and toughness,% strain, breaking energy, and heat resistance were improved.

  In Examples 7 and 10, a small amount of nanofiber was used.

[Example 7]
An extrusion composition comprising a blend of 1 part 95.5% PLA with 3% BCD and 1.5% jojoba oil was prepared as described above, and the extrusion composition was , Blended with an equal portion of 99.5% amorphous PLA containing 0.5% nanosilica fibers, properly combined, dried and extruded as a film.

[Example 8]
An extrusion composition comprising 98.4% crystalline PLA, 1.5% jojoba oil and 0.1% nanosilica fibers is suitably combined as described above, dried and then formed. Extruded as a film.

[Example 9]
Extruded compositions containing 99.9% amorphous PLA and 0.1% nanosilica fibers were appropriately combined, dried and then extruded as a film.

[Example 10]
A portion of 95.5% crystalline PLA, a mixture of 3% BCD and 1.5% jojoba oil, and a portion of 95.75% crystalline PLA containing 0.25% nanosilica fibers; Extruded compositions containing 4% white pigment were combined appropriately and dried to form and then extruded as a film.

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

  In Examples 11-13, a small amount of nanofiber was used.

[Example 11]
Extruded compositions containing 97.8% amorphous PLA, 0.2% nanosilica fibers, and 2% white pigment were combined in an appropriate combination, dried and then extruded as a film.

[Example 12]
Extruded compositions containing 94.7% amorphous PLA, 0.3% nanosilica fibers, 1.0% mica, and 4.0% white pigment are combined in an appropriate combination and dried. And then extruded as a film.

[Example 13]
An extrusion composition comprising 92.15% amorphous PLA, 0.75% jojoba oil, 0.1% nanosilica fiber, 3.0% mica, and 4.0% white pigment is suitable. In combination, dried and then extruded as a film.

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

[Example 14]
To illustrate an extrusion composition that mimics PET for a container, an extrusion composition comprises jojoba oil added to crystalline PLA, 0.5% nanosilica, 2.0% BCD, A masterbatch was formed by stirring with 1.0% kuzu turmeric and 20.0% mica and drying. PolyOne 20% green pigment was added to 80% masterbatch in a ribbon mixer. To this was added 100% crystalline PLA. The final overall composition is:
89.7% Crystalline PLA
0.4% BCD
1.6% jojoba oil 0.1% nanosilica fiber 4.0% mica 0.2% kuzukon 4.0% green pigment

[Example 15]
To illustrate an extrusion composition that mimics HDPE for bottles and caps, an extrusion composition was formed as described above. The final overall composition is:
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

  The stress / strain data for Examples 14 and 15 compared to Comparative Example 6 (100% PLA) and Comparative Example 8 (100% HDPE) are shown in Table 5. The DSC data of Example 15 (EarthBottle (registered trademark) EB-HDPE) as compared with Comparative Example 8 is shown in FIG.

[Example 16]
To illustrate an extruding composition having a white color for containers, the extruding composition is combined with 4.8% safflower oil and 0.4% shea butter brightener, then 0.0. A masterbatch was formed by adding 4% nanosilica. This is then stirred with 59.6% crystalline PLA and then 1.6% BCD, 24% TiO ₂ colorant, 0.8% kuzukon, 8% mica, 0.4% cande Stir with the rear wax (blocker) and dry. The masterbatch was combined with 50% TiO ₂ colorant and 50% 100% crystalline PLA. The final overall composition is:
92.9% crystalline PLA
0.4% BCD
1.2% safflower oil 0.1% nano silica fiber 2.0% mica 0.2% kuzukon 3.0% TiO2 colorant 0.1% shea butter brightener 0.1% canderia blocker

[Example 17]
To illustrate an extruding composition with an amber color for a container, combine 6.0% jojoba oil and 0.5% shea butter brightener, then add 0.5% nanosilica. To form a master batch. This is then stirred with 78.7% crystalline PLA and then 2.0% BCD, 1.0% amber colorant (0.040 g black, 0.018 g blue, 0.210 g red) , And 0.160 yellow), 1.0% kuzukon, 10.0% mica, 0.5% canderia wax blocker and dried. This was combined with 24% amber colorant and 76% 100% crystalline PLA. The final overall composition is:
95.7% Crystalline PLA
0.4% BCD
1.2% jojoba oil 0.1% nanosilica fiber 2.0% mica 0.2% kuzukon 0.2% amber colorant 0.1% shea butter brightener 0.1% canderia blocker

[Example 18]
To illustrate an extruding composition having a green color for a container, the extruding composition combines 6.0% jojoba oil and 0.5% shea butter brightener, then 0.0. Add 5% nanosilica, then stir with 78.0% 100% crystalline PLA, then 2.0% BCD, 1.5% chlorophyllin colorant, 1.0% kuzukon, 10.0% Stir with mica and 0.5% canderia wax blocker and dry. The masterbatch was combined with 24% chlorophyllin colorant and 76% 100% crystalline PLA. The final overall composition is:
95.6% crystalline PLA
1.2% Jojoba oil 0.1% Nanosilica fiber 0.4% BCD
2.0% mica 0.2% kuzukon 0.3% chlorophyllin colorant 0.1% shea butter brightener 0.1% canderia blocker

[Examples 14a and 14b]
To illustrate the barrier properties of the extrusion composition, the composition of Example 14 was extruded into bottles with varying amounts of mica, except for the percentage of mica (14a and 14b). The oxygen transfer rate (OTR) and water vapor transfer rate (WVTR) were measured. The results are shown in Table 6 and Table 7.

  The oxygen transfer rates shown and observed by the bottles prepared from the compositions of Examples 19-22 are comparable to PET and HDPE.

  The water vapor transfer rate shown and observed by the bottles prepared from the compositions of Examples 23-26 is comparable to PET.

  To illustrate the barrier properties of the composition for extrusion, the composition of pure PLA is compared to Example 14a containing 2% mica and Example 18 containing 2% mica and canderia wax. . The water vapor transfer rate (WVTR) was measured. The results are shown in Table 8.

While the embodiments of the present invention have been described above, the specific forms described in detail in this specification do not limit the invention as defined by the appended claims, but rather the appended claims. It should be understood that various modifications may be made without departing from the spirit and scope of the invention as defined in

Claims (58)

A composition for extrusion molding having a heat deflection temperature of about 50 ° C. or higher and a melting point of about 80 ° C. to 190 ° C.
(A) about 60 to about 99.8% partially crystalline or crystalline polylactic acid;
(B) about 0.05 to about 8% cyclodextrin;
(C) about 0.1 to about 8% natural oil, fatty acid, fatty acid ester, wax or wax ester;
(D) about 0.01 to about 5% nanofibers;
(E) about 0 to about 10% of a crystallizing agent;
(F) about 0 to about 1% starch-based melt rheology modifier;
(G) from about 0 to about 5% colorant;
(H) from about 0 to about 1% plasticizer;
(I) about 0 to about 1% brightener;
(J) An extrusion composition comprising about 0 to about 1% of a blocking agent.   The composition for extrusion molding according to claim 1, wherein the cyclodextrin is β-cyclodextrin.   The natural oil is lard, beef tallow, fish oil, coffee oil, soybean oil, safflower oil, oilseed oil, tall oil, calendula oil, rapeseed oil, peanut oil, linseed oil, sesame oil, grape seed oil, olive oil, jojoba oil, dehydrated castor oil The composition for extrusion according to claim 1, selected from the group consisting of: beef tallow oil, sunflower oil, cottonseed oil, corn oil, canola oil, orange oil, and mixtures thereof.   The composition for extrusion molding according to claim 1, wherein the fatty acid ester is a polymerization product of an unsaturated higher fatty acid.   5. The unsaturated higher fatty acid ester is selected from the group consisting of oleic acid, linoleic acid, lauric acid, myristic acid, stearic acid, palmitic acid, eicosanoic acid, eleostearic acid, glycerol and the like and mixtures thereof. The composition for extrusion molding as described in 2.   Additional plasticizers, impact modifiers, additional fiber reinforcements, antioxidants, antibacterial agents, fillers, UV stabilizers, colorants, glass transition temperature modifiers, melting point modifiers and heat deflection temperature modifiers The composition for extrusion molding according to claim 1, further comprising an additive selected from the group consisting of agents.   The composition for extrusion molding according to claim 1, wherein the nanofibers are derived from silica or cellulose fibers.   The composition for extrusion molding according to claim 1, wherein the crystallization agent is selected from the group consisting of mica, kaolin, clay, talc, calcium carbonate, aluminum oxide and mixtures thereof.   The composition for extrusion according to claim 1, comprising a moisture level of about 0.02% or less water.   The composition for extrusion molding according to claim 1, wherein the starch-based melt rheology modifier is kuzu turmeric.   The composition for extrusion molding according to claim 1, wherein the plasticizer is carboxylic acid ethyl ester.   The composition for extrusion molding according to claim 11, wherein the carboxylic acid ethyl ester is triethyl citrate.   A product formed from the composition for extrusion molding according to claim 1.   14. The product of claim 13, wherein the product is selected from the group consisting of bottles, lids, caps, closures, containers, packages and canisters.   The product of claim 13, wherein the product is a container.   The container according to claim 15, wherein the cyclodextrin is β-cyclodextrin.   The natural oil is lard, beef tallow, fish oil, coffee oil, soybean oil, safflower oil, oilseed oil, tall oil, calendula oil, rapeseed oil, peanut oil, linseed oil, sesame oil, grape seed oil, olive oil, jojoba oil, dehydrated castor oil 16. The container of claim 15, selected from the group consisting of: beef tallow oil, sunflower oil, cottonseed oil, corn oil, canola oil, orange oil, and mixtures thereof. A container formed from an extrusion composition derived from renewable resources, the container comprising:
(A) about 70-95% crystalline polylactic acid;
(B) about 0.05-8% cyclodextrin;
(C) about 0.1 to about 8% natural oil, fatty acid, fatty acid ester, wax or wax ester;
(D) about 0.01-5% nanofibers;
(E) about 0.01 to 10% of a crystallization agent;
(F) about 0.01 to 1% starch-based melt rheology modifier;
(G) A container containing about 0.01 to 8% of a colorant.   The container according to claim 18, wherein the cyclodextrin is β-cyclodextrin.   The natural oil is lard, beef tallow, fish oil, coffee oil, soybean oil, safflower oil, oilseed oil, tall oil, calendula oil, rapeseed oil, peanut oil, linseed oil, sesame oil, grape seed oil, olive oil, jojoba oil, dehydrated castor oil 19. The container of claim 18, selected from the group consisting of: beef tallow oil, sunflower oil, cottonseed oil, corn oil, canola oil, orange oil, and mixtures thereof.   The container according to claim 18, wherein the fatty acid ester is a polymerization product of an unsaturated higher fatty acid.   22. The unsaturated higher fatty acid ester is selected from the group consisting of oleic acid, linoleic acid, lauric acid, myristic acid, stearic acid, palmitic acid, eicosanoic acid, eleostearic acid, glycerol and the like and mixtures thereof. Container as described in.   Selected from the group consisting of plasticizers, impact modifiers, additional fiber reinforcements, antioxidants, antibacterial agents, fillers, UV stabilizers, glass transition temperature modifiers, melting point modifiers and thermal deflection temperature modifiers The container according to claim 18, further comprising an additive to be added.   The container according to claim 18, wherein the nanofibers are derived from silica or cellulose fibers.   19. A container according to claim 18, wherein the crystallization agent is selected from the group consisting of mica, kaolin, clay, talc, calcium carbonate, aluminum oxide and mixtures thereof.   19. A container according to claim 18 comprising about 0.02% or less water as a moisture level.   19. A container according to claim 18, wherein the starch-based melt rheology modifier is kuzu turmeric.   The container according to claim 18, wherein the plasticizer is carboxylic acid ethyl ester.   29. A container according to claim 28, wherein the carboxylic acid ethyl ester is triethyl citrate.   19. A container according to claim 18, wherein the extrusion composition further comprises canderia wax or shea butter or both. A container sealing device, wherein both the container and the sealing device are formed from a composition for extrusion molding derived from renewable resources,
(A) about 70-95% crystalline polylactic acid;
(B) about 0.05-8% cyclodextrin;
(C) about 0.1 to about 8% natural oil, fatty acid, fatty acid ester, wax or wax ester;
(D) about 0.01 to 10% of a crystallizing agent;
(E) about 0.01 to 1% crystal retarder;
(F) A sealing device comprising about 0.01 to 8% of a colorant.   The sealing device according to claim 31, wherein the cyclodextrin is β-cyclodextrin.   The natural oil is lard, beef tallow, fish oil, coffee oil, soybean oil, safflower oil, oilseed oil, tall oil, calendula oil, rapeseed oil, peanut oil, linseed oil, sesame oil, grape seed oil, olive oil, jojoba oil, dehydrated castor oil 32. The closure of claim 31, selected from the group consisting of: beef tallow oil, sunflower oil, cottonseed oil, corn oil, canola oil, orange oil, and mixtures thereof.   32. The sealing device according to claim 31, wherein the fatty acid ester is a polymerization product of an unsaturated higher fatty acid.   35. The unsaturated higher fatty acid ester is selected from the group consisting of oleic acid, linoleic acid, lauric acid, myristic acid, stearic acid, palmitic acid, eicosanoic acid, eleostearic acid, glycerol and the like and mixtures thereof. The sealing device described in 1.   The sealing device according to claim 31, wherein the cyclodextrin is β-cyclodextrin.   Selected from the group consisting of plasticizers, impact modifiers, additional fiber reinforcements, antioxidants, antibacterial agents, fillers, UV stabilizers, glass transition temperature modifiers, melting point modifiers and thermal deflection temperature modifiers 32. The closure of claim 31, further comprising an additive that is added.   32. The sealing device according to claim 31, wherein the nanofibers are derived from silica or cellulose fibers.   32. The closure of claim 31, wherein the crystallization agent is selected from the group consisting of mica, kaolin, clay, talc, calcium carbonate, aluminum oxide and mixtures thereof.   32. The closure of claim 31, comprising a moisture level of about 0.02% or less water.   32. The sealing device of claim 31, wherein the starch-based melt rheology modifier is kuzu turmeric.   32. The closure of claim 31, wherein the crystal retarder is selected from the group consisting of xanthan gum, guar gum, and locust bean gum.   32. The closure of claim 31, wherein the extrusion composition further comprises canderia wax or shea butter or both.   A bottle, cap or lid formed from an extrusion composition derived from renewable resources, wherein the extrusion composition comprises cyclodextrin and natural oil, fatty acid, fatty acid ester, wax or wax ester Bottles, caps or lids comprising PLA coated with and / or alkyl ester plasticizers and polysaccharide crystal retarders.   The natural oil is lard, beef tallow, fish oil, coffee oil, soybean oil, safflower oil, oilseed oil, tall oil, calendula oil, rapeseed oil, peanut oil, linseed oil, sesame oil, grape seed oil, olive oil, jojoba oil, dehydrated castor oil 49. The bottle, cap or lid of claim 48 selected from the group consisting of: beef tallow oil, sunflower oil, cottonseed oil, corn oil, canola oil, orange oil, and mixtures thereof.   49. The bottle, cap or lid of claim 48, further comprising nanosilica fibers having a diameter of 1 [mu] m or less.   49. The bottle, cap or lid of claim 48 further comprising a crystallization agent.   49. A bottle, cap or lid according to claim 48, wherein the cyclodextrin is [beta] -cyclodextrin.   49. A bottle, cap or lid according to claim 48, wherein the polysaccharide crystalline modifier is xanthan gum.   A method of forming a molded article comprising coating PLA with natural oil, fatty acid, fatty acid ester, wax or wax ester and / or alkyl ester plasticizer, and mixing the coated PLA with cyclodextrin Drying the mixture to a moisture level such that it contains no more than 0.2% water, extruding the dried mixture, and molding the extruded composition into a product; Including methods.   55. The method of claim 54, wherein the PLA and the particles contained therein are coated with natural oil, fatty acid, wax or wax ester, fatty acid ester, and / or alkyl ester plasticizer by use of agitation.   The composition is heated to about 160.degree. F. to about 180.degree. F. for about 4 to about 12 hours, whereby nanofibers, cyclodextrins, crystallization agents, starch-based melt rheology modifiers, and polysaccharides. 55. The method of claim 54, wherein the crystal retarder is substantially saturated with oil, thereby substantially placing the cyclodextrin in the PLA polymer matrix.   55. The method of claim 54, wherein the product is molded using extrusion, injection molding or blow molding.   The method according to claim 54, wherein the cyclodextrin is β-cyclodextrin.   The PLA is lard, beef tallow, fish oil, coffee oil, soybean oil, safflower oil, oilseed oil, tall oil, calendula oil, rapeseed oil, peanut oil, linseed oil, sesame oil, grape seed oil, olive oil, jojoba oil, dehydrated castor oil, 55. The method of claim 54, selected from the group consisting of beef 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 nanofibers, crystallization agents, starch-based melt rheology modifiers, polysaccharide crystal retarders and / or pigments.   54. The method of claim 53, wherein the product is selected from the group consisting of bottles, lids, caps, containers, packages, and canisters.

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