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US20030038405A1 - Method for producing semicrystalline polylactic acid articles - Google Patents

Method for producing semicrystalline polylactic acid articles Download PDF

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Publication number
US20030038405A1
US20030038405A1 US10/223,451 US22345102A US2003038405A1 US 20030038405 A1 US20030038405 A1 US 20030038405A1 US 22345102 A US22345102 A US 22345102A US 2003038405 A1 US2003038405 A1 US 2003038405A1
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sheet
pla
pla resin
crystallinity
joules
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Richard Bopp
Jason Whelan
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NatureWorks LLC
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Cargill Dow LLC
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Assigned to CARGILL DOW LLC reassignment CARGILL DOW LLC ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: BOPP, RICHARD C., WHELAN, JASON
Publication of US20030038405A1 publication Critical patent/US20030038405A1/en
Assigned to ENERGY, UNITED STATES DEPARTMENT OF reassignment ENERGY, UNITED STATES DEPARTMENT OF CONFIRMATORY LICENSE (SEE DOCUMENT FOR DETAILS). Assignors: CARGILL DOW LLC
Priority to US12/163,465 priority patent/US8392851B2/en
Priority to US12/163,466 priority patent/US7670545B2/en
Abandoned legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C51/00—Shaping by thermoforming, i.e. shaping sheets or sheet like preforms after heating, e.g. shaping sheets in matched moulds or by deep-drawing; Apparatus therefor
    • B29C51/002—Shaping by thermoforming, i.e. shaping sheets or sheet like preforms after heating, e.g. shaping sheets in matched moulds or by deep-drawing; Apparatus therefor characterised by the choice of material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C51/00—Shaping by thermoforming, i.e. shaping sheets or sheet like preforms after heating, e.g. shaping sheets in matched moulds or by deep-drawing; Apparatus therefor
    • B29C51/14—Shaping by thermoforming, i.e. shaping sheets or sheet like preforms after heating, e.g. shaping sheets in matched moulds or by deep-drawing; Apparatus therefor using multilayered preforms or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/0005—Condition, form or state of moulded material or of the material to be shaped containing compounding ingredients
    • B29K2105/0008—Anti-static agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/0005—Condition, form or state of moulded material or of the material to be shaped containing compounding ingredients
    • B29K2105/0026—Flame proofing or flame retarding agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/0005—Condition, form or state of moulded material or of the material to be shaped containing compounding ingredients
    • B29K2105/0032—Pigments, colouring agents or opacifiyng agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/0005—Condition, form or state of moulded material or of the material to be shaped containing compounding ingredients
    • B29K2105/0038—Plasticisers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/0005—Condition, form or state of moulded material or of the material to be shaped containing compounding ingredients
    • B29K2105/0047—Agents changing thermal characteristics
    • B29K2105/005—Heat sensitisers or absorbers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0001—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds having particular acoustical properties
    • B29K2995/0002—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds having particular acoustical properties insulating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0037—Other properties
    • B29K2995/004—Semi-crystalline
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones

Definitions

  • the present invention relates to methods for forming heat-resistant, semicrystalline articles from polylactic acid.
  • Polylactic acid is useful for making films, fibers, and various types of formed articles.
  • One limitation on its use in some food packaging and other applications is its tendency to deform when heated. For example, many food packaging applications require the resin to be subjected to the temperature of boiling water without significant deformation. PLA articles often cannot withstand such temperatures.
  • PLA tends to exist in an amorphous state when formed into these kinds of articles.
  • PET poly(ethylene terephthalate)
  • PET poly(ethylene terephthalate)
  • cPET thermoforming a PET sheet is heated until soft enough to be formed, then transferred to a hot mold and formed under vacuum and pressure. The temperature and residence time in the mold are such that crystallites form in the resin. Once the needed crystallinity is obtained, the article is transferred into another mold of identical dimensions.
  • This second mold is held below the glass transition temperature (T g ) of the PET resin, usually near room temperature.
  • T g glass transition temperature
  • the colder temperatures “quench” the resin, “locking in” the as-formed dimensions. If the resulting PET resin is sufficiently crystalline, it may withstand use temperatures some 20-150 C. higher or more than amorphous PET.
  • the PET thermoforming process has the drawbacks of requiring two molds, which increases capital investment and operating costs, and long forming times in the mold to allow crystallization to be completed, which reduces output per unit time and thus increases costs.
  • the cPET thermoforming process is a material-specific one that is designed around the particular characteristics of PET resin.
  • PLA like PET
  • Crestad “Crystallization Kinetics of Poly(L-lactide-co-meso-lactide)”, J. Applied Polymer Science 62, 1079-1091 (1996).
  • the rate of crystallization is affected by various factors, including the lactic acid enantiomer ratio, the use of nucleating agents, and the thermal history of the polymer (i.e. time at crystallization temperature and/or cooling rates).
  • this invention is a method for making formed heat-resistant PLA articles, comprising heating a sheet of an amorphous, crystallizable PLA resin until the sheet has obtained a surface temperature from about 80 to about 155° C., then thermoforming the heated sheet on a mold that is at a temperature below 80° C.
  • this invention is a method for making formed heat-resistant PLA articles, comprising heating a sheet of a semicrystalline PLA resin having a crystallinity of at least 10 Joules/gram to a temperature at which the sheet can be thermoformed but at which the crystallinity of the sheet is not reduced below 10 Joules/gram, and then thermoforming the sheet on a mold that is at a temperature below 80° C. to produce a formed article of PLA resin having a crystallinity of at least 10 Joules/gram.
  • this invention is a method for making formed heat-resistant PLA articles, comprising heating a sheet of an amorphous, crystallizable PLA resin to a temperature at which the PLA resin forms crystallites and for a time sufficient to impart a crystallinity of at least 10 Joules/gram to the PLA resin, and then thermoforming the heated sheet on a mold that is at a temperature below 80° C. to produce a formed article of PLA resin with a crystallinity of at least 10 Joules/gram.
  • This invention provides a simple, efficient method for making formed articles with improved heat resistance from crystallizable PLA resin. Cycle times as short as about 3 seconds or even less for the forming step can be achieved with this method using commercial-scale equipment. Because only a single mold is necessary, capital expense and operating expenses are minimized.
  • the crystallinity of the PLA resin can be controlled over a wide range by adjusting time and temperature during the heating step, and through control of the composition of the PLA resin itself, as described more below. As certain properties of the PLA resin (notably heat resistance) vary with the crystallinity, this process provides a method whereby easy control over those properties can be obtained.
  • this invention provides a rapid and inexpensive process for making formed PLA articles that can resist exposure to temperatures of 100° C. or more with minimal or no distortion. This permits the articles to be used in a variety of applications, in particular food packaging, in which the article and its contents are to be heated.
  • a semicrystalline sheet of PLA resin is thermoformed on a mold that is at a temperature of 80° C. or less.
  • the semicrystalline sheet of PLA resin is obtained by heating a sheet of amorphous PLA resin to a specific temperature range until the desired crystallinity is obtained.
  • the resulting semicrystalline sheet can be immediately thermoformed, or else cooled and later reheated to a thermoforming temperature under conditions that the crystallinity is maintained and then thermoformed.
  • the heating step is performed as part of the overall thermoforming process.
  • a sheet of amorphous but crystallizable PLA resin is heated.
  • the function of the heating is two-fold—to soften the sheet so that it can be formed in the subsequent step, and to introduce crystallinity into the PLA resin.
  • the conditions of the heating are selected to achieve these purposes.
  • Softening is performed such that the sheet can be thermoformed under commercially reasonable conditions, without softening the sheet so much that it is too fluid to transfer to the thermoforming mold and be formed into a part.
  • Crystallinity is introduced such that the sheet develops a crystallinity during the heating step of at least 10 Joules/gram, preferably at least 15 Joules/gram, more preferably at least 20 Joules/gram, even more preferably at least 24 Joules/gram, to about 55 Joules/gram, preferably to about 45 Joules/gram, even more preferably to about 40 Joules/gram.
  • Crystallizable PLA resins are those that will form crystallites rapidly when a sheet of the resin is heated to a sheet surface temperature range which lies above the T g but below its melting temperature (T m ).
  • T m melting temperature
  • the temperature range to which the PLA resin must be heated will be a characteristic of the particular PLA resin, and will depend largely on the lactic acid enantiomer ratio and the presence of nucleating agents and/or plasticizers, as described more fully below. In general, however, the temperature at which the requisite crystallization will occur within commercially reasonable time frames is from about 80° C. to about 160° C. and is more typically from about 90° C. to about 150° C.
  • one method of controlling the process of the invention is to monitor sheet surface temperature.
  • Sheet temperature is generally a suitable process control parameter for sheet thicknesses that are typically used in thermoforming applications, such as up to about 250 mil, preferably about 10-100 mil, even more preferably about 15-50 mil, unless extremely rapid heating rates are used.
  • a thicker sheet, or one that is heated very rapidly, may exhibit a significant temperature gradient between the surface and the center. Under these conditions, therefore, surface temperature measurements alone may be less suitable as a process control parameter.
  • heating conditions will be established empirically with respect to the particular equipment and particular PLA sheet that is used. These empirically derived heating conditions may be developed by establishing suitable and/or optimal temperatures to which a particular PLA resin sheet should be heated, and then relating those temperatures to particular controllable processing conditions such as heating time, line speeds, heater and/or oven temperatures, power to be supplied to heating apparatus, and the like. Alternatively, heating conditions can be empirically derived by measuring the crystallinity of the heated PLA sheet while varying process parameters.
  • the heating step can be carried out in any convenient manner, such as convection heating, radiant heating (using devices of various types such as visible light, infrared radiation, microwave radiation, and the like), conductive heating (such as by passing the sheet over a heated surface or between heated surfaces such as heated rollers) and induction heating.
  • heating is preferably done quickly and uniformly without scorching the sheet or forming significant localized hot spots.
  • the sheet is conveniently held in a clamping frame or other apparatus to give it physical support and to facilitate transfer in and out of the heater and/or to the subsequent forming step.
  • the heating step may also be performed as part of the process of extruding the sheet.
  • the PLA resin is first extruded into sheet form. Because extrusion temperatures are generally higher than the melting temperature (T m ), it is necessary to cool the sheet in order to reduce the temperature below T m and into the temperature range at which crystallization occurs.
  • the heating step of this invention can be accomplished by adjusting the temperature of the freshly extruded sheet into the aforementioned temperature ranges, and holding the temperature there until the requisite crystallinity has been developed.
  • the crystallized sheet can then be cooled below the T g , in order to be thermoformed in a separate, later step. In such a case, the sheet will be re-heated to the thermoforming temperature (but not to so high a temperature that crystallinity is destroyed) when the thermoforming process is performed.
  • the crystallized sheet may be fed directly into the thermoforming step.
  • the PLA sheet is transferred to a mold and thermoformed.
  • the transfer to the mold is performed so that the PLA sheet remains at a temperature suitable for thermoforming until the transfer is complete and the thermoforming accomplished.
  • the mold is at a temperature below 80° C., preferably below the T g of the PLA sheet, more preferably no greater than 50° C., and especially no greater than 35° C. Because of the relatively cold mold temperature, the PLA sheet quickly hardens into the desired shape in the mold. Some additional stress-induced crystallinity may be introduced due to the orientation of the polymer during the thermoforming process, but the amount is generally small.
  • Thermoforming is accomplished by positioning the softened and crystallized sheet over a male or female mold, and drawing and/or pressure forming the sheet on the mold to form a molded part.
  • the mold is most typically a female mold. Multiple formed parts can be made simultaneously or sequentially from a single sheet. Except for the mold temperature, which is held below the temperatures discussed above, the process of this invention can be conducted using conventional types of thermoforming apparatus, which are adapted if necessary to provide a means to maintain the mold at the requisite temperature. Examples of such apparatus and general methods are described, for example, by Throne in “Thermoforming Crystallizing Poly(ethylene Terephthalate) (CPET)”, Advances in Polymer Technology, Vol. 8, 131-146 (1988).
  • CPET Thermoforming Crystallizing Poly(ethylene Terephthalate)
  • the mold may include a male half that is inserted into the female half during the process to provide male mold forming. It may also be desirable to prestretch the sheet; if so a pressure cap or other prestretching device may be used and actuated prior to drawing the sheet into the mold.
  • thermoforming step is preferably operated such that thermoforming cycle time (time to complete one thermoforming cycle and get ready to perform the subsequent cycle) is minimized.
  • Thermoforming cycle times are advantageously less than 20 seconds, preferably less than 10 seconds, more preferably no more than 5 seconds, and even more preferably no more than 3 seconds.
  • the part is formed and cooled below its T g , it is demolded and separated from other parts and trimmed if necessary.
  • Various downstream operations such as applying graphics or labels, assembly to other parts, packaging and the like can be performed if needed, depending on the type of part and its intended use.
  • PLA sheet it is meant a sheet of a thermoplastic poly(lactic acid) homopolymer or copolymer containing at least 50% by weight (based on the PLA resin) of repeating units derived from lactic acid.
  • the PLA is more preferably a homopolymer of lactic acid.
  • the PLA resin may be blended with small (up to about 50% by weight, based on the weight of the polymers) of another polymer which is not a PLA, but is preferably not such a blend.
  • the preferred PLA resin is a homopolymer of either L-lactic acid or D-lactic acid, a random copolymer of L-lactic acid and D-lactic acid, a block copolymer of L-lactic acid and D-lactic acid, or a mixture of two or more of these.
  • the ratio of the lactic acid enantiomers and the manner in which they are copolymerized greatly influences the ability of the PLA sheet to crystallize in the present process.
  • the PLA resin can be formed by polymerizing lactic acid or, preferably, by polymerizing lactide.
  • PLA resin is used herein to include polymers made by polymerizing lactide.
  • Lactide is a dimeric form of lactic acid, in which two lactic acid molecules are condensed to form a cyclic diester.
  • lactide similarly exists in a variety of enantiomeric forms, i.e., “L-lactide”, which is a dimer of two L-lactic acid molecules, “D-lactide”, which is a dimer of two D-lactic acid molecules and “meso-lactide”, which is a dimer formed from one L-lactic acid molecule and one D-lactic acid molecule.
  • any of these forms of lactide, or mixtures thereof, can be copolymerized to form a PLA resin for use in this invention.
  • the L/D ratio in the PLA resin is controlled through the ratio of these enantiomeric forms of lactide that are used in the polymerization.
  • mixtures of L-lactide and meso-lactide are polymerized to form a polymer having a controlled level of D-lactic acid enantiomeric units. Suitable processes for polymerizing lactide to form PLA having controlled L/D ratios are described, for example, in U.S. Pat. Nos. 5,142,023 and 5,247,059, both incorporated herein by reference.
  • the PLA resin may be compounded with various additives and processing aids such as nucleants, other inorganic fillers, plasticizers, reinforcing agents, slip agents, lubricants, UV-stabilizers, thermal stabilizers, flame retardants, foaming agents, antistatic agents, antioxidants, colorants, and the like, with finely divided inorganic solids being of particular importance as discussed more below.
  • additives and processing aids such as nucleants, other inorganic fillers, plasticizers, reinforcing agents, slip agents, lubricants, UV-stabilizers, thermal stabilizers, flame retardants, foaming agents, antistatic agents, antioxidants, colorants, and the like, with finely divided inorganic solids being of particular importance as discussed more below.
  • the PLA sheet is amorphous and capable of being crystallized to the extent of 10 Joules/gram through heating at a temperature between its T g and T m .
  • it is capable of being crystallized to a crystallinity of at least 15 Joules/gram, more preferably at least 20 Joules/gram, even more preferably at least 24 Joules/gram, especially at least 30 Joules/gram.
  • a PLA sheet is considered “amorphous” if it exhibits a crystallinity of less than 10 Joules/g when measured by differential scanning calorimetry (DSC) as described more fully below.
  • DSC differential scanning calorimetry
  • composition of the PLA sheet is also preferably such that the sheet can be crystallized to the desired extent in a short period.
  • Three important parameters affecting this are the ratio of the lactic acid enantiomers in the PLA resin, the use of nucleating agents and the use of plasticizers.
  • PLA ability of PLA to crystallize, all other things being equal, is greatest when only one of the lactic acid enantiomeric forms is present in polymerized form in the polymer.
  • homopolymers of L-lactic acid or D-lactic acid are the forms of PLA that tend to crystallize most completely and rapidly.
  • random copolymers of the L- and D-enantiomers the ability to crystallize falls off rapidly as more of the second enantiomer is present.
  • the proportion of “D” and “L” lactic acid repeating units in enantiomeric polylactic acid (PLA) copolymers can be accomplished by high performance liquid chromatography.
  • a suitable chromatograph is a Waters LC Module I HPLC with a Sumichiral OA6100 column set and a Model 486 variable wavelength UV detector.
  • the PLA enantiomeric copolymer Prior to analysis, the PLA enantiomeric copolymer is fully hydrolyzed in a basic aqueous solution into its constituent D- and L-lactic acid monomer units.
  • Enantiomer ratio is conveniently determined by neutralizing the solution with 1N HCl and injecting it into the HPLC through a 0.45 micron filter.
  • the concentration of the lactic acid enantiomers is determined by comparison of the HPLC results to standard curves generated using pure standards such as are supplied by the Aldrich and Sigma Chemical Companies.
  • the PLA resin may be compounded with a nucleating agent in order to improve its ability to crystallize quickly.
  • Suitable nucleating agents include finely divided solids that do not react under the conditions of the heating step or the thermoforming process. Particles having a median particle size of less than 5 ⁇ m, preferably less than 1 ⁇ m, are particularly suitable.
  • the most preferred nucleating agent is talc, as it often provides a measure of reinforcement in addition to performing the nucleation function well.
  • suitable commercially available talc products are UltratalcTM 609, available from Specialty Minerals, Inc., and Zemex HTP Ultra SCTM, available from Zemex Fabi Benwood LLC.
  • Nucleating agents are used in effective amounts, but if used in too large quantities they can cause the physical properties of the PLA resin to deteriorate.
  • Preferred amounts for most nucleating agents are from about 0.1, preferably from about 0.5 to about 10, preferably to about 5, more preferably to about 2.5 percent of the combined weight of the PLA resin and the nucleating agent.
  • talc it may be desirable to employ larger quantities in order to obtain a desirable reinforcement effect.
  • preferred usage levels for talc are from about 0.5, more preferably from about 3, even more preferably from about 5 to about 40, more preferably to about 30 and even more preferably to about 20 percent of the combined weight of the PLA resin and the talc.
  • Nucleating agents are conveniently melt compounded into the PLA resin using any suitable melt compounding equipment, such as single and twin screw extruders, roll mills, Banbury mixers, Farrell continuous mixers and the like.
  • the nucleating agent can also be added during the sheet extrusion process.
  • Plasticizers also tend to improve the rate at which PLA crystallizes.
  • a suitable plasticizer is one that is compatible with the PLA resin and stable under the conditions of the heating and thermoforming steps.
  • Suitable plasticizers include phthalates (including dioctyl phthalate), citric acid esters, lactic acid esters such as ethyl lactate, lactide esters, mineral oil, triphenyl phosphate, glycerine, acetin and butyrin. Those that are biodegradable are preferred.
  • Suitable amounts of plasticizer are from about 0.5 to about 30 percent, based on the combined weight of the PLA resin plus the plasticizer. Plasticizers are conveniently melt compounded into the PLA resin or added during the sheet extrusion process as described before.
  • the ability of a PLA resin to crystallize at a given temperature can be expressed in terms of a crystallization half-time, as described more fully by Kolstad in “Crystallization Kinetics of Poly(L-lactide-co-meso-lactide)”, J. Appl. Poly. Sci. 62:1079-1091 (1986), incorporated herein by reference.
  • the crystallization half-time is the time required for a PLA resin to achieve one-half of its ultimate extent of crystallization under particular heating conditions. Sheets of PLA resins exhibiting crystallization half-times of less than 10 minutes, preferably less than 3 minutes, and especially less than 1 minute at the temperatures of the heating step are suitable. Sheets of PLA resins that exhibit crystallization half-times of less than about 10 seconds may crystallize too rapidly to provide good process control.
  • the sheet may be a multilayer type, in which at least one layer is a crystallizable PLA resin as described. Other layers may also be of crystallizable PLA resin, an amorphous PLA resin, or may be composed of a different polymer (such as a barrier plastic), provided that the sheet can be thermoformed under the conditions described herein. Multilayer sheets may be formed by, for example, coextrusion or lamination.
  • the sheet may also be cellular.
  • Cellular sheet can be made by incorporating a foaming agent into the PLA resin during the sheet extrusion process, and extruding the sheet under conditions such that the foam agent generates a gas and expands the sheet when the sheet is extruded. Extrusion foaming processes are well known and applicable here.
  • Cellular sheet is preferably mainly closed celled and has a density as low as about one lb/ft 3 .
  • a cellular sheet can be formed by foaming it during the softening/crystallization step of this process.
  • the sheet will contain a foaming agent that generates a gas under the conditions of the heating step.
  • Suitable blowing agents include lower hydrocarbons, halogenated alkanes such as fluorinated alkanes and perfluorinated alkanes, and water, as well as chemical blowing agents such as citric acid/sodium bicarbonate mixtures, gasses such as carbon dioxide and nitrogen, and the like.
  • Formed articles made according to the invention have improved resistance to heat, compared to PLA articles that are formed with lower crystallinity.
  • Formed PLA articles having a crystallinity of about 15 Joules/gram or more have been found to withstand boiling water for several minutes without significant dimensional changes or distortion.
  • the formed articles can be used as containers for hot foods, as microwavable food trays, or in other applications where they are exposed to moderately high temperatures (up to about 100° C. in many cases, and up to the crystalline melting point of the article for more highly crystalline articles).
  • moderately high temperatures up to about 100° C. in many cases, and up to the crystalline melting point of the article for more highly crystalline articles.
  • PLA resin is hydrolyzable, the length of time for which the article can withstand elevated temperatures will depend on whether, and how much, water is present. In general, the presence of liquid water or increasing humidity tends to shorten this time, as the PLA tends to hydrolyze under those conditions.
  • the formed articles tend to be opaque to somewhat translucent in appearance, even when a nucleating agent is used.
  • the degree of opacity is generally related to the number and size of the spherulitic crystallites developed in the crystallization step.
  • the opacity can be reduced through more effective crystal nucleation. More effect nucleation is favored by using smaller nucleating particles, in larger numbers.
  • the PLA resin may become oriented during the forming process. This may cause some reduction in opacity in the areas in which the orientation occurs.
  • beverage cups other foodware such as trays and plates, including those having attached lids; trays and plates for non-food applications and separate lids or covers for any of the foregoing.
  • a single-stage, shuttle-type lab-scale thermoformer without plug assist and a heating oven equipped with an IR radiant heater positioned above and below the sheet is used to evaluate the processing conditions for a nucleated PLA resin sheet.
  • 20-mil sheets made from an amorphous, random copolymer of 98.3% L-lactic acid and 1.7% D-lactic acid and containing 10% by weight UltratalcTM 609 (trademark of Specialty Minerals, Inc.) talc are placed for varying, predetermined times in the pre-heated thermoformer oven with the heaters set at 80% power. After the predetermined time in the oven, the sheets are racked out and their surface temperature measured using a RaytekTM ST IR surface thermometer.
  • the DSC measurements are made using a Mettler Toledo DSC 821e calorimeter running Star V. 6.0 software. Samples are 5-10 milligrams. Heating is performed from 25-225° C. at 20° C./minute, under air.
  • the sheet At a heating time of less than 16 seconds under these conditions, the sheet is too rigid to form, even though the measured crystallinity was less than 22 J/g.
  • the PLA sheet contains less than 10 Joules/g crystallinity, indicating that the sheet has reached too high a temperature, thereby destroying the crystallinity.
  • the sheet At more than 55 seconds residence time, the sheet is too fluid to form. Within the range of 16 to 30 seconds heating time, the sheet becomes thermoformable and attains the desired crystallinity.
  • Sheets of amorphous PLA resin as described in A above are thermoformed by heating them in the pre-heated thermoformer oven for 15 seconds at 90% power, and then immediately vacuum forming the heated sheets onto a 23° C., single compartment tray mold having dimensions of 31 ⁇ 8 ⁇ 35 ⁇ 8 ⁇ 1.5 inches.
  • the time on the mold is varied in order to determine the minimum cycle time and to assess the effect of in-mold residence time on crystallinity. All parts come off the mold rigid, regardless of in-mold residence time.
  • Table 2 summarized in Table 2 below. TABLE 2 Time on Mold (s) Overall Cycle Time (s)* Crystallinity (J/g) 4 19 16.7 3 18 16.1 2 17 16.4
  • thermoformed articles of semi-crystalline PLA are easily prepared via the process of the invention. Note that under these conditions, the in-mold residence time has no effect on crystallinity, indicating that all crystallinity is developed in the thermoformer oven during the heating step. This is confirmed by DSC evaluation of a sheet that is taken from the thermoformer oven and rapidly cooled without undergoing the forming step.
  • a 98.8% L/1.2% D PLA resin containing 5% Ultratalc 609 is used in this Example. It is extruded into 16′′ wide, 20 mil sheet using a single screw extruder equipped with a general purpose screw, a Maddock mixing head and a 28′′ horizontal cast sheet die. The freshly extruded, substantially amorphous sheet is run through a heated three roll stack, trimmed and wound into rolls.
  • This sheet is thermoformed on an Irwin Mini Mag 28 in-line thermoformer equipped with a 6′′ soup bowl mold.
  • the machine is operated at 14′′ and 24′′ index lengths. Index length affects oven residence time, with larger indices reducing residence time proportionately, for a given cycle time.
  • the oven is operated at a top oven temperature of between 480 and 675° F. and a bottom oven temperature of between 430 and 635° F., as indicated in Table 3 below.
  • the temperature of the sheet is measured as it leaves the oven just prior to forming, using an IR thermometer.
  • the mold temperature is about 23° C.
  • In-mold residence time is less than 3 seconds. Samples of the sheet trim and the molded bowls are taken in order to measure crystallinity.

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Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1659068A1 (fr) * 2004-11-22 2006-05-24 Coopbox Europe S.P.A. Plateau en plastique pour l'emballage d'aliments susceptibles de dégager des liquids
US20070176315A1 (en) * 2004-03-17 2007-08-02 Masanori Hashiba Process for producing woody molding
WO2008051443A1 (fr) * 2006-10-20 2008-05-02 Natureworks Llc Résines de polylactide à résistance aux chocs modifiée
WO2008057214A3 (fr) * 2006-10-26 2008-07-17 Natureworks Llc Compositions stéréocomplexes d'acide polylactique et procédés de production et d'utilisation correspondants
US20080303194A1 (en) * 2007-06-08 2008-12-11 Sabic Innovative Plastics Ip B.V. Mold apparatus for forming polymer and method
US20090115104A1 (en) * 2007-10-26 2009-05-07 Sabic Innovative Plastics Ip B.V. System and Method for Forming Polymer
US20090155611A1 (en) * 2007-12-17 2009-06-18 Tedford Jr Richard A Thermoformed article made from renewable polymer and heat-resistant polymer
US20090274920A1 (en) * 2008-05-05 2009-11-05 International Paper Company Thermoformed Article Made From Bio-Based Biodegradable Polymer Composition
US20090297652A1 (en) * 2002-12-26 2009-12-03 Toshiyuki Aritake Polylactic acid polymer compositon for thermoforming, polylactic acid polymer sheet for thermoforming, and thermoformed object obtained therefrom
US20090311511A1 (en) * 2005-05-12 2009-12-17 Mitsui Chemicals, Inc. Lactic acid polymer composition, molded article comprising the composition and process for producing the molded article
US20100179239A1 (en) * 2009-01-14 2010-07-15 Automotive Interior Consulting Method of minimizing compression set of foam
US20100221471A1 (en) * 2007-09-28 2010-09-02 Green Robert A Polylactide stereocomplex conjugate fibers
US20110135863A1 (en) * 2009-12-08 2011-06-09 International Paper Company Thermoformed articles made from reactive extrusion products of biobased materials
CN102294808A (zh) * 2010-06-24 2011-12-28 苏州希普生物科技有限公司 高分子材料聚乳酸射出成型工艺
US8182734B1 (en) * 2007-08-20 2012-05-22 E. I. Du Pont De Nemours And Company Thermoformed articles and compositions of poly(hydroxyalkanoic acid) and polyoxymethylene
WO2012121960A1 (fr) * 2011-03-04 2012-09-13 Cryovac, Inc. Procédé pour la préparation d'un article en mousse d'acide polylactique résistant à la chaleur
US20150086768A1 (en) * 2012-05-18 2015-03-26 Kao Corporation Polylactic acid resin sheet for thermal molding use
US9381693B2 (en) 2012-12-24 2016-07-05 Innovia Films Limited Packaging and labelling films
US10807344B2 (en) * 2016-04-28 2020-10-20 Natureworks Llc Polymer foam insulation structure having a facing of a multi-layer sheet that contains a heat resistant polymer layer and a polylactide resin layer
WO2023182687A1 (fr) * 2022-03-22 2023-09-28 주식회사 엘지화학 Composition de résine de polylactide ayant un excellent demi-temps de cristallisation, et son procédé de préparation

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003253009A (ja) 2002-03-06 2003-09-10 Unitika Ltd ポリ乳酸系成形体およびその製造方法
ATE543862T1 (de) * 2004-03-26 2012-02-15 Natureworks Llc Mit kohlendioixd getriebene extrudierte polylactidschaumstoffe
US8133558B2 (en) 2004-08-30 2012-03-13 Plastics Suppliers, Inc. Polylactic acid blown film and method of manufacturing same
CA2606419A1 (fr) 2005-04-19 2006-10-26 Plastic Suppliers, Inc. Film retractables en acide polylactique et procede de fabrication correspondant
JP4260794B2 (ja) * 2005-11-10 2009-04-30 花王株式会社 生分解性樹脂成形品の製造法
ES2615341T3 (es) 2005-11-21 2017-06-06 Plastic Suppliers, Inc. Métodos de moldeo de películas encogibles de ácido poliláctico
DE102007034486A1 (de) * 2007-07-24 2009-02-05 Illig Maschinenbau Gmbh & Co. Kg Thermoformmaschine und Verfahren zum Herstellen von Tiefziehprodukten aus erwärmten thermoplastischen Halbzeugen
WO2009023848A2 (fr) * 2007-08-15 2009-02-19 University Of Washington Procédé de fabrication d'articles de polyacide lactique microcellulaire façonnable
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US12172362B2 (en) 2019-01-09 2024-12-24 Purac Biochem, B.V. Thermoforming of PLA-based articles
CN111375222B (zh) * 2020-03-27 2021-06-18 箐谷生物科技(嘉兴)有限公司 聚乳酸容器制品的模外结晶生产线
CN113895060A (zh) * 2021-11-10 2022-01-07 晋江市新迪新材料科技有限公司 一种以pla为主要基料全降解塑料制品多次结晶设备

Citations (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4118454A (en) * 1975-09-02 1978-10-03 Sumitomo Bakelite Company Limited Method for producing transparent plastic molded articles
US4719246A (en) * 1986-12-22 1988-01-12 E. I. Du Pont De Nemours And Company Polylactide compositions
US4950532A (en) * 1986-10-30 1990-08-21 Azdel, Inc. Process for producing glass fiber reinforced thermoplastic compression molded materials and said molded materials
US5180765A (en) * 1988-08-08 1993-01-19 Biopak Technology, Ltd. Biodegradable packaging thermoplastics from lactides
US5213754A (en) * 1990-03-27 1993-05-25 Polyplastics Co., Ltd. Thermoforming process for forming a sheet of polybutylene terephthalate into a transparent container
US5338822A (en) * 1992-10-02 1994-08-16 Cargill, Incorporated Melt-stable lactide polymer composition and process for manufacture thereof
US5498650A (en) * 1995-02-24 1996-03-12 Ecological Chemical Products Poly(lactic acid) composition having improved physical properties
US5766748A (en) * 1995-11-30 1998-06-16 Mitsui Chemicals, Inc. Stretched film of lactic acid-based polymer
US5981619A (en) * 1995-09-14 1999-11-09 Takiron Co., Ltd. Material for osteosynthesis and composite implant material, and production processes thereof
US5992832A (en) * 1995-11-30 1999-11-30 Automobiles Peugeot Sphere, in particular a pneumatic sphere, for example for automotive hydropneumatic suspensions
US6001439A (en) * 1996-05-09 1999-12-14 Kureha Kagaku Kogyo K.K. Stretch blow molded container and production process thereof
US6005068A (en) * 1992-10-02 1999-12-21 Cargill Incorporated Melt-stable amorphous lactide polymer film and process for manufacture thereof
US6136905A (en) * 1994-05-19 2000-10-24 Mitsui Chemicals, Inc. L-lactic acid polymer composition, molded product and film
US6248430B1 (en) * 1998-08-11 2001-06-19 Dainippon Ink And Chemicals, Inc. Lactic acid-based polymer laminated product and molded product
US6290896B1 (en) * 1992-08-24 2001-09-18 Mitsui Chemicals, Inc. Preparation process of the formed product of L-lactic acid base polymer
US6506873B1 (en) * 1997-05-02 2003-01-14 Cargill, Incorporated Degradable polymer fibers; preparation product; and, methods of use
US6652983B1 (en) * 1998-02-27 2003-11-25 Nissha Printing Co., Ltd. Sheet for in-mold decorating and in-mold decorated article
US6669771B2 (en) * 1999-12-08 2003-12-30 National Institute Of Advanced Industrial Science And Technology Biodegradable resin compositions
US6715200B2 (en) * 1999-02-12 2004-04-06 General Electric Company Methods for making data storage media
US6736848B2 (en) * 2001-05-29 2004-05-18 Sdgi Holdings, Inc. Method and apparatus for using formable polymers for orthopedic support

Family Cites Families (29)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5424346A (en) * 1988-08-08 1995-06-13 Ecopol, Llc Biodegradable replacement of crystal polystyrene
BE1005080A3 (fr) * 1991-07-19 1993-04-13 Solvay Soc Anomyme Film souple, elastique et biodegradable en polymere a base d'acide lactique pouvant notamment convenir pour la realisation de pansements medicaux.
US5464878A (en) * 1993-06-11 1995-11-07 Camelot Technologies, Inc. Degradable polymeric form and process for making
US5714573A (en) * 1995-01-19 1998-02-03 Cargill, Incorporated Impact modified melt-stable lactide polymer compositions and processes for manufacture thereof
JP3217240B2 (ja) * 1995-07-10 2001-10-09 三菱樹脂株式会社 ポリ乳酸系成形体
JP3797444B2 (ja) * 1996-05-24 2006-07-19 大日本インキ化学工業株式会社 乳酸系ポリエステル組成物及びその成形物
US5963204A (en) * 1996-09-20 1999-10-05 Nikon Corporation Electronic camera with reproduction and display of images at the same timing
US6701011B1 (en) 1997-01-20 2004-03-02 Canon Kabushiki Kaisha Image processing apparatus and image processing method and storage medium
DE69918233T2 (de) * 1998-03-05 2005-02-24 Mitsui Chemicals, Inc. Polymilchsäure zusammensetzung und daraus hergestellter film
DE19829991C2 (de) * 1998-07-04 2001-08-30 Mafo Systemtech Gmbh & Co Kg Verfahren zur Herstellung einer Polylactid-Folie
DE19829936A1 (de) * 1998-07-04 2000-01-13 Mafo Systemtech Gmbh & Co Kg Verfahren zur Herstellung eines Formteils aus einer Polyactid-Folie
JP2000044716A (ja) * 1998-07-30 2000-02-15 Mitsui Chemicals Inc ポリ乳酸系発泡体製造用組成物、発泡体の製造方法、及び、発泡体
US6453078B2 (en) 1998-08-28 2002-09-17 Eastman Kodak Company Selecting, arranging, and printing digital images from thumbnail images
JP4231579B2 (ja) 1999-01-22 2009-03-04 オリンパス株式会社 画像処理装置及び画像処理プログラムを記録した記録媒体
JP2001034775A (ja) * 1999-05-17 2001-02-09 Fuji Photo Film Co Ltd 履歴画像表示方法
JP2000355089A (ja) * 1999-06-15 2000-12-26 Dainippon Ink & Chem Inc 導電性を付与した生分解性ポリマー積層体又は容器
US20020033959A1 (en) 2000-08-02 2002-03-21 Jitsuhiko Ando Image printing system and image printing apparatus
JP2003305027A (ja) 2002-04-16 2003-10-28 Konica Minolta Holdings Inc 医用画像処理装置、医用画像処理方法、及びプログラム
JP2004070912A (ja) 2002-06-10 2004-03-04 Konica Minolta Holdings Inc 携帯端末装置
JP2004056641A (ja) 2002-07-23 2004-02-19 Fuji Photo Film Co Ltd 画像ファイル編集方法、画像ファイル編集装置、及び画像ファイル編集プログラム
US20040160630A1 (en) 2003-01-20 2004-08-19 Konica Minolta Holdings, Inc. Image printing system
JP3743664B2 (ja) 2003-06-09 2006-02-08 コニカミノルタホールディングス株式会社 画像編集方法及び画像表示方法
US8139262B2 (en) 2003-09-25 2012-03-20 Dai Nippon Printing Co., Ltd. Image output apparatus and image output method for printing out the photographed image which is captured by a digital camera
JP2005096301A (ja) 2003-09-25 2005-04-14 Dainippon Printing Co Ltd 画像出力装置、画像補正方法、画像調整方法、プログラム、記録媒体
US7528990B2 (en) 2004-06-16 2009-05-05 Ricoh Company, Ltd. Image-forming system with improved workability by displaying image finish and setting items in course of processing
JP2006067235A (ja) 2004-08-26 2006-03-09 Ricoh Co Ltd 画像形成装置、画像形成方法、その方法をコンピュータに実行させるプログラム、画像処理装置、および画像処理システム
JP2006067157A (ja) * 2004-08-26 2006-03-09 Sony Corp 情報処理装置および方法、並びにプログラム
US7570839B1 (en) 2005-06-15 2009-08-04 Apple Inc. Tool range selection
JP4853399B2 (ja) 2007-06-21 2012-01-11 ブラザー工業株式会社 画像処理装置、画像処理方法および画像処理プログラム

Patent Citations (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4118454A (en) * 1975-09-02 1978-10-03 Sumitomo Bakelite Company Limited Method for producing transparent plastic molded articles
US4950532A (en) * 1986-10-30 1990-08-21 Azdel, Inc. Process for producing glass fiber reinforced thermoplastic compression molded materials and said molded materials
US4719246A (en) * 1986-12-22 1988-01-12 E. I. Du Pont De Nemours And Company Polylactide compositions
US5180765A (en) * 1988-08-08 1993-01-19 Biopak Technology, Ltd. Biodegradable packaging thermoplastics from lactides
US5213754A (en) * 1990-03-27 1993-05-25 Polyplastics Co., Ltd. Thermoforming process for forming a sheet of polybutylene terephthalate into a transparent container
US6290896B1 (en) * 1992-08-24 2001-09-18 Mitsui Chemicals, Inc. Preparation process of the formed product of L-lactic acid base polymer
US5484881A (en) * 1992-10-02 1996-01-16 Cargill, Inc. Melt-stable amorphous lactide polymer film and process for manufacturing thereof
US6093791A (en) * 1992-10-02 2000-07-25 Cargill, Incorporated Melt-stable semi-crystalline lactide polymer film and process for manufacture thereof
US5338822A (en) * 1992-10-02 1994-08-16 Cargill, Incorporated Melt-stable lactide polymer composition and process for manufacture thereof
US6005068A (en) * 1992-10-02 1999-12-21 Cargill Incorporated Melt-stable amorphous lactide polymer film and process for manufacture thereof
US6136905A (en) * 1994-05-19 2000-10-24 Mitsui Chemicals, Inc. L-lactic acid polymer composition, molded product and film
US5498650A (en) * 1995-02-24 1996-03-12 Ecological Chemical Products Poly(lactic acid) composition having improved physical properties
US5981619A (en) * 1995-09-14 1999-11-09 Takiron Co., Ltd. Material for osteosynthesis and composite implant material, and production processes thereof
US5992832A (en) * 1995-11-30 1999-11-30 Automobiles Peugeot Sphere, in particular a pneumatic sphere, for example for automotive hydropneumatic suspensions
US5766748A (en) * 1995-11-30 1998-06-16 Mitsui Chemicals, Inc. Stretched film of lactic acid-based polymer
US6001439A (en) * 1996-05-09 1999-12-14 Kureha Kagaku Kogyo K.K. Stretch blow molded container and production process thereof
US6506873B1 (en) * 1997-05-02 2003-01-14 Cargill, Incorporated Degradable polymer fibers; preparation product; and, methods of use
US6652983B1 (en) * 1998-02-27 2003-11-25 Nissha Printing Co., Ltd. Sheet for in-mold decorating and in-mold decorated article
US6248430B1 (en) * 1998-08-11 2001-06-19 Dainippon Ink And Chemicals, Inc. Lactic acid-based polymer laminated product and molded product
US6715200B2 (en) * 1999-02-12 2004-04-06 General Electric Company Methods for making data storage media
US6669771B2 (en) * 1999-12-08 2003-12-30 National Institute Of Advanced Industrial Science And Technology Biodegradable resin compositions
US6736848B2 (en) * 2001-05-29 2004-05-18 Sdgi Holdings, Inc. Method and apparatus for using formable polymers for orthopedic support

Cited By (34)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090297652A1 (en) * 2002-12-26 2009-12-03 Toshiyuki Aritake Polylactic acid polymer compositon for thermoforming, polylactic acid polymer sheet for thermoforming, and thermoformed object obtained therefrom
US7988905B2 (en) * 2004-03-17 2011-08-02 Toyota Boshoku Kabushiki Kaisha Process for producing woody molding
US20070176315A1 (en) * 2004-03-17 2007-08-02 Masanori Hashiba Process for producing woody molding
EP1659068A1 (fr) * 2004-11-22 2006-05-24 Coopbox Europe S.P.A. Plateau en plastique pour l'emballage d'aliments susceptibles de dégager des liquids
US8227060B2 (en) * 2005-05-12 2012-07-24 Mitsui Chemicals, Inc. Lactic acid polymer composition, molded article comprising the composition and process for producing the molded article
US20090311511A1 (en) * 2005-05-12 2009-12-17 Mitsui Chemicals, Inc. Lactic acid polymer composition, molded article comprising the composition and process for producing the molded article
US20100144971A1 (en) * 2006-10-20 2010-06-10 Laura Mae Babcock Impact Modified Polylactide Resins
US8183321B2 (en) 2006-10-20 2012-05-22 Natureworks Llc Impact modified polylactide resins
WO2008051443A1 (fr) * 2006-10-20 2008-05-02 Natureworks Llc Résines de polylactide à résistance aux chocs modifiée
US8962791B2 (en) 2006-10-26 2015-02-24 Natureworks Llc Polylactic acid stereocomplex compositions and methods for making and using same
WO2008057214A3 (fr) * 2006-10-26 2008-07-17 Natureworks Llc Compositions stéréocomplexes d'acide polylactique et procédés de production et d'utilisation correspondants
US20100152415A1 (en) * 2006-10-26 2010-06-17 Natureworks Llc Polylactic acid stereocomplex compositions and methods for making and using same
US8021135B2 (en) 2007-06-08 2011-09-20 Sabic Innovative Plastics Ip B.V. Mold apparatus for forming polymer and method
US20080303194A1 (en) * 2007-06-08 2008-12-11 Sabic Innovative Plastics Ip B.V. Mold apparatus for forming polymer and method
US8840386B2 (en) 2007-06-08 2014-09-23 Sabic Innovative Plastics Ip B.V. Mold apparatus for forming polymer and method
US8182734B1 (en) * 2007-08-20 2012-05-22 E. I. Du Pont De Nemours And Company Thermoformed articles and compositions of poly(hydroxyalkanoic acid) and polyoxymethylene
US20100221471A1 (en) * 2007-09-28 2010-09-02 Green Robert A Polylactide stereocomplex conjugate fibers
US8377353B2 (en) * 2007-09-28 2013-02-19 Natureworks Llc Process of making conjugate fibers
US9096009B2 (en) 2007-10-26 2015-08-04 Sabic Global Technologies B.V. Method for forming a polymer part
US20090115104A1 (en) * 2007-10-26 2009-05-07 Sabic Innovative Plastics Ip B.V. System and Method for Forming Polymer
US7678444B2 (en) 2007-12-17 2010-03-16 International Paper Company Thermoformed article made from renewable polymer and heat-resistant polymer
US20090155611A1 (en) * 2007-12-17 2009-06-18 Tedford Jr Richard A Thermoformed article made from renewable polymer and heat-resistant polymer
US20090274920A1 (en) * 2008-05-05 2009-11-05 International Paper Company Thermoformed Article Made From Bio-Based Biodegradable Polymer Composition
US20100179239A1 (en) * 2009-01-14 2010-07-15 Automotive Interior Consulting Method of minimizing compression set of foam
US8231954B2 (en) 2009-12-08 2012-07-31 International Paper Co. Thermoformed articles made from reactive extrusion products of biobased materials
US20110135863A1 (en) * 2009-12-08 2011-06-09 International Paper Company Thermoformed articles made from reactive extrusion products of biobased materials
CN102294808A (zh) * 2010-06-24 2011-12-28 苏州希普生物科技有限公司 高分子材料聚乳酸射出成型工艺
WO2012121960A1 (fr) * 2011-03-04 2012-09-13 Cryovac, Inc. Procédé pour la préparation d'un article en mousse d'acide polylactique résistant à la chaleur
US9045611B2 (en) 2011-03-04 2015-06-02 Cryovac, Inc. Process for preparing a heat resistant polylactic acid foamed article
US20150086768A1 (en) * 2012-05-18 2015-03-26 Kao Corporation Polylactic acid resin sheet for thermal molding use
US9938406B2 (en) * 2012-05-18 2018-04-10 Kao Corporation Polylactic acid resin sheet for thermal molding use
US9381693B2 (en) 2012-12-24 2016-07-05 Innovia Films Limited Packaging and labelling films
US10807344B2 (en) * 2016-04-28 2020-10-20 Natureworks Llc Polymer foam insulation structure having a facing of a multi-layer sheet that contains a heat resistant polymer layer and a polylactide resin layer
WO2023182687A1 (fr) * 2022-03-22 2023-09-28 주식회사 엘지화학 Composition de résine de polylactide ayant un excellent demi-temps de cristallisation, et son procédé de préparation

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DK1463619T3 (da) 2008-02-25
CN1571718A (zh) 2005-01-26
DE60224729T2 (de) 2009-01-22
JP2004538178A (ja) 2004-12-24
JP4307254B2 (ja) 2009-08-05
EP1463619A1 (fr) 2004-10-06
CN1319716C (zh) 2007-06-06
WO2003016015A1 (fr) 2003-02-27
ES2295384T3 (es) 2008-04-16
US20080259054A1 (en) 2008-10-23
US8392851B2 (en) 2013-03-05
DE60224729D1 (de) 2008-03-06
EP1463619A4 (fr) 2004-11-03
EP1463619B1 (fr) 2008-01-16
ATE383934T1 (de) 2008-02-15

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