WO1992004410A1 - Films contenant des acides polyhydroxy ainsi qu'un agent de compatiblite - Google Patents

Films contenant des acides polyhydroxy ainsi qu'un agent de compatiblite Download PDF

Info

Publication number
WO1992004410A1
WO1992004410A1 PCT/US1991/006299 US9106299W WO9204410A1 WO 1992004410 A1 WO1992004410 A1 WO 1992004410A1 US 9106299 W US9106299 W US 9106299W WO 9204410 A1 WO9204410 A1 WO 9204410A1
Authority
WO
WIPO (PCT)
Prior art keywords
film
composition
compatibilizer
acid
polymer
Prior art date
Application number
PCT/US1991/006299
Other languages
English (en)
Inventor
Harold Edward Bellis
Kang Lin
Original Assignee
E.I. Du Pont De Nemours And Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by E.I. Du Pont De Nemours And Company filed Critical E.I. Du Pont De Nemours And Company
Publication of WO1992004410A1 publication Critical patent/WO1992004410A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C08L23/0853—Vinylacetate

Definitions

  • compositions useful in making films and their preparation which compositions comprise polyhy ⁇ roxyacid (PHA) and a co patibilizer. It also relates to films comprising such compositions and other polymers- High molecular weight polymers of hydroxy acids and cyclic dimer products of esterification, of 2-hydroxy acids, particularly glycolic acid and lactic acid, are well known to be degradable. These materials can be useful in disposable packaging that will substantially and readily deteriorate to harmless by-products under conditions existing in the natural enviroment or employed in suitable waste treatment facilities. Highly useful films are made from many known polymers, such as polyolefins, polycarbonates, nylon and cellophane.
  • polyolefin films pose a waste disposal problem because by themselves they are not degradable in the environment.
  • Polyolefin films have been rendered degradable to the extent of degeneration to polyolefin flakes, by incorporating starches into the polymer. While these polyolefin/starch blends have a number of uses such as garbage bags, their utility is limited because they are not transparen .
  • compositions comprising a polyhydroxy acid (PHA) and a compatibilizer.
  • PHA polyhydroxy acid
  • compatibilizer a compatibilizer
  • Polyhydroxy acids as used herein means polymers containing at least one hy ⁇ droxy acid unit selected from among:
  • the PHA is present in amounts from 5-90 weight percent.
  • the compatibilizer is present in amounts from 5 to about 75 weight % of the PHA/compatibilizer composition.
  • compatibilizers are compositions that when introduced into a blend of substantially immiscible polymers will bring about an intimate blending of the polymers that does not exhibit gross symptoms of polymer segregation.
  • the compatibilizer brings about a compatible blend that is homogeneous on a macroscopic level; a blend that is heterogeneous on a macroscopic level is not compatible.
  • a compatibilizer is specific for specific polymer blends because it must contain chemical components that are compatible with each of the other polymers.
  • the compatibilizers must all contain a chemical or physical ability to be compatib-ilized with the PHA and also with the other part ⁇ ular polymer component.
  • the selection of an e ffective compatibilizer will be made based on the know., chemical and physical characteristics of the other polymer component of the blend. If more than a single polymer is present in the other polymer component, more than one compatibilizer may be required to give a homogeneous blend. Examples of compatibilizers that, when mixed with PHAs will give compatible compositions, are listed in Table I.
  • PHA Composition Compatibilizer Other Polymer polyglycolic acid ethylene/vinyl polyethylene homopolymer acetate copo ⁇ lymer
  • the amount of compatibilizer needed will vary depending on the relative amounts of PHA and the overall PHA/compatibilizer/polymer blend proportions.
  • the polymer other than those of formalae (i) to (v) in the preferred compositions is present in amounts up to about 90 weight % of the final 3 or more component product.
  • the F ./compatibilizer compositions of this invention are p-...-.pared by dry mixing or melt blending the PHA with a compatibilizer that is compatbile with the PHA and the particular 3rd component other polymer.
  • the films of this invention are prepared by melt processing the PHA/compatibilizer/polymer compositions under sufficient mechanical agitation to obtain a uniform composition that is a solution or intimately homogeneous small particle blend.
  • the film product is ther ormed by conventional techniques, such as solution casting, extruding, or tubular blowing, to produce a film of uniform thickness normally from about 0.01 to 2 mm.
  • non-hydroxy acid comonomers include those capable of condensation pol ⁇ aerization with ?- .-ctide or lactic acid; i.e., lactones such as epsilon-caprolactone, beta-propiolactone; alpha-dimethyl-beta-propiolactcne; glycolide; and dodecanola ⁇ tone and lactams.
  • lactones such as epsilon-caprolactone, beta-propiolactone
  • alpha-dimethyl-beta-propiolactcne glycolide
  • dodecanola ⁇ tone and lactams dodecanola ⁇ tone and lactams.
  • Polyhydroxy acid containing compositions of this invention have average molecular weights at le ⁇ st high enough to provide sufficient viscosity and strength to form sustainable film from the total polymer melt.
  • weight average molecular weights from about 2,000 to about 600,000 can be used.
  • a molecular weight of the PHA from about 20,000 to about 450,000 is used where the PHA comprises over half of the polymer content of the final film produc containing the other compatibilizer polymer; and 4,00-. ro 20,000 where the PHA comprises less than half of the polymer content of the final film product.
  • degradation as used here with respect to the polyhydroxy acids means that the polyhydroxy acid portion of the degradable material is biodegradable and, more importantly, degradable by hydrolysis.
  • the degradation rate is consistent with its intended usage, i.e., the product does not degrade significantly in normal storage and usage, but will degrade in a reasonable time, after discarding.
  • hydrolytic degradation of a polymer can be tailored readily to meet the requirements of use and disposal of the film. It depends primarily on the nature of groups in the chains.
  • Certain conditions such as moisture, pH, temperature, ion strength, sunlight, enzymes, polymer crystallinity and hydrophilicity of the polymer affect degradation of the polymer, as is well known.
  • Rate of degradation of polyhydroxy polymers can be too great for many typical packaging applications (i.e., the packaging film will deteriorate excessively in less time than the expected shelf-life of the package, which includes the warehousing time of the packaging film between its production and application of the product) .
  • the reduced tensile strength of the film caused by the deterioration results in film ruptures while being processed on shrink-wrap machinery and would be unacceptable for commercial packaging applications.
  • the amount of shrinkage or the resistance of the films may be inappropriate for particular uses.
  • Preferred non-polyhydroxy r lymers of this invention include polyolefins, polyet rs, polyesters, polyamides, polyvinyl chlorides, polycarbonates, polysulfones, copolyetheresters, polyurethanes, ethylene/vinyl alcohol copolymers, copolyamidoetheresters, ethylene/vinyl ester copolymers and terpolymers,ethylene/acrylic acid and terpolymers and their metal salts, ethylene-carbon monoxide copolymers, and copolyetherimidoesters.
  • "Hazy" products outside the scope of this invention, have impaired transparency caused by insufficient compatibilization, extruding of low molecular weight plasticizer to the surfaces of the films, high crystalline content of the starting polymer, and the like.
  • ambient temperature means the highest temperature at which the film product will be exposed during use or storage. Normally, this will range from room temperature (20"C) or below when under refrigeration, up to 40 ⁇ C or more when in warehouse storage.
  • Preferred polyhydroxy acids of this invention are those wherein 50-99 mol% is the PHA component composed of hydroxy acid units (i) wherein R' is hydrogen and R" is the methyl radical, and having 80-97 mol% of asymmetric carbon atoms R- configuration and 3-20 mol% S- configuration or 80-97 mol% S- configuration and 3-20 mol% R- configuration; and wherein 1-45 mol% is tfc-> minor component composed of either h ydroxy acid unit (i) of such asymmetric carbon content that the total R- or S- configuration in major and minor components do not exceed 97 mol% of asymmetric carbon atoms, or any hydroxy acid units (ii) to (iv) or suitable non-hydroxy acid comonomers.
  • a preferred polyhydroxy acid may, for example, contain a major component of 67 mol% hydroxy acid unit (i) in which 90 mol% of asymmetric carbon atoms are S- configuration.
  • the minor polyhydroxy acid component will be 35 mol%, and might be completely composed of hydroxy acid unit (ii) or a suitable non-hydroxy acid comonomer.
  • the minor component of the PHA might be additional hydroxy acid unit (i) but the fraction of asymmetric carbon atoms which are S- configuration component can be no greater than that which when added to the S- atoms of the PHA component does not raise the S- atom content of the total above 97 mol%.
  • the range of R- and S- asymmetric carbon atoms in the polyhydroxy acid is 85-96 mol%.
  • R- and S- refer to the standard nomenclature for identifying stereoisomer configurations on the asymmetrical carbon.
  • the percentages of R- and S- carbons indicated herein refer only to fractions of asymmetrical carbon atoms in the PHA polymer chains and not to total carbon atoms in the polymer chains.
  • Asymmetrical carbon atoms are those having less than four different substituent radical groups attached to them.
  • the preferred compositions have narrow ranges of selected asymmetrical carbon atoms because polymers containing more equal fractions of R- and S- carbon atoms demonstrate accelerated degradation by hydrolysis, produce films adjacent layers of which often adhere to each other and which are prone to degradation during processing to form film.
  • films made outside these ranges may be hazy and/or brittle.
  • polymer films having fractions above the S- carbon atom range are substantially crystalline after hot processing, such as in film production. Crystallinity is detrimental to film-forming capability, and to optical clarity of films formed from crystalline polymers.
  • a method for reducing the negative effects of highly crystalline polymer on film properties is to plasticize the polymer by incorporating and dispersing monomeric, low molecular weight oligomeric ' species within the polymer matrix.
  • Plasticizers for polyhydroxy acids of this invention are monomeric hydroxy acids, lactides of monomeric hydroxy acids, lactyl lactate non-cyclic dimers of monomeric hydroxy acids and other oligomers of monomoric hydroxy acids up to molecular weight of about 450.
  • amounts of plasticizers produces films of uneven thickness. Where films are made by casting onto drums, excessive plasticizer may separate from the film, stick to and foul the drum, or may cause the film to stick to the drum. Thus, it has been found necessary to use polymer containing a minimal 3mount of plasticizer.
  • the amount of plasticizers need ; to obtain useful films of this invention is from about 0.10 to about 8 wt%, and preferably from about 0.2 to 6 wt%.
  • a highly preferable composition range is from about 0.2 to 0.4 wt% plasticizer. These plasticizer levels are based upon the concentrations of the polyhydroxy acid and plasticizer in the feedstock to the film production process and not necessarily to the concentrations of the plasticizer in the film produced from compositions of this invention. Plasticizer content may be determined by lactide content analysis methods taught in Journal of Applied Polymer Science, Kohn, Van den Berg, Van de Ridder and Feyen, volume 29, pages 4265-4277 (1984) . When necessary to reduce the concentration of plasticizers in a plasticizer-rich composition, a devolatilizing extruder can be used either as a separate step or during film extrusion.
  • the compatibilizers used in these Examples are: TRX-101 HFTM (Du Pont Co.), aleic anhydride grafted on ethylene-propylene copolymer; ElvaxTM 360 (Du Pont Co.), a copolymer of ethylene and vinyl acetate; FusabondTM D-100 and FusabondTM D-111 (Du Pont Co.), maleic anhydride grafted on PE; and NucrelTM 0407 (Du Pont Co.) and NucrelTM 0903(Du Pont Co.) copolymer of ethylene and acrylic acid.
  • SurylnTM Ionomer #1650 and #1601 (Du Pont Co.) are NucrelTM salts.
  • EMATM 2205 and 2207 are ethylene and methylacrylic acid copolymers. These compatibilizers all have both hydrophyllic and hydrophobic end groups. Examples 1-5
  • a 50% polylactic acid/50% polyglycolic acid (PLA/PGA) copolymer is prepared by heating a mixture of 1667g of crystalline glycolic acid, 1894g of R-lactic acid, and 3.3g of stannous octoate. The reaction is heated from room temperature to 136 ⁇ C under atmospheric pressure. The pressure is then reduced to 100mm. while heating over 3 hrs. to 190 ⁇ C. -li ⁇ lt is then heated for an additional 5 hours at 190°C under 2mm v ⁇ ⁇ u . There is produced a 50/50 copolymer with an average molecular weight of 6000 with a softening point of about 120"C.
  • Blends as shown in Table I, are then prepared using low-density polyethylene (LDPE) , Exxon #3060, with a melt index of 2.0; and the compatibilizers listed in Table I.
  • LDPE low-density polyethylene
  • Exxon #3060 Exxon #3060
  • melt index of 2.0 melt index of 2.0
  • compatibilizers listed in Table I The above described 50/50 copolymer, the LDPE, and the compatibilizer are mixed together in a Banbury mixer above the melting points of the three ingredients and then is crushed to 1/4" average diameter particles. The particles are then dried in an oven.
  • blown films are prepared as follows: The particles are then fed to a screw feeder having a 1" dia eter die. It is maintained at 175-225*C in tht- heating and melt zones. The screw is run at 32 rpm. Films are tnen extruded ar. - conventionally blown to 2-4 mil. (.05-.lmm) thickness.
  • Examples 1, 4 and 5 are first tested and then are heated in distilled water for 28 days at 70°C. Table II shows the results of these tensile tests in PSI before and after the water treatment. MD is the extrusion direction; TD is the transverse or circumferential direction.
  • Examples 4 and 5 this invention show high strengths as blown compared to Example 1 (100% PE) , and also shows lower strengths (degradation) after water treatment. Similar films are prepared by casting the film directly without blowing. These films have similar properties of strength, clarity and degradability.
  • Example 7 Several films are blown on commercial equipment .04-.05mm thickness from a blend containing 10% of 50/50% PLA/PGA copolymer, 10% of ElvaxTM 360, and 80% of LDPE (Exxon 3060) . These films of the present invention are clear and flexible and have elongations at break and tensile strengths ' comparable to a 100% LDPE control. Accelerated tests are run on these films simulating exposure to municipal sewage in a treatment plant bio-digester. After 5 days exposure a biological oxygen demand is (BOD) of 300ppm is obtained. After 20 days the BOD is increased further to 1400ppm. The films are completely broken down by the biological degradation of + ⁇ e PLA/PGA component of the films.
  • BOD biological oxygen demand
  • Comparative film of 100% LDPE has inferior strength and elongation properties and does not degrade in the simulated sewage test.
  • Example 1 PLA of inherent viscosity of 1.1 is blended in a Banbury mixer in a 1:2 ratio with FusabondTM D-111. The resulting blend is crushed to 1/4" average diameter particles and blown films are made as in Example 1. The resulting films are significantly degradable.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Biological Depolymerization Polymers (AREA)

Abstract

L'invention concerne certaines compositions utiles dans la fabrication de films et dans leur préparation, lesdites compositions comprenant de l'acide polyhydroxy (APH) ainsi qu'un agent de compatibilité. L'invention concerne également des films comprenant lesdites compositions ainsi que d'autres polymères.
PCT/US1991/006299 1990-09-11 1991-09-09 Films contenant des acides polyhydroxy ainsi qu'un agent de compatiblite WO1992004410A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US58052790A 1990-09-11 1990-09-11
US580,527 1990-09-11

Publications (1)

Publication Number Publication Date
WO1992004410A1 true WO1992004410A1 (fr) 1992-03-19

Family

ID=24321463

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1991/006299 WO1992004410A1 (fr) 1990-09-11 1991-09-09 Films contenant des acides polyhydroxy ainsi qu'un agent de compatiblite

Country Status (8)

Country Link
EP (1) EP0548209A4 (fr)
JP (1) JPH06500819A (fr)
CN (1) CN1059919A (fr)
AU (1) AU8611391A (fr)
IE (1) IE913195A1 (fr)
MX (1) MX9101008A (fr)
PT (1) PT98914A (fr)
WO (1) WO1992004410A1 (fr)

Cited By (37)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5247059A (en) * 1992-01-24 1993-09-21 Cargill, Incorporated Continuous process for the manufacture of a purified lactide from esters of lactic acid
US5247058A (en) * 1992-01-24 1993-09-21 Cargill, Incorporated Continuous process for manufacture of lactide polymers with controlled optical purity
US5258488A (en) * 1992-01-24 1993-11-02 Cargill, Incorporated Continuous process for manufacture of lactide polymers with controlled optical purity
US5274073A (en) * 1992-01-24 1993-12-28 Cargill, Incorporated Continuous process for manufacture of a purified lactide
WO1994000163A1 (fr) * 1992-06-26 1994-01-06 The Procter & Gamble Company Compositions de films monocouches biodegradables et impermeables aux liquides
WO1994006866A1 (fr) * 1992-09-22 1994-03-31 Biopak Technology, Ltd. Regulation de degradation de materiaux jetables, degradables par l'environnement
US5338822A (en) * 1992-10-02 1994-08-16 Cargill, Incorporated Melt-stable lactide polymer composition and process for manufacture thereof
US5391423A (en) * 1992-06-26 1995-02-21 The Procter & Gamble Company Biodegradable, liquid impervious multilayer film compositions
JPH07207041A (ja) * 1994-01-11 1995-08-08 Mitsubishi Plastics Ind Ltd ポリ乳酸系フイルム
US5444113A (en) * 1988-08-08 1995-08-22 Ecopol, Llc End use applications of biodegradable polymers
US5472518A (en) * 1994-12-30 1995-12-05 Minnesota Mining And Manufacturing Company Method of disposal for dispersible compositions and articles
US5502158A (en) * 1988-08-08 1996-03-26 Ecopol, Llc Degradable polymer composition
US5525706A (en) * 1992-10-02 1996-06-11 Cargill, Incorporated Melt-stable lactide polymer nonwoven fabric and process for manufacture thereof
WO1996022330A2 (fr) * 1995-01-19 1996-07-25 Cargill, Incorporated Compositions polymeres a base de lactides stables a haute temperature et a comportement aux chocs ameliore, et leurs procedes d'obtention
US5665474A (en) * 1992-10-02 1997-09-09 Cargill, Incorporated Paper having a melt-stable lactide polymer coating and process for manufacture thereof
WO1998029585A2 (fr) * 1996-12-31 1998-07-09 Kimberly-Clark Worldwide, Inc. Fibre multiconstituants
US5939467A (en) * 1992-06-26 1999-08-17 The Procter & Gamble Company Biodegradable polymeric compositions and products thereof
US6005068A (en) * 1992-10-02 1999-12-21 Cargill Incorporated Melt-stable amorphous lactide polymer film and process for manufacture thereof
US6005067A (en) * 1992-01-24 1999-12-21 Cargill Incorporated Continuous process for manufacture of lactide polymers with controlled optical purity
US6135987A (en) * 1997-12-22 2000-10-24 Kimberly-Clark Worldwide, Inc. Synthetic fiber
US6194483B1 (en) 1998-08-31 2001-02-27 Kimberly-Clark Worldwide, Inc. Disposable articles having biodegradable nonwovens with improved fluid management properties
US6197237B1 (en) * 1997-12-22 2001-03-06 Kimberly Clark Corporation Method of making a multicomponent fiber and nonwoven web containing the same
US6197860B1 (en) 1998-08-31 2001-03-06 Kimberly-Clark Worldwide, Inc. Biodegradable nonwovens with improved fluid management properties
US6201068B1 (en) 1997-10-31 2001-03-13 Kimberly-Clark Worldwide, Inc. Biodegradable polylactide nonwovens with improved fluid management properties
US6261677B1 (en) 1997-12-22 2001-07-17 Kimberly-Clark Worldwide, Inc. Synthetic fiber
US6268434B1 (en) 1997-10-31 2001-07-31 Kimberly Clark Worldwide, Inc. Biodegradable polylactide nonwovens with improved fluid management properties
US6306782B1 (en) 1997-12-22 2001-10-23 Kimberly-Clark Worldwide, Inc. Disposable absorbent product having biodisintegratable nonwovens with improved fluid management properties
US6309988B1 (en) 1997-12-22 2001-10-30 Kimberly-Clark Worldwide, Inc. Biodisintegratable nonwovens with improved fluid management properties
US6323307B1 (en) 1988-08-08 2001-11-27 Cargill Dow Polymers, Llc Degradation control of environmentally degradable disposable materials
US6326458B1 (en) 1992-01-24 2001-12-04 Cargill, Inc. Continuous process for the manufacture of lactide and lactide polymers
JP2003002984A (ja) * 2002-06-14 2003-01-08 Mitsubishi Plastics Ind Ltd ポリ乳酸系フィルム
US6544455B1 (en) 1997-12-22 2003-04-08 Kimberly-Clark Worldwide, Inc. Methods for making a biodegradable thermoplastic composition
WO2003033563A1 (fr) * 2001-10-15 2003-04-24 Jvs-Polymers Oy Revetement biodegradable
US6579814B1 (en) 1994-12-30 2003-06-17 3M Innovative Properties Company Dispersible compositions and articles of sheath-core microfibers and method of disposal for such compositions and articles
EP1340690A1 (fr) * 2000-09-22 2003-09-03 Sony Corporation Materiel d'emballage et supports d'enregistrement de donnees emballes avec le materiel d'emballage
EP2233527A1 (fr) * 2007-12-27 2010-09-29 Kureha Corporation Composition de résine de polypropylène, article moulé produit à partir de la composition de résine et procédé pour la production de l'article moulé
CN102250453A (zh) * 2011-05-29 2011-11-23 江苏华信塑业发展有限公司 Pha与petg共混物薄膜及其制备方法

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07205278A (ja) * 1994-01-11 1995-08-08 Mitsubishi Plastics Ind Ltd ポリ乳酸系重合体延伸フイルムの製造方法
JP2010513604A (ja) * 2006-12-14 2010-04-30 パクティヴ・コーポレーション ギ酸メチル系発泡剤を用いて得られた、生分解性および低排出性の膨張および押出発泡体
CN101875764B (zh) * 2010-06-30 2012-08-15 中国蓝星（集团）股份有限公司 一种可定型的聚乳酸树脂组合物及其塑料条的制备方法
CN103756102A (zh) * 2014-01-24 2014-04-30 常熟市明瑞包装材料厂 一种能生物降解的包装袋
CN109867849A (zh) * 2019-02-15 2019-06-11 江苏莱顿博瑞生物科技有限公司 一种用于火龙果的气调保鲜袋及其制备方法
CN109968755A (zh) * 2019-04-22 2019-07-05 刘建林 可生物降解的复合包装膜及包装袋
CN114075373B (zh) * 2020-08-19 2023-07-11 国家能源投资集团有限责任公司 改性聚乙醇酸组合物及其制备方法与应用
CA3213362A1 (fr) * 2021-03-30 2022-10-06 Takenori TOSE Corps moule, element d'outil de fond et outil de fond

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4393167A (en) * 1980-11-18 1983-07-12 Imperial Chemical Industries Plc Polymer blends containing polymer of β-hydroxybutyric acid and chlorine or nitrile group containing polymer
WO1984000303A1 (fr) * 1982-07-16 1984-02-02 Univ Groningen Polyester contenant un materiau filamenteux
US4500686A (en) * 1982-03-19 1985-02-19 Toyo Boseki Kabushiki Kaisha Polyester type block copolymer composition
US4565851A (en) * 1983-04-25 1986-01-21 Eastman Kodak Company Containers having improved gas barrier properties
US4912161A (en) * 1988-03-17 1990-03-27 Bayer Aktiengesellschaft Thermoplastic moulding compounds of great toughness and good processability in the molten state

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4709808A (en) * 1986-04-25 1987-12-01 Owens-Illinois Plastic Products Inc. Degradable polymer composition and articles prepared from same
JPH0623260B2 (ja) * 1989-11-08 1994-03-30 工業技術院長 微生物崩壊性熱可塑性樹脂成形物及びその製造方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4393167A (en) * 1980-11-18 1983-07-12 Imperial Chemical Industries Plc Polymer blends containing polymer of β-hydroxybutyric acid and chlorine or nitrile group containing polymer
US4500686A (en) * 1982-03-19 1985-02-19 Toyo Boseki Kabushiki Kaisha Polyester type block copolymer composition
WO1984000303A1 (fr) * 1982-07-16 1984-02-02 Univ Groningen Polyester contenant un materiau filamenteux
US4565851A (en) * 1983-04-25 1986-01-21 Eastman Kodak Company Containers having improved gas barrier properties
US4912161A (en) * 1988-03-17 1990-03-27 Bayer Aktiengesellschaft Thermoplastic moulding compounds of great toughness and good processability in the molten state

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP0548209A4 *

Cited By (68)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6323307B1 (en) 1988-08-08 2001-11-27 Cargill Dow Polymers, Llc Degradation control of environmentally degradable disposable materials
US5502158A (en) * 1988-08-08 1996-03-26 Ecopol, Llc Degradable polymer composition
US5444113A (en) * 1988-08-08 1995-08-22 Ecopol, Llc End use applications of biodegradable polymers
US5274073A (en) * 1992-01-24 1993-12-28 Cargill, Incorporated Continuous process for manufacture of a purified lactide
US6326458B1 (en) 1992-01-24 2001-12-04 Cargill, Inc. Continuous process for the manufacture of lactide and lactide polymers
US5357035A (en) * 1992-01-24 1994-10-18 Cargill, Incorporated Continuous process for manufacture of lactide polymers with purification by distillation
US5258488A (en) * 1992-01-24 1993-11-02 Cargill, Incorporated Continuous process for manufacture of lactide polymers with controlled optical purity
US6277951B1 (en) 1992-01-24 2001-08-21 Cargill, Incorporated Continuous process for manufacture of lactide polymers with controlled optical purity
US6005067A (en) * 1992-01-24 1999-12-21 Cargill Incorporated Continuous process for manufacture of lactide polymers with controlled optical purity
US5247059A (en) * 1992-01-24 1993-09-21 Cargill, Incorporated Continuous process for the manufacture of a purified lactide from esters of lactic acid
US5247058A (en) * 1992-01-24 1993-09-21 Cargill, Incorporated Continuous process for manufacture of lactide polymers with controlled optical purity
WO1994000163A1 (fr) * 1992-06-26 1994-01-06 The Procter & Gamble Company Compositions de films monocouches biodegradables et impermeables aux liquides
US5391423A (en) * 1992-06-26 1995-02-21 The Procter & Gamble Company Biodegradable, liquid impervious multilayer film compositions
US5939467A (en) * 1992-06-26 1999-08-17 The Procter & Gamble Company Biodegradable polymeric compositions and products thereof
WO1994006866A1 (fr) * 1992-09-22 1994-03-31 Biopak Technology, Ltd. Regulation de degradation de materiaux jetables, degradables par l'environnement
US6005068A (en) * 1992-10-02 1999-12-21 Cargill Incorporated Melt-stable amorphous lactide polymer film and process for manufacture thereof
US5773562A (en) * 1992-10-02 1998-06-30 Cargill, Incorporated Melt-stable semi-crystalline lactide polymer film and process for manufacture thereof
US5536807A (en) * 1992-10-02 1996-07-16 Cargill, Incorporated Melt-stable semi-crystalline lactide polymer film and process for manufacture thereof
US6121410A (en) * 1992-10-02 2000-09-19 Cargill, Incorporated Melt-stable semi-crystalline lactide polymer film and process for manufacture thereof
US5475080A (en) * 1992-10-02 1995-12-12 Cargill, Incorporated Paper having a melt-stable lactide polymer coating and process for manufacture thereof
US5585191A (en) * 1992-10-02 1996-12-17 Cargill, Incorporated Melt-stable amorphous lactide polymer film and process for manufacture thereof
US5525706A (en) * 1992-10-02 1996-06-11 Cargill, Incorporated Melt-stable lactide polymer nonwoven fabric and process for manufacture thereof
US5484881A (en) * 1992-10-02 1996-01-16 Cargill, Inc. Melt-stable amorphous lactide polymer film and process for manufacturing thereof
US5665474A (en) * 1992-10-02 1997-09-09 Cargill, Incorporated Paper having a melt-stable lactide polymer coating and process for manufacture thereof
US6355772B1 (en) 1992-10-02 2002-03-12 Cargill, Incorporated Melt-stable lactide polymer nonwoven fabric and process for manufacture thereof
US6207792B1 (en) 1992-10-02 2001-03-27 Cargill, Incorporated Melt-stable amorphous lactide polymer film and process for manufacture 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
US5852166A (en) * 1992-10-02 1998-12-22 Cargill, Incorporated Paper having a melt-stable lactide polymer coating and process for manufacture thereof
US5798436A (en) * 1992-10-02 1998-08-25 Cargill, Incorporated Melt-stable amorphous lactide polymer film and process for manufacture thereof
US5807973A (en) * 1992-10-02 1998-09-15 Cargill, Incorporated Melt-stable lactide polymer nonwoven fabric and process for manufacture thereof
JPH07207041A (ja) * 1994-01-11 1995-08-08 Mitsubishi Plastics Ind Ltd ポリ乳酸系フイルム
US5472518A (en) * 1994-12-30 1995-12-05 Minnesota Mining And Manufacturing Company Method of disposal for dispersible compositions and articles
US5508101A (en) * 1994-12-30 1996-04-16 Minnesota Mining And Manufacturing Company Dispersible compositions and articles and method of disposal for such compositions and articles
US5763065A (en) * 1994-12-30 1998-06-09 Minnesota Mining And Manufacturing Company Water dispersible multi-layer microfibers
US5630972A (en) * 1994-12-30 1997-05-20 Patnode; Gregg A. Method of making dispersible compositions and articles
US5567510A (en) * 1994-12-30 1996-10-22 Minnesota Mining And Manufacturing Company Dispersible compositions and articles and method of disposal for such compositions and articles
US6579814B1 (en) 1994-12-30 2003-06-17 3M Innovative Properties Company Dispersible compositions and articles of sheath-core microfibers and method of disposal for such compositions and articles
US6495631B1 (en) 1995-01-19 2002-12-17 Cargill, Incorporated Impact modified melt-stable lactide polymer compositions and processes for manufacture thereof
US5922832A (en) * 1995-01-19 1999-07-13 Cargill, Incorporated Impact modified melt-stable lactide polymer compositions and processes for manufacture thereof
WO1996022330A2 (fr) * 1995-01-19 1996-07-25 Cargill, Incorporated Compositions polymeres a base de lactides stables a haute temperature et a comportement aux chocs ameliore, et leurs procedes d'obtention
WO1996022330A3 (fr) * 1995-01-19 1997-01-30 Cargill Inc Compositions polymeres a base de lactides stables a haute temperature et a comportement aux chocs ameliore, et leurs procedes d'obtention
US5714573A (en) * 1995-01-19 1998-02-03 Cargill, Incorporated Impact modified melt-stable lactide polymer compositions and processes for manufacture thereof
WO1998029585A2 (fr) * 1996-12-31 1998-07-09 Kimberly-Clark Worldwide, Inc. Fibre multiconstituants
US5952088A (en) * 1996-12-31 1999-09-14 Kimberly-Clark Worldwide, Inc. Multicomponent fiber
WO1998029585A3 (fr) * 1996-12-31 1998-08-13 Kimberly Clark Co Fibre multiconstituants
AU720669B2 (en) * 1996-12-31 2000-06-08 Kimberly-Clark Worldwide, Inc. Multicomponent fiber
US6201068B1 (en) 1997-10-31 2001-03-13 Kimberly-Clark Worldwide, Inc. Biodegradable polylactide nonwovens with improved fluid management properties
US6268434B1 (en) 1997-10-31 2001-07-31 Kimberly Clark Worldwide, Inc. Biodegradable polylactide nonwovens with improved fluid management properties
US6475418B1 (en) 1997-10-31 2002-11-05 Kimberly-Clark Worldwide, Inc. Methods for making a thermoplastic composition and fibers including same
US6135987A (en) * 1997-12-22 2000-10-24 Kimberly-Clark Worldwide, Inc. Synthetic fiber
US6261677B1 (en) 1997-12-22 2001-07-17 Kimberly-Clark Worldwide, Inc. Synthetic fiber
US6544455B1 (en) 1997-12-22 2003-04-08 Kimberly-Clark Worldwide, Inc. Methods for making a biodegradable thermoplastic composition
US6306782B1 (en) 1997-12-22 2001-10-23 Kimberly-Clark Worldwide, Inc. Disposable absorbent product having biodisintegratable nonwovens with improved fluid management properties
US6309988B1 (en) 1997-12-22 2001-10-30 Kimberly-Clark Worldwide, Inc. Biodisintegratable nonwovens with improved fluid management properties
US6197237B1 (en) * 1997-12-22 2001-03-06 Kimberly Clark Corporation Method of making a multicomponent fiber and nonwoven web containing the same
US6194483B1 (en) 1998-08-31 2001-02-27 Kimberly-Clark Worldwide, Inc. Disposable articles having biodegradable nonwovens with improved fluid management properties
US6197860B1 (en) 1998-08-31 2001-03-06 Kimberly-Clark Worldwide, Inc. Biodegradable nonwovens with improved fluid management properties
US6245831B1 (en) 1998-08-31 2001-06-12 Kimberly-Clark Worldwide, Inc. Disposable articles having biodegradable nonwovens with improved fluid management properties
EP1340690A1 (fr) * 2000-09-22 2003-09-03 Sony Corporation Materiel d'emballage et supports d'enregistrement de donnees emballes avec le materiel d'emballage
EP1340690A4 (fr) * 2000-09-22 2004-06-16 Sony Corp Materiel d'emballage et supports d'enregistrement de donnees emballes avec le materiel d'emballage
US7285318B2 (en) 2000-09-22 2007-10-23 Sony Corporation Packaging material and information recording media packaged by packaging material
WO2003033563A1 (fr) * 2001-10-15 2003-04-24 Jvs-Polymers Oy Revetement biodegradable
JP2003002984A (ja) * 2002-06-14 2003-01-08 Mitsubishi Plastics Ind Ltd ポリ乳酸系フィルム
EP2233527A1 (fr) * 2007-12-27 2010-09-29 Kureha Corporation Composition de résine de polypropylène, article moulé produit à partir de la composition de résine et procédé pour la production de l'article moulé
EP2233527A4 (fr) * 2007-12-27 2011-08-10 Kureha Corp Composition de résine de polypropylène, article moulé produit à partir de la composition de résine et procédé pour la production de l'article moulé
CN102250453A (zh) * 2011-05-29 2011-11-23 江苏华信塑业发展有限公司 Pha与petg共混物薄膜及其制备方法
CN102250453B (zh) * 2011-05-29 2013-02-27 江苏华信塑业发展有限公司 Pha与petg共混物薄膜及其制备方法

Also Published As

Publication number Publication date
MX9101008A (es) 1992-05-04
JPH06500819A (ja) 1994-01-27
EP0548209A4 (en) 1993-09-01
CN1059919A (zh) 1992-04-01
IE913195A1 (en) 1992-03-11
PT98914A (pt) 1992-07-31
AU8611391A (en) 1992-03-30
EP0548209A1 (fr) 1993-06-30

Similar Documents

Publication Publication Date Title
WO1992004410A1 (fr) Films contenant des acides polyhydroxy ainsi qu'un agent de compatiblite
CA2113521C (fr) Compositions biodegradables traitables a la chaleur et articles en contenant
WO1992004412A1 (fr) Films contenant des acides polyhydroxy
EP0428620A1 (fr) Méthode pour la plastification de polymères de lactide.
NL2017891B1 (en) Biaxially stretched starch-based foil
EP0540641B1 (fr) Melange polymere biodegradable contenant un copolymere de 3-hydroxybutyrate/3-hydroxyvalerate
WO2013101821A1 (fr) Mélanges de polyesters renforcés
EP3162841B1 (fr) Plastique biodigestible, biocompostable, biodégradable
KR102459032B1 (ko) 바이오매스 기반의 생분해 수지 조성물 및 그 제조방법
US9925707B2 (en) Process for preparation of biodegradable biocompostable biodigestible polyolefins
Debiagi et al. Thermoplastic starch-based blends: processing, structural, and final properties
KR102579310B1 (ko) 폴리비닐알코올을 포함하는 생분해성 수지 조성물 및 그 제조방법
EP4071211A1 (fr) Composition de résine biodégradable et procédé pour sa production
KR20220035142A (ko) 증가된 강도 및 기타 특성을 위해 소립자의 전분 및 전분계 물질을 합성 폴리머와 혼합
CN114430759A (zh) 包含pbat、pla和基于碳水化合物的聚合物材料的共混物的聚合物制品
AU2010304033A1 (en) Reactive polymeric mixture
Sungsanit Rheological and mechanical behaviour of poly (lactic acid)/polyethylene glycol blends
AU2015249059B2 (en) A process for preparation of biodegradable biocompostable biodigestible peplene polymer
CA2910848C (fr) Un procede de preparation de polymere de peplene biodigestible, biocompostable et biodegradable
BG3278U1 (bg) Състав на мастърбач за производство на биоразградим полимерен материал
TW202409192A (zh) 生物可降解樹脂組合物、生物可降解樹脂成型品及其製造方法
AU4223889A (en) Degradable thermoplastic from lactides
BG67371B1 (bg) Състав на мастърбач за производство на биоразградим полимерен материал
NZ239123A (en) Biodegradeable polymer blend comprising a copolymer containing 3-hydroxy

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AU BB BG BR CA CS FI HU JP KP KR LK MC MG MN MW NO PL RO SD SU

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE BF BJ CF CG CH CI CM DE DK ES FR GA GB GN GR IT LU ML MR NL SE SN TD TG

WWE Wipo information: entry into national phase

Ref document number: 1991916712

Country of ref document: EP

WWP Wipo information: published in national office

Ref document number: 1991916712

Country of ref document: EP

WWW Wipo information: withdrawn in national office

Ref document number: 1991916712

Country of ref document: EP

NENP Non-entry into the national phase

Ref country code: CA