WO1994024198A1 - Polylactide a revetement metallique ou d'oxyde de silicium utilise comme materiau d'emballage - Google Patents

Polylactide a revetement metallique ou d'oxyde de silicium utilise comme materiau d'emballage Download PDF

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Publication number
WO1994024198A1
WO1994024198A1 PCT/EP1994/001114 EP9401114W WO9424198A1 WO 1994024198 A1 WO1994024198 A1 WO 1994024198A1 EP 9401114 W EP9401114 W EP 9401114W WO 9424198 A1 WO9424198 A1 WO 9424198A1
Authority
WO
WIPO (PCT)
Prior art keywords
polylactide
lactide
film
packaging material
coated
Prior art date
Application number
PCT/EP1994/001114
Other languages
German (de)
English (en)
Inventor
Aktiengesellschaft Basf
Original Assignee
Sterzel, Hans-Josef
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 Sterzel, Hans-Josef filed Critical Sterzel, Hans-Josef
Publication of WO1994024198A1 publication Critical patent/WO1994024198A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/38—Packaging materials of special type or form
    • B65D65/42—Applications of coated or impregnated materials
    • 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
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/048—Forming gas barrier coatings
    • 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
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/06—Coating with compositions not containing macromolecular substances
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/20—Metallic material, boron or silicon on organic substrates
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
    • Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics

Definitions

  • Polylactides are produced by ring-opening polymerization of the cyclic lactide. Starting from L-lactide, D-lactide or DL-lactide, poly-L-lactide, poly-D-lactide or poly-DL-0 lactide are obtained. There is no inversion at the optically active carbon atom during the polymerization, as a result of which the tacticity is retained. Under appropriate processing conditions, poly-L- and poly-D-lactide can be used as semicrystalline polymers with a glass softening temperature of 50 - 55 ° C and a temperature of 100 - 120 ° C
  • Crystallite melting point around 175 ° C can be obtained.
  • the ring-opening polymerization gives copolymers with a reduced crystallization rate and a reduced crystalline fraction. The melting point drops, but the glass softening temperature is retained. However, if you want to lower the glass softening temperature, you carry out a copolymerization with the cyclic glycolide.
  • the homopoly polyglycolide has a glass softening temperature of 20 - 25 ° C 5.
  • the glass transition temperature of the copolymer can accordingly be set between 20-25 ° C to 50-55 ° C.
  • the glass softening temperature of the polylactide plays a special role in the composting of the polymer or in its absorption into body tissue.
  • the degradation of the material takes place in the first step by unspecific hydrolysis of the polyester chains to lactic acid.
  • the lactic acid formed is broken down by microorganisms or enzymatically.
  • the rate-specific is the unspecific ester hydrolysis.
  • the rate of ester hydrolysis is extremely dependent on the glass softening temperature of the polymer. This takes place 5 - 10 ° C above the glass softening temperature approx. 100 times faster than 5 - 10 ° C below the glass softening temperature.
  • Polylactides are gaining increasing interest as packaging materials that can be composted without the development of non-natural degradation materials. It is essential that 5 polylactides are stable at normal storage temperatures down to 0 ° C. and that degradation takes place only above or in the range of the glass softening temperature. In quick composting plants The temperatures are usually longer than 50 ° C., which results in rapid ester hydrolysis. pH values above 7 accelerate the hydrolysis considerably. For example, bottles made of poly-L-lactide including the 2 - 3 mm thick screw thread are degraded at pH 8 to 10 within 2 weeks, at pH 3 - 7 within approx. 8 weeks, the temperature being higher than Must be 50 ° C.
  • the solid polymers are melted and the melt is pressed into molds by means of nozzles or films are produced.
  • polylactides obtain particularly good properties such as strength, rigidity, heat resistance, gas tightness or solvent resistance if they are multiaxial at a temperature between the glass softening temperature and the melting temperature, starting from the amorphous state stretched, stretched or stretched. The material is oriented, and it crystallizes simultaneously to crystalline proportions of up to 80%. Films, bottles, deep-drawn cups and foams thus have stiffnesses of 3000 to 6000 N / mm 2, measured as tensile modulus at room temperature.
  • polylactides are characterized by high strength and rigidity combined with low gas permeability and good resistance to solvents. Because of the high rigidity, moldings or foils can advantageously be produced with smaller wall thicknesses than the corresponding parts or foils based on polyolefins, which saves material.
  • the oxygen permeability of a 100 ⁇ m thick film is around 200 cm 3 / m 2 ⁇ bar and the water vapor permeability of a 100 ⁇ m thick film at 23 ° C. and 0 to 85% relative humidity is approximately 30 g / m2 x day.
  • the traditional coffee packaging therefore contains a 9 ⁇ m thick aluminum foil which is embedded between plastic foils in the lamination process.
  • the oriented polyester film in this composite fulfills the requirement for mechanical strength, printability and high surface gloss, while a PE film on the inside of the packaging ensures sealability.
  • metallized polyester film is also used, or attempts are made to completely dispense with AI as a barrier medium.
  • the 0 2 barrier reached today by metallized 12 ⁇ m polyethylene terephthalate (PET) films is below 1 cm 3 / m 2 xdx bar.
  • PET polyethylene terephthalate
  • ethylene vinyl alcohol copolymers EVOH must be used as the barrier plastic.
  • the required layer thickness under standard ambient conditions 23 ° C, 50% rh) is ⁇ 10 ⁇ m.
  • Typical permeability values for PET (12 ⁇ m) are less than 1 cm 3 / (m 2 xdx bar) for 0 2 , or less than 0.25 g / (m 2 xd) for water vapor for PP (20 ⁇ m).
  • a disadvantage for many packaging applications is the loss of transparency in metallized films.
  • Metallized foils are also only of limited suitability for use in packaging for microwave dishes, since the microwaves are reflected by the aluminum layer.
  • the evaporation of foils with SiO x was therefore developed.
  • the loading takes place Stratification, in high vacuum.
  • the thin layer forms an effective barrier against oxygen and water vapor, but does not impair the transparency of the film and allows microwaves to pass through.
  • the barrier properties that can be achieved are comparable to those of metallized films.
  • DOS 2 239 277 which claims a water-soluble container and process for its manufacture.
  • the core of this composite container can then consist of a water-soluble "polylactic acid", the cover foils from water-insoluble films. Since high-molecular, film-forming polylactides are water-insoluble, these can only be very low-molecular lactyllactic acids with degrees of condensation from 2 to 5, which are used as an adhesive layer and have no properties of free-standing films.
  • the aluminum coatings are applied to the film using methods customary in the art, such as vacuum evaporation of aluminum and deposition of the vapor.
  • the layer thicknesses are 0.01 to 1 ⁇ m, preferably 0.05 to 0.1 ⁇ m.
  • barrier layers metals other than aluminum can be used as barrier layers. It is also possible to apply non-metallic barrier layers, such as SiO x, via the decomposition of siloxanes in a plasma.
  • the films coated on one side are used for the production of packaging, the barrier layer on the inside facing the filling material.
  • Gas and liquid-tight seams are produced by gluing, flanging or a combination thereof according to the prior art.
  • a polylactide film formed by slot extrusion is passed over the coated cold polylactide film after it emerges from the nozzle on the cooling roll.
  • the polylactides used are preferably poly-L-lactide or poly-D-lactide.
  • Copolymers lactides are only of interest if they still have melting points above 150 ° C, ie only up to about 5 mol% comonomer units.
  • Comonomers are 1,3-dioxan-2-ones of the structure
  • the radicals R 1 to R 6 can be the same or different and contain hydrogen, a branched or unbranched alkyl, alkylene or alkyne group having 1 to 12, preferably 1 to 4, carbon atoms, optionally substituted by halogens, hydroxyl groups, alkoxy groups , Formyl groups, acrylic groups, amino, alkylamino, dialkylamino or cycloalkyl groups are substituted.
  • the homo- or copolymers lactides are produced ring-opening starting from the monomer melt at temperatures of 180 to 230 ° C.
  • BF 3 etherate, titanium alcoholates and further manganese, zinc, tin, lead, antimony or aluminum compounds can be used as polymerization catalysts.
  • Tin-II compounds are most commonly used as alkoxides or carboxylic acid salts.
  • Tin-II-octoate or tin-II-ethyl-2-hexanoate is preferably used in concentrations of 10 "6 to 10 " 3 moles per mole of monomer mixture.
  • the granules were then placed in a funnel of a film extruder flooded with argon and the material was melted at 200 ° C. and extruded through a slot die into films of approximately 20 cm in width. After leaving the slot die, the film was quenched into amorphous poly-L-lactide by means of a cooling roll cooled to 25 ° C. In the course of the further drawdown, it was heated to 90-100 ° C. using infrared emitters and then drawn off faster by a factor of five and thereby stretched and crystallized unidirectionally. Partly crystalline films with a thickness of approx. 30, 60 and 100 ⁇ m were produced.
  • Pieces of these foils with approx. 20 x 20 cm were evaporated in a laboratory evaporation plant with an approx. 0.03 ⁇ m thick aluminum layer. Additional pieces of film were provided with a 0.04 to 0.06 ⁇ m thick SiO x layer.
  • the coated films and, as a control, an uncoated film were buried in wire baskets in a municipal composting plant. After 6 weeks - during this time the temperature was 70 to 80 ° C - the baskets were excavated. No film residues were found.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Laminated Bodies (AREA)

Abstract

Matériau d'emballage composé de polylactide enduit par vaporisation, sur une face, d'un revêtement métallique ou d'oxyde de silicium.
PCT/EP1994/001114 1993-04-22 1994-04-11 Polylactide a revetement metallique ou d'oxyde de silicium utilise comme materiau d'emballage WO1994024198A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19934313136 DE4313136A1 (de) 1993-04-22 1993-04-22 Mit Metallen oder Siliziumoxid beschichtetes Polyactid als Verpackungsmaterial
DEP4313136.0930422 1993-04-22

Publications (1)

Publication Number Publication Date
WO1994024198A1 true WO1994024198A1 (fr) 1994-10-27

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1994/001114 WO1994024198A1 (fr) 1993-04-22 1994-04-11 Polylactide a revetement metallique ou d'oxyde de silicium utilise comme materiau d'emballage

Country Status (2)

Country Link
DE (1) DE4313136A1 (fr)
WO (1) WO1994024198A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0802219A2 (fr) * 1996-04-18 1997-10-22 Mitsui Toatsu Chemicals, Inc. Feuille de polyester aliphatique revêtue
EP0974615A1 (fr) 1998-07-22 2000-01-26 Toyo Boseki Kabushiki Kaisha Film de polyester aliphatique et film de barrière aux gaz
US7588813B2 (en) 2004-10-26 2009-09-15 Ishida Co., Ltd. Display strip and a display strip and product assembly

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19609033A1 (de) * 1996-03-08 1997-09-11 Beiersdorf Ag Klebfilm mit Haftvermittler
DE19954403A1 (de) * 1999-11-12 2001-05-17 Wolff Walsrode Ag Ein- und mehrschichtige, biologisch abbaubare, thermoplastische Folien mit verbesserten Barriereeigenschaften sowie deren Verwendung als Verpackungsfolie oder in Kosmetik- und Hygieneartikeln
US20040076778A1 (en) 2001-02-05 2004-04-22 Hirotsugu Mori Biodegradable bags for packing foods available in high speed production
EP1394043B1 (fr) 2002-08-30 2006-04-26 Ishida Co., Ltd. Bande de présentation
DE102007041485A1 (de) * 2007-08-31 2009-03-05 Henkel Ag & Co. Kgaa Siliziumoxid-beschichtetes Behältnis enthaltend eine Pickering-Emulsion
DE102008037214A1 (de) * 2008-08-11 2010-02-18 Linden, Rolf-Dieter, Dipl.-Ing. Verfahren zur Herstellung eines Verpackungsmaterials
US9314999B2 (en) 2008-08-15 2016-04-19 Toray Plastics (America), Inc. Biaxially oriented polylactic acid film with high barrier
US9150004B2 (en) 2009-06-19 2015-10-06 Toray Plastics (America), Inc. Biaxially oriented polylactic acid film with improved heat seal properties
EP2480710B1 (fr) 2009-09-25 2018-01-24 Toray Plastics (America) , Inc. Film d'acide polylactique multicouche très étanche à la vapeur et son procédé de production
US9221213B2 (en) 2009-09-25 2015-12-29 Toray Plastics (America), Inc. Multi-layer high moisture barrier polylactic acid film
US9492962B2 (en) 2010-03-31 2016-11-15 Toray Plastics (America), Inc. Biaxially oriented polylactic acid film with reduced noise level and improved moisture barrier
WO2011123165A1 (fr) 2010-03-31 2011-10-06 Toray Plastics (America), Inc. Film d'acide polyactique à orientation biaxiale doté de niveau de bruit réduit

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04298336A (ja) * 1991-03-27 1992-10-22 Dainippon Printing Co Ltd 分解性積層包材
WO1993004112A1 (fr) * 1991-08-12 1993-03-04 E.I. Du Pont De Nemours And Company Articles degradables enduits d'une substance repulsive
EP0576993A2 (fr) * 1992-06-29 1994-01-05 MITSUI TOATSU CHEMICALS, Inc. Matériau composite dégradable

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04298336A (ja) * 1991-03-27 1992-10-22 Dainippon Printing Co Ltd 分解性積層包材
WO1993004112A1 (fr) * 1991-08-12 1993-03-04 E.I. Du Pont De Nemours And Company Articles degradables enduits d'une substance repulsive
EP0576993A2 (fr) * 1992-06-29 1994-01-05 MITSUI TOATSU CHEMICALS, Inc. Matériau composite dégradable

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Derwent World Patents Index; AN 92-402198[49] *

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0802219A2 (fr) * 1996-04-18 1997-10-22 Mitsui Toatsu Chemicals, Inc. Feuille de polyester aliphatique revêtue
EP0802219A3 (fr) * 1996-04-18 1998-05-13 Mitsui Toatsu Chemicals, Inc. Feuille de polyester aliphatique revêtue
US5914188A (en) * 1996-04-18 1999-06-22 Mitsui Chemicals, Inc. Coated aliphatic polyester film
US6139948A (en) * 1996-04-18 2000-10-31 Mitsui Chemicals, Inc. Coated aliphatic polyester film
EP0974615A1 (fr) 1998-07-22 2000-01-26 Toyo Boseki Kabushiki Kaisha Film de polyester aliphatique et film de barrière aux gaz
US6600008B1 (en) 1998-07-22 2003-07-29 Toyo Boseki Kabushiki Kaisha Aliphatic polyester film and gas barrier film
US6649732B2 (en) 1998-07-22 2003-11-18 Toyo Boseki Kabushiki Kaisha Aliphatic polyester film and gas barrier film
EP1785449A3 (fr) * 1998-07-22 2007-08-29 Toyo Boseki Kabushiki Kasisha Film polyester aliphatique et film à barrière contre les gaz
EP1967603A3 (fr) * 1998-07-22 2008-12-10 Toyo Boseki Kabushiki Kaisha Film de polyester aliphatique et film de barrière aux gaz
EP2236548A3 (fr) * 1998-07-22 2010-12-08 Toyo Boseki Kabushiki Kaisha Film polyester aliphatique et film à barrière contre les gaz
US7588813B2 (en) 2004-10-26 2009-09-15 Ishida Co., Ltd. Display strip and a display strip and product assembly

Also Published As

Publication number Publication date
DE4313136A1 (de) 1994-10-27

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