WO1998049006A1 - Film en polypropylene multicouche, thermosoudable, etire, muni d'une couche de barrage au gaz en polycetone - Google Patents

Film en polypropylene multicouche, thermosoudable, etire, muni d'une couche de barrage au gaz en polycetone Download PDF

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Publication number
WO1998049006A1
WO1998049006A1 PCT/EP1998/002348 EP9802348W WO9849006A1 WO 1998049006 A1 WO1998049006 A1 WO 1998049006A1 EP 9802348 W EP9802348 W EP 9802348W WO 9849006 A1 WO9849006 A1 WO 9849006A1
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WO
WIPO (PCT)
Prior art keywords
layer
ethylene
composite film
film according
acid
Prior art date
Application number
PCT/EP1998/002348
Other languages
German (de)
English (en)
Inventor
Bernd Sperlich
Rainer Brandt
Original Assignee
Wolff Walsrode Ag
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 Wolff Walsrode Ag filed Critical Wolff Walsrode Ag
Priority to BR9809372-0A priority Critical patent/BR9809372A/pt
Priority to EP98922756A priority patent/EP0977665A1/fr
Priority to CA002288158A priority patent/CA2288158A1/fr
Priority to AU75279/98A priority patent/AU7527998A/en
Publication of WO1998049006A1 publication Critical patent/WO1998049006A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/16—Layered products comprising a layer of synthetic resin specially treated, e.g. irradiated
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/0008—Electrical discharge treatment, e.g. corona, plasma treatment; wave energy or particle radiation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/31—Heat sealable
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/514—Oriented
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/514—Oriented
    • B32B2307/516—Oriented mono-axially
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/514—Oriented
    • B32B2307/518—Oriented bi-axially
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/724—Permeability to gases, adsorption
    • B32B2307/7242—Non-permeable
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2310/00—Treatment by energy or chemical effects
    • B32B2310/14—Corona, ionisation, electrical discharge, plasma treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2323/00—Polyalkenes
    • B32B2323/10—Polypropylene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2439/00—Containers; Receptacles
    • B32B2439/70—Food packaging
    • 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
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/10—Homopolymers or copolymers of propene
    • C08J2323/12—Polypropene
    • 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
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment

Definitions

  • the present invention relates to a sealable, stretched multilayer film which, owing to its gas barrier properties, is particularly suitable as packaging film for goods which require low gas permeability and aroma protection.
  • Polyamides as barrier materials have significantly poorer barrier properties, which are not sufficient for many applications.
  • a heat-sealable composite film made of a biaxially stretched polypropylene film as the base film, an adhesion promoter layer made of modified system polyolefin, a gas barrier layer of a copolymer of one or more olefins and carbon monoxide and a heat seal layer of olefin polymers, characterized in that the base film carries at least on one surface an optionally at least monoaxially oriented layer combination, which is composed of
  • the base film optionally carries a layer A, a layer combination A to E, A to D or B and C on at least one of its surfaces.
  • B and C or C and D can be combined to form a layer by mixing the corresponding polymers.
  • the biaxially stretched and heat sealable polypropylene film made by a sequential process contains a gas barrier layer made from a copolymer of carbon monoxide and one or more olefinically unsaturated compounds.
  • a gas barrier layer made from a copolymer of carbon monoxide and one or more olefinically unsaturated compounds.
  • all monomers of this class of compounds can be considered as olefinically unsaturated compounds.
  • Ethylene and C 3 - to Cio-alkenes such as propylene, 1-butene, 2-butene, 1-pentene, 1-hexene, 1-octene, 1-nonen, 1-decene are preferred. Are particularly preferred
  • the barrier layer material preferably consists of a copolymer of 25 to 50 mol% of ethylene, 0-25 mol% of propylene and 50 mol% of carbon monoxide, the olefinically unsaturated compounds and carbon monoxide are incorporated alternately in the copolymer.
  • the partial exchange of ethylene with higher olefins lowers the melting point and improves the stretchability of the copolymer.
  • the polypropylene of the core film is preferably an isotactic polypropylene with a density of 0.90 to 0.91 g / cm 3 and a melt flow index of 1 to 4 g / 10 min at 230 ° C / 2.16 kp / cm 2 pressure (DIN 53 735).
  • a propylene / ethylene copolymer is particularly preferably characterized in that it contains 1.0 to 10% by weight of polyethylene.
  • the density of the sealing layer polymer should preferably be in the range from 0.895 to 0.960 g / cm 3 and the crystallite melting point, depending on the type, in the range from 125 to 148 ° C.
  • Preferred antistatic agents are alkali alkane sulfonates, polyether-modified, ie ethoxylated and / or propoxylated, polydiorganosiloxanes (polydialkylsiloxanes, polyalkylphenylsiloxanes and the like) and / or the essentially straight-chain and saturated aliphatic, tertiary amines with an aliphatic radical, having 10 to 20 to 20 atoms which are substituted with ⁇ -hydroxy (C 1 -C 4 ) alkyl groups, N, N-bis (2-hydroxyethyl) alkylamines having 10 to 20 carbon atoms, preferably 12 to 18 carbon atoms, being particularly suitable in the alkyl radical .
  • the effective amount of antistatic is in the range of 0.05 to 0.5% by weight.
  • Glycerol monostearate is also suitable and is used in an amount of 0.03% to 0.5% by weight as an antistatic.
  • Suitable antiblocking agents are inorganic additives such as silicon dioxide, calcium carbonate, magnesium silicate, aluminum silicate, calcium phosphate and the like and / or incompatible organic polymers such as polyamides, polyacrylates, polymethacrylates, polyesters, polycarbonates and the like; preference is given to using polymethacrylates and silicon dioxide.
  • the effective amount of antiblocking agent is in the range of 0.1 to 2% by weight, preferably 0.1 to 0.8% by weight.
  • the average particle size is between 1 and 6 ⁇ m, in particular 2 and 5 ⁇ m, particles with a spherical shape being particularly suitable.
  • Lubricants are higher aliphatic acid amides, higher aliphatic acid esters, waxes and metal soaps as well as polydimethylsiloxanes.
  • the effective amount of lubricant is in the range of 0.01 to 3% by weight, preferably 0.02 to 1% by weight.
  • the addition of higher aliphatic acid amides in the range from 0.01 to 0.25% by weight is particularly suitable.
  • a particularly suitable aliphatic acid amide is erucic acid amide.
  • polydimethylsiloxanes in the range from 0.02 to 2% by weight is preferred, in particular polydimethylsiloxanes with a viscosity of
  • Modified polyolefins are used to produce the adhesion promoter layer. These are preferably polyolefins with carboxyl groups, such as polypropylene or polyethylene, which contain copolymers of at least one monomer from the group of the ⁇ , ⁇ -monounsaturated dicarboxylic acids, such as maleic acid, fumaric acid, itaconic acid or their acid anhydrides, acid esters, acid amides and acid imides Ethylene with ⁇ , ß-monounsaturated carboxylic acids, such as acrylic acid, methacrylic acid and / or their metal salts (Zn, Na) and / or their alkyl (C 1 -C 4 ) esters or corresponding graft polymers on polyolefins such as polyethylene or polypropylene or already Saponified copolymers described which have been graft-polymerized with a monomer of the abovementioned unsaturated acids.
  • carboxyl groups such as polyprop
  • polyolefins such as polypropylene or copolymers of propylene and ethylene with a maximum of 1.0% by weight of grafted on ⁇ , ⁇ -monounsaturated dicarboxylic acid anhydride such as maleic anhydride or their saponified copolymers.
  • adhesion promoter polymer is incorporated either in the sealable layer A or in the gas barrier layer C, up to 40% by weight, preferably 25-30% by weight, based on layer-forming polymers, of the modified polyolefin are used to produce the corresponding polymers.
  • the invention further relates to packaging preferably for oxygen-sensitive foods made from the multilayer film according to the invention.
  • the films according to the invention can be prepared using the customary processes such as lamination,
  • Coating or melt coextrusion can be produced.
  • the film is stretched in the running direction (lengthways) with a stretching ratio of 4/1 to 7/1 at a temperature of 120 ° C - 150 ° C.
  • the stretch ratio in the transverse direction is preferably between 8/1 and 12/1 and the transverse stretching of the film is carried out at a temperature between 130 ° C. and 170 ° C.
  • the subsequent heat setting is preferably carried out at 1 ° C - 40 ° C below the transverse stretching temperature.
  • a corona (spray) pretreatment In order to ensure the affinity of the largely non-polar film surface for the printing inks, it is necessary to subject the film to a corona (spray) pretreatment.
  • the atmospheric oxygen is stored in the form of carbonyl, epoxy, ether or alcohol groups on the film surface.
  • Other methods of pretreating polypropylene films are flame, plasma and fluorine pretreatment. example
  • 98.7% by weight of a propylene-ethylene copolymer with 4.5% by weight of ethylene had a density of 0.90 g / cm 3 with a melt index of 5 g / 10 min for layer A 230 ° C / 2.16 kp / cm 2 and the crystalline melting point 140 ° C 0.5 wt .-% N, N-bis (2-hydroxyethyl) - (C 12 -C 16 ) alkylamine, 0, 3 wt .-% of a polydimethylsiloxane with a density of 0.985 g / cm 3 at 20 ° C.
  • a modified polypropylene such as a saponified copolymer with 0.7% by weight of grafted maleic anhydride and a melt index of 5 g / 10 min at 250 ° C / 216 kp / cm 2 for the adhesion promoter layers and an alternating carbon monoxide-ethylene copolymer (F.
  • the layer structure and the layer thicknesses are summarized in Table 1.
  • the oxygen barrier of the composite film is 15 cm 3 / m 2 d bar.

Landscapes

  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Plasma & Fusion (AREA)
  • Thermal Sciences (AREA)
  • Laminated Bodies (AREA)
  • Shaping By String And By Release Of Stress In Plastics And The Like (AREA)

Abstract

L'invention concerne un film composite thermosoudable comprenant un film en polypropylène étiré biaxialement servant de film de base, une couche d'accrochage en polyoléfine modifiée, une couche de barrage au gaz réalisée en un copolymère en éthylène et en monoxyde de carbone et une couche de thermosoudage en polymérisats d'oléfine. Le film de base porte sur au moins une surface une couche combinée éventuellement au moins à orientation monoaxiale, qui comprend: A) une couche extérieure thermosoudable réalisée dans un homo-, co- ou terpolymérisat oléfinique; B) une couche d'accrochage en polyoléfine modifiée; C) une couche de barrage au gaz réalisée dans un copolymère comprenant une ou plusieurs oléfines et du monoxyde de carbone (polycétone); D) une couche d'accrochage en polyoléfine modifiée et E) une couche en polyéthylène et un polymérisat d'éthylène comportant au moins 3 % en poids d'éthylène. Le film de base porte sur au moins une de ses surfaces éventuellement une couche A, une combinaison de couches A à E, A à D ou B et C.
PCT/EP1998/002348 1997-04-30 1998-04-21 Film en polypropylene multicouche, thermosoudable, etire, muni d'une couche de barrage au gaz en polycetone WO1998049006A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
BR9809372-0A BR9809372A (pt) 1997-04-30 1998-04-21 Folha de polipropileno selável a quente, estirada, de várias camadas com camada de bloqueio de gás de policetona
EP98922756A EP0977665A1 (fr) 1997-04-30 1998-04-21 Film en polypropylene multicouche, thermosoudable, etire, muni d'une couche de barrage au gaz en polycetone
CA002288158A CA2288158A1 (fr) 1997-04-30 1998-04-21 Film en polypropylene multicouche, thermosoudable, etire, muni d'une couche de barrage au gaz en polycetone
AU75279/98A AU7527998A (en) 1997-04-30 1998-04-21 Multi-layered stretched hot-sealable polypropylene film with a polyketone gas barrier layer

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19718199.6 1997-04-30
DE19718199A DE19718199A1 (de) 1997-04-30 1997-04-30 Mehrschichtige, gereckte, heißsiegelbare Polypropylenfolie

Publications (1)

Publication Number Publication Date
WO1998049006A1 true WO1998049006A1 (fr) 1998-11-05

Family

ID=7828172

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1998/002348 WO1998049006A1 (fr) 1997-04-30 1998-04-21 Film en polypropylene multicouche, thermosoudable, etire, muni d'une couche de barrage au gaz en polycetone

Country Status (6)

Country Link
EP (1) EP0977665A1 (fr)
AU (1) AU7527998A (fr)
BR (1) BR9809372A (fr)
CA (1) CA2288158A1 (fr)
DE (1) DE19718199A1 (fr)
WO (1) WO1998049006A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI405666B (zh) * 2010-12-09 2013-08-21 Ind Tech Res Inst 阻氣熱封複合膜及包含此複合膜之真空絕熱板

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040197589A1 (en) * 2001-08-01 2004-10-07 Detlef Busch Transparent biaxially oriented polyolefin film with improved sealing qualities
DE102015003516A1 (de) * 2015-03-20 2016-09-22 Wihuri Packaking Oy Tiefziehfolie

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0735081A2 (fr) * 1995-03-31 1996-10-02 Kuraray Co., Ltd. Film en polyalcool et film laminé le contenant

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0735081A2 (fr) * 1995-03-31 1996-10-02 Kuraray Co., Ltd. Film en polyalcool et film laminé le contenant

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI405666B (zh) * 2010-12-09 2013-08-21 Ind Tech Res Inst 阻氣熱封複合膜及包含此複合膜之真空絕熱板
US8747986B2 (en) 2010-12-09 2014-06-10 Industrial Technology Research Institute Gas-barrier heat-seal composite films and vacuum insulation panels comprising the same

Also Published As

Publication number Publication date
CA2288158A1 (fr) 1998-11-05
BR9809372A (pt) 2000-07-04
EP0977665A1 (fr) 2000-02-09
DE19718199A1 (de) 1998-11-05
AU7527998A (en) 1998-11-24

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