EP1951792A2 - Materiau stratifie a fort effet barriere contre l'oxygene - Google Patents

Materiau stratifie a fort effet barriere contre l'oxygene

Info

Publication number
EP1951792A2
EP1951792A2 EP06821178A EP06821178A EP1951792A2 EP 1951792 A2 EP1951792 A2 EP 1951792A2 EP 06821178 A EP06821178 A EP 06821178A EP 06821178 A EP06821178 A EP 06821178A EP 1951792 A2 EP1951792 A2 EP 1951792A2
Authority
EP
European Patent Office
Prior art keywords
laminated material
material according
substrate
barrier properties
gas
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP06821178A
Other languages
German (de)
English (en)
Inventor
Angelo Montenero
Marco Passera
Marco Rocchetti
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Psp-Progetti Sistemi Packaging Srl
Original Assignee
Psp-Progetti Sistemi Packaging Srl
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 Psp-Progetti Sistemi Packaging Srl filed Critical Psp-Progetti Sistemi Packaging Srl
Priority to EP10156592A priority Critical patent/EP2213700A1/fr
Publication of EP1951792A2 publication Critical patent/EP1951792A2/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/02—Polysilicates
    • 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
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • 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
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • 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
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D129/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Coating compositions based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Coating compositions based on derivatives of such polymers
    • C09D129/02—Homopolymers or copolymers of unsaturated alcohols
    • C09D129/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • 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
    • C08J2429/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/008—Additives improving gas barrier properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond

Definitions

  • the present invention relates to a laminated material having gas-barrier properties, which is particularly suitable for use in the packaging sector, for instance for the packaging of foodstuffs or pharmaceutical products.
  • Materials suitable for use as a packaging should possess gas- barrier properties, in particular against oxygen, water vapour, carbon dioxide and other gases which could cause the content of the packaging to deteriorate.
  • European Patent Application EP -L 384 571 discloses, for example, a laminated material having gas-barrier properties/ which comprises an intermediate barrier layer interposed between a lower thin layer and an upper thin layer of an inorganic material / these lower, intermediate and upper layers being laminated in this order on a substrate of a plastic material.
  • the intermediate barrier layer is obtained by deposition on the lower thin layer of a coating agent formed by an aqueous composition of a water-soluble polymer, such as polyvinyl alcohol (PVA) , and a metal alkoxide such as tetraethoxysilane (TBOS) , and subsequent consolidation by heat treatment and drying.
  • PVA polyvinyl alcohol
  • TBOS tetraethoxysilane
  • laminated materials comprising a hybrid organic-inorganic barrier layer of the type described above.
  • These laminate materials always include at least one thin layer, generally of an inorganic material such as a metal or a metal oxide, interposed between the hybrid organic-inorganic barrier layer and the substrate of a plastic material, said thin layer being adapted to increase the flexibility and/or the barrier properties of the laminated material and/or to improve the adhesion of the barrier layer to the substrate.
  • the inventors have now developed a particular coating composition which, when deposited on a substrate of a plastic material and subjected to an appropriate heat treatment, is surprisingly able to provide a laminated material having the necessary barrier and flexibility properties required by applications in the packaging sector, without the need for the use of other intermediate materials between the barrier layer and the substrate of a plastic material.
  • This coating composition further guarantees satisfactory adhesion to the substrate thereby making it possible to eliminate any preliminary operation to activate the substrate.
  • this laminate does not lose its barrier properties even when immersed in water for four days at 65°C or exposed to water vapour for 3 days at 65°C.
  • the coating composition developed by the inventors enables the production of a simple laminate material of small thickness (the barrier layer having a thickness of approximately 1 ⁇ m) which advantageously results in the simplification of preparation procedures and a reduction of the consumption of starting materials, with significant economic and environmental benefits .
  • the invention therefore relates to a laminated material characterised in that it comprises a substrate of a plastic material and at least one hybrid organic-inorganic layer having gas-barrier properties, the barrier layer being formed on at least one surface of the substrate of a plastic material by deposition of an.
  • aqueous or hydroalcoholic coating composition comprising from 0.1 to 25% by weight of polyvinyl alcohol and from 0.1 to 30% by weight of a metal alkoxide .
  • the laminated material of the present invention is therefore characterised in that the barrier layer is formed directly on the plastic film acting as a substrate without the interposition of any adhesive material or other intermediate layer.
  • the laminated material may comprise a single barrier layer formed on one surface of the substrate or, as an alternative/ two barrier layers each formed on a surface of the substrate of plastic material.
  • the substrate of plastic material is preferably a film of polyolefin, polyamide or polyester material.
  • Polyethylene (PE) polyethylene terephthalate (PET) , polypropylene (PP) , oriented polypropylene (OPP), polyester (PET) and nylon 6,6 axe preferred.
  • the metal alkoxide of the coating composition is a compound which may be represented by the formula MR n ,. in which M is a metal atom, preferably Si, Al, Zr o Ti, n is the valency of M and the groups R taken n times each independently represent an alkyl or alkyloxy radical having from 1 to 4 carbon atoms (such as methyl, ethyl, propyl, butyl, methoxy, ethoxy, propoxy, butoxy) , provided that at least two of the groups R are alkyloxy radicals.
  • the most preferred metal alkoxide is tetraethoxysilane (TEOS) in which M is silicon (Si) , n is 4 and each of the groups R is ethyl.
  • TEOS tetraethoxysilane
  • Polyvinyl alcohol is a polymer obtained from the basic hydrolysis of polyvinyl acetate and has the following structure:
  • Fully hydrolysed PVA (approximately 97-100% of the acetate groups substituted) or partially hydrolysed PVA (approximately 86-89% of the acetate groups substituted) , both of which are commercially available, may be used for the preparation of the laminated material of the invention.
  • the solvent used for the coating composition may be water or a mixture of water and ethyl alcohol, preferably at a v/v ratio between water and ethyl alcohol varying between 100:0 and 70:30.
  • the pH of the coating composition is preferably adjusted to slightly acidic values, for instance by adding approximately 0.03 to approximately 1% by weight of hydrochloric acid (HCl) .
  • the preparation of the laminated material of the invention is a very simple method involving a first coating step, during which the coating composition is deposited on at least one surface of the film of a plastic material and a second step to consolidate the barrier layer by heat treatment and optionally drying.
  • Coating may take place by means of the sol-gel method using spraying, dip-coating or spin-coating techniques or any other appropriate conventional technique.
  • the heat consolidation treatment may advantageously be carried out at relatively low temperatures, preferably between 40°C and 90°C, more preferably 60°C, for relatively small times, preferably below 5 minutes, for instance for 60 seconds ,
  • the coating composition deposited has good adhesion, is colourless and provides a laminated material having excellent gas-barrier properties against nitrogen, carbon dioxide, water vapour and in particular oxygen.
  • the barrier values are maintained at high levels even in conditions of high relative humidity, for instance up to a relative humidity of 75%.
  • the barrier layer is preferably transparent. Printing ink and/or a normal adhesive may be applied on it without decrease of the barrier properties .
  • the barrier layer appears completely transparent, colourless " and shows no haze phenomena .
  • Oxygen-barrier properties are typically measured by means of oxygen permeation (OTR) which is expressed in cm 3 /m* day*atm. Materials with values lower than or equal to approximately 0.5 cm 3 /m 2 *day*atm are generally considered to have a high barrier effect.
  • OTR oxygen permeation
  • the oxygen permeation of the laminated material of the present invention was measured using the MOCON method based on diffusion cells. The instrument used had a detection limit of 0.05 cm 3 /m 2 *day*atm.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Laminated Bodies (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)

Abstract

La présente invention concerne un matériau stratifié comprenant une pellicule de matière plastique comme substrat recouvert d'au moins une couche organique-inorganique hybride présentant des propriétés de barrière contre le gaz. La couche organique-inorganique hybride à propriétés de barrière contre le gaz est formée sur au moins une surface de la pellicule de matière plastique par dépôt, à l'aide de la technique sol-gel, d'une composition de revêtement aqueuse ou hydroalcoolique comprenant de 0,1 à 25 % en poids d'alcool polyvinylique et de 0,1 à 30 % en poids d'un alcoxyde métallique.
EP06821178A 2005-10-10 2006-10-09 Materiau stratifie a fort effet barriere contre l'oxygene Withdrawn EP1951792A2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP10156592A EP2213700A1 (fr) 2005-10-10 2006-10-09 Composition de revêtement à fort effet barrière contre l'oxygène

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IT000718A ITTO20050718A1 (it) 2005-10-10 2005-10-10 Materiale laminato ad elevato effetto barriera all'ossigeno
PCT/IB2006/053694 WO2007042993A2 (fr) 2005-10-10 2006-10-09 Materiau stratifie a fort effet barriere contre l'oxygene

Publications (1)

Publication Number Publication Date
EP1951792A2 true EP1951792A2 (fr) 2008-08-06

Family

ID=37840502

Family Applications (2)

Application Number Title Priority Date Filing Date
EP06821178A Withdrawn EP1951792A2 (fr) 2005-10-10 2006-10-09 Materiau stratifie a fort effet barriere contre l'oxygene
EP10156592A Withdrawn EP2213700A1 (fr) 2005-10-10 2006-10-09 Composition de revêtement à fort effet barrière contre l'oxygène

Family Applications After (1)

Application Number Title Priority Date Filing Date
EP10156592A Withdrawn EP2213700A1 (fr) 2005-10-10 2006-10-09 Composition de revêtement à fort effet barrière contre l'oxygène

Country Status (3)

Country Link
EP (2) EP1951792A2 (fr)
IT (1) ITTO20050718A1 (fr)
WO (1) WO2007042993A2 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB0817224D0 (en) * 2008-09-19 2008-10-29 Dupont Teijin Films Us Ltd Coated polymeric substrates
IT1396554B1 (it) 2009-02-03 2012-12-14 Metalvuoto S P A Lacche da macromolecole naturali ad effetto barriera ai gas modulabile in situ e relativi metodi di preparazione
JP5414426B2 (ja) * 2009-09-01 2014-02-12 富士フイルム株式会社 複合フィルム
WO2020221589A1 (fr) 2019-04-29 2020-11-05 Sabic Global Technologies B.V. Procédé de préparation d'un film formant barrière à l'oxygène

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62295931A (ja) * 1986-06-16 1987-12-23 Mitsubishi Monsanto Chem Co ガスバリヤ性の優れた熱可塑性樹脂フイルムまたはシ−ト
DE69430927T2 (de) 1993-09-30 2003-02-06 Toppan Printing Co. Ltd., Tokio/Tokyo Gasundurchlässiges Verbundmaterial
JPH07126419A (ja) * 1993-11-04 1995-05-16 Toppan Printing Co Ltd ガスバリア性積層体
WO2000075248A1 (fr) * 1999-06-04 2000-12-14 Jsr Corporation Composition de revetement formant barriere pour les gaz, procede de production de ladite composition et film de revetement formant barriere pour les gaz
JP4085814B2 (ja) 2001-04-09 2008-05-14 凸版印刷株式会社 積層体
KR20020092812A (ko) * 2001-06-05 2002-12-12 가부시끼가이샤 도꾸야마 가스 차단제, 가스 차단 필름 및 그 제조 방법
KR20030078011A (ko) * 2002-03-27 2003-10-04 제이에스알 가부시끼가이샤 가스 배리어 코팅 조성물 및 그의 제조 방법

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2007042993A2 *

Also Published As

Publication number Publication date
ITTO20050718A1 (it) 2007-04-11
WO2007042993A3 (fr) 2009-09-24
WO2007042993A2 (fr) 2007-04-19
EP2213700A1 (fr) 2010-08-04

Similar Documents

Publication Publication Date Title
US6503634B1 (en) Barrier films
US5645923A (en) Gas barrier laminated material
EP1927465B1 (fr) Film stratifié à propriété de barrière contre les gaz
CA2507030C (fr) Film multicouche permeable au gaz
WO2009027648A1 (fr) Revêtement étanche aux gaz à adhérence améliorée
JPH0970917A (ja) 透明ガスバリア性積層体
JP4217511B2 (ja) ガスバリア性フィルムの製造方法
EP1951792A2 (fr) Materiau stratifie a fort effet barriere contre l'oxygene
JP2000254994A (ja) 蒸着フィルム積層包装材料
TW587991B (en) Gas-barrier material, gas-barrier film and method for manufacturing the same
CN113621280A (zh) 水性涂布液和阻气膜
JP4065266B2 (ja) ガスバリア性フィルム及びその製造方法
JP2013202822A (ja) ガスバリア性積層フィルム
JP4654662B2 (ja) 加熱処理耐性を有するガスバリア性フィルム積層体を用いた包装体
JP2002036419A (ja) ガスバリア性透明積層体
JP4978066B2 (ja) ガスバリアフィルム積層体の製造条件の評価方法
JP2011051277A (ja) ガスバリア性積層フィルム
JP4215522B2 (ja) ガスバリア性組成物及びこれを用いたガスバリア性フィルム
JP4374967B2 (ja) ガスバリア性積層体
JP2002321301A (ja) 透明ガスバリア性フイルム
JP3438257B2 (ja) 耐ボイル性を有するガスバリア材
JPH1016150A (ja) ガスバリア性積層フィルム
JP2010000657A (ja) ガスバリア積層フィルム
JP3438256B2 (ja) 耐ボイル性を有するガスバリア材
JP2002046209A (ja) バリア性積層フィルム

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20080509

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR

AX Request for extension of the european patent

Extension state: AL BA HR MK RS

R17D Deferred search report published (corrected)

Effective date: 20090924

17Q First examination report despatched

Effective date: 20100504

DAX Request for extension of the european patent (deleted)
GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

INTG Intention to grant announced

Effective date: 20140103

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20140430