EP2588307A1 - Feuille multicouches antibuée transparente claire - Google Patents

Feuille multicouches antibuée transparente claire

Info

Publication number
EP2588307A1
EP2588307A1 EP11746431.3A EP11746431A EP2588307A1 EP 2588307 A1 EP2588307 A1 EP 2588307A1 EP 11746431 A EP11746431 A EP 11746431A EP 2588307 A1 EP2588307 A1 EP 2588307A1
Authority
EP
European Patent Office
Prior art keywords
layer
antifog
film
multilayer film
layers
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Withdrawn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
EP11746431.3A
Other languages
German (de)
English (en)
Inventor
Helwig Heinrich Daum
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.)
Kobusch Sengewald GmbH
Original Assignee
Kobusch Sengewald GmbH
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 Kobusch Sengewald GmbH filed Critical Kobusch Sengewald GmbH
Publication of EP2588307A1 publication Critical patent/EP2588307A1/fr
Withdrawn legal-status Critical Current

Links

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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • 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
    • 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
    • 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
    • B65D65/40—Applications of laminates for particular packaging purposes
    • 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
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/31909—Next to second addition polymer from unsaturated monomers
    • Y10T428/31924—Including polyene monomers

Definitions

  • the invention relates to a polyolefin multilayer film which has at least one antifogging sealant layer, a higher sealant overcoat layer, optionally gas and / or moisture barrier layers.
  • polyolefin multilayer films are understood as meaning those which contain more than 25% of polypropylene, based on the total film or all layers of the film.
  • Polypropylene has the properties of a high melting point and thus good sterilizability, good availability and good mechanical properties in terms of stability, rigidity, tensile and scratch resistance.
  • multilayer films are used in the packaging of water-containing material, such as foods that form condensates when stored.
  • multi-layer films are used as windows or bags that should be as clear and transparent as possible to allow a good inspection of the contents of the packaging on possible decomposition, mold or size and quality of the contents.
  • the delivery of water from the so packaged goods leads to condensation on the packaging, especially lidding, to water droplets, which restrict the view of the product or prevent.
  • Film surface and the dripping moisture causes an acceleration of rot and mold on the food.
  • Antifog properties of films can be achieved by coating with anti-fog solution or by mixing anti-fog additives into film layers on the product side.
  • antifogging additives are generally divalent compounds having a non-polar aliphatic region for anchoring in the polyolefin matrix and a polar hydrophilic region capable of interacting with water and lowering the surface tension of the water droplets to form a transparent film of water on the film.
  • This polar region causes the incompatibility of antifogging additives with pure polyolefins, such as polyethylene, which leads to migration of the additive to the film surface.
  • the polar region of the antifog agent is then directed outward and can thus interact with water.
  • the anti-fog Additv lowers the contact angle of the water droplets, allowing the formation of a continuous transparent water film on the film surface.
  • Antifog additives are thus surface-active additives, which are preferably used as a combination of different classes of substances. Suitable substances which are used in conjunction with one another as antifogging additive are described, for example, in WO 97/22655 A1, to which reference is hereby expressly made to avoid repetitions.
  • Components of an antifogging agent combination are, for example, fatty acid esters and their derivatives, aliphatic alcohols and their esters, polyethoxylated aromatic alcohols, one or more esterified sorbitol esters, one or more esterified glycerol esters, mixed glycerol esters, ethoxylated sorbitan esters, ethoxylated amines.
  • the abovementioned esters are usually based on esterification of the particular acid with medium or long-chain fatty acids.
  • Typical are, for example, drug combinations from the three classes of substances: glycerol esters, sorbitol esters and ethoxylated amines.
  • the sealing layer of a composite film may be coated with a corresponding antifogging lacquer.
  • Antifogging coated layer has a low lifespan, as it is instantly dissolved in water - the active substance (esterified surfactants) is consumed quickly and the number of cycles is limited.
  • the antifogging additives can be incorporated directly or via a concentrate, a so-called masterbatch, in polymer layers of the film itself.
  • Masterbatches are polyolefin / antifogging compositions containing the antifogging additives in an increased concentration relative to the film layer, generally from 10 to 50% by weight, preferably from 15 to 40% by weight of the additive, based on the total weight of the additive masterbatches.
  • the polyolefins of the masterbatch are generally common polyolefins, such as polyethylenes or polypropylenes.
  • Antifog additives and corresponding masterbatches are known and commercially available.
  • An additive mixed into the sealing film migrates out of the sealing layer in the direction of the product, but also in the direction of the covering layer, as a result of which the overall properties of the multilayer film deteriorate.
  • Antifog agents act poorly change. Polypropylene films with anti-fogging properties are already known. Thus, JP 58079044 A and also JP 02187441 A polypropylene layers for multilayer films with special anti-fogging agents, which are less migratory
  • JP09248880A illustrates a polypropylene laminate in which a
  • Antifogstoffumble layer is extruded together with a polypropylene layer.
  • polypropylene anti-fog films are disadvantageous in terms of printability and / or transparency or the hot-tack properties of the film. Furthermore, the known films need to be improved with regard to the anti-fog properties, in particular also with regard to the long-term stability of these properties.
  • the multilayer films according to the invention have very good optical properties, ie. H. have high transparency and good gloss, as well as sealing properties, in particular a good hot-tack.
  • This antifogging agent barrier layer can be, for example, polypropylene. Due to its high crystallinity, it prevents migration to the polar components of the multilayer films or the composite. Preferably
  • Polypropylene homo used, alternatively, a block polypropylene or random polypropylene.
  • the cover layer of the film composite also has barrier properties with respect to the antifogging agent in order to prevent the antifogging agent from migrating out of the sealing layer onto the film roll into the cover layer and to guarantee the function of the barrier film even on a roll.
  • antifogging properties (cold fog) of stage 5 can be ensured over at least 6 months, with the practice showing that the antifogging effect is maintained even beyond the period.
  • Siegelschchten in the context of the present invention are the product-facing layers that are heat-sealable.
  • hot sealing refers to sealing with permanently heated / pulse-heated / ultrasonic tools, with sealing jaws compressing the composite to be sealed and at least the inner layer of the composite with another sealing layer - that of the same composite (for example, with sealed bags) or with the polymer Surface of another object, such as a bowl-like container - merges.
  • Cover layers are those layers which form outermost layers. They can be selected for properties such as: mechanical stability, strength, gloss. In the present case, they preferably also have barrier properties with respect to the antifogging agent.
  • Preferred cover layers are polypropylene, polyester and polyamide.
  • Intermediate layers are the layers present between the cover layer and the sealing layer; in general, these can be adhesives (adhesion promoters, laminating adhesives); Moisture barrier layers; Antifogschperr- layers, gas barrier layers, such as those skilled in the art act.
  • Typical gas barrier layers are known, for example, from DE 10 2004 062 204 A1.
  • the gas barrier layer prevents the entry and exit of gases. In particular, it should be prevented that oxygen reaches the food, favors the rot and mold, and that optionally introduced in the packaging protective gases, such. As nitrogen or carbon dioxide, escape.
  • Such gas barrier layers contain e.g. essentially polyamide, lacquered cellophane, ethylene-vinyl alcohol polymers (EVOH) or other vinyl alcohol polymers (PVOH) or are also built up of these materials in multiple layers.
  • Polyamide and / or EVOH is inherently water vapor permeable and has poor seal properties, i. is not suitable for welding, as is usually necessary for the packaging of food and feed.
  • the packaging films are usually also provided with an additional layer as a water vapor barrier.
  • an additional layer as a water vapor barrier.
  • the gas barrier layer are thus suitable polyamides, lacquered cell glass, ethylene-vinyl alcohol polymers (EVOH) or other vinyl alcohol polymers (PVOH).
  • the barrier layer may consist essentially of one of these materials. It is also possible to construct the barrier layer itself in a multilayered manner, e.g. from an EVOH layer, which is provided on one or both sides with a polyamide layer. This multi-layer barrier layer can be produced by coextrusion or by lamination and / or painting.
  • Water vapor barrier films are familiar to those skilled in the art. Particularly suitable are polyisobutylene and / or butyl rubber polymers, styrene polymers, such as SEBS or also phyllosilicate-filled polyamides.
  • the additional layer serving as a water vapor barrier can have good sealing properties, so that on the one hand a weldable packaging film is obtained through this layer and, on the other hand, this packaging film is additionally water vapor-tight in the generally desired manner.
  • an antifog film is provided, such as for packaging food and animal feed or as an antifogging layer in film composites such as plastic glass panes, which optionally holds protective gases and / or water in the packaging and protects the food from oxygen.
  • This film has a barrier layer which has a high barrier function for antifogging agents.
  • This barrier thus fulfills the requirements of keeping antifogging agents away from overlying films and of preventing the antifogging agent from possibly containing protective gases introduced into the packaging in the packaging.
  • the film additionally has a superficial sealing layer with anti-fogging agent, which has good sealing properties.
  • the sealing layer impairs the functional properties of the barrier layer. Since the barrier against gases and moisture is caused by the at least one gas / water vapor barrier layer, the sealing layer may also be gas-permeable.
  • gas barrier or “gas-permeable” is meant a barrier or permeability to substances which are gaseous at normal ambient temperatures, in particular for oxygen, nitrogen and
  • the antifogging agent barrier layer of the film generally contains at least 80% by weight, preferably 90 to 100% by weight, in particular 98 to ⁇ 100% by weight, in each case based on the antifogging agent barrier layer, of a propylene polymer described below. This anti-fog agent barrier layer is not added to any anti-fog additive.
  • a barrier layer of polypropylene advantageously contributes to the desired property profile of the film.
  • the antifogging additives migrate from the sealing layer only to the barrier layer, since this antifogging agent barrier layer acts as an effective migration barrier over the antifogging additive.
  • the sealing layer acts as an antifogging agent reservoir, due to the barrier can be an antifogging loss by migrating into other film layers can be avoided.
  • the propylene polymer of the antifogging agent barrier layer particularly preferably contains at least> 98 to 100% by weight of propylene.
  • the corresponding comonomer content of from 0 to at most 2% by weight, based on the propylene, if present, is generally ethylene.
  • the propylene homopolymer generally has a melting point of 140 to 170 C.
  • the antifogging agent barrier layer may also comprise conventional stabilizers and neutralizing agents, as known to those skilled in the art.
  • the film shows the desired anti-fog properties, in particular, these are surprisingly uniform and long-term stability.
  • the sealant layer forms the antifoaming reservoir from which the antifogging additive can migrate for a long time, so that even after several days no dripping on the film occurs when it is used for packaging moist foods.
  • the adverse effects of anti-fog additives on transparency and cohesion surprisingly do not occur.
  • the film shows good adhesion of the layers to one another and very good transparency.
  • the primer layer 12 is not saturated by the antifoggant barrier layer and can accordingly generate adhesion promotion. This allows corresponding dosages in the sealing layer 10.
  • the anti-fog agent barrier layer provides an effective barrier to migration of the anti-fog additive to the surface of the topcoat.
  • the film has anti-fog properties, which are particularly long-term stable and uniform and still has a very good transparency, good hot-tack properties and is also, if desired, printable.
  • the antiperspirant film according to the invention is also suitable as antifog film or antifogging layer for windshields, sports glasses, helmet visors or plastic glasses or mineral glass panes and greenhouse films of any type.
  • Fig. 2 shows a 5-layer film composite with oxygen barrier layer
  • FIG. 4 shows a multilayer film with the composite of FIG. 3;
  • FIG. 5 shows a further multilayer film with the composite of FIG. 3
  • Fig. 1 is a simple co-extruded film composite without gas barrier, which is supplemented in the finished composite by other films, shown schematically.
  • An anti-fog agent-containing sealing layer 10 made of PE with anti-fogging agent is covered by an antifogging barrier layer 20 of polypropylene, on which in turn a polyethylene layer 40 is extruded as a cover layer.
  • Film composite is suitable for the packaging of goods in which no gas barrier properties are necessary.
  • further cover layers can be applied to this composite to the Resistance of the film to improve temperature and / or to increase the mechanical stability.
  • Films of this type are primarily suitable for greenhouse films.
  • Fig. 2 shows an anti-fog multilayer film with gas barrier 30 and improved roll life.
  • a polypropylene outer layer 40 is applied, which protects the composite against diffusion of
  • the film shows good stability and good transparency in use.
  • a six-layer antifog multilayer film is shown in the directly to the anti-fog agent-containing sealing layer 10 - as in Fig. 1 - a
  • Polypropylene antifoggant barrier layer 20 is alsext rudiert.
  • Polypropylene layer 20 prevents the antifogging agent from migrating into the film and forces it into the sealing layer 10.
  • EVOH is bound as gas barrier layer 30.
  • the migration of antifog agents into EVOH is generally favored because of the polar nature of the EVOH, but leads to undesirable changes in the EVOH properties as well as the properties of the EVOH
  • Adhesive 12 and thus in the worst case for delamination.
  • FIG. 4 shows a complete composite film with the film combination of FIG. 3.
  • the hard layer is then applied to the outer layer 40 by means of a laminating adhesive 14, which causes the corresponding gloss and scratch resistance of the film.
  • This may be, for example, oriented / stretched polypropylene, oriented / stretched polyamide, polyester.
  • Figure 5 shows another complete composite film having improved moisture and gas barrier properties through the use of a polyamide polypropylene barrier layer and EVOH. Both materials complement each other in terms of their blocking function outstanding, so that a particularly good blocking multi-layer film is obtained.
  • the structure of the film of Fig. 5 is similar to that of Fig. 2, except that a double barrier layer is mounted on the anti-fog agent sealing layer.
  • the cover layer is - as in the combination of Fig. 2 possible, laminated.
  • the total thickness of the polypropylene film according to the invention can vary within wide limits and depends on the intended use. It is preferably 0.004 to 0.120 mm, in particular 0.005 to 0.080 mm, wherein the antifogging agent barrier layer accounts for about 10 to 50% of the total film thickness.
  • the invention further relates to a process for the preparation of the novel polypropylene film according to the known coextrusion process.
  • the polymers or polymer blends of the individual layers are each compressed and liquefied in extruders, it being possible for the optionally added additives to be already present in the polymer or in the polymer mixture or incorporated as a master batch.
  • the melts are then simultaneously pressed through flat nozzles (slot die) and form films that still run together warm and together staple on cooling and solidification.
  • Suitable materials for the gas barrier layer are polyamides, lacquered cell glass, ethylene-vinyl alcohol polymers (EVOH) or other vinyl alcohol polymers (PVOH).
  • the barrier layer may consist essentially of one of these materials.
  • the barrier layer itself multilayered, for example, from an EVOH layer, which is provided on one side or on both sides with a polyamide layer.
  • This multi-layer barrier layer can be produced by coextrusion or by lamination and / or painting.
  • Temperatures in which longitudinal and transverse stretching are carried out can vary within a relatively wide range and depend on the desired properties of the film.
  • cover layer composite such that one of the layers is (at least partially) printed.
  • the print can be protected by overlaying with another cover layer.
  • the polypropylene barrier layer 20 acts as an additive barrier and prevents loss of the antifog agent by migration within the film. This ensures a consistent and constant antifogging property over time.
  • the inventive composition of the film, the antifog additives virtually do not increase the haze of the film. This is essential for a transparent packaging film that is supposed to make the packaged goods look their best.
  • Classic thickness ratios of the individual films in a composite according to the invention can be as follows: 0.004mm - 0.1mm, preferably 0.008mm - 0.05mm
  • 0.004mm -0.1mm preferably 0.008mm - 0.1mm 0.001mm -0.1mm, preferably 0.002mm - 0.01mm 0.00mm -0.01mm, preferably 0.002mm - 0.008mm 0.008mm -0.1mm, preferably 0.01mm - 0.04mm

Landscapes

  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Laminated Bodies (AREA)
  • Wrappers (AREA)

Abstract

L'invention concerne une feuille multicouches antibuée transparente claire ayant une capacité de résistance améliorée à l'encontre de la délamination et une bonne fiabilité, qui présente au moins une couche de scellement (10) de polyoléfine contenant un additif antibuée (10), une couche (20) barrière à l'agent antibuée et une couche de recouvrement (40).
EP11746431.3A 2010-07-02 2011-04-11 Feuille multicouches antibuée transparente claire Withdrawn EP2588307A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE202010007972U DE202010007972U1 (de) 2010-07-02 2010-07-02 Klare transparente Antifog-Mehrschicht-Folie
PCT/DE2011/075071 WO2012037931A1 (fr) 2010-07-02 2011-04-11 Feuille multicouches antibuée transparente claire

Publications (1)

Publication Number Publication Date
EP2588307A1 true EP2588307A1 (fr) 2013-05-08

Family

ID=43308092

Family Applications (1)

Application Number Title Priority Date Filing Date
EP11746431.3A Withdrawn EP2588307A1 (fr) 2010-07-02 2011-04-11 Feuille multicouches antibuée transparente claire

Country Status (7)

Country Link
US (1) US20130164551A1 (fr)
EP (1) EP2588307A1 (fr)
CA (1) CA2803664C (fr)
DE (1) DE202010007972U1 (fr)
EA (1) EA201370010A1 (fr)
WO (1) WO2012037931A1 (fr)
ZA (1) ZA201209660B (fr)

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DE102011009359A1 (de) 2011-01-25 2012-07-26 Technoform Glass Insulation Holding Gmbh Abstandshalterprofil und Isolierscheibeneinheit mit einem solchen Abstandshalterprofil
DE102011108402A1 (de) 2011-07-26 2013-01-31 Sig Technology Ag Flächenförmiger verbund mit kunststoffschichten unterschiedlicher vicat-erweichungstemperaturen
DE102011108401A1 (de) 2011-07-26 2013-01-31 Sig Technology Ag Robuster flächenförmiger Verbund mit einer Zwischenschicht mit erhöhter Vicat-Erweichungstemperatur
DE102012217047A1 (de) * 2012-09-21 2014-05-28 Bayerische Motoren Werke Aktiengesellschaft Kraftfahrzeug
CN105579231B (zh) * 2013-09-27 2017-10-03 Dic株式会社 防雾性多层膜、使用其的层叠体和包装材
US9409380B2 (en) 2014-10-31 2016-08-09 Mcs Industries, Inc. Anti-fog mirror apparatus having a multi-layer film
CN109476216A (zh) * 2016-07-20 2019-03-15 日本板硝子株式会社 防雾性膜
EP3666520A1 (fr) * 2018-12-14 2020-06-17 Cryovac, LLC Film antibuée multicouches
US11987026B2 (en) 2020-05-27 2024-05-21 Proampac Holdings Inc. Recyclable laminated polyolefin-based film structures
MX2022014257A (es) 2020-05-27 2022-12-07 Proampac Holdings Inc Estructuras con una pelicula a base de poliolefina laminada reciclable.
MX2022015510A (es) * 2020-06-08 2023-01-24 Amcor Flexibles North America Inc Envase esterilizable en retorta resistente al calor listo para reciclaje.
US11718075B2 (en) 2020-07-24 2023-08-08 Proampac Holdings Inc. High clarity, recyclable, polyethylene-based packaging films

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DE102004055323A1 (de) * 2004-11-16 2006-05-18 Cfs Kempten Gmbh Transparente tiefziehfähige Folien mit Antifog-Eigenschaften

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DE102004055323A1 (de) * 2004-11-16 2006-05-18 Cfs Kempten Gmbh Transparente tiefziehfähige Folien mit Antifog-Eigenschaften

Also Published As

Publication number Publication date
WO2012037931A1 (fr) 2012-03-29
EA201370010A1 (ru) 2013-06-28
DE202010007972U1 (de) 2010-12-09
CA2803664C (fr) 2018-07-10
CA2803664A1 (fr) 2012-03-29
ZA201209660B (en) 2013-08-28
US20130164551A1 (en) 2013-06-27

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