EP2588307A1 - Clear, transparent, multi-layer anti-fog film - Google Patents
Clear, transparent, multi-layer anti-fog filmInfo
- 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- Withdrawn
Links
- 230000004888 barrier function Effects 0.000 claims abstract description 67
- 239000000654 additive Substances 0.000 claims abstract description 28
- 230000000996 additive effect Effects 0.000 claims abstract description 14
- 229920000098 polyolefin Polymers 0.000 claims abstract description 9
- 230000032798 delamination Effects 0.000 claims abstract description 3
- -1 fatty acid esters Chemical class 0.000 claims description 36
- 229920001155 polypropylene Polymers 0.000 claims description 32
- 239000002131 composite material Substances 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 238000004806 packaging method and process Methods 0.000 claims description 13
- 235000013305 food Nutrition 0.000 claims description 10
- 239000002318 adhesion promoter Substances 0.000 claims description 5
- 239000000565 sealant Substances 0.000 claims description 5
- 150000002314 glycerols Chemical class 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 3
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical class OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 claims description 2
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 2
- 229930195729 fatty acid Natural products 0.000 claims description 2
- 239000000194 fatty acid Substances 0.000 claims description 2
- 239000010410 layer Substances 0.000 claims 12
- 230000006750 UV protection Effects 0.000 claims 1
- 239000012790 adhesive layer Substances 0.000 claims 1
- 239000002346 layers by function Substances 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 abstract description 44
- 238000007789 sealing Methods 0.000 abstract description 28
- 230000014759 maintenance of location Effects 0.000 abstract 1
- 239000004743 Polypropylene Substances 0.000 description 28
- 239000007789 gas Substances 0.000 description 22
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 17
- 239000004715 ethylene vinyl alcohol Substances 0.000 description 17
- 239000004952 Polyamide Substances 0.000 description 10
- 230000005012 migration Effects 0.000 description 10
- 238000013508 migration Methods 0.000 description 10
- 229920002647 polyamide Polymers 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 description 6
- 239000004698 Polyethylene Substances 0.000 description 5
- 239000012785 packaging film Substances 0.000 description 5
- 229920006280 packaging film Polymers 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 230000007774 longterm Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 239000004594 Masterbatch (MB) Substances 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- RZXDTJIXPSCHCI-UHFFFAOYSA-N hexa-1,5-diene-2,5-diol Chemical compound OC(=C)CCC(O)=C RZXDTJIXPSCHCI-UHFFFAOYSA-N 0.000 description 3
- 239000012939 laminating adhesive Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000010422 painting Methods 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920002959 polymer blend Polymers 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 229920001384 propylene homopolymer Polymers 0.000 description 2
- 229920000298 Cellophane Polymers 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical class OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229920002367 Polyisobutene Polymers 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000004596 additive masterbatch Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 230000003254 anti-foaming effect Effects 0.000 description 1
- 230000001166 anti-perspirative effect Effects 0.000 description 1
- 239000003213 antiperspirant Substances 0.000 description 1
- 125000003118 aryl group Polymers 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000000254 damaging effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000000890 drug combination Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 150000004668 long chain fatty acids Chemical class 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 150000004667 medium chain fatty acids Chemical class 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 230000001617 migratory effect Effects 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 235000021485 packed food Nutrition 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229910052615 phyllosilicate Inorganic materials 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920006149 polyester-amide block copolymer Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
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
Abstract
The invention relates to a clear, transparent, multi-layer anti-fog film with improved resistance to delamination and with good retention of function, which comprises at least one polyolefin sealing layer (10) comprising anti-fog additive, and also comprises an anti-fog-agent barrier layer (20) and an outer layer (40).
Description
Klare transparente Antifog-Mehrschicht-Folie Clear transparent anti-fog multi-layer film
Die Erfindung betrifft eine Polyolefin-Mehrschichtfolie, welche mindestens eine Antifogsiegelschicht, eine Deckschicht mit höherer Siegeltemperatur, gegebenenfalls Gas- und/oder Feuchtigkeitssperrschichten aufweist. 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.
Unter Polyolefin-Mehrschichtfolien werden im Zusammenhang mit dieser Anmeldung solche verstanden, die mehr als 25% Polypropylen, bezogen auf die Gesamtfolie bzw. alle Schichten der Folie, enthalten. Polypropylen hat die Eigenschaften eines hohen Schmelzpunktes und damit guter Sterilisierbarkeit, guter Verfügbarkeit und guter mechanischer Eigenschaften hinsichtlich Stabilität, Rigidität, Zug- und Kratzfestigkeit. In the context of this application, 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.
Derartige Mehrschichtfolien finden Einsatz in der Verpackung von wasserhaltigem Material, wie Lebensmitteln, die bei Lagerung derselben Kondensate bilden. Dabei werden Mehrschichtfolien als Sichtfenster oder aber Beutel eingesetzt, die möglichst klar und transparent sein sollen, um eine gute Inspektion des Inhalts der Verpackung über mögliche Zersetzung, Schimmelbildung oder aber Größe und Beschaffenheit des Inhalts zu ermöglichen. Die Abgabe von Wasser aus den so verpackten Waren führt zu Kondensatbildung an der Verpackung, speziell an Deckelfolien, zu Wassertropfen, welche die Sicht auf das Produkt einschränken bzw. verhindern. Diese so gebildeten Wassertropfen werden als„fog" bezeichnet und Mittel, welche Wassertropfen vermeiden, als „Antifog-Mittel" oder„Antifog-Additive". Bei Folien, die keine oder mangelhafte Antifog-Eigenschaft haben, führt der Feuchtegehalt der verpackten Lebensmittel zu einer Bildung von Wassertropfen durch Kondensation auf der Such multilayer films are used in the packaging of water-containing material, such as foods that form condensates when stored. In this case, 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. These water droplets formed in this way are referred to as "fog" and agents which avoid water droplets as "antifogging agents" or "antifogging additives." In the case of films which have no or poor antifogging property, the moisture content of the packaged foods results in a Formation of water droplets by condensation on the
Folienoberfläche. Diese Tropfenbildung beeinträchtigt die Transparenz und die Haltbarkeit des Packgutes. Die Tropfen haften nicht unbegrenzt auf der Film surface. This dripping impairs the transparency and the durability of the packaged goods. The drops do not adhere indefinitely to the
Folienoberfläche und die heruntertropfende Feuchtigkeit verursacht eine Beschleunigung der Fäulnis-und Schimmelbildung auf dem Lebensmittel. Film surface and the dripping moisture causes an acceleration of rot and mold on the food.
Darüber hinaus wirken die Tropfen auf der Folienoberfläche bei Lichteinfall wie eine Brennlinse. Folien mit Antifog-Eigenschaften verhindern diese schädigende Wirkung der tropfenförmigen Wasserdampfkondensation.
Antifogeigenschaften von Folien können durch Beschichten mit Antifog-Lösung oder aber durch Einmischen von Antifog-Additiven in produktseitige Folienschichten erzielt werden. Derartige Antifogadditive sind allgemein bivalente Verbindungen, die einen unpolaren aliphatischen Bereich zur Verankerung in der Polyolefinmatrix und einen polaren hydrophilen Bereich haben, der mit Wasser wechselwirken kann und die Oberflächenspannung der Wassertröpfchen so herabsetzt, dass sich ein transparenter Wasserfilm auf der Folie bildet. Dieser polare Bereich bewirkt die Unverträglichkeit von Antifog-Additiven mit reinen Polyolefinen, wie Polyethylen, die zur Migration der Additve an die Folienoberfläche führt. Der polare Bereich des Antifog-Mittels ist dann nach Aussen gerichtet und kann so mit Wasser wechselwirken. Das Antifog-Additv senkt den Kontaktwinkel der Wassertröpfchen und erlaubt so die Ausbildung eines kontinuierlichen transparenten Wasserfilms auf der Folienoberfläche. In addition, the drops on the surface of the film act like a focal lens when exposed to light. Films with anti-fog properties prevent this damaging effect of the droplet-shaped water vapor condensation. 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. Such 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-Additive sind somit oberflächenaktive Additive, die bevorzugt als Kombination aus verschiedenen Substanzklassen eingesetzt werden. Geeignete Substanzen, die in Verbindung miteinander als Antifog-Additiv eingesetzt werden, sind beispielsweise in der WO 97/22655A1 beschrieben, auf welche hiermit ausdrücklich zur Vermeidung von Wiederholungen Bezug genommen wird. Komponenten einer Antifogmittel-Kombination sind bspw. Fettsäureester und deren Derivate, aliphatische Alkohole und deren Ester, mehrfach ethoxylierte aromatische Alkohole, ein oder mehrfache veresterte Sorbitol Ester, ein oder mehrfach veresterte Glycerolester, gemischte Glycerolester, ethoxylierte Sorbitanester, ethoxylierte Amine. Die vorstehend genannten Ester beruhen meist auf einer Veresterung der jeweiligen Säure mit mittel- oder langkettigen Fettsäuren. 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.
Typisch sind bspw. Wirkstoffkombinationen aus den drei Substanzklassen : Glycerolester, Sorbitolester und ethoxylierte Amine. Typical are, for example, drug combinations from the three classes of substances: glycerol esters, sorbitol esters and ethoxylated amines.
Um Antifog-Eigenschaften zu erzielen, kann die Siegelschicht einer Verbundfolie mit einem entsprechenden Antifoglack beschichtet sein. Eine In order to achieve antifogging properties, the sealing layer of a composite film may be coated with a corresponding antifogging lacquer. A
Antifoglackbeschichtete Schicht hat nur eine geringe Lebensdauer, da sie sich
sofort im Wasser löst - die Wirksubstanz (veresterte Tenside) ist schnell verbraucht und die Zyklenanzahl begrenzt. 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.
Die Antifog-Additive können direkt oder über ein Konzentrat, ein sogenanntes Masterbatch, in Polymerschichten der Folie selbst eingearbeitet werden. Mas- terbatches sind Polyolefine/Antifogmittel-Mischungen, welche die Antifog-Additive in einer gegenüber der Folienschicht erhöhten Konzentration enthalten, im allgemeinen 10 - 50 Gew.-%, vorzugsweise 15 - 40 Gew.-% des Additivs, bezogen auf das Gesamtgewicht des Masterbatches. Die Polyolefine des Master- batches sind im allgemeinen gängige Polyolefine, wie Polyethylene oder Polypropylene. Antifog-Additive und entsprechende Masterbatche sind bekannt und kommerziell erhältlich. 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.
Ein in die Siegelfolie eingemischtes Additiv wandert aus der Siegelschicht in Richtung Produkt, aber auch in Richtung Deckschicht, wodurch sich die Gesamteigenschaften der Mehrschichtfolie verschlechtern. 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.
Batchsysteme zeigen bei Mehrschichtfolien mit Haftvermittlern und EVOH-Foli- enschichten - einer üblichen Sauerstoffsperrschicht - eine Migration der Antifog- Wirkstoffe auch in Richtung der polaren ( EVO H )-We rkstoffe , wodurch diese Eintrüben bzw. ihre Hafteigenschaften an den übrigen Folien der Mehrschichtfolie verlieren. Dies führt zu schlechteren Antifogeigenschaften bis zum Totalausfall. In multilayer films with adhesion promoters and EVOH film layers-a conventional oxygen barrier layer-batch systems show migration of the antifog agents also in the direction of the polar (EVO H) substances, as a result of which these cloudinesses or their adhesive properties on the other films of the multilayer film are lost , This leads to poorer antifogging properties until total failure.
Bei Kaschierverbunden treten diese Eigenschaften sogar noch verstärkt auf durch chemische Wechselwirkung der Antifog-Mittel mit Klebern und mengenmäßig mehr polaren Materialien, welche das Antifog-Mittel bevorzugt absorbieren. Da die Migration dieser Stoffe unbegrenzt stattfindet, ist eine Funktionsgarantie derartiger Antifog-Folien über längere Zeiträume nicht gegeben. In laminated composites, these properties are even more pronounced due to chemical interaction of the antifog agents with adhesives and quantitatively more polar materials which preferentially absorb the antifogging agent. Since the migration of these substances takes place indefinitely, a functional guarantee of such antifogging films over extended periods is not given.
Besonders problematisch sind Polypropylen-Mehrschichtfolien, die aufgrund ihrer relativ guten Temperaturbeständigkeit etc. beliebt sind, aber mit Particularly problematic are polypropylene multilayer films, which are popular because of their relatively good temperature resistance, etc., but with
Antifogmitteln schlecht Wechsel wirken.
Polypropylen-Filme mit Anti-Fogeigenschaften sind bereits bekannt. So beschreibt die JP 58079044 A und auch die JP 02187441 A Polypropylen- Schichten für Mehrschichtfolien mit speziellen Antifogmitteln, die weniger migrationsfreudig sind 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 erläutert ein Polypropylen-Laminat, bei dem eine JP09248880A illustrates a polypropylene laminate in which a
Antifogmittelhaltige Schicht gemeinsam mit einer Polypropylen Schicht extru- diert wird. . Antifogmittelhaltige layer is extruded together with a polypropylene layer. ,
Die im Stand der Technik bekannten Polypropyien-Antifog-Folien sind nachteilig hinsichtlich der Bedruckbarkeit und/oder Transparenz oder der Hot-Tack Eigenschaften der Folie. Des weiteren sind die bekannten Folien verbesserungsbedürftig bezüglich der Antifog-Eigenschaften, insbesondere auch im Hinblick auf die Langzeitbeständigkeit dieser Eigenschaften. The known in the art 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.
Es ist Aufgabe der vorliegenden Erfindung, eine siegelfähige Mehrschicht Folie mit guten und langzeitbeständigen Antifogeigenschaften, auch bei langer Lagerung auf der Rolle, zur Verfügung zu stellen. It is an object of the present invention to provide a sealable multilayer film with good and long-term antifogging properties, even with long storage on the roll available.
Die Aufgabe wird durch die Merkmale des Patentanspruches 1 gelöst. Vorteilhafte Weiterbildungen ergeben sich aus den abhängigen Ansprüchen. The object is solved by the features of claim 1. Advantageous developments emerge from the dependent claims.
Überraschenderweise hat sich gezeigt, dass die erfindungsgemäßen Mehrschichtfolien sehr gute optische Eigenschaften, d. h. hohe Transparenz und guten Glanz, sowie Siegeleigenschaften, insbesondere einen guten Hot-Tack aufweisen. Surprisingly, it has been found that 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.
Um Migration des Antifogmittel-Wirkstoffs zu polaren Gruppen innerhalb der Folie/ des Verbundes zu verhindert und den Antifogmittel- Wirkstoff an die Oberfläche der Siegelschicht zu zwingen, wird erfindungsgemäß eine In order to prevent migration of the antifogging agent to polar groups within the film / composite and to force the antifogging agent to the surface of the sealant layer, according to the invention a
Polypropylen-Barriere für die Antifogmittel- Wirkstoffe zwischen die Siegelschicht und dahinterliegende polare Schichten gelegt.
Diese Antifogmittel- Barriereschicht kann bspw. Polypropylen sein. Es verhindert aufgrund seiner hohen Kristallinität die Migration zu den polaren Bestandteilen der Mehrschicht Folien bzw. des Verbundes. Vorzugsweise wird Polypropylene barrier for the antifog agents placed between the sealing layer and underlying polar layers. 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
Polypropylen-homo eingesetzt, alternativ auch ein Block- Polypropylen bzw. Random-Polypropylen. Polypropylene homo used, alternatively, a block polypropylene or random polypropylene.
Es ist besonders bevorzugt, dass auch die Deckschicht des Folienverbundes Sperreigenschaften gegenüber dem Antifogmittel aufweist, um ein Herauswandern des Antifogmittels aus der Siegelschicht auf der Folienrolle in die Deckschicht zu vermeiden und die Funktion der Sperrschichtfolie auch auf Rolle zu garantieren. It is particularly preferred that 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.
Erfindungsgemäss können Antifogeigenschaften (Cold-fog) der Stufe 5 (sehr gut) über mindestens 6 Monate gewährleistet werden, wobei die Praxis zeigt, dass auch über den Zeitraum hinaus die Antifogmittel- Wirkung erhalten bleibt. According to the invention, antifogging properties (cold fog) of stage 5 (very good) can be ensured over at least 6 months, with the practice showing that the antifogging effect is maintained even beyond the period.
Siegelschchten im Sinne der vorliegenden Erfindung sind die dem Produkt zugewandten Schichten, die heisssiegelbar sind. Unter Heisssiegeln wird hier das Siegeln mit dauerbeheizten/impulsbeheizten/Ultraschall Werkzeugen verstanden, wobei Siegelbacken den zu siegelnden Verbund zusammenpressen und mindestens die innere Schicht des Verbundes mit einer anderen Siegelschicht - welche vom gleichen Verbund (bspw. bei gesiegelten Beuteln) oder aber mit der Polymer-Oberfläche eines anderen Gegenstandes, wie eines schalenartigen Behälters - verschmilzt. Siegelschchten in the context of the present invention are the product-facing layers that are heat-sealable. The term "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.
Deckschichten sind diejenigen Schichten, welche aussenliegende Schichten bilden. Sie können nach Eigenschaften wie: mechanische Stabilität, Festigkeit, Glanz ausgewählt werden. Im vorliegenden Falle haben sie bevorzugt auch Sperreigenschaften gegenüber dem Antifogmittel. 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.
Bevorzugte Deckschichten sind Polypropylen, Polyester und Polyamid.
Zwischenschichten sind die zwischen der Deckschicht und der Siegelschicht vorhandenen Schichten, im allgemeinen kann es sich dabei um Kleber (Haftvermittler, Kaschierkleber); Feuchtigkeitssperrschichten; Antifogmittelsperr- schichten, Gassperrschichten, wie sie dem Fachmann geläufig sind, handeln. 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; Antifogmittelperr- layers, gas barrier layers, such as those skilled in the art act.
Typische Gassperrschichten sind bspw. aus DE 10 2004 062 204 A1 bekannt. Die Gassperrschicht verhindert den Eintritt und Austritt von Gasen. Insbesondere soll dabei verhindert werden, dass Sauerstoff an die Lebensmittel gelangt, der Fäulnis und Schimmelbildung begünstigt, und dass gegebenenfalls in der Verpackung eingebrachte Schutzgase, wie z. B. Stickstoff oder Kohlendioxid, entweichen. Solche Gassperrschichten enthalten z.B. im Wesentlichen Polyamid, lackiertes Zellglas, Ethylen-Vinylalkohol-Polymere (EVOH) oder andere Vinylalkohol-Polymere (PVOH) oder sind auch mehrschichtig aus diesen Materialien aufgebaut. Polyamid und/oder EVOH ist an sich wasserdampfdurchlässig und weist schlechte Siegeleigenschaften auf, d.h. eignet sich nicht für ein Schweißen, wie dies für die Verpackung von Lebensmitteln und Futtermitteln in der Regel notwendig ist. Um die Lebensmittel vor einem Austrocknen zu schützen, werden die Verpackungsfolien üblicherweise auch mit einer zusätzlichen Schicht als Wasserdampfsperre versehen. Als Werkstoff für die Gas-Sperrschicht eignen sich also Polyamide, lackiertes Zellglas, Ethylen-Vinylalkohol- Polymere (EVOH) oder andere Vinylalkohol-Polymere (PVOH). Die Sperrschicht kann im Wesentlichen aus einem dieser Werkstoffe bestehen. Es ist auch möglich, die Sperrschicht selbst mehrschichtig aufzubauen, z.B. aus einer EVOH-Schicht, die einseitig oder beidseitig mit einer Polyamid-Schicht versehen ist. Diese mehrschichtige Sperrschicht kann durch Koextrusion oder durch Kaschieren und/oder Lackieren hergestellt werden. 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. To protect the food from drying out, the packaging films are usually also provided with an additional layer as a water vapor barrier. As a material for 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.
Wasserdampf Sperrschicht-Folien sind dem Fachmann geläufig. Besonders eignen sich Polyisobutylen und/oder Butylkautschukpolymere, Styrolpolymere, wie SEBS oder auch Schichtsilikatgefüllte Polyamide. Die als Wasserdampf- Sperre dienende zusätzliche Schicht kann gute Siegeleigenschaften aufweisen, so dass durch diese Schicht zum einen eine schweißbare Verpackungsfolie erhalten wird und zum Zweiten diese Verpackungsfolie auch in der im Allgemeinen erwünschten Weise zusätzlich wasserdampfdicht ist.
Erfindungsgemäß wird eine Antifog-Folie - wie zur Verpackung von Lebensmitteln und Futtermitteln oder aber als Antibeschlagschicht in Folienverbunden wie Kunststoffglasscheiben zur Verfügung gestellt, die gegebenenfalls Schutzgase und/oder Wasser in der Verpackung hält und die Lebensmittel vor Sauerstoff schützt. Diese Folie weist eine Sperrschicht auf, die eine hohe Barrierefunktion für Antifogmittel hat.. Diese Sperrschicht erfüllt damit die Forderungen, -Antifogmittel von darüberliegenden Folien fernzuhalten und den Antifogmit- telverlust zu verhindern, eventuell in die Verpackung eingebrachte Schutzgase in der Verpackung zu halten. 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. According to the invention, 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.
Um eine solche Folie auch schweißbar zu machen, so dass sich die Folie auch als Verpackungsfolie eignet, weist die Folie zusätzlich eine oberflächliche Siegelschicht mit Antifogmittel auf, die gute Siegeleigenschaften besitzt. Die Siegelschicht beeinträchtigt die funktionalen Eigenschaften der Sperrschicht. Da die Sperre gegen Gase und Feuchtigkeit durch die mindestens eine Gas/Wasserdampf-Sperrschicht bewirkt wird, kann die Siegelschicht auch gasdurchlässig sein. Unter "Gasbarriere" bzw. "gasdurchlässig" wird eine Barriere bzw. Durchlässigkeit für Substanzen verstanden, die bei normalen Umgebungstemperaturen gasförmig sind, insbesondere für Sauerstoff, Stickstoff und In order to make such a film also weldable, so that the film is also suitable as a packaging film, 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. By "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
Kohlenstoffdioxid. Carbon dioxide.
Die Antifogmittel-Sperrschicht der Folie enthält im allgemeinen mindestens 80 Gew.-%, vorzugsweise 90 bis 100 Gew.-%, insbesondere 98 bis < 100 Gew.-%, jeweils bezogen auf die Antifog-Mittel Sperrschicht, eines nachstehend beschriebenen Propylenpolymeren. Dieser Antifog-Mittel Sperrschicht wird kein Antifog Additiv zugefügt. 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.
Es wurde gefunden, dass eine Sperrschicht aus Polypropylen vorteilhaft zu dem gewünschte Eigenschaftsprofil der Folie beiträgt. Die Antifog-Additive wandern aus der Siegelschicht nur bis zur Sperrschicht, da diese Antifog-Mittel Sperrschicht gegenüber dem Antifog-Additiv als effektive Migrationssperre wirkt. It has been found that 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.
Somit wirkt nur die Siegelschicht als Antifogmittel-Reservoir, wobei aufgrund
der Sperre ein Antifogmittel-Verlusst durch Einwandern in andere Folienschichten vermieden werden kann. Thus, only 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.
Das Propylenpolymer der Antifog-Mittel Sperrschicht enthält besonders bevorzugt mindestens > 98 bis 100 Gew.-% Propylen. Der entsprechende Comonomergehalt von 0 bis höchstens 2 Gew.-% bezogen auf das Propylen besteht, wenn vorhanden, im allgemeinen aus Ethylen.. Isotaktisches 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. Isotactic
Propylenhomopolymer ist bevorzugt. Propylene homopolymer is preferred.
Das Propylenhomopolymere hat im allgemeinen einen Schmelzpunkt von 140 bis 170 C. The propylene homopolymer generally has a melting point of 140 to 170 C.
Im allgemeinen kann die Antifog-Mittel Sperrschicht auch übliche Stabilisatoren und Neutralisationsmittel aufweisen, wie sie dem Fachmann auf dem Gebiet geläufig sind.. In general, the antifogging agent barrier layer may also comprise conventional stabilizers and neutralizing agents, as known to those skilled in the art.
Überraschenderweise ist es durch die spezielle Zusammensetzung der Folie mit hohen Additivgehalten nur in der Siegelschicht möglich, verschiedene erwünschte Gebrauchseigenschaften der Folie nebeneinander zu realisieren. Die Folie zeigt die gewünschten Antifog-Eigenschaften, insbesondere sind diese überraschend gleichmässig und langzeitbeständig. Die Siegelschicht bildet das Antifogreservoir, aus welchem das Antifogmittel-Additiv über lange Zeit nachmigrieren kann, so dass es auch nach mehreren Tagen zu keiner Tropfenbildung auf der Folien kommt, wenn diese zum Verpacken feuchter Lebensmittel verwendet wird. Gleichzeitig treten die nachteiligen Auswirkungen der Antifog- Additive auf Transparenz und Kohäsion überraschenderweise nicht auf. Die Folie zeigt trotz guter Antifog-Eigenschaften eine gute Adhäsion der Schichten aneinander und eine sehr gute Transparenz. Die Haftvermittlerschicht 12 wird durch die Antifogmittelsperrschicht nicht abgesättigt und kann entsprechend Haftvermittlung erzeugen. Dieses erlaubt entsprechende Dosierungen in der Siegelschicht 10.
Die Antifog-M ittel Sperrschicht bildet eine wirksame Barriere gegenüber einer Migration des Antifog-Additivs zur Oberfläche der Deckschicht. Es wird somit eine Folie zur Verfügung gestellt, die eine besonders vorteilhafte Surprisingly, it is possible by the special composition of the film with high additive contents only in the sealing layer to realize different desired performance characteristics of the film side by side. 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. At the same time, the adverse effects of anti-fog additives on transparency and cohesion surprisingly do not occur. Despite good antifogging properties, 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. There is thus provided a film which is a particularly advantageous
Eigenschaftskombination aufweist. Die Folie hat Anti-Fog-Eigenschaften, die besonders langzeit stabil und gleichmässig sind und hat noch immer eine sehr gute Transparenz, gute Hot-Tack Eigenschaften und ist auch, falls erwünscht, bedruckbar. Has property combination. 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.
Außerhalb der Lebensmittelverpackung eignet sich die erfindungsgemäße An- tibeschlagfolie auch als Antibeschlagfolie oder Antibeschlagsschicht für Windschutzscheiben, Sportbrillen, Helmvisiere oder Kunststoffgläser oder mineralische Glasscheiben sowie Gewächshausfolien jeglicher Art. Outside of the food packaging, 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.
Nachfolgend wird die Erfindung detaillierter anhand von Beispielen sowie der begleitenden Zeichnung erläutert, auf welche sie jedoch keinesfalls In the following, the invention will be explained in more detail by way of examples and the accompanying drawings, to which, however, they by no means
eingeschränkt ist. Darin zeigt: is restricted. It shows:
Fig. 1 einen 3-schichtigen Folienverbund als Folienunterkombination für Mehrschichtfolien ; 1 shows a 3-layer film composite as a film subcombination for multilayer films;
Fig. 2 einen 5-schichtigen Folienverbund mit Sauerstoffsperrschicht Fig. 2 shows a 5-layer film composite with oxygen barrier layer
Fig. 3 einen 6 schichtigen Folienverbund; 3 shows a 6-layer film composite;
Fig. 4 eine Mehrschichtfolie mit dem Verbund der Fig. 3; FIG. 4 shows a multilayer film with the composite of FIG. 3; FIG.
Fig. 5 eine weitere Mehrschichtfolie mit dem Verbund der Fig. 3 5 shows a further multilayer film with the composite of FIG. 3
In Fig. 1 ist ein einfacher coextrudierter Folienverbund ohne Gassperre, der im fertigen Verbund durch weitere Folien ergänzt wird, schematisch dargestellt. Eine Antifogmittelhaltige Siegelschicht 10 aus PE mit Antifogmittel wird von einer Antifogmittel-Sperrschicht 20 aus Polyproplen bedeckt, auf der wiederum eine Polyethylenschicht 40 als Deckschicht aufextrudiert ist. Dieser In 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. This
Folienverbund eignet sich für die Verpackung von Gütern, bei denen keine Gassperreigenschaften notwendig sind. Gegebenenfalls können noch weitere Deckschichten auf diesen Verbund aufgebracht werden, um die
Widerstandsfähigkeit der Folie gegenüber Temperatur zu verbessern und/oder die mechanische Stabilität zu erhöhen. Film composite is suitable for the packaging of goods in which no gas barrier properties are necessary. Optionally, 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.
Folien dieser Art sind vornehmlich für Gewächshausfolien geeignet. Films of this type are primarily suitable for greenhouse films.
Fig. 2 zeigt eine Antifog-Mehrschichtfolie mit Gassperre 30 und verbesserter Haltbarkeit auf der Rolle. Die mit Antifogmittel ausgerüstete Siegelschicht 10 - hier im Wesentlichen aus PE, wird von einer EVOH-Gassperrschicht 30 überlagert, die über einen Haftvermittler 12 angebunden ist. Auf der Aussenseite der Gassperrschicht ist mittels eines weitern Haftvermittlers 12 eine Polypropylen Aussenschicht 40 aufgebracht, die den Verbund gegen Eindiffusion von Fig. 2 shows an anti-fog multilayer film with gas barrier 30 and improved roll life. The sealing layer 10 equipped with antifogging agent - here essentially of PE, is superimposed by an EVOH gas barrier layer 30, which is connected via a bonding agent 12. On the outside of the gas barrier layer by means of a further adhesion promoter 12, a polypropylene outer layer 40 is applied, which protects the composite against diffusion of
Antifogmittel auf der Rolle sowie den Austritt des Antifogmittels aus der Deckschicht 40 - hier aus Polypropylen - schützt. Die Folie zeigt gute Stabilität und eine gute Transparent im Einsatz. Antifog agent on the roll and the exit of the antifog agent from the cover layer 40 - here polypropylene protects. The film shows good stability and good transparency in use.
In Fig. 3 ist eine sechs-schichtige Antifog-Mehrschichtfolie gezeigt, bei der direkt an die Antifogmittelhaltige Siegelschicht 10 - wie bei Fig. 1 - eine In Fig. 3, 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
Polypropylen- Antifogmittel-Sperrschicht 20 aufext rudiert ist. Diese Polypropylene antifoggant barrier layer 20 is aufext rudiert. These
Polypropylen-Schicht 20 hindert das Antifogmittel am Einwandern in die Folie und zwingt es in die Siegelschicht 10. Auf der Polypropylen-Schicht ist mittels eines Haftvermittlers EVOH als Gassperrschicht 30 angebunden. Dadurch, dass bei dieser Ausführungsform die Polypropylen-Schicht 20 die Gassperrschicht 30 schützt, ist ein Einwandern des Antifogmittel in dieselbe unmöglich. Das Einwandern von Antifog-Mittel in EVOH ist grundsätzlich wegen des polaren Charakters des EVOH begünstigt, führt aber zu unerwünschter Änderung der EVOH-Eigenschaften und auch der Eigenschaften des Polypropylene layer 20 prevents the antifogging agent from migrating into the film and forces it into the sealing layer 10. On the polypropylene layer, by means of an adhesion promoter, EVOH is bound as gas barrier layer 30. By virtue of the polypropylene layer 20 protecting the gas barrier layer 30 in this embodiment, migration of the antifogging agent into it is impossible. 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
Haftvermittlers 12 und somit im schlimmsten Falle zur Delamination. Adhesive 12 and thus in the worst case for delamination.
Fig. 4 zeigt eine vollständige Verbundfolie mit der Folienkombination der Fig. 3. Auf die Außenschicht 40 wird nun mittels eines Kaschierklebers 14 die Hartschicht aufgebracht, welche den entsprechenden Glanz und Kratzfestigkeit der Folie bedingt. Diese kann bspw. orientiertes/gerecktes Polypropylen, orientiertes/gerecktes Polyamid, Polyester sein.
Fig. 5 zeigt eine weitere vollständige Verbundfolie mit verbesserten Sperreigenschaften gegenüber Feuchtigkeit und Gasen durch die Verwendung einer Polypropylensperrschicht aus Polyamid sowie EVOH. Beide Materialien ergänzen sich hinsichtliche ihrer Sperrfunktion hervorragend, so dass eine besonders gut sperrende Mehrschichtfolie erhalten wird. Im übrigen ist der Aufbau der Folie der Fig. 5 ähnlich derjenigen der Fig. 2, nur dass eine zweifache Sperrschicht auf der Antifogmittel-Siegelschicht befestigt ist. Die Deckschicht wird - wie auch bei der Kombination der Fig. 2 möglich, aufkaschiert. 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. Incidentally, 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.
Es versteht sich von selbst, dass gegebenenfalls durch die übliche Verarbeitung von Folienregenerat in den übrigen Schichten der Folie geringfügige Mengen Antifog Additiv enthalten sein können. Diese Menge muss jedoch so gering gehalten werden, dass keine störenden Mengen zur zweiten äusseren It goes without saying that, if appropriate, the usual processing of film regenerate in the other layers of the film may contain minor amounts of antifogging additive. However, this amount must be kept so low that no disturbing amounts to the second outer
Oberfläche der Folie migrieren. Migrate the surface of the film.
Die Gesamtdicke der erfindungsgemässen Polypropylenfolie kann innerhalb weiter Grenzen variieren und richtet sich nach dem beabsichtigten Einsatz. Sie beträgt vorzugsweise 0,004 bis 0,120 mm, insbesondere 0,005 bis 0,080mm, wobei die Antifog-Mittel Sperrschicht etwa 10 bis 50 % der Gesamtfoliendicke ausmacht. 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.
Die Erfindung betrifft weiterhin ein Verfahren zur Herstellung der erfindungsgemässen Polypropylenfolie nach dem an sich bekannten Coextrusionsverfahren. The invention further relates to a process for the preparation of the novel polypropylene film according to the known coextrusion process.
Dabei werden - wie beim Coextrusionsverfahren üblich - die Polymeren bzw. die Polymermischungen der einzelnen Schichten jeweils in Extrudern komprimiert und verflüssigt, wobei die gegebenenfalls zugesetzten Additive bereits im Polymer bzw. in der Polymermischung enthalten sein können oder als Master- batch eingearbeitet werden. Die Schmelzen werden dann gleichzeitig durch Flachdüsen (Breitschlitzdüse) gepresst und bilden Folien, die noch warm zusammenlaufen und sich beim Abkühlen und Verfestigen aneinanderheften.
Als Werkstoff für die Gas-Sperrschicht eignen sich Polyamide, lackiertes Zellglas, Ethylen-Vinylalkohol-Polymere (EVOH) oder andere Vinylalkohol-Poly- mere (PVOH). Die Sperrschicht kann im Wesentlichen aus einem dieser Werkstoffe bestehen. Es ist auch möglich, die Sperrschicht selbst mehrschichtig aufzubauen, z.B. aus einer EVOH-Schicht, die einseitig oder beidseitig mit einer Polyamid-Schicht versehen ist. Diese mehrschichtige Sperrschicht kann durch Koextrusion oder durch Kaschieren und/oder Lackieren hergestellt werden. As is customary in the 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. It is also possible to construct 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.
Gegebenenfalls kann man die so erhaltene Folie noch recken, was zu einer Orientierung der Molekülketten und zu Schrumpfeigenschaften der Folie führt. Temperaturen, bei denen Längs-und Querstreckung durchgeführt werden, können in einem relativ grossen Bereich variieren und richten sich nach den gewünschten Eigenschaften der Folie. Optionally, one can still stretch the resulting film, resulting in an orientation of the molecular chains and shrinkage properties of the film. 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.
Es ist auch möglich, den Deckschichtverbund so zu gestalten, dass eine der Schichten (zumindest teilweise) bedruckt ist. Der Druck kann durch Überlagerung mit einer weiteren Deckschicht geschützt werden. It is also possible to make the 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.
Überraschenderweise genügt die ausschliessliche Rezepturierung der inneren Siegelschicht 0 mit Antifog-Additven, um gleichbleibend gute Antifog-Eigen- schaften der Folie zu erzielen. Die Polypropylen-Sperrschicht 20 fungiert als Additiv-Sperre und verhindert Verlust des Antifog-Mittels durch Migration innerhalb der Folie. Damit wird eine gleichbleibende und zeitlich konstant gute Antifog Eigenschaft gewährleistet. Surprisingly, the exclusive formulation of the inner sealing layer 0 with antifog additives suffices to achieve consistently good antifogging properties of the film. 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.
Es wurde gefunden, dass durch die erfindungsgemässe Zusammensetzung der Folie die Antifog-Additive die Trübung der Folie praktisch nicht erhöhen. Dies ist für eine transparente Verpackungsfolie, die das Packgut optisch attraktiv zur Geltung bringen soll, unerlässlich. It has been found that 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.
Klassische Dickenverhälnisse der Einzelfolien in einem erfindunggemässen Verbund können wie folgt sein:
0,004mm - 0,1mm, vorzugsweise 0,008mm - 0,05mm 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, vorzugsweise 0,008mm - 0,1mm 0,001mm -0,1mm, vorzugsweise 0,002mm - 0,01mm 0,00 mm -0,01mm, vorzugsweise 0,002mm - 0,008mm 0,008mm -0,1mm, vorzugsweise 0,01mm - 0,04mm 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
Obwohl die Erfindung anhand bevorzugter Ausführungsbeispiele näher erläutert wurde, ist sie keineswegs auf dasselbe eingeschränkt sondern dem Fachmann ist offensichtlich, dass verschiedenste Ausführungen im Rahmen des Schutz- umfangs der beiliegenden Ansprüche möglich sind.
Although the invention has been explained in more detail with reference to preferred embodiments, it is by no means restricted to the same, but it is obvious to the person skilled in the art that a very wide variety of embodiments are possible within the scope of the appended claims.
Bezugszeichenliste LIST OF REFERENCE NUMBERS
10 Siegelschicht mit Antifogmittel 10 sealing layer with antifogging agent
12 Haftvermittler 12 adhesion agents
14 Kaschierkleber 14 laminating adhesive
20 Antifog-Sperrschicht 20 antifogging barrier
30 Sauerstoffsperrschicht 30 oxygen barrier layer
40 Aussenschicht/Hartschicht/Deckschicht
40 outer layer / hard layer / top layer
Claims
1 . Klare transparente Antifog-Mehrschicht-Folie mit verbesserter 1 . Clear transparent antifog multilayer film with improved
Widerstandsfähigkeit gegen Delamination und gutem Funktionserhalt, die mindestens Resistance to delamination and good functional integrity that at least
eine Antifog-Additiv haltige Polyolefin-Siegelschicht (10), an antifog additive-containing polyolefin sealant layer (10),
eine Antifogmittelsperrschicht (20), und an antifoggant barrier layer (20), and
eine Deckschicht (40) a cover layer (40)
aufweist. having.
2. Antifog-Mehrschicht-Folie nach Anspruch 1 , dadurch gekennzeichnet, dass sie mindestens eine weitere funktionelle Schicht, ausgewählt aus Gas-Sperrschichten, UV-Schutzschichten, Haftvermittlerschichten; Kleberschichten, Deck- oder 2. Antifog multilayer film according to claim 1, characterized in that it comprises at least one further functional layer selected from gas barrier layers, UV protection layers, adhesion promoter layers; Adhesive layers, cover or
Hartschichten, Wasserdampf-Sperrschichten sowie Kombinationen derselben aufweist. Hard layers, water vapor barrier layers and combinations thereof.
3. Antifog-Mehrschicht-Folie gemäss Anspruch 1 oder 2, dadurch gekennzeichnet, dass die Antifogmittelsperrschicht (20) mindestens 90 Gew.-% eines 3. Antifog multilayer film according to claim 1 or 2, characterized in that the antifoggant barrier layer (20) at least 90 wt .-% of a
Propylenpolymer enthält. Contains propylene polymer.
4. Antifog-Mehrschicht-Folie gemäss einem oder mehreren der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass das Antifog-Additiv aus den folgenden ausgewählt ist : Fettsäureester, aliphatische Alkohole, ethoxylierte aromatische Alkohole, ein-oder mehrfach veresterte Sorbitolester, ein-oder mehrfach veresterte Glycerolester, ethoxylierte Sorbitanester, ethoxylierte Amine sowie beliebigen Kombinationen derselben. 4. Antifog multilayer film according to one or more of claims 1 to 3, characterized in that the antifogging additive is selected from the following: fatty acid esters, aliphatic alcohols, ethoxylated aromatic alcohols, mono- or polyesterified sorbitol esters, on- or multiple esterified glycerol esters, ethoxylated sorbitan esters, ethoxylated amines and any combinations thereof.
5. Antifog-Mehrschicht-Folie gemäss einem der vorangehenden Ansprüche, dadurch gekennzeichnet, dass die Deckschicht (40) mindestens zu 90% ein Propylenpolymer enthält. 5. Antifog multilayer film according to one of the preceding claims, characterized in that the cover layer (40) contains at least 90% of a propylene polymer.
6. Antifog-Mehrschicht-Folie gemäß einem der vorangehenden Ansprüche, dadurch gekennzeichnet, dass über der Deckschicht (40) eine Hartschicht aufgebracht ist. 6. Antifog multilayer film according to one of the preceding claims, characterized in that over the cover layer (40) has a hard layer is applied.
7. Antifog-Mehrschichtfolie gemäß einem der vorangehenden Ansprüche, dadurch gekennzeichnet, dass mindestens ein Teilverbund der Mehrschichtfolie koextrudiert ist. 7. Antifog multilayer film according to one of the preceding claims, characterized in that at least one partial composite of the multilayer film is coextruded.
8. Antifog-Mehrschichtfolie gemäss einem der vorangehenden Ansprüche, dadurch gekennzeichnet, dass sie mit dauerbeheizten/impulsbeheizten/Uitraschai! 8. Antifog multilayer film according to one of the preceding claims, characterized in that they are permanently heated / pulse-heated / Uitraschai!
Werkzeugen siegelbar ist. Tools is sealable.
9. Antibeschlagfolie mit einem Gehalt an einer Mehrschichtfolie nach einem der vorangehenden Ansprüche für Lebensmittelverpackung, für Scheiben, Sichtfenster, Brillen, Gewächshäuser. 9. anti-fogging film containing a multilayer film according to one of the preceding claims for food packaging, for windows, windows, spectacles, greenhouses.
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DE202010007972U DE202010007972U1 (en) | 2010-07-02 | 2010-07-02 | Clear transparent anti-fog multi-layer film |
PCT/DE2011/075071 WO2012037931A1 (en) | 2010-07-02 | 2011-04-11 | Clear, transparent, multi-layer anti-fog film |
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EP2588307A1 true EP2588307A1 (en) | 2013-05-08 |
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EP11746431.3A Withdrawn EP2588307A1 (en) | 2010-07-02 | 2011-04-11 | Clear, transparent, multi-layer anti-fog film |
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EP (1) | EP2588307A1 (en) |
CA (1) | CA2803664C (en) |
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Families Citing this family (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102011009359A1 (en) | 2011-01-25 | 2012-07-26 | Technoform Glass Insulation Holding Gmbh | Spacer profile and insulating disk unit with such a spacer profile |
DE102011108401A1 (en) | 2011-07-26 | 2013-01-31 | Sig Technology Ag | Robust laminar composite with an intermediate layer with increased Vicat softening temperature |
DE102011108402A1 (en) | 2011-07-26 | 2013-01-31 | Sig Technology Ag | SURFACE CONNECTION WITH PLASTIC LAYERS OF DIFFERENT VICAT IMPROVEMENT TEMPERATURES |
DE102012217047A1 (en) * | 2012-09-21 | 2014-05-28 | Bayerische Motoren Werke Aktiengesellschaft | Motor vehicle for use with camera system for image processing, has housing, in which electric and electronic components, such as control devices and chip are arranged, where camera system is arranged in vehicle interior |
JP5962864B2 (en) * | 2013-09-27 | 2016-08-03 | Dic株式会社 | Anti-fogging multilayer film, laminate using the same, and packaging material |
US9409380B2 (en) | 2014-10-31 | 2016-08-09 | Mcs Industries, Inc. | Anti-fog mirror apparatus having a multi-layer film |
CN109476216A (en) * | 2016-07-20 | 2019-03-15 | 日本板硝子株式会社 | Anti-fog properties film |
EP3666520A1 (en) * | 2018-12-14 | 2020-06-17 | Cryovac, LLC | Antifog multilayer film |
WO2021243071A1 (en) | 2020-05-27 | 2021-12-02 | Proampac Holdings Inc. | Recyclable laminated polyolefin-based film structures |
KR20230028733A (en) * | 2020-06-08 | 2023-03-02 | 암코르 플렉서블스 노스 아메리카, 인코포레이티드 | easy to recycle heat resistance retort packaging |
US11718075B2 (en) | 2020-07-24 | 2023-08-08 | Proampac Holdings Inc. | High clarity, recyclable, polyethylene-based packaging films |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE10018049A1 (en) * | 2000-04-12 | 2001-10-25 | Wolff Walsrode | Multilayer, sealable laminating film, used for production of food packaging material, has inner layer of ethylene-vinyl alcohol copolymer and contains small amount of sorbitan mono-ester |
DE102004055323A1 (en) * | 2004-11-16 | 2006-05-18 | Cfs Kempten Gmbh | Transparent thermoformable films with anti-fog properties |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5879044A (en) | 1981-11-06 | 1983-05-12 | Mitsui Toatsu Chem Inc | Resin composition for polypropylene film having improved fog resistance |
JPH02187441A (en) | 1989-01-17 | 1990-07-23 | Kohjin Co Ltd | Heat-shrinkable polypropylene-based film having excellent fog resistance |
US5567533A (en) * | 1993-05-11 | 1996-10-22 | W. R. Grace & Co.-Conn. | Antifog film laminates |
DE69612569T2 (en) | 1995-12-15 | 2001-11-22 | Cryovac Inc | FILM WITH EXCELLENT COLOR ADHESIVITY AND WITH IMPROVED SLIP, ANTI-FOG AND AND / OR ANTISTATIC PROPERTIES |
JP3667427B2 (en) | 1996-03-15 | 2005-07-06 | 大日本印刷株式会社 | Laminated body |
US20040234797A1 (en) * | 2003-05-23 | 2004-11-25 | Cryovac, Inc. | Oxygen scavenging film with antifog properties |
DE102004062204A1 (en) | 2004-05-03 | 2005-12-01 | Süd-Chemie AG | Layered material, in particular for the packaging of oxygen-sensitive products |
US20060014002A1 (en) * | 2004-07-14 | 2006-01-19 | Moulton Jeffrey D | High barrier antifog laminate for case ready meat packaging |
US20060099436A1 (en) * | 2004-11-05 | 2006-05-11 | Cryovac, Inc. | Reduced antifog level in oxygen scavenging film with antifog properties |
-
2010
- 2010-07-02 DE DE202010007972U patent/DE202010007972U1/en not_active Expired - Lifetime
-
2011
- 2011-04-11 US US13/808,005 patent/US20130164551A1/en not_active Abandoned
- 2011-04-11 WO PCT/DE2011/075071 patent/WO2012037931A1/en active Application Filing
- 2011-04-11 CA CA2803664A patent/CA2803664C/en not_active Expired - Fee Related
- 2011-04-11 EA EA201370010A patent/EA201370010A1/en unknown
- 2011-04-11 EP EP11746431.3A patent/EP2588307A1/en not_active Withdrawn
-
2012
- 2012-12-19 ZA ZA2012/09660A patent/ZA201209660B/en unknown
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE10018049A1 (en) * | 2000-04-12 | 2001-10-25 | Wolff Walsrode | Multilayer, sealable laminating film, used for production of food packaging material, has inner layer of ethylene-vinyl alcohol copolymer and contains small amount of sorbitan mono-ester |
DE102004055323A1 (en) * | 2004-11-16 | 2006-05-18 | Cfs Kempten Gmbh | Transparent thermoformable films with anti-fog properties |
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DE202010007972U1 (en) | 2010-12-09 |
ZA201209660B (en) | 2013-08-28 |
WO2012037931A1 (en) | 2012-03-29 |
US20130164551A1 (en) | 2013-06-27 |
CA2803664C (en) | 2018-07-10 |
EA201370010A1 (en) | 2013-06-28 |
CA2803664A1 (en) | 2012-03-29 |
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