Stack sealable heat shrinkable film

0001The present invention refers to a multilayer heat shrinkable film characterized by a combination of desirable properties, such as high shrinkage, good optical properties, excellent sealability and stack sealability. The invention further is directed to a method of producing a packaged food item by using said film. The invention is further directed to the use of said film or bags and pouches made therefrom for packaging goods as for example food products.

0002Generally, the packaging of food items by means of a heat shrinkable bag comprises the following steps <ol id="ol0001" ol-style=""><li>1. Putting the food item inside the bag and removing the air (vacuumizing) with the help of a vacuum device.</li><li>2. Sealing of the open end of the bag.</li><li>3. Placing the vacuum pack in a heat shrinking media such as hot water under a temperature that ensures the shrink of the pack(eg 90°C).</li><li>4. The pack is ready and is characterized by appealing appearance and long shelf life because of the absence of oxygen.</li></ol>

0003These films need high shrink properties and good optics to ensure an excellent appearance and excellent sealability so that there is no entrance of oxygen to the pack as this would be detrimental for the shelf life of the food.

0004In some cases, where the food is stored in frozen conditions for example, there is the possibility to use a non gas barrier film. The other characteristics remain the same.

0005Packaging films with the above properties are well known in the art.

0006A problem that is often found in the art is that during the packaging process the operators must put the food in the bags with extra care, as they must avoid the overlapping of the bags. When overlapped or semi overlapped packs are vacuumized and sealed, the outer surfaces of the two (or more) bags seal the one to the other under the temperature and pressure conditions used to guarantee the sealability of the inner surfaces. This may lead to high rejects and loss of productivity. This situation in particular occurs in stack sealing procedures, i.e. in a situation, wherein two or more products are situated one upon the other and then are sealed.

0007If the operator tries to modify the temperature, seal time, pressure conditions there is a high possibility that the inner surfaces do not seal sufficiently.

0008Using bags that can be heat sealed when overlapping occurs, without problems of insufficient seal strength and sealing of the outer surfaces could lead to higher productivity, smaller cycle of each packed product and less attention required by the operator.

0009The problem to be solved has been addressed in the past: <ul id="ul0001" list-style="none"><li><patcit id="pcit0001" dnum="EP1131205A"><text>EP 1131205</text></patcit> refers to the use of a high melting point polyamide in the outer layer. The use of this material has the disadvantage that it reduces the shrinkage of the final film because of the high vicat of this resin. Therefore, this approach is not suitable for heat-shrinkable films and products made thereof.</li><li><patcit id="pcit0002" dnum="EP0810087A"><text>EP0810087</text></patcit> also suggests the use of polyester, polyamide and EVOH materials in coextrusion.</li><li><patcit id="pcit0003" dnum="EP1060077A"><text>EP 1060077</text></patcit> refers to the use of a polyester material in the outside layer and a polyamide in a core layer. This material also has a high vicat and reduces the shrinkage of the multilayer product.</li><li><patcit id="pcit0004" dnum="EP1415930A1"><text>EP 1415930 A1</text></patcit> refers to the use of peelable combinations comprising polybutylene in the outer layer. The problem in this case is that there is a high risk of deteriorating the optical properties as the outer layer (which contributes a lot to the optical properties of the combination) consists of the blend of two incompatible polymers able to make a cohesive peel. The outer layer should comprise an easily peelable combination so that stack sealability is easily achieved. The peelable composition is applied by "extrusion, co-extrusion or coating of a substrate".</li></ul>

SUMMARY OF THE INVENTION

0010Therefore, the problem underlying the invention is to provide a heat sealable film, which can be advantageously be used in stack sealing applications. It is a further problem of the invention to avoid that the outer surfaces of the two (or more) bags in stack sealing applications seal the one to the other under the temperature and pressure conditions used to guarantee the sealability of the inner surfaces. It is a still further problem to provide bags that can be heat sealed when overlapping occurs, without problems of insufficient seal strength and sealing of the outer surfaces. It is an additional problem to provide a film for stack sealing applications which has excellent optical properties and high heat shrinkability. It is still a further problem to avoid the use of polyamide resin in the structure because of the following disadvantages: <ol id="ol0002" compact="compact" ol-style=""><li>1. Polyamide has no dimensional stability in conditions of high humidity. This means that it may potentially create problems to stabilize the length and width of bags exposed to the atmosphere.</li><li>2. Shrinkability of polyamide is low.</li></ol>

0011These problems are overcome by the subject-matter of the independent claims. Preferred embodiments are set forth in the dependent claims.

0012The inventors have managed to overcome all of these problems by discovering a film combining <ol id="ol0003" compact="compact" ol-style=""><li>1. Excellent overlapping sealability</li><li>2. Excellent sealing properties over a big range of machine conditions.</li><li>3. Excellent optical properties</li><li>4. Manufacturing in a stable and controlled way.</li><li>5. High heat shrinkability</li></ol>

0013This is achieved by a heat shrinkable film which incorporates an outer layer from polyester elastomer and a core layer comprising EVOH and/or PVDC.

Definitions:

0014In this application the following definitions are used: <ul id="ul0002" list-style="none"><li>The term "film" refers to a flat or tubular flexible structure of thermoplastic material.</li><li>The term "heat shrinkable" refers to a film that shrinks at least 10% in at least one of the longitudinal and transverse directions when heated at 90°C for 4 seconds. The shrinkability is measured according to ASTM 2732.</li><li>The phrase "longitudinal direction" or " machine direction" herein abbreviated " MD" refers to a direction along the length of the film.</li><li>The phrase "outer layer" refers to the film layer which comes in immediate contact with the outside environment (atmosphere).</li><li>The phrase "inner layer" refers to the film layer that comes in direct contact with the product packed. This is also called "sealing layer" as this layer must be hermetically sealed in order to protect the product from ingress of air.</li><li>The phrase "core layer" refers to all film layers that exist between the outer and inner film layers.</li><li>The phrase "adjacent layer" refers to a layer which is to bond the outer layer to the core barrier layer. The adjacent layer preferably comprises maleic anhydrite modified polyolefin or other polyolefinic tie layer.</li></ul>

0015As used herein, the term "homopolymer" refers to a polymer resulting from polymerization of a single monomer.

0016As used herein, the term "copolymer" refers to a polymer resulting from polymerization of at least two different polymers.

0017As used herein, the term "polymer" includes both above types.

0018As used herein the term "polyethylene" identifies polymers consisting essentially of the ethylene repeating unit. The ones that have a density more than 0.940 are called high density polyethylene (HDPE), the ones that are have less than 0.940 are low density polyethylene (LDPE).

0019As used herein the phrase "ethylene alpha olefin copolymer" refers to polymers like linear low density polyethylene (LLDPE), medium density polyethylene (MDPE), very low density polyethylene (VLDPE), ultra low density polyethylene (ULDPE), metallocene catalysed polymers and polyethylene plastomers and elastomers.

0020As used herein the phrase "styrene polymers" refers to styrene homopolymer such as polystyrene and to styrene copolymers such as styrene-butadiene copolymers, styrene-butadiene-styrene copolymers, styrene-isoprene-styrene copolymers, styrene-ethylene-butadiene-styrene copolymers, ethylene-styrene copolymers and the like.

0021As used herein the phrase "ethylene methacrylate copolymers" refers to copolymers of ethylene and methacrylate monomer. The monomer content is less than 40%.

0022As used herein the phrase "ethylene vinyl acetate copolymer" refer to copolymers of ethylene and vinyl acetate.

0023As used herein, the term EVOH refers to saponified products of ethylene vinyl ester copolymers. The ethylene content is typically in the range of 25 to 50%.

0024As used herein the term PVDC refers to a vinylidene chloride copolymer wherein a major amount of the copolymer comprises vinylidene chloride and a minor amount of the copolymer comprises one or more monomers such as vinyl chloride and/or alkyl acrylates and methacrylates. Usually the PVDC copolymer may comprise heat stabilizers and plasticizers as is well known in the art.

0025As used herein the term polyamide refers to homopolymers and copolymers.

0026As used herein the term "polyester elastomer" refers to block copolymers where hard and soft blocks exist in the chain of the polymer. Examples of this kind of polymers are polyester ether and polyester ester copolymers, such as ARNITEL^® from DSM, HYTREL^® from Dupont and RITEFLEX^® from TICONA.

0027All measurement methods mentioned herein are readily available for the skilled person. For example, they can be obtained from the American National Standards Institute at: <u style="single">www.webstore.ansi.org</u>

DETAILED DESCRIPTION OF THE INVENTION

0028According to a first aspect the present invention is directed to a heat shrinkable film having a shrinkage of at least 10% measured according to ASTM 2732 in water at 90°C in at least one of MD, TD directions, where the film comprises an outer layer of comprising polyester elastomer and a core layer comprising EVOH and/or PVDC.

0029A preferable resin for the outer layer according to the invention is a polyester elastomer, preferably a polyester ether elastomer. The melting point of this material is preferably 190°C to 220°C. A blend of this polymer with a non elastomeric copolyester (eg polybutylene terephthalate) is also beneficial.

0030The adjacent layer comprises preferably maleic anhydrite modified polyolefin or other polyolefinic tie layer. The purpose of this layer is to bond the outer layer to the core barrier layer.

0031The adjacent layer comprises an oxygen barrier material selected from EVOH and PVDC. PVDC is preferable for higher shrinkability.

0032In the case of EVOH, a minor proportion of special polyamide can be used to increase the flexibility of EVOH.

0033Between the sealing layer and the oxygen barrier layer, a tie layer could be used. Preferred materials for this tie layer may be ethylene ester copolymers, such as ethylene vinyl acetate copolymers, ethylene methyl acrylate copolymers and other materials well known in the art. A preferred version might include maleic anhydrite modified ethylene ester copolymers or maleic anhydrite modified LLDPE. Commercial trademarks are for example BYNEL from Dupont and ADMER from Mitsui.

0034The inner heat sealing layer of the film may comprise ethylene alpha olefin copolymers and/or ethylene propylene copolymers or terpolymers. Typical examples are the homogeneous polymers AFFINITY^® (DOW), EXACT^® (EXXON), TAFMER^® (MITSUI), Ethylene vinyl acetate copolymers and other well known in the art sealing layer polymers.

0035Between the outer and the barrier layer there may be another layer incorporating a tie layer. Preferred materials for this tie layer may be ethylene ester copolymers, such as ethylene vinyl acetate copolymers, ethylene methyl acrylate copolymers and other materials well known in the art. A preferred version might include maleic anhydrite modified ethylene ester copolymers or maleic anhydrite modified LLDPE. Commercial trademarks are for example BYNEL from Dupont and ADMER from Mitsui.

0036Any of the layers described above may also include additives well known in the art such as slip agents, antiblock, polymer processing aids, antistatic, antifog, acid scavengers, odour scavengers and the like. A person skilled in the art may select the right additives according to any particular needs.

0037In a preferred embodiment, the heat shrinkable film is irradiated after the extrusion. E beam is a recommendable process to crosslink the structure and increase mechanical properties.

0038In a further aspect, the invention is directed to the use of the films or the bag or pouch of the invention for packaging food and a method for packaging a food item. For example, the food item is putted inside the bag and the air is removed (vacuumising) with the help of a vacuum device. Subsequently, the open end of the bag is sealed and the vacuum pack is placed in a heat shrinking media such as hot water under a temperature that ensures the shrink of the pack (eg 90°C). The pack than is ready and is characterized by appealing appearance and long shelf life because of the absence of oxygen.

0039The present invention is now described by the following Examples:

EXAMPLE 1

0040A 5 layer film is produced in a double bubble commercial line with the following recipe Inner (sealing layer), 32% P1+ 30% P2+ 20% E1+ 10% E2+ 8% ADDITIVES

0041The percentage is in wt% unless otherwise indicated. <tables id="tabl0001" num="0001"><table frame="none"><tgroup cols="2" colsep="0" rowsep="0"><colspec colnum="1" colname="col1" colwidth="25mm" /><colspec colnum="2" colname="col2" colwidth="39mm" /><tbody><row><entry>Adjacent layer</entry><entry>D1</entry></row><row><entry>Barrier layer</entry><entry>PVDC commercial grade</entry></row><row><entry>Adjacent layer</entry><entry>D2</entry></row><row><entry>Outer layer</entry><entry>PEE1</entry></row></tbody></tgroup></table></tables> See table 1

0042The thickness of the structure is 26/ 7/ 7/ 7/ 8 starting from the inner and going to the outer layer.

EXAMPLE 2

0043A 5 layer film is produced in a double bubble commercial line with the following recipe Inner(sealing layer), 32% P1+ 30% P2+ 20% E1+ 10% E2+ 8% ADDITIVES <tables id="tabl0002" num="0002"><table frame="none"><tgroup cols="2" colsep="0" rowsep="0"><colspec colnum="1" colname="col1" colwidth="25mm" /><colspec colnum="2" colname="col2" colwidth="44mm" /><tbody><row><entry>Adjacent layer</entry><entry>D1</entry></row><row><entry>Barrier layer</entry><entry>EVOH 44% ethylene content</entry></row><row><entry>Adjacent layer</entry><entry>D2</entry></row><row><entry>Outer layer</entry><entry>PEE1</entry></row></tbody></tgroup></table></tables> See table 1

0044The thickness of the structure is 26/ 7/ 7/ 7/ 8 starting from the inner and going to the outer layer. <tables id="tabl0003" num="0003"><table frame="all"><title>TABLE 1</title><tgroup cols="6"><colspec colnum="1" colname="col1" colwidth="14mm" /><colspec colnum="2" colname="col2" colwidth="25mm" /><colspec colnum="3" colname="col3" colwidth="35mm" /><colspec colnum="4" colname="col4" colwidth="33mm" /><colspec colnum="5" colname="col5" colwidth="25mm" /><colspec colnum="6" colname="col6" colwidth="28mm" /><thead><row><entry valign="top">Type</entry><entry valign="top">Description</entry><entry valign="top">Manufacturer</entry><entry valign="top">Melt Index g/10 min</entry><entry valign="top">Density g/cm³</entry><entry valign="top">Melting point ° C.</entry></row></thead><tbody><row><entry>E1</entry><entry>EVA</entry><entry>Dupont 3135 X</entry><entry>0.35</entry><entry>0.93</entry><entry>95</entry></row><row><entry>E2</entry><entry>EVA</entry><entry>1005 VN2</entry><entry>0.40</entry><entry>0.928</entry><entry>102</entry></row><row rowsep="0"><entry>D1</entry><entry>MODIFIED</entry><entry>MITSUI ADMER 518</entry><entry>3</entry><entry>0.91</entry><entry /></row><row><entry /><entry>LLDPE</entry><entry /><entry /><entry /><entry /></row><row><entry>P1</entry><entry>Plastomer</entry><entry>Dow Affinity VP 8770</entry><entry>1.0</entry><entry>0.885</entry><entry>74</entry></row><row rowsep="0"><entry>PEE1</entry><entry>POLYESTER</entry><entry>ARNITEL EM 630</entry><entry>7 at 230C</entry><entry>1.25</entry><entry>213</entry></row><row><entry /><entry>ELASTOMER</entry><entry /><entry /><entry /><entry /></row><row rowsep="0"><entry>D2</entry><entry>EVA</entry><entry>BYNEL 3861</entry><entry /><entry /><entry /></row><row><entry /><entry>MODIFIED</entry><entry /><entry /><entry /><entry /></row><row rowsep="0"><entry>P2</entry><entry>PLASTOMER</entry><entry>DOW AFFINITY PL</entry><entry>1.0</entry><entry>0.902</entry><entry>100</entry></row><row><entry /><entry /><entry>1880</entry><entry /><entry /><entry /></row></tbody></tgroup></table></tables>

Tests

0045<ol id="ol0004" ol-style=""><li>1. Haze measurement. The haze measurement was done according to ASTM D 1003.</li><li>2. Gloss measurement. This was done according to BS 2782.</li><li>3. Shrinkage measurement done according to ASTM 2732.</li><li>4. Sealing window.</li></ol>

0046This final test was done on a Bosch vacuum sealing machine. We put one piece of the tube of each material on another so that there is an overlap area. We seal this area and then we pull. The material is thought to be OK if the outer surfaces are easily pulled without any delamination or resistance and the inner(sealing layers) are at the same time strongly sealed. Different sealing times were applied in order to see which of the three materials has a more extended operating window.

0047The results are displayed on table 2 <tables id="tabl0004" num="0004"><table frame="all"><title>TABLE 2</title><tgroup cols="5"><colspec colnum="1" colname="col1" colwidth="23mm" /><colspec colnum="2" colname="col2" colwidth="14mm" /><colspec colnum="3" colname="col3" colwidth="16mm" /><colspec colnum="4" colname="col4" colwidth="36mm" /><colspec colnum="5" colname="col5" colwidth="60mm" /><thead><row><entry align="center" valign="top" /><entry align="center" valign="top">HAZE</entry><entry align="center" valign="top">GLOSS</entry><entry align="center" valign="top">SHRINKAGE(MDITD)</entry><entry align="center" valign="top">STACK SEAL WINDOW (sealing times)</entry></row></thead><tbody><row><entry align="center">Material 1</entry><entry align="center">6</entry><entry align="center">93</entry><entry align="center">52/40</entry><entry align="center">4-10</entry></row><row><entry align="center">Material 2</entry><entry align="center">7</entry><entry align="center">98</entry><entry align="center">42/41</entry><entry align="center">4-10</entry></row><row><entry align="center">Comparison</entry><entry align="center">10</entry><entry align="center">95</entry><entry align="center">35/42</entry><entry align="center">4-10</entry></row></tbody></tgroup></table></tables>

0048So, the materials have the same stack sealable operating window and they combine much improved shrinkage properties as well as excellent optics in the case of material 1,2.