The present invention relates to printed oxygen-barrier nylon films and particularly to printed oxygen-barrier nylon films having a solvent-barrier coating of polyvinylidene chloride.
It is common practice to package articles such as food products in multilayer films or laminates to protect the packaged product from abuse and exterior contamination. The multilayer films or laminates provide convenient and durable packages for transportation and ultimate sale to the end user. It is usual to include printed indicia like decorations and text on packaging films. Printed thermoplastic films for use in food packaging applications are well known. Generally, printed images are applied to the non-food outside layer of the packaging film (i.e., the side of the film opposite the food contact side) utilizing printing techniques that are known in the art. Such printing techniques include gravure, rotary screen, or flexographic techniques. Ink systems for forming the printed image or wording on packaging films are also known in the art. Standard or conventional ink systems typically include pigments carried in a resin solubilized in a carrier solvent. Typical carrier solvents for the resins include hydrocarbon solvents, such as alcohols, acetates, aliphatic hydrocarbons, aromatic hydrocarbons, and ketones.
In gravure printing, for example, the printing surface is typically a rotating cylinder, frequently a copper cylinder, which rotates in a bath of the ink to pick up the ink in the engraved elements of the cylinder. Excess ink is removed from the roller by a blade and the roller then comes into contact with the packaging film to be printed. The image is thereby transferred to the film, which then passes into an oven where the ink solvent is vaporized so that the ink is dried and a secure print image remains on the substrate. A typical gravure ink may include from 40% to 60% by weight of solvent, based on the total weight of the ink formulation.
Spectacular visual effects can often be achieved by printing multiple layers of printing ink and/or covering larger areas of a packaging film. Such complex printing has the advantage of allowing visual depth and spatial effects to be more convincing and realistic. However, some food packaging materials, particularly oxygen-barrier films having a nylon exterior surface, absorb printing solvents into the film structure before they are vaporized. Even small amounts of ink solvent absorbed into packaging film is a particularly difficult problem to resolve since it can slowly permeate through the film and eventually contaminate packaged food. Consequently, it becomes necessary to limit the amount of printing to these packaging materials in order to minimize or eliminate the amount of absorbed solvent.
Therefore, oxygen-barrier food packaging films with a nylon exterior surface having complex printed graphics are highly desired.
The present invention provides an oxygen-barrier food packaging film having a coating on the nylon exterior surface which prevents the absorption of hydrocarbon solvent into the film and provides a surface for printed graphics layer.
In one aspect, the present invention provides an oxygen-barrier food packaging film which is substantially free of organic solvent comprising a multilayer substrate having an exterior surface of nylon; wherein the substrate has an oxygen transmission rate of less than 0.016 cm3/mil/100 in2/24 h at 73° F. and 0% RH (or 0.24 cm3/mil/m224 h at 23° C. and 0% RH). The packaging film comprises a primer coating on the nylon exterior surface layer of the substrate; a polyvinylidene chloride coating overlying the primer coating, and a printed graphics layer covering at least a portion of the polyvinylidene chloride coating.
In another aspect, the present invention provides an oxygen-barrier food packaging film having multiple layers of printing which is substantially free of organic solvent, and comprising a multilayer substrate having an exterior surface of nylon, wherein the substrate has an oxygen transmission rate of less than 0.016 cm3/mil/100 in2/24 h at 73° F. and 0% RH (or 0.24 cm3/mil/m2/24 h at 23° C. and 0% RH). The packaging film comprises a primer coating on the nylon exterior surface layer of the substrate; a polyvinylidene chloride coating overlying the primer coating, a printed graphics layer covering at least a portion of the polyvinylidene chloride coating, and an over lacquer or varnish covering the printed graphics layer.
The present invention provides a printed oxygen-barrier packaging film substantially free of organic solvent.
As used herein, the phrase “substantially free of organic solvent” means a film having a total retained solvent value of less than 7500 mg/ream as measured in accordance with ASTM F1884-04.
In a specific embodiment, the printed packaging film of the present invention may have a total retained solvent value of between 7500 mg/ream to 5000 mg/ream. In another specific embodiment, the printed packaging film of the present invention may have a total retained solvent value of less than 5000 mg/ream.
Referring to
Once substrate 30 is formed, an aqueous solution of polyurethane based primer 23 is coated onto the nylon exterior surface layer 31. Any number of methods well known in the art may be used to coat layer 31 with primer 23 including, but not limited to, flexographic or rotogravure printing methods. Preferably, primer coat 23 is applied to layer 31 by gravure printing methods. The polyurethane based primer 23 is applied in a thickness from about 0.2 to about 0.5 lbs./ream, and preferably from about 0.3 to 0.4 lbs./ream. After excess water from the primer coat has been removed by passing substrate 30 through a drying oven, a liquid coating of polyvinylidene chloride 22 is then deposited onto the dried primer coating 23 using conventional flexographic or rotogravure printing methods. Excess water from the polyvinylidene chloride coating 22 is removed passing substrate 30 through a drying oven. Substrate 30 is then placed on a printing press where graphics is applied to the surface of the polyvinylidene chloride coating layer 22. Any known printing technique can be used to print a graphics layer 21 including gravure printing, ink jet printing, silk screen printing, flexographic printing, lithographic printing, electrophotographic printing, intaglio printing, tampo printing, pad printing, letter press printing, etc., preferably gravure or flexographic printing, and more preferably, flexographic printing methods. Any solvent-based printing ink that that has previously been used for printing graphics on flexible food packaging films can be used for forming the printed graphics such as images and/or indicia of the inventive food packaging film. A particular advantage of this invention is that amount of ink and/or number of ink layers need not be limited since polyvinylidene chloride 22 acts as a barrier to ink solvents. As a result, multiple layers of ink can be used to improve the visual depth and spatial effects of the printed graphics. After each layer of ink is applied, it is dried before the next layer of ink is applied. After the final layer of ink is applied and dried, an overprint varnish may be applied to the exterior surface of printed graphics layer 21 if desired.
Overcoat or overprint varnish 24 may be applied to the printed side of the substrate 30, preferably covering the printed graphics layer 21 of the substrate. The overprint varnish 24 may enhance the print or perform a desired result, such as increasing the resistance performance of the print, as is known in the art. Preferably, the overprint varnish is transparent. The overprint varnish is applied in a thickness effective to provide the desired scratch resistance (during film handling and processing) and/or chemical resistance (e.g., to fatty acids, oils, processing aids). However, the overprint varnish thickness should be thin enough not to restrict the film substrate from shrinking or flexing with the film substrate as required by the desired application. Useful overprint varnish thicknesses include from about 0.004 to 0.50 mils (about 0.1 to about 12 μm) preferably from about 0.02 to 0.40 mils (0.5 to about 10 μm), more preferably from about 0.04 to 0.32 mils (1.0 to about 8 μm), and most preferably from about 0.06 to 0.20 mils (1.5 to about 5 μm).
The total thickness of a representative, multilayer substrate used in a printed packaging film of the present invention, as described herein, is generally from about 24.5 μm (1 mil) to about 380 μm (15 mils), typically from about 51 μm (2 mils) to about 150 μm (6 mils), most typically from about 61.3 μm (2.5 mils) to about 98 μm (4 mils).
In accordance with the present invention, the multilayer substrate can be any polymeric substrate with an exterior surface of nylon which has an oxygen transmission rate of less than 0.015 cm3/mil/100 in2/24 h at 73° F. and 0% RH (or 0.25 cm3/mil/m2/24 h at 23° C. and 0% RH). In another embodiment, the substrate may have an oxygen transmission rate of less than 0.008 cm3/mil/100 in2/24 h at 73° F. and 0% RH (or 0.13 cm3/mil/m2/24 h at 23° C. and 0% RH).
The above description and the following examples illustrate certain embodiments of the present invention and are not to be interpreted as limiting. Selection of particular embodiments, combinations thereof, modifications, and adaptations of the various embodiments, conditions and parameters normally encountered in the art will be apparent to those skilled in the art and are deemed to be within the spirit and scope of the present invention.
Specifically, the film had the following structures, from the outer to the inner (sealing or food contact) layer:
Example 1 is one embodiment of a packaging film of the present invention having a structure and layer compositions as described below and as illustrated in
Example 2 is another embodiment of a packaging film of the present invention prepared with a structure and layer compositions as described below and as illustrated in
Example 2 had a thickness of between 74 μm (3.0 mils) to 78 μm (32 mils).
Example 3 is still another embodiment of a packaging film of the present invention prepared with an identical structure as described above for Example 2 and illustrated in
Comparative Example was prepared having a structure and layer compositions as described below and as illustrated in
Comparative Example had a thickness of between 83 μm (3.4 mils) to 88 μm (3.6 mils).
Oxygen Transmission Rate:
Oxygen transmission rate of films of Example 2, Example 3 and Comparative Example were measured according to ASTM D-3985 test method at 73° F. (23° C.) and 0% Relative Humidity (RH). The results are shown in Table 1. Oxygen transmission rate of films of Example 2, Example 3 and Comparative Example were measured according to ASTM D-3985 test method at 73° F. (23° C.) and 85% Relative Humidity (RH). The results are shown in Table 2. All oxygen transmission rates are expressed per thickness (mils) of each sample.
Water Vapor Transmission Rate:
Water vapor transmission rate of the film of Example 2, Example 3 and Comparative Example were measured according to ASTM D-F-1249 test method at 100° F. (38° C.) and 90% Relative Humidity (RH). Results are shown in Table 3. All water vapor transmission rates are expressed per thickness (mils) of each sample.
Residual Solvents:
The residual solvents released from the films of Example 2, Example 3 and Comparative Example were measured in according to ASTM F-1884 test method. Results are shown in Table 4.