Packing material, absorbing oxygen

FIELD: chemistry; packing.

SUBSTANCE: oxygen-absorptive packing material is intended for packing of food products. Material includes solid layer of base from paper, oxygen-absorbing composition, placed on at least one side of base layer and film layer from polypropylene film, placed on oxygen-absorbing layer. Oxygen-absorbing composition includes adhesive emulsion and suspended in it absorbent of oxygen, which contains electrolytically restored iron and salt as electrolyte. One of said base layers and said film layer can have printed letters for provision of information, relating to packed product.

EFFECT: prevention of decomposition, spoiling and oxidation of food products.

13 cl, 12 ex, 1 tbl, 6 dwg

 

The present invention, in General, refers to compositions that absorbs oxygen and, in particular, to compositions, oxygen absorbent according to the present invention.

The prior art of the INVENTION

Many of the products when in contact with oxygen degrade, denature, growth of mold, deterioration, rancid, oxidation or other deterioration. Examples of such products include beer, wine, juice, vinegar, sauces, dressings, cooked food, bread, vegetables, meat products and amongst certain pharmaceutical products and chemical substances. The preservation of such products when there are fungi, bacteria and other organisms that are actively growing in the presence of oxygen, is difficult. These organisms cause decomposition and change in taste or quality of the product. Additionally, some of the products themselves have a tendency to undergo oxidation, which changes the taste or quality of the product. To prevent such oxidation and growth of organisms and, thus, increase the stability during storage of these products, you should remove oxygen from the container in which to store the products.

One of the technological ways to avoid or reduce the oxygen content, is the use of vacuum packaging. This technological method includes vacuo the licensing of the container after loading a product. Another technological method is a filling or replacement of gas. In this case, an inert gas such as nitrogen, to displace air and thus oxygen in the containers. The substitution can be performed before or after the product is loaded into the container.

The standard of the disadvantages associated with the above-described technological methods include the need for large-scale process and the complexity of the removal of oxygen dissolved in the product. Also, in the General case, when these technological methods remains from 0.2% to 5% oxygen in the container. This is the amount of oxygen in the container is sufficient for adverse effects on many products.

A simpler, more effective method of removing oxygen involves placing the container with the product of the oxygen absorbent. For these purposes, use the deposition of the oxygen absorbent resin which is a solid at room temperature. For example, in U.S. patent No. 5143763 described compositions comprising absorbent material, deposited on a resin, such as polyethylene, polypropylene, and, among others, ethylenevinylacetate copolymer. In U.S. patent No. 5089323 described composition comprising an absorbent of oxygen contained in thermoplastic resins, such as branched polyethylene low density is STI, high-density polyethylene, homopolymers of propylene and, among others, ethylene and vinyl acetate copolymers.

In the method of applying the solution by screen printing, however, there are some limitations. In order to print the solution, the stencil must be pressed against the substrate, on which shall be printed the solution. When the stencil is lifted to move to another place of application to the substrate, the surface friction and the viscosity of the solution is such that there is a clear, complete separation of the solution, which was applied on the substrate, and the solution remaining on or before the stencil. This leads to poor quality prints that are hard to control.

Another disadvantage of these methods is that often requires a separate device, such as a sachet or container, which must be placed, for example, in the food or pharmaceutical product. Among others, this leads to the necessity, consisting in the fact that the consumer when opening the packaging is faced with such a device. Additionally, many of such sachets or containers are marked "not for food"that can be interpreted by the consumer as undesirable to mix with food, pharmaceuticals or other consumable products.

The INVENTION

The present invention includes the t in yourself packing material, absorbing the oxygen containing layer of the framework oxygen absorbent composition deposited on at least one side of the layer base, a film layer deposited on the oxygen absorbent layer and printed letters to denote information about the product, who must reside in the packing material. Absorbing the oxygen absorbent composition includes oxygen contained in the emulsion. Imprinting occurs or on one or on both sides of the layer of the substrate and the film layer. Absorbent oxygen composition can be on one or on both sides of the layer basics up until it is covered with a film layer.

It should be understood that subsequent General description and following detailed description are examples of execution of the invention and not intended as exhaustive or limiting.

BRIEF DESCRIPTION of DRAWINGS

The invention is better understood from the subsequent detailed description when considered in conjunction with the attached drawings, on which:

Figure 1 is a top view of a variant example of implementation of the present invention;

Figure 2 is a view in cross section of a variant example of implementation of Figure 1;

Figure 3 is a closeup view of the cross-section marked by circles in figure 2;

F. g is a variant of implementation of the present invention, includes absorbing oxygen map printed text;

Figa is a top view of a coupon according to the present invention;

Fig 5B is a side view of the coupon with Figa; and

6 is a cross section of a variant of implementation of the present invention with the simultaneous perforation on the thin film layer and on the substrate.

DETAILED description of the INVENTION

The present invention provides a combination of packaging material, which may be text or advertising, and the oxygen absorbent composition, due to which the consumer is not aware of the presence of the oxygen absorbent composition. Oxygen scavengers (or "reagents") dispersed in a multicomponent medium, such as emulsions, dispersions or suspensions, or other mixture. In the dispersion of the oxygen scavenger, in such a multicomponent system, the resulting composition can be easily applied at an acceptable substrate and coated with a membrane, permeable to oxygen. On the substrate or the film, one or the other is text, such as instructions for use inside the product, or other text, such as advertising information, which thus combines the properties of absorption of oxygen and functional packaging material. But only flew the t on the packing material can be seen by the consumer, who cannot see an absorbent composition, because it is part of the packaging material and is hidden in it.

Figure 1 shows the preferred implementation, where the packaging tray 100 constructed in accordance with the present invention. Pizza 150 shown elevated from the tray, in order to show the statement 160 on cooking, which were printed on the surface of the top layer of the tray 100. The tray 100 is a multilayer packaging material, which consists of a layer of substrate and oxygen scavenger is covered with a thin, permeable to oxygen layer. Thin permeable to oxygen layer is printed on it, in order to provide the consumer with instructions for cooking pizza. No need for extra oxygen absorbent packing or the material inside the package, and thus, no additional packaging or visible oxygen absorbent package, freely inside the food or pharmaceutical packaging. Indeed, the consumer is not always even suspects that the oxygen scavenger is present inside the package. Figure 2 shows the cross-section of the packaging tray 100, and figure 3 shows the plot of the cross-section of part of the packaging tray 100, marked punchin the th line 200 in figure 2.

As best seen in figure 2, three layers of tray 100 consists of base 310 (preferably paper), absorber 320 oxygen, and a thin film cover layer 330, which is permeable to oxygen. Each of these layers is described in more detail below.

In the embodiment of the invention described above, the basis on which put the oxygen absorbent composition, respectively is a solid paper that can serve as a support structure in a package for a food product, such as frozen pizza or baked product. Thus, the consumer receives the product, placed, as it seems, on a single sheet supporting paper. There is no oxygen absorbent package or other device. On the packaging there is a printed text, which may include a coupon for their next purchase, instructions for warming or cooking or simply promotional materials of similar or other products or services. The text can also be placed on the side of the base, opposite side, which is applied to the oxygen scavenger and a thin film. Thus, the text can be applied as a layer of a thin film, as shown in figure 1, and on the reverse side of the paper backing (not shown) to provide additional advertising on the product packaging.

In another embodiment of the invention, the packaging material can be used on dual-use substances as oxygen scavenger, and a coupon. In the case of using the material as a coupon, or can be used coming off coupon, developed as part of the overall package, or can be used freely located within a larger package coupon. In the first case it is possible to provide a perforation or cut line, to facilitate consumer tearing off coupon from the rest of the package. Figure 4 shows the last alternative implementation, in which free oxygen absorbent coupon 400 included in the package of Figure 1. Of course, if the oxygen absorbent coupon 400 is large enough and, thus, has at least the minimum oxygen absorbent surface, the tray can be any of the numerous non-absorbing oxygen trays in the prior art. At the same time, preferably, the invention provides a triple function - supporting the design, the text and the oxygen scavenger is combined in the packing material, which in the opinion of the consumer has only dual function support with printed information.

The packaging material of the present invention profitably used in the t of the emulsion, which can be easily applied by direct printing on the substrate. Absorbing the oxygen composition of the present invention, due to the oxygen scavenger contained in the emulsion can contain a larger amount of oxygen scavenger and have a better permeability for oxygen, as compared with the known compositions containing solids or solutions containing the reagents. Additionally, the use of emulsions allows to include in the composition of other components, such as hydrogels, which allow the use of the composition under conditions of low humidity.

The emulsion used in the present invention have a viscosity and total solids content sufficient to keep the reactants in a stable emulsion, as well as surface tension and viscosity, which changes when mixing or stirring thixotropic or pseudoplastic-type way. These properties make the emulsion is suitable for printing using, for example, rotary screen printing, reverse roll or printer gravure printing.

Additionally, the emulsion used in the present invention are chemically, biochemically and physically compatible with the reagents, materials of the substrate (on which are compositions and products that protect the from the presence of oxygen. Compatibility with reagents means that the emulsion does not react with any of the reagents or inhibits the reaction of the reactants with oxygen. Compatibility with the substrate material requires that the surface tension of the emulsion was significantly low, and film-forming properties were such that a homogeneous layer can be applied and maintained until the gelatin or drying. Compatible with the protected products requires that the emulsion was suitable for direct contact with food, pharmaceuticals, medical diagnostic tools or other products.

Oxygen scavengers that may be contained in the emulsion used in the present invention include iron and glucoseoxidase. Can be used salt as an electrolyte to oxidize the iron. Iron can be an iron reduced by hydrogen, electrolytic reduced iron or chemically reduced iron. Although iron is preferred as the metal absorbing oxygen agent. Obviously, that can be used other metals. Metals such as example and without limitation, are aluminum, zinc, titanium, magnesium and tin. Also other items that can be used in simple or partially oxide is Noi form are sodium, manganese, iodine, sulfur and phosphorus.

Salt of the electrolyte may be a sodium chloride or any other suitable compatible with food products salt, including, but not limited to, sodium sulfate, potassium chloride, ammonium chloride, ammonium sulfate, calcium chloride, sodium phosphate, calcium phosphate and magnesium phosphate. For non-food products can be used for other non-food salt. And salt, and iron preferably have a particle size from 48 to 325 mesh.

Composition, oxygen absorbent used in the present invention, are intended for use in conditions or low humidity or high humidity. Some packages have a high moisture content. In the case of such packages, composition, oxygen absorbent used in the present invention may contain a desiccant, such as silicagel or zeolite for the activation mechanism for the absorption of oxygen and absorb moisture from the container. Other packaging, such as packaging for preservation of fried foods (e.g. potato chips) have a very low moisture content, and composition, oxygen absorbent may contain carrying moisture material, such as hydrogel, activated carbon or other material to release moisture required for the activation mechanism of absorption Ki is the oxygen.

The following are some of the emulsion, are given as examples that combine the specific requirements outlined above, and are used for the suspension absorbing the oxygen in the reagents. Each of these emulsions has different functional properties and several excellent intended application. These emulsions are purely examples of emulsions, which can be used in the present invention to provide support functions, oxygen scavenger and printed information in the packaging material for consumer looks as providing the only support and printed information.

First, the emulsion system alginate gel is described as a carrier for reagents and, optionally, the hydrogel and the other binding moisture components.

Secondly, it describes the emulsion system xanthan resin. This emulsion can be used for suspension of the reagents and allows the use of alcohol as part of the system. Alcohol use, because it speeds up the drying. In the specified composition can also be used hydrogel.

Thirdly, can be used emulsion system microcrystalline cellulose. This emulsion may also contain alcohol and water, or both. The system is as compatible with the hydrogel, and with the reagents and, optionally, has an extremely low surface tension. Low surface tension makes it possible for clean separation of the composition from the substrate to print from the composition, for example, on a rotary stencil screen printing apparatus during fast "margin"required for high-speed printing, when the printer switches from one print to another printing area. Additionally, microcrystalline cellulose has termozulia feature, which gives the stability of the printed film after drying. The system may also include some amount of xanthan resin to maintain viscosity and pseudoplastic-type characteristics of the stream.

From various emulsion composition with microcrystalline cellulose is the most adapted to maintain a stable suspension of all of the various ingredients, such as iron, hydrogel and salt. The composition is also the most sensitive to salt than other emulsions.

In conclusion, describes three manufactured on an industrial scale adhesive emulsion to the suspension of the reagents that absorbs oxygen. These adhesive emulsions are emulsions of acrylic polymer in a water emulsion of polyvinyl acetate in water and the emulsion is IsolatedStorage copolymer in water.

Emulsions that can be used in the present invention will now be illustrated in more detail by the following examples. However, it should be understood that the scope of the present invention is not limited to these specific examples.

Tests on oxygen uptake in the following examples were carried out in ceramic vessels volume in pint, quart and two quart. The compositions described in the examples were printed on a substrate or by using manual printing when using the net for rotary screen printing, or applied with a gravure No. 24. The composition on the substrate was then placed inside blood vessels, which are then rolled, and measured the oxygen absorbed card. In all examples, with one exception, the vessels also contained water on filter paper attached to the wall of the vessel to supply moisture for the reaction. The only exception was represented by the example of hydrogel, which is itself supplied the water, so there was no need for additional water source. In the tests, which used water on filter paper, typed or printed material that absorbs oxygen, dried at 200°C.

Oxygen was absorbed cards that were different compositions was determined by the analyzer is m oxygen, available from Illinois Instruments, which determined the level of oxygen in each vessel, while the card was in the vessel. In that case, if the test vessel was filled with carbon dioxide, measured the initial oxygen content. The low content of oxygen contained in the vessel, believed the amount of oxygen absorbed by the card. In all examples, the amount of absorbed oxygen was significant.

EXAMPLE 1: EMULSION ALGINATE GEL

To obtain emulsion alginate gel combined the following ingredients in percent by weight:

Sodium alginate (low viscosity)of 2.25%
Polysorbate 801,00%
The sodium propionate0,20%
Distilled water96,55%

To obtain the necessary high shear mixer. In the present example used a mixer brand Kitchen Aid five quart. The ingredients were first dispersible in water, then mixed at low speed for 15 minutes, then mixed at high speed for 15 minutes. Mixing led to the appearance of foam on the emulsion and the inclusion of air into the emulsion. PEFC the mixing took a few hours (during the night in this example) for the destruction of foam and to release entrained air.

One part alginate emulsion described above was then combined with one part 200 mesh electrolytic restored iron containing two percent by weight of sodium chloride, to obtain a composition that absorbs oxygen. The composition was printed on a substrate to obtain a card. Printed composition that absorbs oxygen, dried by heating, but leave enough moisture on the deposited layer, so that no additional source of moisture. The cards were then placed in a ceramic vessels and the rate of their absorption of oxygen was measured in the following way (the variation between the three tests of equal mass printed application was a normal variation when testing):

The speed of absorption of oxygen
No. 1No. 2No. 3
The mass marked imprint per square inch1.50 g1.50 g1.50 g
16 hour13 cm3About214 cm3About2 20 cm3About2
24 hour16 cm3About214 cm3About222 cm3About2
47 hour26 cm3About222 cm3About234 cm3About2
135 h54 cm3About241 cm3About262 cm3About2

In the emulsions of this example used sodium alginate (instead of propylene glycol alginate), because it is soluble and stable at neutral to slightly alkaline pH. Used a variant with low viscosity, since it makes it possible to obtain a higher concentration of alginate in the emulsion without excessively high viscosity. The product used in this example had the trade name Keltrol KNLV, available from Merck & Co., Inc. Although in the above example contained 2.25 percent by weight of sodium alginate, the percentage by weight of sodium alginate may be in the range from 0.2% to 10%, with a preferred range from 0.1% to 3.5%.

In this example, the emulsions as superficial the IDT-active substances used Polysorbate 80 to reduce surface tension. Without surfactant, the emulsion is not marked clearly or remains in the form of a thin film. Because the environment was water, there was a need for a hydrophilic surface-active substance. Polysorbate 80 with hydrophilic-lipophilic balance 14-45 is the most hydrophilic available surfactant food applications. The product used in this example has a trade name Durfax 80 from Van den Berg Foods. Although in the above example contained 1.0 percent by weight of Polysorbate 80, percent by weight of Polysorbate 80 may be in the range from 0.1% to 10%, with a preferred range from 0.5% to 1.5%.

In this emulsion as preservative used sodium propionate, because alginate remain some metabolisme hydrocarbons. In fact, not present simple sugars, yeast and bacteria are not the primary classes of damaging organisms. Need protection from fungi and fungi that can break down complex hydrocarbons. Many of the possible candidates, such as solutes and benzoate derivatives, or have limited solubility at neutral pH, or minimally effective in the form of salts. Used in this example, the sodium propionate is an effective preservative.

This item is the iMER used the ratio of iron to alginate gel 1:1. It can be increased to 2:1. The preferred range of the mass percent of iron in alginate suspension is from 50% to 60%, but may be acceptable in the range from 30% to 80%. Iron may contain by weight from 0.1 to 5% sodium chloride with a preferred range from 1.5% to 2.5%.

For mixing the ingredients of the emulsion in water can be used in a planetary mixer with a wire beater; in the beginning slowly add the alginate gel pellets in the water, so that each grain is moistened separately to avoid aggregation. After this is done, you can add Polysorbate 80. Propionate can, optionally, be added prior to the resin, so that it is easily dissolved.

In an alternative embodiment, the hydrogel can interfere in the emulsion at a content of up to 40 percent by weight when it is ready for printing or coating. The preferred range of percent by weight of the hydrogel ranges from 8% to 18%. The amount of hydrogel to be added to the emulsion depends on the amount of iron in the emulsion. The less iron, the more hydrogel can be added.

You can add two percent by weight of finely ground CaCl2to print the dispersion to cause gelation of alginate. It is anticipated that any compound containing calcium will cause Galero is the W.

As an alternative method of application, the emulsion can first be printed or applied as a coating on a substrate, and then it can be applied compound that absorbs oxygen. After coating or printing in any way, if necessary, the emulsion may be precipitated ion of the divalent metal, such as finely ground powder CaCl2in order to cause gelation of alginate. For these purposes, as a satisfactory alternative can serve as Ca(OH)2.

The emulsion in this example is ready for use, after formed by mixing the foam collapses and goes entrained air. The emulsion remains stable for several weeks at room temperature, although over time the iron can react with water in the emulsion. Increasing the pH of the emulsion may help prevent reaction (applicable for all these songs).

EXAMPLE 2: EMULSION XANTHAN RESIN

To obtain emulsion xanthan resin combined the following ingredients in percent by mass.

Xanthan gum2,0%
Isopropyl alcohol43,0%
Tap water55,0%

Xanthan gum is available in a single degree of purity from Merck under the trade name Keltrol KT. Xanthan gum may be present in the emulsion in amounts of from 0.1 to 5.0 percent by weight, with the preferred range from 0.5% to 1.5%. The manufacturing method of the dispersion was similar to the process method used for alginate emulsion, neat because you add to the water to prevent aggregation.

The components were mixed in a planetary mixer. Xanthan resin one was slowly added to the water. The addition took 5 to 10 minutes in the mixer at medium-low speed mixing. The result is a very heavy suspension resin. Immediately after obtaining a homogeneous dispersion is very slowly added to the alcohol. Once this was done, the suspension was radigales to transparent fluid suspension of the gel (which was stable for several months). Isopropyl alcohol and water can be used in any proportion.

One part of the emulsion xanthan resin was then combined with one part 200 mesh electrolytic restored iron, containing one percent by weight of sodium chloride. The composition was printed on a substrate with various quantities for polucheniya. Printed composition that absorbs oxygen, dried by heating, but leave enough moisture on the deposited layer, so that no additional source of moisture. The card was then placed into a ceramic vessels and the rate of their absorption of oxygen was measured in the following way:

The speed of absorption of oxygen
No. 1No. 2No. 3
The mass marked imprint per square inch2.64 g3.94 g3,05 g
16 hour45 cm3About2150 cm3About258 cm3About2
24 hour57 cm3About2151 cm3About276 cm3About2
48 hours76 cm3About2206 cm3About2120 cm3About2
137 h100 cm3About2222 cm3About2148 cm3About2

In emulsions xanthan resin may contain more iron without deposition than in emulsions of sodium alginate, due to the higher viscosity of the emulsion xanthan resin. Possible compositions of iron in percent by weight in the range from 15% to 80%, with a preferred range from 50% to 70%. Iron may contain from 0.1% to 5% sodium chloride by weight with a preferred range from 0.5% to 1.2%.

Emulsion xanthan resin is suitable, since it is possible to stabilize the reaction components, absorbing the oxygen in the emulsion when used as alcohol and water. This composition was not necessary to add as a surfactant, and a preservative, although one to two percent by weight of Polysorbate 80 may improve the ability to imprinting. In other words, the alcohol acts as a preservative and surfactant. The emulsion can be prepared without alcohol, but in this case it is necessary to use a surfactant and a preservative, which will perform the same function as in alginate emulsion described above. As surfactants and conser the Anta can be used Polysorbate 80 and Na-propionate, respectively.

When the emulsion xanthan resin ready for zapechatyvanie or coating, it can also be added up to 40 percent by weight of the hydrogel. Tests when applied when using desktop stencil showed that may equally well be applied up to 60 percent by weight of 200 mesh iron suspended in the emulsion. The emulsion containing the hydrogel is stable for several hours, whereas emulsion containing 60% iron, is stable for about an hour before the iron begins to precipitate.

Because xanthan gum, in General, is not resistant to salts, the emulsion xanthan resin should be done with a smaller amount of salt, unless you use more resistant to salts xantanovu resin.

EXAMPLE 3: the EMULSION of MICROCRYSTALLINE CELLULOSE

Microcrystalline emulsion was obtained using the following percent by weight:

Microcrystalline cellulose1,8%
Xanthan gum0,2%
Ethanol (95%)44,0%
Water (distilled)54,0%

Used microcrystalline cellulose had the trade name Avicel RC-591. For dispersion of the components used planetary mixer with a wire beater. First combined water and alcohol. Then the microcrystalline cellulose is completely moistened with careful adding in a mixture of water/alcohol. Then add xanthan resin to increase viscosity. Hydration of the mixture took several hours. After the initial mixture was obtained and was mixed for about 15 minutes, the mixture was stirred for 2-3 minutes every 15 minutes during the next two hours. This mixture was then stable for several weeks.

Two parts of cellulose emulsion was combined with 3.5 parts of 200 mesh electrolytic restored iron, containing one percent by weight of sodium chloride and three percent by weight of sodium diacetate. Sodium diacetate is added to the composition, because iron is more preferable removes oxygen from carbon dioxide than elemental oxygen in the atmosphere of oxygen and dioxide carbon without sodium diacetate. In the presence of sodium diacetate iron reacts with oxygen, not carbon dioxide. Instead of sodium diacetate can be used other acetates and salts of the acids known in the art.

Then the status is in printed on a substrate in varying amounts to obtain cards. The cards were then placed in a ceramic vessels that were filled with carbon dioxide to lower the oxygen content and the simulation container filled with gas, and the speed of their absorption of oxygen was measured in the following way:

The speed of absorption of oxygen
No. 1No. 2No. 3
The mass marked imprint per square inch1, 80 g1.29 g1.12 g
17 h19 cm3About29,9 cm3About213 cm3About2
25th hour20 cm3About212 cm3About214 cm3About2
49 h35 cm3About225 cm3About230 cm3About2
137 h137 cm3About2 82 cm3About264 cm3About2

Then the two parts of cellulose emulsion described above was combined with one part 200 mesh electrolytic restored iron containing two percent by weight of sodium chloride and 0.6 parts of the hydrogel. The composition was printed on a substrate in varying amounts to obtain cards. The cards were then placed in a ceramic vessels and the rate of their absorption of oxygen was measured in the following way:

121 cm3About2
The speed of absorption of oxygen
No. 1No. 2No. 3
The mass marked imprint per square inch3,53 g3,39 gof 3.60 g
18 h46 cm3About251 cm3About248 cm3About2
39 hours111 cm3About291 cm3About2100 cm3About2
47 hour96 cm3About2120 cm3About2
75 hour134 cm3About2122 cm3About2130 cm3About2
160 hour135 cm3About2125 cm3About2130 cm3About2

One part of cellulose emulsion described above was then combined with one part 200 mesh electrolytic restored iron containing two percent by weight of sodium chloride. The composition was printed on a substrate in varying amounts to obtain cards. The cards were then placed in a ceramic vessels and the rate of their absorption of oxygen was measured in the following way:

td align="left"> 23 h
The speed of absorption of oxygen
No. 1No. 2No. 3
The mass marked imprint per square inch3,01 g2,46 gto 2.29 g
47 cm3About287 cm3About296 cm3About2
44 hour74 cm3About2173 cm3About2195 cm3About2
52 hours83 cm3About2200 cm3About2214 cm3About2
75 hour118 cm3About2271 cm3About2275 cm3About2
159 h126 cm3About2345 cm3About2339 cm3About2

The advantage of microcrystalline cellulose is that it is as resistant to alcohol, and salts. As in emulsion using alcohol, there is also no need to use surfactants or preservatives. The alcohol serves both purposes.

The choice of the alcohol used in the emulsions is limited solely by the requirement of contact of the total composition with food. Greatly is part of the alcohol is lost during drying, however, there remains a certain amount of alcohol that can be transferred to the protected product. In the case of some products, it may prevent the use of alcohol as a solvent. In such cases it will be necessary to add surfactants and preservatives. Will be acceptable surfactants and preservatives used in the case of alginate composition. To this emulsion will need a longer drying.

The emulsion of microcrystalline cellulose allows to obtain particularly stable suspension of hydrogel or iron. The content of the hydrogel in the emulsion to 40% by weight will remain in suspension almost indefinitely. Emulsion 60% by weight of iron will remain suspended for several days. Additionally, the viscosity and surface tension of microcrystalline cellulose are such that application of a rotary screen printing is the best at high speeds.

The range of percent by weight of microcrystalline cellulose, which can be used is from 0.2% to 7.0%. The preferred range is from 0.9% to 2.7%. The range of percent by weight xanthan resin is from 0.1% to 4.0% with a preferred range from 0.1% to 0.5%. Can use any ratio of ethanol is water. The range of percent by mass of iron, which can be added to the emulsion of microcrystalline cellulose, from 10% to 80% with the preferred range from 40% to 60%. The percentage by mass of sodium chloride in the gland may be from 0.1% to 5.0% with a preferred range from 0.8% to 1.5%. The percentage by weight of sodium diacetate in the gland may be from 0.1% to 30% with the preferred range from 2.0% to 5.0%. The hydrogel can be added to the microcrystalline emulsion in percent by weight in the range from 1% to 40%, with a preferred range from 8% to 18%.

Printed composition that absorbs oxygen, dried by heating, but leave enough moisture on the deposited layer, so that no additional source of moisture. If the coating that absorbs oxygen, or imprint dried to dryness, then you need a source of moisture to initiate the oxidation of iron to cause the absorption of oxygen. Moisture is normally supplied food product, which is Packed oxygen absorber. In the case of dry food, oxygen scavenger requires its own source of moisture. This can be achieved due to incomplete drying of the coating. You can also add the hydrogel to the emulsion before coating, but even in this case, the coating should not be dried to dryness to pokrytiemdo to put their own moisture.

During storage of the material that absorbs oxygen, can form hydrogen, because in the absence of oxygen, the iron will react with water, with the formation of iron oxides and hydrogen. To prevent this, the pH of the coating or emulsion should be increased to values in excess of 9.0 when using Foundation. The preferred bases are the hydroxides, such as sodium hydroxide or potassium hydroxide. Can be used only compatible alkaline materials.

In the above-described tests with dried coatings water-rich piece of filter paper size of two square inch were placed in a ceramic vessel as a source of moisture. If the floor or used the hydrogel remained water, the water in the filter paper is not used.

EXAMPLE 4: EMULSION ACRYLIC POLYMER

Used in water emulsion of acrylic resin was a resin grade Neocryl A-5117 from Zeneca Resins. A composition comprising 50 percent by weight of the specified acrylic emulsion and 50 percent by weight iron mixture containing 200 mesh electrolytic restored iron containing 2 percent by weight of sodium chloride, was printed on a polypropylene substrate size eight square inches and dried by heating. The weight of the imprint was 0,0135 g/inch2. Map which was homesale in ceramic vessel with water-saturated slice filter paper sizes two square inches. The rate of oxygen uptake was measured as follows:

The speed of absorption of oxygen
No. 1No. 2No. 3Average
48 hours13 cm3About216 cm3About215 cm3About215 cm3About2
114 hour13 cm3About218 cm3About215 cm3About215 cm3About2

Then 2.5 pound emulsion brand Neocryl A-5117 combined with 6,88 pounds of iron (iron was obtained from SCM Corporation under the SCM labeling A-220) with two percent by weight of NaCl and 40 g of water. This composition, which had a viscosity of 2700 CP, was applied to a polypropylene film which is oriented in two mutually perpendicular directions, using a gravure cylinder No. 24. The coating composition weight 0,0523 g/inch2(containing 86.5 per cent by weight of iron) was applied to the total weight of the film 0,0725 g/inch 2.

Applied as a coating film was heated to dryness and a piece of filter paper the size of two square inches, saturated with water, were placed in a ceramic vessel with a film that absorbs oxygen, so that it acted as a source of moisture. Mentioned applied film has absorbed 11,4 cm3About2/in2during 39-44 hours.

Then 2.8 lb Neocryl A-5117 was combined with 5.0 pounds of iron SCM A-220 with two percent by weight of NaCl and 34 g of gasifier brand Celagen (pair-toluensulfonate). The blowing agent causes the formation of very small bubbles within the coating, which increase the permeability of the coating to oxygen. The coating weight 0,0742 g/inch2(80.6% by weight of iron) of the said composition, which had a viscosity 1410 CP, then was applied to a polypropylene film as described above, to the total mass of the film 0,0943 g/inch2. Mentioned applied film has absorbed 9.8 cm3About2/in2during 39-44 hours.

In acrylic emulsion range percent by weight acrylic polymer stamps Neocryl A-5117 can be from 15% to 90% with a preferred range from 25% to 35%. The iron used in the emulsion may range in percent by weight from 10% to 85% with a preferred range from 65% to 75%. Iron can combine with chloride of soda which I, in percent by weight from 0.1% to 5.0% with a preferred range of sodium chloride from 1.5% to 2.5%.

The ratio of acrylic emulsion and iron also depends on the used acrylic emulsion and a given viscosity. Water is added to adjust the viscosity, which in turn increases the iron content. These ranges will be different for other acrylic emulsions. This is common to all these emulsions.

EXAMPLE 5: polyvinyl acetate EMULSION

Used in water emulsion of the polyvinyl acetate had a brand Vinac XX-210 from Air Products and Chemicals, Inc. Forty-three percent by weight of the emulsion of polyvinyl acetate was combined with 57 percent by weight iron mixture containing 200 mesh electrolytic restored iron containing 2 percent by weight of sodium chloride. The composition was then printed on a polypropylene substrate size eight square inches of mass fingerprint was 0.026 g/inch2. The map was placed in a ceramic vessel and the rate of oxygen uptake was measured as follows:

The speed of absorption of oxygen
No. 1No. 2No. 3Average
48 hours2 cm 3About222 cm3About222 cm3About222 cm3About2
114 hour25 cm3About225 cm3About225 cm3About225 cm3About2

Then 2.0 lb emulsion brand Vinac XX-210 combined with 2.67 lb iron SCM A-220 and two percent by weight of NaCl. This composition was applied to a polypropylene film which is oriented in two mutually perpendicular directions, using a gravure cylinder No. 24. The coating composition weight 0,034 g/inch2(containing 70.8 percent by weight of iron) was applied to the total mass of the film 0,054 g/inch2. Applied as a coating film was dried to dryness by heating. When the test sample in a ceramic vessel, ceramic vessel was placed a filter paper saturated with water so that it acted as a source of moisture. Mentioned applied film has absorbed 4,6 cm3About2/in2during 39-44 hours.

The range of percent by weight of polyvinyl acetate brand Vinac XX-210 can be from 15% to 90% with a preferred range from 40% to 50%. Iron can be added to procentage weight from 10% to 85% with a preferred range from 50% to 60%. The percentage by mass of sodium chloride in the gland may be 0.1% to 5.0% with a preferred range from 1.5% to 2.5%.

You can add water to adjust the viscosity, and thus, to increase the iron content. The ratio of iron to polivinilatsetatnoj emulsion may be different for other polyvinyl acetate emulsions.

EXAMPLE 6: EMULSION VINYLACETYLENE COPOLYMER

Used in water emulsion vinylacetate copolymer had the trademark Airflex 440 from Air Products and Chemicals, Inc. the Composition of 70% by weight of the specified emulsion vinylacetylene copolymer was combined with 30 percent by weight iron mixture containing 200 mesh electrolytic restored iron containing 2 percent by weight of sodium chloride, and was printed on a polypropylene substrate size eight square inches with a mass fingerprint of 0.015 g/inch2. The map was placed in a ceramic vessel and the rate of oxygen uptake was measured as follows:

The speed of absorption of oxygen
No. 1No. 2No. 3Average
48 hour 11 cm3About210 cm3About28 cm3About210 cm3About2
114 hour12 cm3About210 cm3About210 cm3About211 cm3About2

Applied as a coating film was dried to dryness by heating. When the test sample in a ceramic vessel, ceramic vessel was placed a filter paper saturated with water so that it acted as a source of moisture.

Then received another emulsion when using the brand Airflex 400 instead of the trademark Airflex 440. In the specified example, 3.88 lb emulsion trademark Airflex 400 combined with 5.25 pound iron SCM A-220 with two percent by weight of NaCl and 300 grams of water. This composition, which had a viscosity 4550 CP, was applied to a polypropylene film which is oriented in two mutually perpendicular directions, using a gravure cylinder No. 24. The coating composition weight 0,0423 g/inch2(containing 71.1% by weight of iron) was applied to the total mass of the film, 0.0625 g/inch2. Applied as a coating film was dried to dryness by heating. When tested the samples and in a ceramic vessel, in the ceramic vessel was placed a filter paper saturated with water so that it acted as a source of moisture. Mentioned applied film has absorbed 3.6 cm3About2/in2during 39-44 hours and 9.9 cm3About2/in2during 306-312 hours.

Then 3.88 lb emulsion trademark Airflex 400 combined with 5,63 pound iron SCM A-220 and two percent by weight of NaCl and 150 grams of water. The coating weight 0,0447 g/inch2(72.7% by weight of iron) of the said composition, which had a viscosity of 2000 centipoise, and then was applied to a polypropylene film as described above, to the total mass of the film 0,0648 g/inch2. Applied as a coating film was dried to dryness by heating. When the test sample in a ceramic vessel, ceramic vessel was placed a filter paper saturated with water so that it acted as a source of moisture. Mentioned applied film to absorb 3.3 cm3About2/in2during 39-44 hours and 11.3 cm3About2/in2during 306-312 hours.

The range of percent by weight of the emulsion trademark Airflex 440 may be from 15% to 99% of the composition, with the preferred range from 65% to 75%. The range of percent by mass of iron that can be added to the composition is from 1.0% to 85% with a preferred range from 25% to 35%. The range of percent by mass of the sodium chloride, which can be used with iron, ranging from 0.1% to 5.0% with a preferred range of sodium chloride from 1.5% to 2.5%.

You can add water to adjust the viscosity and, thus, to increase the iron content. The ratio of iron to emulsion vinylacetylene copolymer may be different for other emulsions vinylacetylene copolymer.

The range of percent by weight of the emulsion trademark Airflex 400 can range from 15% to 99% of the composition, with the preferred range from 35% to 50%. The range of percent by mass of iron that can be added to the composition is from 1.0% to 85% with a preferred range from 50% to 65%. The range of percent by mass of sodium chloride that can be used with iron, ranging from 0.1% to 5.0% with a preferred range of sodium chloride from 1.5% to 2.5%. You can add water to adjust the viscosity and, thus, to increase the iron content.

These suspensions also may be printed or applied to the film and only partially dried by heating, so that was not required source of moisture. Under this option, the specified materials, oxygen absorbent can be used in a dry atmosphere. If the moisture is stored in the oxygen scavenger, pH must be raised to in excess of 9.0, so that during storage of the oxygen scavenger is not obrazovym is the very hydrogen.

Also conducted other experiments to show the effectiveness of the oxygen absorbent emulsions containing less than 10% by weight of oxygen scavenger contained in the emulsion.

EXAMPLE 7

Polypropylene film was coated with the composition of 50.0 grams of acrylic emulsion S.C. Johnson Jonbond 751 and 2.6 grams of SCM A-131 325 mesh iron containing 1.0% sodium chloride. The final dried coating had an iron content of 8.6%, and the coating weight of 0.05 grams per square inch. After 9 days the said coating has absorbed 1,94 cm3oxygen 5 square inches.

EXAMPLE 8

Polypropylene film was coated with the composition of 50.0 grams of acrylic emulsion S.C. Johnson Jonbond 751 and 1.2 grams SCM A-131 325 mesh iron containing 1.0% sodium chloride. The final dried coating had an iron content of 4.2% and the coating weight 0.04 gram per square inch after 6 days. After 9 days the said coating has absorbed 1,94 cm3oxygen 5 square inches.

EXAMPLE 9

Polypropylene film was coated with the composition of 50.0 grams of the emulsion vinylacetylene copolymer Airflex 400 from Air Products & Chemicals and 2.6 grams of SCM A-131 325 mesh iron containing 1.0% sodium chloride. The final dried coating had an iron content of 8.6%, and the coating weight of 0.06 gram per square inch. The said coating has absorbed on average 2,10 cm3oxygen 5 is uadratic inch after 9 days.

EXAMPLE 10

Polypropylene film was coated with the composition of 50.0 grams of the emulsion vinylacetylene copolymer Airflex 400 from Air Products & Chemicals and 1.2 grams SCM A-131 325 mesh iron containing 1.0% sodium chloride. The final dried coating had an iron content of 4.2% and a coating weight of 0.05 grams per square inch. The said coating has absorbed average of 1.46 cm3oxygen 5 square inches after 6 days. After 9 days the said coating has absorbed 3,07 cm3oxygen 5 square inches.

EXAMPLE 11

Polypropylene film was coated with the composition of 50.0 grams of the emulsion of vinyl acetate homopolymer Airflex XX-210 from Air Products & Chemicals and 2.6 grams of SCM And 1-131 325 mesh iron containing 1.0% sodium chloride. The final dried coating had an iron content of 8.6%, and the coating weight of 0.05 grams per square inch. After 9 days the said coating has absorbed 0,81 cm3oxygen 5 square inches.

EXAMPLE 12

Polypropylene film was coated with the composition of 50.0 grams of the emulsion of vinyl acetate homopolymer Airflex XX-210 from Air Products & Chemicals and 1.2 grams SCM A-131 325 mesh iron containing 1.0% sodium chloride. The final dried coating had an iron content of 4.2% and the coating weight of 0.07 grams per square inch. This combination has absorbed on average 0,097 cm3oxygen 5 square inches after 6 days 9 days specified coating has absorbed 2,43 cm 3oxygen 5 square inches.

As discussed above in relation to Figure 3, a thin film cover layer 330 is applied on top of the oxygen absorbent composition 320. Thin film cover layer 330 can be applied by printing or other known technological methods. In the embodiment of the invention, depicted in Figure 5, the thin film cover layer 330 is fixed above oxygen absorbent composition 320 by simultaneously attaching to the oxygen absorbent composition 320 and to the periphery 510 of the substrate 310, where a thin film cover layer 330 and the substrate 310 in direct contact (without located between oxygen absorbent composition 320). It should be understood that it is possible to use additional linking material between the thin film cover layer 330 and the substrate 310 at the periphery 510, where they are in direct contact or, in alternative embodiments, the implementation of the connecting material between the thin film cover layer 330 and the substrate 310, due to their relative physical characteristics, may be sufficient to avoid the need for additional means of attachment.

Thin film cover layer 330 represents permeable to oxygen but not porous polymeric cover the s on top of the oxygen absorbent composition 16. Thin film cover layer 330 is a single layer that forms a film over the oxygen absorbent composition 320. Absorbent oxygen composition 320, as described in more detail above, is a flexible film, which corresponds to a given form of packages of diverse products, with which it can be used. Thin film cover layer 330 should be flexible enough to remain attached to the oxygen absorbent composition 320 regardless of the form, which takes oxygen absorbent composition 320. Thin film cover layer 330 is a thin layer of coating, which is attached to a smooth continuous film, which forms the oxygen absorbent composition 320. There is no need for an intermediate adhesive layer between the oxygen absorbent composition 320 and a thin film cover layer 330.

Under “oxygen permeability” means that the rate of penetration of oxygen through the thin film must be at least 10 cm3/100 inch2/day at 73°F at a relative humidity of 50% and, preferably, exceed 20 cm3/100 inch2/day at 73°F at a relative humidity of 50%, but not be porous with respect to oxygen.

Thin film cover layer 330 prepact the tion is made of a polymer, dispersed in water. Organic solvents generally cannot be used if the purpose of the packaging material is to absorb oxygen in food containers. Polymer dispersion in water is acceptable for contact with food. The solids content of polymer in the aqueous dispersion is in the range from 50 to 100%. After drying the thin film cover layer is a permeable to oxygen, as defined here.

However, despite the fact that the thin film cover layer is made from permeable to oxygen material, as defined here, is the total rate of absorption of oxygen may optionally be controlled by punching or forming small holes, namely, a Microperforation in the thin film cover layer, layer basics, or, and and other. By forming such a Microperforation you can increase the amount of oxygen that can reach the oxygen absorbent composition. Thus, optional education or selective education in the layers surrounding the oxygen absorbent composition of Microperforation of a certain frequency can contribute to the overall performance of the packaging material. An example of Microperforation shown in Fig.6, which is piperacetazine layered packaging material in which Microperforation 600 formed in the main substrate layer and Microperforation 610 shown in thin film cover layer.

A variety of typical polymers suitable for thin film coating layer 330, tested on oxygen absorbent compositions (without a Microperforation). The results of these tests are shown in Table I below. In these examples, the oxygen absorbent composition consisting of 25% acrylic resin and 75% 325 mesh iron powder, mixed with 2% sodium chloride is first applied on a polyester film and then dried. The coating was carried out using the plate cylinder gravure printing, and the final weight of the dry coating was 30.8-36,9 pounds per revolution. Then on the oxygen absorbent composition was applied each of the different polymer top coating listed in Table I, using the 0.3 level of the bar to obtain 0.3 ml coverage. For each composition coating the samples with a size of 5 square inches was placed in a sealed vessel at 100% relative humidity and room temperature. The samples were taken by syringe to measure the oxygen content in the sealed vessel, in order to determine the rate of absorption of oxygen in each of the samples. The results given in table I represent the average of three trials for each sample. All of the specimens were well attached to the oxygen absorbent composition.

Table I
The absorption rate of oxygen samples with different layer film coating (cm3oxygen per square inch)
The solids contentAfter 3 daysAfter 6 daysAfter 10 daysAfter 13 days
Standard (without the coating)9,611,312,413,5
Tyvek (film coating)8,211,513,514,7
Cellulose acetate (film coating)8,810,010,912,1
Airflex 400 (vinylacetate copolymer)55,0%4,8of 5.49,3 11,0
Pierce & Stevens Latiseal A-7734A (ethylene vinyl acetate)44,0%a 4.97,810,510,7
Airflex 300 (vinyl acetate)55,0%5,96,99,1the 10.1
Vinac XX-210 (vinyl acetate Homo-polymer)55,0%3,75,18,19,3
Airflex 421 (acetamidobenzoyl copolymer)52,0%4,25,57,78,7
Vycar 526 (plasticized polymer of vinyl chloride)of 57.5%2,73,65,36,8
Jonbond 751 (Acrylic emulsion)56,0%2,34,26,16,7
llied Signal 316 (oxidized polyethylene homopolymer) 30,0%3,24,4the 5.76,3
Witco W232 (aqueous polyurethane dispersion)29,8%1,93,45,66,2

The amount of oxygen that has been absorbed oxygen absorbent composition in each of the samples listed in Table I, depends on the permeability of the coating layer. Tyvek showed the highest permeability of the presented samples with permeability, gradually decreasing to Witco W232 (aqueous polyurethane dispersion) at end of table I. In accordance with the present invention as a thin film coating layer 330 may also be used other water-soluble polymers known in the art.

The methods and equipment used for printing information on the basis of the film or layer (or both), well-known specialists in this field of technology. Such methods include gravure printing, screen printing, printing with elastic forms or full color printing.

On top of the printed layer can be used an additional optional layer. This layer bude is napechatanny layer. Preferably optional napechatanny layer will be a glossy finish and, most preferably, structured glossy finish so glossy top layer only covers the printed text. The purpose of the top layer will prevent separation of printed text from its background (layer framework layer or film) and also prevent direct contact, used for printing ink and content packaging. Of course, any such printing ink and glossy coating should be a suitable, recognized with compatibility with the intended contents of the package, such as printing inks for food and varnishes for industrial goods or printing ink for pharmacological preparations and lucky for pharmacological drugs, etc. Typical preferred lacquers are polyethylene, urethane and acrylic paints.

In another embodiment the invention, the oxygen absorbent composition is applied on both sides of the substrate, and both sides coated with a thin film cover layer.

Although the present invention is illustrated and described herein with reference to certain specific embodiments of, nevertheless, not intended to be ogranichivat what it presents a detailed description. Rather, the description can be made of various modifications that are within the scope and range of equivalents of the claims, without departing from the scope of the invention.

1. Absorbent oxygen packaging material used for packaging food products containing
the hard layer of the base, made of paper;
absorbent oxygen composition located on at least one side a layer basis, specified oxygen absorbent composition comprises adhesive emulsion and suspended therein an oxygen scavenger containing the electrolytic reduced iron and sodium chloride as the electrolyte;
film layer, located at a specified oxygen absorbent layer and is made of polypropylene film;
at least one of the specified layer framework and a specified film layer has printed letters to represent information relating to the product, which must be contained in the specified packaging material.

2. The packaging material according to claim 1, in which the specified emulsion is an alginate gel in water emulsion.

3. The packaging material according to claim 1, in which the specified emulsion is a xanthan resin in water emulsion.

4. The packaging material according to claim 1, in which the specified emulsion is the Wallpaper microcrystalline cellulose in an aqueous emulsion.

5. The packaging material according to claim 1, in which the specified emulsion is an acrylic polymer in an aqueous emulsion.

6. The packaging material according to claim 1, in which the specified emulsion is a polyvinyl acetate water emulsion.

7. The packaging material according to claim 1, in which the specified emulsion is vinylacetate copolymer in water emulsion.

8. The packaging material according to claim 1, further comprising a hydrogel, suspended in a specified emulsion.

9. The packaging material according to claim 1, further comprising a surfactant in a specified emulsion.

10. The packaging material according to claim 1, further comprising a preservative in the specified emulsion.

11. The packaging material according to claim 1, in which the specified emulsion includes alcohol as a component.

12. The packaging material according to claim 1, wherein said film layer has formed therein a perforation.

13. The packaging material according to claim 1 which includes the printed letters are covered with a glossy top layer.



 

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