A method of manufacturing coloradoboulder layer or products

 

(57) Abstract:

Usage: techniques for manufacturing products that absorb oxygen in the media containing the oxygen-sensitive products, in particular food products and drinks. The inventive kislorodoprovoda layers or articles made from the composition containing oxidizable organic compound and a catalyst based on transition metal, and exposed to irradiation of actinic rays with a wavelength in the range from 200 nm to 750 nm, a dose of at least 0.1 j/g, or e-ray dose of about 0.2 to 20 Mrad. Preferable as the oxidizing organic compounds to use a substituted or unsubstituted ethyleneamines hydrocarbon. Preferably also be included in the composition of the used composition photoinitiator or antioxidant to enhance and/or control kislorodoprovody properties of the film or article. 18 C.p. f-crystals, 12 tab.

The invention relates to a method intended for the manufacture of products that absorb oxygen in the media containing the oxygen-sensitive products, in particular food products and drinks.

It is well known that limitation is R, limiting the influence of oxygen on food packaging, support high quality food and avoid its damage. This package allows you to avoid loss products and, consequently, the need for them to recharge caused by these losses.

The packaging industry is already known several tools to limit oxygen exposure.

Currently, the most commonly used are the ways of modified atmospheric packaging (UIA), vacuum packaging and packaging using film that prevents the penetration of oxygen. In the first two cases in the packaging process employ the technique of reducing the oxygen content, while in the latter creates a physical barrier to the penetration of oxygen into the package.

Another, more modern way of limiting exposure to oxygen, is the introduction of an oxygen scavenger into the packaging structure. Introduction absorber in the package can provide the effect of a uniform absorption through packaging. In addition, this introduction provides the retention and absorption of oxygen as it passes through the walls of the packaging (referred to below as the "barrier layer preventing proniknovenie the R oxygen scavenger introduced into the packaging described in European applications NN 301719 and 380319, and in PCT applications NN 90/00578 and 90/00504 (see also U.S. patent N 5,021,515). The oxygen scavenger described in these sources, consists of a catalyst of a transition metal and polyamide.

Thanks catalytic oxygen polyamide packing material regulates the amount of oxygen penetrating into the inside of the packaging (barrier layer that prevents the penetration of oxygen). However, it was found that the absorption efficiency of oxygen packing material in an amount up to 5 cm3/m2a day at room temperature may not occur during the period of time up to 30 days (see example 10 below). Delay absorption efficiency of oxygen indicated below as the induction period.

In fact, other oxygen scavengers and packaging materials, including such materials may also have an induction period. For example, oxygen scavengers, consisting of catalyst transition metal and Ethylenediamine connection, for example polybutadiene, polyisoprene, digidratirovannogo castor oil, and others, can also have an induction period. These absorbers are described in side the oxygen". If the absorber contains polybutadiene, the induction period may exceed 30 days. Absorbers containing polyisoprene or digidratirovannogo castor oil, characterized by a shorter induction period of about 14 days and one day respectively. Obviously, the duration of induction periods depends on several factors, some of which are not clear or are not controlled.

Accordingly, when using oxygen absorbers with long induction period should withstand oxygen scavengers or layers, absorbing oxygen and products based on them, before their use as absorbents in order to ensure their reliable operation.

On the other hand, the use of absorbers with a shorter induction periods layers and products based on them need to prepare quickly and to use them as soon as possible, sometimes immediately, in order to maximize the effectiveness of them as absorbers. In other words, they should be stored in an atmosphere not containing oxygen, which can be expensive.

One of the methods that can be used to initiate the process of pigloo rubber, that is, CIS-1,4-polyisoprene, and a photosensitive dye on the inner surface of the package and subsequent exposure of this surface in visible light (see Rooney, M. L. "Oxygen Skavenging a Novel Use of Rubber Photo-Oxidation", Chemistry and Industry, March 1982, pp.l97-198).

However, although this method allows you to initiate the process of absorption of oxygen for several minutes, and thereby makes it possible, when required, to start the process of absorption of oxygen, he (method) requires a permanent exhibition of packing light to maintain the absorption effect.

Further, since the method uses a dye, it is difficult to use in areas that require colorless packaging, especially clear and typically colorless packaging for food and beverages.

The objective of the invention is to develop ways of making coloradohomemade layer or products that are effective to control the absorption properties of the oxygen scavenger, by creating the means for initiating the absorption of oxygen when required.

The invention is also creating ways to initiate oxygen absorption in multilayer product containing products, sensitive is the procedure of manufacturing coloradohomemade layer or articles from the composition, containing the polymer and the catalyst based on transition metal, according to this invention as the polymer used oxidizable organic compound, and the resulting layer or the product is subjected to actinic radiation rays with a wavelength in the range from 200 nm to 750 nm, a dose of at least 0.1 j/g or radiation to carry out e-ray dose of about 0.2 to 20 Mrad.

This method can be used for oxygen absorbers in plastic film layer or multi-layer products, especially those that are used for packaging products sensitive to oxygen.

This method can be used in the film production process or the product containing the oxygen scavenger, or for finished products. If the layer or article manufactured for packaging products sensitive to oxygen, the method can be used before, during and after packaging products.

When using this method is especially preferable to apply the composition comprising (a) a substituted or unsubstituted ethyleneamines hydrocarbon and (b) a catalyst based on a transition metal.

It is preferable that the composition contained photoinitiator and/or antseranana (a) and (b), used in any layer, for example in the film, you can also make new products for packaging products sensitive to oxygen. When using these products in conjunction with the method according to this invention can adjust the amount of oxygen, while the product acts as a barrier layer for the active oxygen and/or as a means for the absorption of oxygen inside the product.

The above and other objectives will be apparent from the following description.

The method according to this invention can be used for packaging products that are used in various fields. Product packaging is usually done in a variety of packaging, including rigid containers, flexible packages and combinations thereof, and the like. Typical rigid or semi-rigid products include plastic, paper or cardboard boxes or bottles, for example containers for juice, soft drinks, termoformowanie trays or cups with a wall thickness in the range from 100 to 1000 μm. Typical flexible packages are those that are used for many food and usually have a thickness of from 5 to 250 μm. The walls of these products are made of single-layer or multilayer material.

Spaniagasse components or layers, for example, coatings, gaskets, seals, sticky or non-sticky sheet liners, sealants or fibrous inserts.

Products in these packages can be not only food and beverages, and pharmaceuticals, medical devices, corroding metals or articles, such as electronic devices, etc.

For implementing the method according to the invention using a composition containing oxidizable organic compounds. Such compounds include compounds of carbon containing benzyl, allyl groups and/or atoms of the tertiary carbon (this list does not limit the number of possible connections).

Specific representatives of such compounds are polymers and copolymers of olefins. Examples of such polymers are polyethylene, low density polyethylene, very low density polyethylene and low density, polypropylene, polybutylene, i.e. poly(1-butene), copolymers of propylene, copolymers of butylene, hydrogenated polydiene etc.

Suitable oxidizing compounds are aromatic polyamides, such as poly-m-xylylenediamine. Other suitable polyamides are described in European patent application N 301719.

In the context of this description under ethyleneamines hydrocarbon understand any compound that contains at least one aliphatic carbon-carbon double bond and the carbon and hydrogen is 100% Substituted ethylenediamines hydrocarbon is a compound that contains at least one aliphatic carbon-carbon double bond and about 50-99 wt%. carbon and hydrogen. It is preferable to use a substituted or unsubstituted Ethylenediamine hydrocarbons containing two or more Ethylenediamine groups in the molecule.

The most preferred polymeric compounds containing three or more Ethylenediamine groups and having an average molecular weight equal to or greater than 1000.

Preferred, but not limiting examples of the unsubstituted Ethylenediamine hydrocarbons are diene polymers such as polyisoprene, polybutadiene (especially 1,2-polybutadienes, that is, polybutadienes containing 50% or more of 1,2-units) and their copolymers, such as styrene-butadiene. Such hydrocarbons include polymers of the type polypetala, Polichinelle and other polymers, obtained by the metathesis of olefin, oligodiens, the or other monomers, containing more than one carbon-carbon double bond (paired or unpaired). These hydrocarbons include carotenoids, such as b-carotene.

Preferred substituted Ethylenediamine hydrocarbons are compounds that include oxygen-containing fragments, esters, carboxylic acids, aldehydes, ethers, ketones, alcohols, peroxides, and/or gidroperekisi. Examples of such compounds, without limiting the invention are condensation polymers such as polyesters, based on the monomers containing carbon-carbon double bonds, unsaturated fatty acids, such as oleic, ricinoleic, digidrirovanny ricinoleic and linoleic acids and their derivatives, such as esters. Such hydrocarbons include polymers or copolymers based on (meth)allyl(meth)acrylate.

The composition may also contain a mixture of two or more substituted or unsubstituted Ethylenediamine hydrocarbons described above.

It is also clear that for the absorption of oxygen in packages described above, it is preferable to use Ethylenediamine hydrocarbons, forming solid transparent layers at room temperature. For bolshakovo light.

Particularly preferred transparent layers and packaging, absorbing oxygen, based on 1,2-polybutadiene. These films are, for example, transparency, mechanical and technological properties similar to the properties of polyethylene. In addition, these films retain their transparency and mechanical integrity even after most or all of the amount of oxygen absorbed by these films, and even if the diluent polymer is absent or present in small numbers. Moreover, such films have a relatively high absorption capacity and, as soon as the absorption of oxygen begins, they also exhibit a relatively high rate of absorption of oxygen.

As described above, according to the method according to this invention, are compositions; layers or products that contain catalysts based on transition metal. Not based on any theory, it is preferable to use those catalysts that can easily jump from one oxidized state to another (see Sheldon R. A. Kochi Y. K. Metal-Catalyzed Oxidations of Organic Compounds", Academic Press, New York, 1981).

It is preferable to use the catalyst in the form of a metal salt, selected from the group vkluchu, iron II or III, cobalt II or III, Nickel II or III, Cu 1 or II, Rhodium II, III or IV and EN. It is not necessary that the condition of the metal at the time of introduction of the catalyst was active.

As a metal, preferably iron, Nickel or copper, more preferably manganese, and most preferably cobalt.

Suitable anions for metals are preferred, but not limiting the invention are the chlorides, acetates, stearates, palmitate, 2-ethylhexanoate, neodecanoate or naphthenate. Particularly preferably be used as salts 2-ethylhexanoate, cobalt(II) and neodecanoate cobalt(II). The metal salt can also be ionomers, in this case, as the anion used polymeric anion. Such ionomers are well known in the prior art.

As will be evident from the following, according to the method according to this invention can be initiate oxygen absorption layer or the product made from the composition containing only the oxidizing organic compound and a catalyst based on a transition metal.

However, components such as photoinitiator or antioxidants may be added to further facilitate or teli, you can add to get layers, especially suitable as packaging materials.

For example, it is often preferable to add photoinitiator or a mixture of different photoinitiators to compositions used to prepare oxygen absorbers, if the composition of these songs introduced antioxidants to prevent premature oxidation.

Suitable photoinitiator well known from the prior art. Examples, not limiting the invention are benzophenone, o-methoxybenzophenone, acetophenone, o-methoxyacetophenone, acenaphthenequinone, methyl ethyl ketone, valerophenone, hexanine, a-phenylbutyrate, p-morpholinopropan, dibenzosuberone, 4-morpholinobutyrophenone, benzoin, benzoylmethylene ether, 4-o-morpholinomethyl, p-diacetylbenzene, 4-aminobenzophenone, 4'-methoxyacetophenone, a-tetralone, 9-acetylphenanthrene, 2-acetylphenanthrene, 10-thioxanthene, C-acetylphenanthrene, C-acetylindole, 9-fluorenone, 1-indanone, 1,3,5-treceiver, thioxanthen-9-he, xanthene-9-he, 7-h-Benz[de]anthracene-7-he bestinternational ether, 4,4'bis(dimethylaminobenzophenone), G-acetonaphthone, 2'-acetonaphthone, acetonaphthone and 2,3-butandiol, Benz [a]anthracene-7,12-dione, 2,2-dimethoxy-2-pentarou you can also use kislorodoprovoda photosensitive substance, such as Rose Bengal, methylene blue and tetraphenylporphin. Polymeric initiators include a copolymer of ethylene with carbon monoxide and oligo[2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone] Using photoinitiator preferable, as it usually provides a more rapid and effective initiation. When using actinic radiation, these initiators can also provide initiation for large wavelengths, which is cheaper and less harmful.

As mentioned above, the antioxidants can be used in this invention to control the initiation of absorption.

As an antioxidant according to this invention using any compound which inhibits the oxidative degradation or crosslinking of the polymers. Typically, these antioxidants added to facilitate the processing of polymeric materials and/or prolong their life. In relation to this invention, these additives increase the induction period of the process of absorption of oxygen in the absence of irradiation. Subsequently, when it is necessary to provide the absorbing properties of the layer or article, the last (and any contained photoinitiator) can be subjected to irradiation. For the phenol (BHT). 2,2'-methylenbis(b-tert.-butyl-p-cresol), triphenylphosphite, Tris(nonylphenyl)FOSFA and delayintolerant.

The method according to this invention can be used for layers that absorb oxygen and containing film-forming polymers. These polymers are thermoplastics and make the film more suitable for use as packaging. They can also to some extent to oxidize and thereby serve as part of the oxygen scavenger as oxidized organic compound.

As diluents can be used polyethylene, low density polyethylene, polyethylene, very low and polyethylene, ultralow-density, polyethylene terephthalate (PET), polyvinyl chloride and copolymers of ethylene, such as ethylene-vinyl acetate, alkyl(meth)acrylates, (meth)acrylic acid and ethylene(meth)acrylate ionomers. In the case of hard goods, such as containers for beer, often using PET. You can also use a mixture of different solvents. However, the choice of polymeric diluent largely depends on the type manufactured products and the scope of its use. Factors influencing the choice of diluent, well known from the prior art.

N which may adversely affect such properties, as transparency, purity, effective absorption, permeability, mechanical properties and/or structure of the product.

In layers, absorbing oxygen, you can also enter other additives, including, for example, fillers, pigments, dyes, stabilizers, processing AIDS, plasticizers, flame retardants, additives preventing clouding, etc.

To prepare coloradoguy layers or products necessary components are preferably mixed in the molten state at 50 - 300oC. However, it is possible to carry out the mixing in a solvent followed by evaporation. The mixing can be carried out before formation of the final product, or before preparing masterbatches or intermediate that is then used in the production of final packaging. When the mixture is used for the manufacture of thin film layers or products, it is usually processed by the methods of (co)extrusion, molding from a solution, injection molding, blow molding, extrusion, thermoforming, extrusion coating, coating and curing the layup or combined methods.

Use the s, layers and/or products that absorb oxygen.

Thus, the amount of oxidizing organic compounds, catalysts based on transition metal and any photoinitiator, antioxidant, polymer diluents and additives depend on the type of product and its purpose.

For example, the primary function of oxidizing organic compounds in the oxygen scavenger is an irreversible reaction with oxygen in the process of absorption of oxygen, while the primary function of the catalyst is to accelerate this process. So, to a large extent the amount of oxidizable organic compounds will affect the absorption capacity of the composition, i.e. the amount of oxygen that can be absorbed by the composition. The amount of catalyst will affect the rate of absorption of oxygen. Because it affects the absorption rate, it will also affect the induction period.

The amount of oxidizing organic compounds can range from 1 to 99%, preferably from 10 to 99% by weight of the composition or layer that contains oxidizable organic compound and a catalyst based on transition metal (below called "pahili layers, in which present and oxidizing the compound and the transition metal compound as catalyst).

Usually the amount of catalyst may vary from 0.001 to 1% (10 to 10,000 parts per million (ppm) by weight which people absorb guided component in the calculation only on the metal content (including ligands, anions, and so on). If the amount of catalyst is less than 1% of the principal absorbing component comprises oxidizing an organic compound and a diluent, or additive, i.e. it contains more than 99% of oxidizing organic compounds.

When using photoinitiator, its primary function is to increase and facilitate the initiation of the absorption of oxygen during irradiation. The number of photoinitiator may vary. In many cases, this number will depend on the used oxidizing compounds, wavelength and intensity of irradiation, the nature and quantity of antioxidants, as well as the type of photoinitiator. The number of photoinitiator also depends on how you use absorbent component. For example, if the component containing photoinitiator, placed under the layer that partially opaque to radiation, it may be necessary bol is to be will be in the range from 0.01 to 10% by weight of the entire composition.

The quantity of any antioxidant may be present in the composition will also affect the results. As mentioned previously, such substances are usually present in oxidizing organic compounds or polymers thinners to prevent oxidation and/or gilotinirovaniya polymers. Usually they are contained in an amount of from 0.01 to 1 wt%. However, there may be added an additional amount of antioxidant, if it is desirable to modify the induction period, as described above.

When using one or more polymers, diluents, these polymers can be, in General, to 99% by weight of the absorbing component. The number of any other additives used is usually not more than 10% by weight of the absorbing component, preferably less than 5% by weight of the absorbing component.

Also, the invention provides the use of one coloradohomemade layer or coloradohomemade layer in a multilayered product. A single product can be produced by casting from solution or by extrusion. Layered products are usually manufactured using coextrusion, application of a coating is their penetration of oxygen ("barrier layers"), then there are the layers of material which are characterized by the transmission rate of oxygen equal to or less than 500 cm3/m2a day under normal conditions (temperature about 25oC). Typical barrier layers are composed of a copolymer of ethylene with vinyl alcohol, polyacrylonitrile, polyvinyl chloride, polyvinylidenechloride, polyethylene terephthalate, silicon dioxide and polyamides. You can also use the copolymers of the above compounds and metal foil.

Other additional layers may include one or more layers, permeable to oxygen. In one preferred embodiment, the packaging, usually of flexible packaging for the food, the layers include, in order starting from the outside of the package before lying deep within: (i) a barrier layer for oxygen, (ii) an absorbent layer, that is, an absorbent component, as it is indicated above, and possibly (iii) a layer permeable to oxygen.

The control properties of the barrier layer (i) allows you to adjust the length of the preservation properties of absorption of oxygen packaging by limiting the rate of supply of oxygen to devouring component (ii), thus, limit the rate of disappearance of absorption str the ti absorption of oxygen throughout the structure regardless of the composition of the absorbing component (ii). This can be used to increase the "time of life" films in the presence of air prior to sealing the package.

In addition, the layer (iii) can serve as a barrier to the migration of the individual components in the film or by-products of the process of absorption inside the package. Moreover, the layer (iii) also improves the ability to thermogenetic, transparency, and resistance to adhesion of the multilayer film.

You can use other additional layers, such as adhesive. Compounds commonly used for the adhesive layer include polyolefins with functional anhydrite groups and other well-known adhesives.

When the components are selected and mixed in a certain ratio to obtain the desired coloradohomemade layer or products, the method according to the invention provides the effect on the layer or article irradiation to initiate the absorption of oxygen to the induction period significantly reduced or disappeared. As described above, the induction period is the time period until when the absorbing layer or the product would be useful absorbing properties.

At that time, as the exact mechanism of initiation of popuptitle oxygen is one or more of the following phenomena:

a) a significant decrease in the amount of any antioxidant(s), if any, which promotes oxidation;

b) activation of the catalyst based on transition metal by changing its oxidation state and/or configuration of the ligands increases the effect of a catalyst on the absorption process; or

C) a significant increase in the number of free radicals and/or residual peroxide in the system, despite the inhibiting effect of any antioxidant(s), if he (they) are present or remain in the system.

According to this method using actinic radiation such as ultraviolet or light with a wavelength of about 200-750 nm, preferably 200-400 nm. When using this preferably subjected to irradiation coloradoguy layer or the product dose of at least 0.1 j/, a Typical dose is in the range of 10-100 j/,

You can also use the irradiation of electron rays dose of about 0.2-20 Mrad, preferably about 1-10 Mrad. Other sources of radiation are ionizing radiation, such as gamma rays, x-rays and corona discharge. The effect of the radiation is preferably carried out in the presence of oxygen. The duration of exposure could be the x layers, the amount of any antioxidant, wavelength and intensity of the radiation source.

When using layers or products that absorb oxygen, irradiation carried out during manufacture of the layer or article or thereafter. If the resulting layer or the product should be used for packaging products sensitive to oxygen exposure carried out before, during or after packaging. But in any case, the effects of irradiation prior to use of the layer or article as an oxygen scavenger.

To ensure greater uniformity of radiation exposure should be implemented in the manufacturing process, when the layer or article have the form of a flat sheet.

In order to use the method according to this invention most effectively, it is preferable to determine the characteristics of the absorption of oxygen, for example the speed and performance of the oxygen scavenger. To determine the rate of absorption of oxygen determine the time elapsed until the reduction of oxygen in an airtight container up to a certain limit. In some cases, the speed can be adequately determined by placing Ada environment, for example, air, which typically contains 20.6 percent oxygen by volume. Then after a certain period of time in air samples from the container to determine the number of remaining oxygen. Usually the value of velocity will vary depending on temperature and atmospheric conditions. Speed, below, determined at room temperature and a pressure of 1 ATM, as these conditions are most appropriate to the conditions in which the oxygen scavenger and/or layers or products will be used.

When necessary the barrier layer for the active oxygen, the absorption rate can be so low that is 0.05 cm3oxygen (02) per gram of oxidizable organic compound in the absorbing component in the day when 25oC and a pressure of 1 ATM. However, some compositions, for example containing Ethylenediamine oxidizing organic compounds, characterized by a velocity equal to or greater than 0.5 cm3O2/gden, making them suitable for the absorption of oxygen from the packaging, and also for use as barrier layers for active oxygen. Absorbers containing Ethylenediamine hydrocarbons, capable of providing more than a preference for the s layers, suitable for use as an active barrier layers have a low absorption rate, which is 1 cm3O2/m2day (measured in air at 25oC and a pressure of 1 ATM).

However, layers, including Ethylenediamine hydrocarbons, capable of a speed of absorption exceeding 10 cm3O2/m2day, and can have an absorption rate equal to or exceeding 25 cm3O2/m2day under the same conditions. Such velocities acquisitions allow you to use these layers as to absorb oxygen from the packaging, and as a barrier layer for the active oxygen.

When it is desirable to use the method according to this invention in the fields, using barrier layers for active oxygen-initiated activity oxygen uptake in combination with any barrier layer for oxygen will provide a total bandwidth of oxygen less than 1.0 cm3O2/m2day 25oC and atmospheric pressure. The performance of the oxygen scavenger should be such that it provides a transmission rate of oxygen not exceeding the specified value at least within two days.

" A New Age in Food Preservation Mitsubishi Gas and Chemical Company, Inc. date of publication unknown).

As soon as the process of absorption of oxygen began, coloradoguy layer or a product made with the absorber, must reach the value of its bandwidth (performance) (the amount of oxygen that is capable of absorbing layer or the product prior to the exhaustion of their effectiveness).

In practice, the performance required for a particular application depends on:

1) the amount of oxygen initially present in the package,

2) the permeation rate of oxygen into the package in the absence of absorptive capacity, and

3) the intended shelf life of the package.

When using absorbers containing Ethylenediamine connection performance may be low up to 1 cm3O2/g, but may be at least 50 cm3O2/, If such absorbers are contained in the layer, the performance of such a layer will be at least 250 cm3O2/g thickness, and more preferably at least 1200 cm3O2/g thickness.

For illustration the measures however, in no way limit the invention, but merely illustrate it. The number of components in the examples are given in mass percent. All samples, including the control, non-irradiated, were at room light during testing. I believe that this fact may explain some differences in their properties characterizing its absorptive capacity.

Example 1.

Preparation of masterbatches.

Uterine mixture containing the compound of the transition metal, is prepared by continuously mixing and granulation. In particular, a dry mixture of a copolymer of ethylene with vinyl acetate content of 9% vinyl acetate (EVA-9) and pellets of catalyst neodecanoate cobalt (22.5% of the weight. cobalt grade TEN - CEMProduced by Mooney Chemicals, as catalyst, are placed in the hopper of the twin screw extruder of Brabenderequipped with belt mouthpiece. The catalyst is injected in the amount of 2.3% of the weight. this corresponds to a content of cobalt in masterbatches equal to 5000 parts per million (ppm). The temperature in the extruder 120oC, and the mouthpiece 110oC. the resulting tape is served in a water bath for cooling and then dried using a squeegee air the mix", then used in the compositions described below.

In the same way, prepare the second fallopian mixture containing 10% of photoinitiator-benzophenone (Aldrich) and 5000 ppm TEN-CEMcobalt. This uterine mixture below called "Royal mixture of cobalt with benzophenone".

Example 2.

Izgotovlenie and the test film.

From cobalt masterbatches in example 1 by extrusion is made of a multilayer film. The obtained film is double-layered and has a thickness of about 3 mm, the First layer is made of a copolymer of ethylene with vinyl acetate, and the second (absorbing) layer of 80% of 1,2-polybutadiene (RB830, manufactured by Japan Synthetic Rubber), 10% cobalt masterbatches and 10% of a copolymer of ethylene with carbon monoxide (10% CO) manufactured by Dow Chemical, as photoinitiator. The absorbing layer has a thickness of about 1.5 to 2.0 mm Samples of this film weighing about 5 g each are irradiated and then hermetically closed in a protective package containing 400 cm3air. Then take gas samples (4 cm3of these bags by using gas-tight needle through sticky rubber tape and analyze oxygen analyzer type MOCONmodel LC 700F. The following table summarizes absorbing Alice 1 and in tables in other examples means, what samples did not.

The results below show that the samples of the film obtained in example 1, the irradiated ultraviolet light and electron beams are more effective than the control. The greatest effect of initiation is achieved by the use of high-dose electron irradiation.

Example 3.

Another film was made and tested as in example 2, except that the absorbent layer is made of 90% 1,2-polybutadiene RB830 and 10% masterbatches cobalt with benzophenone as in example 1. Table 2 shows the results of the tests, the type and duration or dose.

The data in table 2 show that the benzophenone used in this film is more effective than a copolymer of ethylene with carbon monoxide (see example 2).

These data also show that for this type of film UV-irradiation is more effective than email.

Example 4.

This sample film also produce and test as in example 2, except that the absorbent layer is made of 90% 1,2-polybutadiene brand RB830 and 10% cobalt masterbatches according to example 1.

Table 3 shows the results of the tests, the type and duration is without photoinitiator, able to initiate the process of absorption of oxygen.

Example 5.

This film is made and experience, as in example 2. except that the absorbent layer is made of 80% 1,2-polybutadiene RB830, 10% of a copolymer of ethylene with carbon monoxide (10% CO) and 10% masterbatches cobalt with benzophenone as in example 1. Table 4 shows the results of the tests, the type and duration or dose. These results indicate that for this type of film you can use a mixture of initiators.

Example 6.

A composition comprising 90% of a copolymer of ethylene with propylene (5% ethylene units) and 10% masterbatches cobalt with benzophenone prepared in the BRABENDER mixer. Then on laboratory media type CARVERwere pressed two films weighing 3 grams each, these films were subjected to the tests as described in example 2. Table 6 contains the results of the tests. These results indicate that the absorption of oxygen can be initiated in the films of polymers containing tertiary carbon atoms.

Example 7.

In the BRABENDER mixerprepare a composition including 90% poly(1-butene) (melt index = 20), myprimary 6, two films (2-3 grams) each. Table 6 shows the results of the tests, which are similar to the data given in table 5.

Example 8.

This example shows that the absorption of oxygen can be initiated in a shorter period of time by exposure to UV-B and UV-C as photoinitiators (examples 2 and 3) and without (example 4).

The test results also show the effectiveness of irradiation in a continuous process.

Four specimens of the films described in examples 2-4, is subjected to UV irradiation using installation COLIGHTthat uses a mercury arc lamp medium pressure. The samples are irradiated by two methods.

According to the method And the sample film was attached to a reflective rigid substrate and skipped under the lamp at a speed of 10 m/min According To the method, the roll of film is passed under the lamp at a speed of 10 m/min At the specified rate dose is 180 MJ/see Each sample film weighs about 7 grams, of the test in the package impermeable to oxygen and containing 500 cm3air. Power of UV-irradiation is measured by integrating the UV radiometer, model 365 CHI. Table 7 contains the results of the tests.

the arch RB830, 0.45 g of photoinitiator IRGACURE651 company Ciba-Geigy and a solution of 2-ethylhexanoate cobalt NOURU-DRYcompany AKLO Inc. in sufficient quantity to ensure the contents of cobalt, equal to 500 ppm. Then apressofymay from this part of the film (2-3 grams), which is subjected to the same test as in example 2. Table 8 contains the results of the tests. These results show the effectiveness of 2,2-dimethoxy-2-phenylacetophenone, i.e. photoinitiator IRGACURE651.

Example 10.

The following example shows the initiation of the absorption of oxygen by using poly-(m-xylylenediamine) brand MXD6 6001, manufactured by Mitsubishi Gas and Chemicals. Prepare films of two compositions by the method of irrigation from a solution of the polyamide MXD6 in hot acetic acid. Composition 1 contains 3.3 grams of the above polyamide and the solution NOURU - DRYmanufactured by AKZO Chemical, in sufficient quantity to ensure the cobalt concentration equal to 500 ppm. Composition 2 contains 3.1 g of the same polyamide 0,038 g benzophenone (Aldrich) and the solution NOURU - DRYcobalt in a quantity sufficient to provide a concentration of 500 ppm cobalt. Residual acetic acid was removed from the films in a vacuum dryer. The film I2. Both films are tested in impermeable bags containing 400 cm3air.

Example 11.

The sample film described in example 3 is irradiated with UV light (a) as in example 3. Then the film is subjected to the tests as described in example 2, except that the film is kept in the dark. The results are shown in table 10, indicate that after initiation of the oxygen uptake continues, although the irradiation is terminated.

These test cases show that the method of absorption of oxygen according to this invention requires the presence of a catalyst based on a transition metal.

The control example 1.

Extrusion is used for the film, as in example 2 except that the layer of polybutadiene is a 100% 1,2-polybutadiene RB830. This film is irradiated with electron rays dose of 7.6 Mrad and then subjected to a test as described above. The results are shown in table 11.

Control example 2.

Film weight of 6.7 g is obtained by pressing of the 1,2-polybutadiene RB830. Then this film is irradiated with UV light (A) within 10 minutes (capacity of 1.6 mW/cm2) and subjected to the tests as described above, but "BA. A method of manufacturing coloradoboulder layer or articles made of the composition containing the polymer and the catalyst based on transition metal, characterized in that the polymer used oxidizable organic compound, and the resulting layer or the product is subjected to actinic radiation rays with a wavelength in the range of 200 to 750 nm dose of at least 0.1 j/g or radiation to carry out e-ray dose of about 0.2 to 20.0 Mrad.

2. The method according to p. 1, characterized in that the composition as a catalyst based on a transition metal using salt and cobalt.

3. The method according to p. 1 or 2, characterized in that as oxidizing organic compounds using substituted or unsubstituted ethyleneamines hydrocarbon.

4. The method according to p. 3, characterized in that the substituted ethylenediamines hydrocarbon contains oxygen-containing fragments.

5. The method according to p. 4, characterized in that as the oxygen-containing fragments using fragments of compounds selected from the group comprising esters, carboxylic acids, aldehydes, ethers, ketones, alcohols, peroxides or gidroperekisi.

6. The method according to p. 1 or 2, characterized the CSOs carbon.

7. The method according to p. 1 or 2, characterized in that as oxidizing organic compounds using polybutadiene.

8. The method according to p. 1, characterized in that as the oxidizable organic compound is used as a compound selected from the group comprising polypropylene, polybutylene, copolymers of propylene and copolymers of butylene.

9. The method according to p. 1, characterized in that as oxidizing organic compounds using polyamides.

10. The method according to one or more of the preceding items, characterized in that use composition, optionally containing one or more photoinitiators.

11. The method according to one or more of the preceding items, characterized in that use composition, optionally containing one or more antioxidants.

12. The method according to one or more of the preceding items, characterized in that use composition, optionally containing polymeric diluent.

13. The method according to p. 12, characterized in that the use of a composition of the following composition, wt.

Substituted or unsubstituted ethyleneamines hydrocarbon as oxidizing organic compounds 1 99<1 10

Other additives Else

14. The method according to one or more of the preceding items, wherein the actinic radiation is carried rays with a wavelength of 200 to 400 nm.

15. The method according to one or more of the preceding items, characterized in that the irradiation is subjected to the layer made in the form of a film.

16. The method according to one or more of the preceding items, characterized in that the irradiation is subjected to a layer or a product made in the form of inserts, coatings, sealants, gaskets, sticky and non-sticky inserts, fiber inserts.

17. The method according to one or more of the preceding items, characterized in that the irradiation is subjected to a product made in a multilayer film, aderasa the above layer and one or more layers selected from a layer comprising an oxygen barrier layers, layers, permeable to oxygen, the adhesive layers.

18. The method according to p. 15, characterized in that the irradiation is subjected to the film that is used as packaging for products that are sensitive to oxygen.

19. The method according to p. 17, characterized in that the irradiation is subjected to a multilayer film used for the manufacture of packaging for food, the feeling

 

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FIELD: packing equipment, particularly containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents.

SUBSTANCE: impermeable film material has water vapor transmission rate of 6g/m2/day meeting the American society for Testing Materials standard 398-83 and is selected from group containing polyethylene, polypropylene, polyester, polyamide, polyethylene terephthalate, polyvinyl alcohol, aluminum foil, aluminum oxide or silicon dioxide. The material is adapted for packing absorbent articles, for instance woman's sanitary towels, diapers, tampons, etc, containing at least one moisture-sensitive additive. The package is fully sealed by creating impervious connections or seams and includes at least two layers, wherein one of the layers, namely inner impermeable one, is formed of substantially impermeable film material. Another layer, namely outer one, is created of polyethylene terephthalate, polyethylene or polypropylene.

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8 cl, 3 dwg, 1 tbl, 6 ex

FIELD: packing means, particularly polymeric materials adapted for food packaging.

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23 cl, 1 tbl, 1 ex

FIELD: food industry.

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32 cl, 20 dwg

FIELD: packaging industry.

SUBSTANCE: group of inventions relates to a barrier-type container and a method of its manufacture. The container (1) is made of plastic and comprises a reinforcing structure (2) made of plastic, which is obtained by pressure casting or blow moulding, and at least one barrier element (3a, 3b) made of flexible aluminium sheet. All elements are connected directly in at least one corresponding part. The barrier element (3a, 3b) has the ability to adhere to at least the reinforcing structure (2). The method of manufacturing the barrier-type container comprises treatment of the aluminium sheet, formation of two barrier elements made from aluminium sheets in the press mould, feeding the plastic to form the reinforcing structure having a part for monolithic connection with the barrier elements for obtaining the container.

EFFECT: technical result achieved when using the method of invention for obtaining the container which is rigid or semi-rigid, to ensure their collocation and stacking during placement and transportation and use of a simple method of production a container having flexibility in use, adaptation to specific technical requirements related to packaging of the corresponding product.

9 cl, 28 dwg

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EFFECT: high antimicrobial activity while reducing the harmfulness of the antimicrobial agent.

7 cl

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