MXPA99001449A - Multi-component oxygen scavenging composition - Google Patents
Multi-component oxygen scavenging compositionInfo
- Publication number
- MXPA99001449A MXPA99001449A MXPA/A/1999/001449A MX9901449A MXPA99001449A MX PA99001449 A MXPA99001449 A MX PA99001449A MX 9901449 A MX9901449 A MX 9901449A MX PA99001449 A MXPA99001449 A MX PA99001449A
- Authority
- MX
- Mexico
- Prior art keywords
- oxygen scavenging
- scavenging composition
- composition according
- poly
- ethylene
- Prior art date
Links
- MYMOFIZGZYHOMD-UHFFFAOYSA-N oxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 title claims abstract description 109
- 239000001301 oxygen Substances 0.000 title claims abstract description 109
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 109
- 239000000203 mixture Substances 0.000 title claims abstract description 88
- 230000002000 scavenging Effects 0.000 title claims abstract description 84
- 239000003054 catalyst Substances 0.000 claims abstract description 31
- 150000003097 polyterpenes Polymers 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- 229920005989 resin Polymers 0.000 claims description 21
- 239000011347 resin Substances 0.000 claims description 21
- 239000000969 carrier Substances 0.000 claims description 20
- 238000007254 oxidation reaction Methods 0.000 claims description 17
- 230000003647 oxidation Effects 0.000 claims description 16
- 229920000642 polymer Polymers 0.000 claims description 14
- 239000004698 Polyethylene (PE) Substances 0.000 claims description 13
- 235000013305 food Nutrition 0.000 claims description 10
- -1 polyethylene Polymers 0.000 claims description 10
- 229920000573 polyethylene Polymers 0.000 claims description 9
- 239000006227 byproduct Substances 0.000 claims description 8
- 239000005043 ethylene-methyl acrylate Substances 0.000 claims description 8
- 239000000047 product Substances 0.000 claims description 8
- 239000005062 Polybutadiene Substances 0.000 claims description 5
- 229920002857 polybutadiene Polymers 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- XMGQYMWWDOXHJM-JTQLQIEISA-N (+)-(4R)-Limonene Chemical compound CC(=C)[C@@H]1CCC(C)=CC1 XMGQYMWWDOXHJM-JTQLQIEISA-N 0.000 claims description 4
- GRWFGVWFFZKLTI-IUCAKERBSA-N (-)-α-pinene Chemical compound CC1=CC[C@@H]2C(C)(C)[C@H]1C2 GRWFGVWFFZKLTI-IUCAKERBSA-N 0.000 claims description 4
- CGPRUXZTHGTMKW-UHFFFAOYSA-N ethene;ethyl prop-2-enoate Chemical compound C=C.CCOC(=O)C=C CGPRUXZTHGTMKW-UHFFFAOYSA-N 0.000 claims description 4
- 239000005042 ethylene-ethyl acrylate Substances 0.000 claims description 4
- 239000003211 photoinitiator Substances 0.000 claims description 4
- MTAZNLWOLGHBHU-UHFFFAOYSA-N Butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 3
- 239000002174 Styrene-butadiene Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052803 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- LHEFLUZWISWYSQ-CVBJKYQLSA-L cobalt(2+);(Z)-octadec-9-enoate Chemical group [Co+2].CCCCCCCC\C=C/CCCCCCCC([O-])=O.CCCCCCCC\C=C/CCCCCCCC([O-])=O LHEFLUZWISWYSQ-CVBJKYQLSA-L 0.000 claims description 3
- AMFIJXSMYBKJQV-UHFFFAOYSA-L cobalt(2+);octadecanoate Chemical compound [Co+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O AMFIJXSMYBKJQV-UHFFFAOYSA-L 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 claims description 3
- 239000002537 cosmetic Substances 0.000 claims description 3
- QHZOMAXECYYXGP-UHFFFAOYSA-N ethene;prop-2-enoic acid Chemical compound C=C.OC(=O)C=C QHZOMAXECYYXGP-UHFFFAOYSA-N 0.000 claims description 3
- 150000002430 hydrocarbons Chemical class 0.000 claims description 3
- 229920000554 ionomer Polymers 0.000 claims description 3
- 229920001684 low density polyethylene Polymers 0.000 claims description 3
- 239000004702 low-density polyethylene Substances 0.000 claims description 3
- 239000011115 styrene butadiene Substances 0.000 claims description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 3
- 238000005809 transesterification reaction Methods 0.000 claims description 3
- 229910052723 transition metal Inorganic materials 0.000 claims description 3
- 150000003624 transition metals Chemical class 0.000 claims description 3
- WTARULDDTDQWMU-RKDXNWHRSA-N (+)-β-pinene Chemical compound C1[C@H]2C(C)(C)[C@@H]1CCC2=C WTARULDDTDQWMU-RKDXNWHRSA-N 0.000 claims description 2
- XMGQYMWWDOXHJM-UHFFFAOYSA-N (+-)-(RS)-limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 claims description 2
- WTARULDDTDQWMU-IUCAKERBSA-N (-)-Nopinene Natural products C1[C@@H]2C(C)(C)[C@H]1CCC2=C WTARULDDTDQWMU-IUCAKERBSA-N 0.000 claims description 2
- OYHQOLUKZRVURQ-UHFFFAOYSA-N Linoleic acid Chemical compound CCCCCC=CCC=CCCCCCCCC(O)=O OYHQOLUKZRVURQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004793 Polystyrene Substances 0.000 claims description 2
- 239000001361 adipic acid Substances 0.000 claims description 2
- 229930006725 alpha-pinene Natural products 0.000 claims description 2
- 229930006722 beta-pinene Natural products 0.000 claims description 2
- KDMCQAXHWIEEDE-UHFFFAOYSA-L cobalt(2+);7,7-dimethyloctanoate Chemical compound [Co+2].CC(C)(C)CCCCCC([O-])=O.CC(C)(C)CCCCCC([O-])=O KDMCQAXHWIEEDE-UHFFFAOYSA-L 0.000 claims description 2
- HWVKIRQMNIWOLT-UHFFFAOYSA-L cobalt(2+);octanoate Chemical compound [Co+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O HWVKIRQMNIWOLT-UHFFFAOYSA-L 0.000 claims description 2
- 229920001519 homopolymer Polymers 0.000 claims description 2
- 229930007650 limonene Natural products 0.000 claims description 2
- 229920000092 linear low density polyethylene Polymers 0.000 claims description 2
- 239000004707 linear low-density polyethylene Substances 0.000 claims description 2
- 229940049918 linoleate Drugs 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- 229920001195 polyisoprene Polymers 0.000 claims description 2
- 229920000098 polyolefin Polymers 0.000 claims description 2
- 229920002223 polystyrene Polymers 0.000 claims description 2
- 150000003839 salts Chemical group 0.000 claims description 2
- 239000011780 sodium chloride Substances 0.000 claims description 2
- 229920001897 terpolymer Polymers 0.000 claims description 2
- 239000004215 Carbon black (E152) Substances 0.000 claims 1
- XCGBFXNVKPHVEQ-UHFFFAOYSA-N cobalt;2,3-dihydroxybutanedioic acid;ethane-1,2-diamine Chemical group [Co].NCCN.NCCN.NCCN.OC(=O)C(O)C(O)C(O)=O XCGBFXNVKPHVEQ-UHFFFAOYSA-N 0.000 claims 1
- 239000003814 drug Substances 0.000 claims 1
- 239000005038 ethylene vinyl acetate Substances 0.000 claims 1
- 229920005679 linear ultra low density polyethylene Polymers 0.000 claims 1
- 239000000155 melt Substances 0.000 claims 1
- 239000000575 pesticide Substances 0.000 claims 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims 1
- 229920000058 polyacrylate Polymers 0.000 claims 1
- 238000007789 sealing Methods 0.000 claims 1
- 239000000463 material Substances 0.000 description 13
- PPBRXRYQALVLMV-UHFFFAOYSA-N styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 229920001400 block copolymer Polymers 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 150000001299 aldehydes Chemical class 0.000 description 4
- 229920003245 polyoctenamer Polymers 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 3
- 150000001735 carboxylic acids Chemical class 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 238000009456 active packaging Methods 0.000 description 2
- 230000001747 exhibiting Effects 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 230000001617 migratory Effects 0.000 description 2
- 239000002516 radical scavenger Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- JTXMVXSTHSMVQF-UHFFFAOYSA-N 2-acetyloxyethyl acetate Chemical compound CC(=O)OCCOC(C)=O JTXMVXSTHSMVQF-UHFFFAOYSA-N 0.000 description 1
- 206010073316 Accidental exposures to product Diseases 0.000 description 1
- 102100017978 MNT Human genes 0.000 description 1
- 101700073680 MNT Proteins 0.000 description 1
- 101700052821 SSR2 Proteins 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminum Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000003796 beauty Effects 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001869 cobalt compounds Chemical class 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- 235000019645 odor Nutrition 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000006187 pill Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 230000002035 prolonged Effects 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 231100000489 sensitizer Toxicity 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000007725 thermal activation Methods 0.000 description 1
- 229920001862 ultra low molecular weight polyethylene Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Abstract
An oxygen scavenging composition or system is provided comprising at least one polyterpene and at least one catalyst effective in catalyzing an oxygen scavenging reaction. A film, a multi-phase composition, a multi-layer composition, an article comprising the oxygen scavenging composition, a method for preparing the oxygen scavenging composition, and a method for scavenging oxygen are also provided.
Description
OXYGEN ELIMINATING COMPOSITION, OF MULTIPLE COMPONENTS
Field of the Invention
The present invention relates to an oxygen scavenging system or composition which can be used in films, multilayer films, sheets and molded or thermoformed forms which find use in packaging with a low oxygen content for pharmaceutical, cosmetic, oxygen-sensitive chemical substances, electronic devices, and food.
Background of the Invention
The organic oxygen scavenging materials have been partially developed in response
The goal of the food industry is to have a longer shelf life for packaged foods. A method which is commonly employed involves the use of "active packaging" where the package is modified in some way to control the exposure of the product to oxygen. Such "active packaging" may include sachets containing iron-based compositions such as AGELESS® which remove oxygen within the package by means of an oxidation reaction. However, such an arrangement is not advantageous for a variety of reasons including the accidental ingestion of the pills or the oxygen scavenging material present therein. Other techniques involve the incorporation of an oxygen scavenger into the packaging structure itself. In such an arrangement, the oxygen scavenging materials constitute at least a portion of the package, and these materials remove oxygen from the enclosed packing volume which surrounds the product or which may leak into the package, whereby in the case of food products, inhibit corruption and prolong freshness. Oxygen scavenging materials include low molecular weight oligomers that are typically incorporated into polymers or can be oxidizable organic polymers. Such oxygen scavenging materials are typically employed with a suitable catalyst, for example, an organic or inorganic salt of a transition metal catalyst such as cobalt neodeconate, cobalt stearate, etc. Frequently, these oxygen scavenging compositions are not effective at low temperatures. The compositions require a prolonged induction period or will not eliminate oxygen under storage environments for certain packaged food applications. Another major problem is that a wide variety of organic compounds are produced during the oxidation of certain oxygen scavenging materials. Many of these oxidation products can migrate from the oxygen scavenging material and enter the upper space surrounding the food or even enter the food itself. Some oxidation products, such as aldehydes and low molecular weight carboxylic acids, have unpleasant odors or taste or may be compounds that are otherwise undesirable.
Brief Description of the Invention
It is an object of the present invention to provide an effective composition for the removal of oxygen.
It is another object of the present invention to provide an effective composition for removing oxygen at low temperatures. It is another object of the present invention to provide a composition which produces reduced levels of by-products of oxidation. It is another object of the present invention to provide an article, package or container suitable for the removal of oxygen. It is another object of the present invention to provide a method for preparing an oxygen scavenging composition. It is another object of the present invention to provide a method for removing oxygen. According to the present invention, an oxygen scavenging composition or system is provided, which comprises at least one polyterpene and at least one catalyst effective to catalyze the oxygen scavenging reaction. A film, a multi-phase composition, a multilayer composition, an article comprising the oxygen scavenging composition, a method for preparing the oxygen scavenging composition, and a method for removing oxygen, are also provided.
Brief Description of the Drawings
Figure 1 graphically shows the oxygen scavenging operation of an oxygen scavenging composition comprising 30% of the polyterpene and 70% of the polyethylene. Figures 2-4 show by bar graphs the relative amounts of the specific aldehydes produced from the examples containing the blends of polyethylene with polyterpene, block copolymers of styrene / butadiene, polybutadiene, or polyoctenane. Figure 5 shows the relative amounts of the specific acids produced from the examples containing the blends of polyethylene with the polyterpene, block copolymers of styrene / butadiene, polybutadiene, or polyoctenamer. Figure 6 shows the relative amounts of the specific alkenes produced from the examples containing the blends of polyethylene with polyterpene, block copolymers of styrene / butadiene, pclibutadiene, or polyoctenamer.
Detailed description of the invention
Polyterpenes have been found to be especially effective oxygen scavengers, particularly at low temperatures, for example, at refrigerated food temperatures. Examples of such compounds include poly (alpha-pinene), poly (dipentene), poly (beta-pinene), poly (d-limonene), and poly (d, I-limonene). Polyterpenes can be introduced into the oxygen scavenger system by a variety of techniques. The polyterpenes can be formed into films, coated on a material such as a foil or aluminum foil, formed into bottles or other rigid containers, or still incorporated in a material such as paper, for example, in a flexible and rigid packaging. The polyterpene may also be in an area located on a layer, for example, it may be in a patch that is laminated to another layer. Polyterpene is generally present in an amount sufficient to remove at least 0.1 ccO / gram of oxygen scavenging composition / day. Preferably, it is itself capable of removing at least about 0.5, and more preferably at least about 1 cc 02 / gram of oxygen scavenging composition / day. The amount of the polyterpene employed in the oxygen scavenging composition can vary widely depending on the desired characteristics of the final product. In general, the polyterpene is present in an amount in the range of from about 5 weight percent to about 95 weight percent based on the total oxygen scavenging composition, preferably from about 10 weight percent to about 75 percent in weight, and more preferably from 15 weight percent to 50 weight percent. Polyterpene can also be combined with a carrier resin comprising other oxidizable polymers or polymers having a slower oxidation rate than polyterpene. Examples of other oxidizable polymers include ethylenically unsubstituted or unsubstituted unsaturated hydrocarbons such as polybutadiene, polyisoprene, and styrene-butadiene block copolymers. Other examples include those described in U.S. Nos. 5,211,875 and 5,346,644 of Speer et al. , which are incorporated here for reference in their entirety. Other examples include poly (meta-xylenediamin-adipic acid) (also known as MXD6), acrylates which can be prepared by the transesterification of poly (ethylene-methyl acrylate) such as poly (ethylene-methyl acrylate-acrylate) of benzyl), poly (ethylene-methyl acrylate-tetrahydrofurfuryl acrylate), poly (ethylene-methyl acrylate-nopol acrylate) and mixtures thereof. Such transesterification processes are described in 08 / 475,918 filed on June 7, 1995, the disclosure of which is incorporated herein by reference. In a preferred embodiment, the carrier resin is oxidized at a slower rate than polyterpene. Oxygen scavenging compositions prepared from such carrier resins produced reduced amounts of migratory oxidation byproducts such as low molecular weight aldehydes, alkenes and carboxylic acids. Typical examples of carrier resins exhibiting a slower oxidation rate include polyesters, polyaromatic substances, or polyolefin homopolymers, copolymers, or terpolymers. Specific examples of polymers exhibiting a lower oxidation rate include polyethylene, low density polyethylene, high density polyethylene, linear low density polyethylene, polystyrene, as well as copolymers such as poly (ethylene-acetate) of vinyl), poly (ethylene-methyl acrylate), poly (ethylene-ethyl acrylate), poly (ethylene-butyl acrylate), and poly (ethylene-methyl acrylate) ionomers, poly (ethylene-ethyl acrylate) ), or poly (ethylene-acrylic acid). Polyethylene including low density, low linear density, or ultra low density polyethylene is preferred because of its processability and versatility. The amount of carrier resin used can vary widely. In general, the carrier resin is present in an amount in the range of from about 5 weight percent to about 95 weight percent based on the total weight of the oxygen scavenging composition, preferably from about 25 weight percent to about 90 weight percent, and more preferably from 50 weight percent to 85 weight percent. The catalyst can be any catalyst known in the art which is effective to initiate the oxygen removal reaction. Typical catalysts include the saies of a transition metal. Suitable catalysts are described in U.S. Pat. Nos. 5,211,875 and 5,346,644 to Spear et al., The descriptions of which are incorporated herein by reference in their entirety. Cobalt compounds are preferred and cobalt oleate, cobalt linoleate, cobalt neodecanoate, cobalt stearate and cobalt caprylate are especially preferred. The catalyst is present in an amount sufficient to catalyze the oxygen scavenging reaction. In general, the catalyst will be present in an amount in the range of from about 50 ppm to about 10,000 ppm based on the total weight of the oxygen scavenging composition, preferably from 100 ppm to 10,000 ppp, and more preferably from 100 ppm to 5,000 ppm. The catalyst can be introduced in a manner which r.c reacts with and / or deactivates the catalyst. For example, the catalyst can be applied to the oxygen scavenging material by any suitable means, for example, by coating techniques such as spray coating, extrusion composition (including the formation of masterbatches) or lamination.
The oxygen scavenging composition can be activated by methods known in the art such as ultraviolet radiation, e-rays, or thermal activation. Preferably, the composition is activated with 0.2-5 J / cm2 of UV radiation in the range from 250-400 nm. A photoionizer is useful to reduce the activation time of the catalyst. Effective photoinitiators include those known in the art. In another aspect of the invention, the oxygen scavenging composition comprises a first phase comprising the polyterpene and a second phase comprising the catalyst. The first phase is essentially free of the catalyst. The second phase is in a sufficiently close proximity to the first phase to catalyze the oxygen scavenging reaction. When the polyterpene and the catalyst are in separate phases, processing difficulties, such as deactivation of the catalyst, are avoided. In another aspect of the invention, the catalyst is incorporated into a polymeric material to form at least one layer containing the catalyst. In such a case, the layer containing the catalyst may be located between the contents of the package and an oxygen scavenging layer or between the outer side of the package and the oxygen scavenging layer. Also, the catalyst layer can be located between two oxygen scavenging layers or the oxygen scavenging layer can be located between two catalyst layers. In another aspect of the invention, the oxygen scavenging composition or system may include a polymeric selective barrier layer. The selective barrier layer functions as a selective barrier for certain oxidation byproducts, but not for oxygen itself. Preferably, the layer prevents at least half of the number and / or the amount of the oxidation by-products having a boiling point of at least 40 ° C from passing through the polymeric selective barrier layer. The oxygen scavenging composition may include additives, stabilizers, plasticizers and UV sensitizers (ie, photoinitiators) which do not interfere with the oxygen scavenging function. The oxygen scavenging compositions or systems can be used in the production of packages, both rigid and flexible, by techniques which are known in the art. The oxygen scavenging compositions of the present invention are especially effective in low temperature environments. The compositions of the present invention also produce reduced amounts of migratory oxidation byproducts. Of particular interest is the reduction of oxidation by-products such as aldehydes, alkenes and carboxylic acids of molecular weight below which they can adversely affect the organoleptic characteristics. The present invention is also useful in improving the storage life of packaged oxygen-sensitive products, such as pharmaceutical substances, cosmetics, chemicals, electronic devices, health and beauty products. The system can also be used in molding materials, coatings, patches, bottle cap inserts and molded or thermoformed shapes, such as bottles and plates. In all these applications, the oxygen scavenging composition effectively eliminates oxygen, if it comes from the upper space of the package, is dragged into the food or product, or originates from outside the package. The present invention will now be further described in terms of certain examples which are only illustrative in nature and should not in any way limit the scope of the present invention.
Examples
Mixtures of various resins were prepared as follows. In Run 101, 350 g of PE 1017 resin
Chevron (low density polyethylene) and 150 g of Hercules' Piccolyte C115 resin (polilimonen) were melted at 170 ° C to give a mixture of 70 weight percent polyethylene and 30 weight percent of Piccolyte. Figure 1 demonstrates the oxygen-scavenging properties at 4 ° C of the mixture thus produced from Run 101. Percent oxygen in a top space of 300 cc closed was measured over several days. The sample size was 0.25 g. In the Corrida 102, a 90 weight percent mixture of Dexco Vector 8508D resin (styrene-butadiene block copolymer) and 10 weight percent PE 1017 was prepared. In Run 103, a blend of 54 weight percent Ta tene 1202 rubber (polybutadiene) and 36 weight percent PE 1017 was prepared. In Run 104, a 30 weight percent mixture of Vestenamer resin from Huís (polyoctenamer) and 70 percent PE 1017 was prepared.
The mixtures also contained 1000 ppm by weight of Irganox 1076, and 1000 ppm by weight of cobalt oleate. The mixtures were extruded in films of 0.00254-0.00381 cm (1-1.5 mils). Samples of the film were irradiated with a Brak-Ray UV lamp (254 nm, 5 mW / cm2) for 1 minute. Samples of the film were 2.54 cm (1 inch) away from the UV lamps. A predetermined amount of the samples of the films thus prepared was individually placed in 5.08 cm (2") x 76.2 cm (30") glass tubes and purged at 20-25 ° C with 10-15 ml / minute of oxygen to one percent. The gas was trapped in 3 stages, trap 1 - ice bath, trap 2 - dry ice and acetone, and trap 3 - gas bubbled through water. The gases trapped from the samples were analyzed using gas chromatography and mass spectrometry. The relative amounts of the specific byproducts for Runs 101-104 are indicated by the bars in Figures 2-6. The color white represents Corrida 101. The faint gray color represents Corrida 102. The dark gray color represents Corrida 103. The black color represents Corrida 104.
It is noted that in relation to this date the best method known by the applicant to carry out the aforementioned invention is that which is clear from the present description of the invention.
Having described the invention as above, property is claimed as contained in the following
Claims (38)
1. An oxygen scavenging composition, characterized in that it comprises at least one polyterpene and at least one catalyst effective in catalyzing the removal of oxygen.
2. The oxygen scavenging composition according to claim 1, characterized in that the poiiterpene comprises poly (alpha-pinene), poly (beta-pinene), poly (dipentene), poly (d-limonene), or poly (d, I) -limone).
3. The oxygen scavenging composition according to claim 1, characterized in that it exhibits reduced amounts of oxidation by-products compared to the polymers of ethylenically unsaturated hydrocarbons, substituted or unsubstituted.
. The oxygen scavenging composition according to claim 1, characterized in that the polyterpene is present in an amount ranging from about 5 weight percent to about 95 weight percent based on the total oxygen scavenging composition.
5. The oxygen scavenging composition according to claim 4, characterized in that the polyterpene is present in an amount ranging from about 10 weight percent to about 75 weight percent based on the total oxygen scavenging composition.
6. The oxygen scavenging composition according to claim 5, characterized in that the polyterpene is present in an amount in the range from 15 weight percent to 50 weight percent based on the total oxygen scavenging composition.
7. The oxygen scavenging composition according to claim 1, characterized in that it also comprises at least one carrier resin.
8. The oxygen scavenging composition according to claim 7, characterized in that the carrier resin exhibits a slower oxidation rate than the polyterpene.
9. The oxygen scavenging composition according to claim 8, characterized in that the carrier polymer is a polyester, a polyaromatic compound, or a homopolymer, copolymer, or polyolefin terpolymer.
10. The oxygen scavenging composition according to claim 9, characterized in that the carrier polymer is polyethylene, polystyrene, poly (ethylene-vinyl acetate), poly (ethylene-methyl acrylate), poly (ethylene-ethyl acrylate), poly (ethylene-butyl acrylate), or a poly (ethylene-methyl acrylate) ionomer, poly (ethylene-ethyl acrylate), or poly (ethylene-acrylic acid).
11. The oxygen scavenging composition according to claim 10, characterized in that the carrier polymer is polyethylene, poly (ethylene-methyl acrylate), or a poly (ethylene-methyl acrylate) or poly (ethylene-acrylic acid) ionomer .
12. The oxygen scavenging composition according to claim 11, characterized in that the carrier polymer is low density polyethylene, linear low density polyethylene, or ultra low density polyethylene.
13. The oxygen scavenging composition according to claim 7, characterized in that the carrier resin is present in an amount ranging from about 5 weight percent to about 95 weight percent based on the total oxygen scavenging composition.
14. The oxygen scavenging composition according to claim 10, characterized in that the carrier resin is present in an amount ranging from about 25 weight percent to about 90 weight percent based on the total oxygen scavenging composition.
15. The oxygen scavenging composition according to claim 11, characterized in that the carrier resin is present in an amount in the range from 50 weight percent to 85 weight percent based on the total oxygen scavenging composition.
16. The oxygen scavenging composition according to claim 1, characterized in that the catalyst is a salt of a transition metal.
17. The oxygen scavenging composition according to claim 16, characterized in that the catalyst is a cobalt salt.
18. The oxygen scavenging composition according to claim 17, characterized in that the catalyst is cobalt oleate, cobalt linoleate, cobalt neodecanoate, cobalt stearate, or cobalt caprylate.
19. The oxygen scavenging composition according to claim 1, characterized in that it also comprises a photoinitiator.
20. The oxygen scavenging composition according to claim 1, characterized in that the carrier resin comprises an oxidizable polymer.
21. The oxygen scavenging composition according to claim 20, characterized in that the oxidizable polymer is an ethylenically unsaturated, substituted or unsubstituted hydrocarbon polymer.
22. The oxygen scavenging composition according to claim 21, characterized in that the oxidizable polymer is polybutadiene, polyisoprene, poly (styrene-butadiene), poly (meta-xylenediamin-adipic acid), or polyacrylates which can be prepared by transesterification of the poly (ethylene-methyl acrylate) including poly (ethylene-methyl acrylate-benzyl acrylate), poly (ethylene-methyl acrylate-tetrahydrofurfuryl acrylate), poly (ethylene-methyl acrylate-nopol-acrylate), or mixtures thereof.
23. The oxygen scavenging composition according to claim 8, characterized in that the polyterpene comprises a first phase and the catalyst comprises a second phase, wherein the second phase is in proximity sufficiently close to the first phase to catalyze an oxygen scavenging reaction.
24. The oxygen scavenging composition according to cor. Claim 23, characterized in that the first phase forms a first layer and the second phase forms a second layer.
25. The oxygen scavenging composition according to claim 24, characterized in that the second layer is in contact with the first layer.
26. The oxygen scavenging composition according to claim 24, characterized in that it further comprises an oxygen barrier layer, a selective barrier layer, a polymeric layer, or a thermal sealing layer.
27. The oxygen scavenging composition, characterized in that it comprises at least one polyterpene, at least one carrier resin, and at least one catalyst effective in catalyzing the removal of oxygen, wherein the carrier resin exhibits a slower oxidation rate than the polyterpene.
28. A film, characterized in that it comprises the oxygen scavenging composition according to claim 7.
29. An article, characterized in that it comprises the oxygen scavenging composition according to claim 7.
30. The article according to claim 29, characterized in that the article is a package.
31. The article according to claim 30, characterized in that the article is a package containing a food product.
32. The article according to claim 30, characterized in that the article is a package containing a cosmetic, chemical substance, electronic device, pesticide or pharmaceutical substance.
33. The article according to claim 29, characterized in that the article is a patch, lid insert for a bottle or a molded or thermoformed shape.
34. The article according to claim 33, characterized in that the molded or thermoformed form is a bottle or tray.
35. An oxygen scavenging method, characterized in that it comprises placing an oxygen sensitive product in the package of claim 27.
36. A method for preparing an oxygen scavenging composition, characterized in that it comprises melt mixing at least one polyterpene and at least one catalyst effective in the oxygen scavenging catalyst.
37. The method according to claim 36, characterized in that it further comprises mixing in the melt at least one carrier resin in the oxygen scavenging composition, wherein the carrier resin exhibits a slower oxidation rate than the polyterpene.
38. The method according to claim 37, characterized in that it also comprises at least one photoinitiator.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US08698011 | 1996-08-13 |
Publications (1)
Publication Number | Publication Date |
---|---|
MXPA99001449A true MXPA99001449A (en) | 1999-09-20 |
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