WO2013093168A1 - Matériaux nanocomposites actifs basés sur des sels générant du so2 et de l'edta, et son procédé d'élaboration - Google Patents

Matériaux nanocomposites actifs basés sur des sels générant du so2 et de l'edta, et son procédé d'élaboration Download PDF

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WO2013093168A1
WO2013093168A1 PCT/ES2012/070904 ES2012070904W WO2013093168A1 WO 2013093168 A1 WO2013093168 A1 WO 2013093168A1 ES 2012070904 W ES2012070904 W ES 2012070904W WO 2013093168 A1 WO2013093168 A1 WO 2013093168A1
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material according
edta
matrix
salts
active
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PCT/ES2012/070904
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Spanish (es)
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WO2013093168A9 (fr
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Patricia FERNÁNDEZ SAIZ
Maria Busolo Pons
José Maria LAGARON CABELLO
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Nanobiomatters Research & Development, S. L.
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment

Definitions

  • the present invention relates to active and / or bioactive nanocomposite materials generically based on the use of nano-clays as a support for the active substances. Said activity is obtained through the formulation of a specific type of laminar-type additives or nanoadditives with or without prior modification that are dispersed within a polymeric, plastic matrix and comprising, said additives or nanoadditives, active agents such as EDTA and / or SO2 generating salts that confer said materials with antimicrobial and / or antioxidant and / or oxygen sequestrant properties.
  • active agents such as EDTA and / or SO2 generating salts that confer said materials with antimicrobial and / or antioxidant and / or oxygen sequestrant properties.
  • Such materials may be used in multidisciplinary applications including the food contact sector, as well as in the medical sector and for hygiene products.
  • the present invention describes the process of manufacturing said materials. Therefore, the present invention belongs to the materials engineering sector.
  • nanocomposites based on phyllosilicates and / or synthetic double laminar hydroxides are interspersed with different organic modifiers, and once incorporated into thermoplastic and / or thermostable matrices, they are capable of improving the gas and vapor barrier properties of these.
  • the aforementioned documents are some examples of polymer clay nanocomposites prepared from modified clays. These documents describe a nanocomposite material such as an exfoliated or interleaved plate, with a touch structure of nanometric dimensions, comprising intercalated clay dispersed in a polymer matrix, such as an oligomer, a polymer, or a mixture thereof.
  • Microorganisms and in particular bacteria, are the main cause of diseases caused by the consumption of contaminated food. These can survive the heat treatment required for canning or contaminate the food after such treatment due to sutures or leaks from the container. In addition to its potential health hazard, the proliferation of microorganisms can cause alterations in foods that in turn lead to changes in the physical, chemical and organoleptic properties of the same. Some of the traditional preservation methods such as heat treatments, irradiation, modified atmosphere packaging or addition of salts, cannot be applied to certain types of foods such as vegetables, fresh fruits and meats or ready-to-eat products. On the other hand, the direct application of antibacterial substances on food has limited effects since they neutralize and diffuse rapidly into the food.
  • active packaging is a viable and advantageous way to limit and control bacterial growth in foods, since antimicrobial agents migrate slowly from the material to the surface of the product. The migration can be as extensive as required, so that it covers the time of transport, storage and is guaranteed until consumption.
  • antimicrobial nanoadditives of ethylenediaminetetraacetic acid (EDTA) and its salts once incorporated into the containers, they can inhibit the growth of microorganisms thanks to their chelating property of divalent cations such as Ca 2+ or Mg 2+ , essential factors for microbial growth
  • EDTA is able to destabilize the outer membrane of the microorganism, excessively increasing its permeability.
  • microorganisms are also undesirable in other sectors.
  • it is essential to eliminate the risks of infection in invasive treatments, of open wounds, as well as in routine treatments.
  • coatings with antimicrobial films of catheters and stethoscopes, and the preparation of fabrics in fibers pretreated with silver nitrate or with broad-spectrum antibiotics for wound and burn treatments can be cited.
  • the use of fibers pretreated with antibacterial agents limits the proliferation of microorganisms in the face of sweat, humidity and high temperatures, reducing bad body odors and risks of contagion.
  • Plastic materials with antimicrobial properties can also be used in the manufacture of cranks, handlebars, handles and armrests of public transport elements, in railings and support points of places of high concurrence, in the manufacture of sanitary parts for public and mass use, as well as in headphones and microphones of telephones and audio systems of public places; kitchen tools and food transport, all this in order to reduce the risk of spreading infections and diseases.
  • SO2 generating salts are currently used as preservatives and food bleaching agents. They are used to control the growth of undesirable microorganisms: in viticulture before the process of must fermentation to prevent the growth of acetic bacteria and molds without affecting yeasts in dairy and vegetable products. They are also used as anti-browning agents for vegetables, mainly potatoes.
  • Sodium bisulfite and sodium sulphite are recognized as suitable for food contact, with a specific migration of 10 mg / kg, according to Commission Regulation (EU) No. 10/201 1 of January 14, 201 1 on plastic materials and objects to come into contact with food.
  • the efficiency of the inorganic salts generating SO2 can be significantly enhanced by supporting them in an agent that acts as a vehicle, such as activated carbon, alumina, silica, or clays.
  • an agent that acts as a vehicle such as activated carbon, alumina, silica, or clays.
  • the manufacture of nanoactive materials based on salts generating SO2 has not been protected or patented, as well as their use as oxygen sequestering agents, antimicrobials, free radical scavengers for the manufacture of active packages; or any other functionality or improvement of properties granted by clays to the matrices to which they can be incorporated.
  • a novel option to avoid the action of oxygen in packaged foods is the incorporation of active agents in plastic materials that are subsequently used in the manufacture of items for packaging.
  • Antioxidant systems have been developed for the food industry that illustrate these applications. More specifically, patent CA2278569 describes the manufacture of bilayer films containing antioxidant agents, among other additives, and which are used for packaging meat and pre-cooked products, but also for the manufacture of coatings and bags.
  • the generic use of nano-clays with active and bioactive properties with biocidal and antioxidant properties to develop nanocomposites has also been reported and protected (WO02007 / 074184A1).
  • a plastic material has also been developed for use in wine packaging with the "bag-in box”system; wherein said plastic material contains one or more salts generating SO 2 , mainly calcium sulphite. Additionally, the plastic material contains metal oxides that regulate the release of SO 2 to the beverage. This system is set out in WO2008025085.
  • the present invention relates to a new type of nanocomposite materials, with active and / or bioactive properties, with multisectoral applications, with antimicrobial and / or oxygen sequestration properties and / or with antioxidant character, which substantially improve the effects obtained with materials of the same nature but with slightly different composition.
  • a first aspect of the present invention relates to a nanocomposite material comprising the following elements:
  • - laminar-type additives or nanoadditives with or without prior modification that are dispersed within the matrix, and which comprise at least one active agent selected from EDTA, EDTA salts and / or SO2 generating salts.
  • the matrix: - It is present in the nanocomposite material in a proportion of 5 to 99.99% by weight with respect to the total.
  • thermoplastics thermosets, elastomers and materials derived from biomass and / or biodegradable or mixtures thereof containing typical additives that are added during the manufacture and processing of plastics and bioplastics;
  • they are of the laminar type and are selected from phyllosilicates or synthetic double hydroxides. Preferably they are montmorillonitic or kaolinitic clays.
  • the laminar type additives or nanoadditives are modified and the modifying agents are selected from:
  • - precursor agents which are selected from the group consisting of expanders and / or compatibilizers and / or agents with active and / or bioactive character;
  • the latter compounds are selected from arquad (didecyldimethylammonium chloride) or CTAB (hexadecyltrimethyl ammonium bromide);
  • the nanocomposite material comprises:
  • EDTA modified clays or EDTA salts are suitable in cases where silver-based systems were not efficient due to the presence of sulfur amino acids in the environment. This is the case of a food package for meats, since, as demonstrated in this document, the compound has no negative interaction with this type of food.
  • calcium and sodium ethylene diamino tetracetate (disodium calcium EDTA, E385) is accepted as a food additive in the European Union, but there are numerous possible EDTA salts capable of fulfilling the same function, for example, but not limited to:
  • the nanocomposite material comprises:
  • montmorillonite dispersed in the plastic matrix, wherein said montmorillonite comprises sodium bisulfite as active agent.
  • the nanocomposite material comprises:
  • montmorillonite dispersed in the plastic matrix, wherein said montmorillonite comprises EDTA or salts of EDTA and sodium bisulfite as active agents.
  • a second aspect of the present invention relates to the use of the nanocomposite material described above for the manufacture of plastic materials or plastics coating and more specifically for containers with antimicrobial and / or antioxidant and / or oxygen sequestrant properties.
  • the advantage of using S0 2 generating salts is that they have a minimal impact on color in final applications in plastics, unlike iron-based compounds that have a dark color.
  • a third aspect of the present invention relates to a package comprising the nanocomposite material described above.
  • a fourth aspect of the present invention relates to the use of the above package, for the preservation and / or protection of food, medications, medical instruments or hygiene products.
  • a fifth aspect of the present invention relates to a process for obtaining the nanocomposite materials described above comprising the following steps:
  • step a) -dispersion of the laminar additive or nanoadditive with or without chemical modification or prior physical treatment, in a solution of the active agent selected from EDTA, EDTA salt and / or sodium bisulfite in a clay; - Drying the product obtained in step a) by any industrial drying process known to a person skilled in the art, preferably spraying. - add the product obtained in step b) to a plastic or polymer matrix as described above.
  • the suspension is added directly to the matrix without a prior drying process.
  • Said dispersion is carried out in water, isopropanol or mixtures thereof.
  • the dispersion is carried out in a reactor assisted by simple agitation, homogenizers and / or ultrasound.
  • the product can be dried, stored and resuspended in water, isopropanol or mixtures to add in suspension to the plastic matrix.
  • step b) of drying is carried out in an atomizer, by means of filtroprensa or centrifuge.
  • the additive or nanoadditive has been subjected, prior to the dispersion of step a), to:
  • Figure 1 Shows the results of the thermogravimetric analysis of MMT / Ca 30% EDTA-Na
  • Figure 2 Shows the X-ray diffractogram of Montmorillonite Ca with 30% EDTA-Na
  • Figure 3 Shows the X-ray diffractograms (WAXS) of a sample of unmodified montmorillonite clay and the same clay modified with sodium bisulfite, according to the method described in Example 1, to obtain MMT / NaHS0 3
  • Figure 4 Shows the X-ray diffractograms (WAXS) of a sample of montmorillonite-type clay modified with 30% of arquad and the same clay modified with sodium bisulfite, according to the method described in Example 2, to obtain MMT / NaHSO 3 /30% arch.
  • Figure 5 Shows the graph of contact oxidation inhibition (DPPH method) by action of the MMT / NaHSO 3 and MMT / NaHSO 3 /30% arquad clays, of examples 1 and 2, respectively.
  • DPPH method contact oxidation inhibition
  • Figure 6 Shows the plot of oxygen sequestering capacity in head space of the MMT / NaHSO 3 and MMT / NaHSO 3 /30% arquad clays, of examples 1 and 2, respectively.
  • Figure 7 Shows the graph of contact oxidation inhibition (DPPH method) by action of the films of HDPE and PET composites with clays MMT / NaHSO 3 and MMT / NaHSO 3 /30% arquad.
  • Figure 8 Shows the graph of oxygen sequestering capacity in head space of films of composites of HDPE, PET and elastomer with clays MMT / NaHS0 3 and MMT / NaHSO 3 /30% arch.
  • Example 1 Intercalation of disodium calcium EDTA in montmorillonite clays. Initially, a 3.6% solution of disodium calcium EDTA in water is prepared, in which the clay is dispersed with or without prior modification with CTAB or modified arquad (7.8% by weight). The dispersion is stirred for 6 h at 70 ° C. Finally, the clay is dried by spraying at 220 ° C. The thermogravimetric analysis (TGA) of the resulting clay shows an onset of degradation at approximately 200 ° C (see figure 1).
  • TGA thermogravimetric analysis
  • the X-ray diffractogram of the resulting clay shows that the basal peak has shifted from its initial position (5.55 °, 2 ⁇ ), which indicates that there are changes in the interlaminar distance and that the entire modifier has sandwiched between the sheets.
  • Example 2 Preparation of low density polyethylene (LDPE) composites, with 4 v 7% CaNa? EDTA / MMT or 4 v 7% CaNa? EDTA / 30% CTAB / MMT or 4 v 7%.
  • LDPE low density polyethylene
  • a 10% clay concentrate in LDPE is prepared with a corrotative spindle extruder (ratio R: D 42: 1). Flow rate: 10 Kg / hour. T a : 150 ° C. For this, the clay is previously dispersed in isopropanol (clay: isopropanol 1: 3).
  • Example 3 Antimicrobial capacity of LDPE composites with disodium calcium EDTA clay on a real food.
  • antimicrobial effectiveness was carried out using the same experimental conditions but using a silver-based additive.
  • Table 2 shows the antimicrobial effectiveness of the films obtained on the growth of the three microorganisms at 4 ° C for 24 hours in chicken broth.
  • films that have been added with clay with disodium calcium edetate show a very significant antimicrobial effectiveness against the growth of microorganisms in chicken broth at 4 ° C.
  • samples with silver-based additive do not show detectable antimicrobial effectiveness, probably due to inactivation of the compound in contact with sulfur amino acids present in the food (for example, methionine or cysteine).
  • Example 4 Intercalation of sodium bisulfite (NaHSOs) in montmorillonite clays. MMT / NaHSO Preparation ⁇
  • the clay was filtered by suction and dried in an atomizer.
  • the chemical analysis of the resulting clay shows a NaHS03 content (detected as S0 2 ) of 16.20%.
  • the X-ray diffractogram of the resulting clay shows that the basal peak has not shifted from its initial position (7.02 °, 2 ⁇ ), which indicates that there are no changes in the interlaminar distance.
  • Example 5 Intercalation of sodium bisulfite (NaHSO ⁇ ) in montmorillonite clays, previously modified with 30% arch. Preparation MMT / NaHSO ⁇ / 30% arch.
  • a 3% solution of sodium bisulfite in water is prepared, in which the previously modified montmorillonite clay is dispersed with 30% of arch. The dispersion is stirred for 24 h at 40 ° C. Finally, the clay was filtered by suction and dried in an atomizer. The chemical analysis of the resulting clay shows a NaHS03 content (detected as SO2) of 5.9%. The X-ray diffractogram of the resulting clay ( Figure 4) shows that the interlaminar distance of the clay modified with arch and subsequently modified with NaHS03 has increased 3.2 A (which corresponds to a displacement of the initial angle from 2.9 to 2.6; 2 ⁇ ) .
  • Example 6 NaHSO antioxidant capacity ⁇ / MMT v NaHSO / 30% arquad / MMT
  • the antioxidant effect by contact of the NaHS03-MMT and NaHSO3 / 30% arquad / MMT clays was determined using the DPPH radical discoloration method (2,2-diphenyl-1-pyrilhydracil). For this, weighed in 3 ml glass vials, in triplicate, 30mg portions of each clay. 1 ml of a stock solution 0.05g / L of DPPH in methanol was added in each tube, whose absorbance at 517 nm is 1.2. In parallel, three control samples without clay containing 1 ml of DPPH were prepared. Samples and controls were allowed to incubate in the dark for 24 ° C for 24 hours. Next, the samples were filtered and the absorbance to the supernatant was measured at 517 nm. The results are expressed in% DPPH inhibition:
  • % DPPH inhibition (Abs control - Abs sample) / Abs control
  • Example 8 Preparation of high density polyethylene (HDPE), polyethylene terephthalate (PET) and elastomer composites, with 15% NaHSOs / MMT or 15%
  • Example 9 Sequestrant capacity of MMT / NaHSO 3 /30% arquad v MMT / NaHSO 3 .
  • the clay with the greatest capacity to absorb oxygen is the one that contains only sodium bisulfite, which contains more NaHS0 3 than the clay with double modification arquad / NaHS03.
  • Example 10 Antioxidant capacity of HDPE and PET composites with sodium bisulfite clay.
  • % DPPH inhibition (Abs control - Abs sample) / Abs control
  • Figure 7 shows that, in general, all the composites evaluated exhibit antioxidant capacity, observing the highest activity in composites of
  • HDPE-MMT / NaHS03 26.95% DPPH turn.
  • PET composites there are no significant differences when added with the clay of simple modification (only NaHS0 3 ) or double (NaHS0 3 / arquad).
  • the results show that both HDPE and PET, materials widely used in food packaging, have the property of capturing free radicals from oxygen, a condition that can be advantageous for extending the shelf life of food by delaying oxidation processes.
  • Example 11 Oxygen sequestering capacity of HDPE, PET and elastomer composites with MMT / NaHSO ⁇ / 30% arquad v MMT / NaHSOs.
  • each film was weighed, in duplicate, in 40 ml vials.
  • a cell with 1 ml of water was placed to ensure 100% relative humidity inside, and each vial was closed with a traffic light cap, with open-closed switch and needle inlet. The caps were left in the "closed" position during the test.
  • the vials were placed in a heated space at 25 ° C, under constant artificial light.
  • the oxygen content was measured between 1 and 60 days, using an oxygen sensor.
  • the sequestering capacity results are shown in Figure 8.
  • the graph of volume of oxygen consumed / g clay vs. time indicates that of the composites added with MMT / NaHS0 3 the most active is that of elastomer, which can consume up to 1.88 ml of 02 / g of composite.
  • Composites with HDPE and PET can absorb 1, 54 and 0.91 ml of oxygen per gram of composite, respectively. These differences are due to the matrix effect, which causes the same clay to behave differently depending on the matrix in which it is incorporated.
  • PET added to clay containing arquad in addition to bisulfite shows less activity than PET added to bisulfite modified clay only: 0.51 ml of 02 / g composite.
  • the results indicate that the PET and HDPE composites added with the bisulfite-based clays have the capacity to absorb oxygen, a property that can be beneficial in extending the shelf life of packaged foods susceptible to oxidation, such as fat-based foods and meats.
  • Example 12 Intercalation of sodium bisulfite (NaHSOs) and disodium calcium EDTA in montmorillonite clays. Preparation of CaNa2EDTA / NaHSOr3 ⁇ 4 / MMT
  • Example 13 Oxygen sequestering capacity of CaNa2EDTA / NaHSOa MMT clays.
  • each film was weighed, in duplicate, in 40 ml vials.
  • a cell with 1 ml of water was placed inside each vial to ensure 100% relative humidity inside, and each vial was closed with a traffic light cap, with an open-closed switch and needle inlet. The caps were left in the "closed" position during the test.
  • the vials were placed in a heated space at 25 ° C, under constant artificial light.
  • the oxygen content was measured at 3, 5 and 10 days, using an oxygen sensor.
  • Example 14 Tube macrodilution method to determine antimicrobial activity of CaNa2EDTA / NaHSO MMT clays.
  • Table 6 shows that the clay CaNa2EDTA / NaHS0 3 / MMT can cause a 99.96% reduction in colony forming units with 0.1 g of clay.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Food Preservation Except Freezing, Refrigeration, And Drying (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Anti-Oxidant Or Stabilizer Compositions (AREA)

Abstract

La présente invention concerne des matériaux nanocomposites actifs et/ou bioactifs qui comprennent une matrice plastique ou polymère et des additifs ou des nanoadditifs de type laminaire avec ou sans modification antérieure qui sont dispersés dans ladite matrice, lesdits additifs ou nanoadditifs comprenant au moins un agent actif qui est choisi parmi EDTA ou des sels d'EDTA et des sels générant SO2 comme le bisulfite de sodium. Ces agents actifs confèrent auxdits matériaux des propriétés antimicrobiennes et /ou antioxydantes et/ou piégeant l'oxygène, lesdits matériaux étant appropriés à la fabrication de matériaux plastiques ou au recouvrement de plastiques et plus spécifiquement aux contenants ayant lesdites propriétés utilisables dans le secteur de l'alimentation, ainsi que dans le secteur médical et avec des produits destinés à l'hygiène. En outre, la présente invention concerne le procédé d'élaboration desdits matériaux.
PCT/ES2012/070904 2011-12-21 2012-12-21 Matériaux nanocomposites actifs basés sur des sels générant du so2 et de l'edta, et son procédé d'élaboration WO2013093168A1 (fr)

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ES201132068A ES2415242B1 (es) 2011-12-21 2011-12-21 Materiales nanocompuestos activos basados en sales generadoras de so2 y edta y el procedimiento para su obtención

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106096018A (zh) * 2016-06-24 2016-11-09 西安交通大学 一种在多群数据库中考虑共振弹性散射的方法
WO2020230107A1 (fr) * 2019-05-15 2020-11-19 Polyamyna Nanotech Inc. Nanoargiles antimicrobiennes comprenant des agents antimicrobiens cationiques, procédé de préparation et utilisations de celles-ci

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FR2536045A1 (fr) 1982-11-15 1984-05-18 Gross Peter Systeme pour le traitement et la preservation de fruits emballes
US4739007A (en) 1985-09-30 1988-04-19 Kabushiki Kaisha Toyota Chou Kenkyusho Composite material and process for manufacturing same
CA2278569A1 (fr) 1997-01-21 1998-07-23 Cryovac, Inc. Film de transfert d'additif indique pour une cuisson dans l'emballage
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US20030060555A1 (en) * 2001-09-27 2003-03-27 Lorah Dennis Paul Modified clays and methods for making and using same
WO2007074184A1 (fr) 2005-12-29 2007-07-05 Nanobiomatters, S.L. Procede de fabrication de materiaux nanocomposites destines a des applications multisectorielles
WO2007130755A1 (fr) * 2006-05-03 2007-11-15 Polyone Corporation Nanocomposites de polyoléfine stabilisés
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WO2008025085A1 (fr) 2006-08-30 2008-03-06 Amcor Limited Matériau de conditionnement hydrophobe comprenant un sel de sulfite
CN101530233A (zh) 2009-04-23 2009-09-16 海安县隆泰包装有限公司 一种负离子红外线除臭保鲜粉
EP2332885A1 (fr) * 2008-10-01 2011-06-15 Nanobiomatters, S.L. Matériaux nanocomposés présentant des propriétés protectrices contre le rayonnement électromagnétique et procédé permettant de les obtenir
WO2012164131A1 (fr) * 2011-06-03 2012-12-06 Nanobiomatters Research & Development, S. L. Matériaux nanocomposés à base d'oxydes de métaux à propriétés multifonctionnelles

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Publication number Priority date Publication date Assignee Title
DE2112979A1 (de) 1971-03-17 1972-09-21 Fibreboard Corp Beschichtete Behaelter und zur Beschichtung dienende Harzzusammensetzungen
FR2536045A1 (fr) 1982-11-15 1984-05-18 Gross Peter Systeme pour le traitement et la preservation de fruits emballes
US4739007A (en) 1985-09-30 1988-04-19 Kabushiki Kaisha Toyota Chou Kenkyusho Composite material and process for manufacturing same
CA2278569A1 (fr) 1997-01-21 1998-07-23 Cryovac, Inc. Film de transfert d'additif indique pour une cuisson dans l'emballage
US20020058740A1 (en) * 2000-09-21 2002-05-16 Lorah Dennis Paul Nanocomposite compositions and methods for making and using same
US20030060555A1 (en) * 2001-09-27 2003-03-27 Lorah Dennis Paul Modified clays and methods for making and using same
US7306777B2 (en) 2003-12-16 2007-12-11 Eastman Kodak Company Antimicrobial composition
WO2007074184A1 (fr) 2005-12-29 2007-07-05 Nanobiomatters, S.L. Procede de fabrication de materiaux nanocomposites destines a des applications multisectorielles
WO2007130755A1 (fr) * 2006-05-03 2007-11-15 Polyone Corporation Nanocomposites de polyoléfine stabilisés
WO2008025085A1 (fr) 2006-08-30 2008-03-06 Amcor Limited Matériau de conditionnement hydrophobe comprenant un sel de sulfite
EP2332885A1 (fr) * 2008-10-01 2011-06-15 Nanobiomatters, S.L. Matériaux nanocomposés présentant des propriétés protectrices contre le rayonnement électromagnétique et procédé permettant de les obtenir
CN101530233A (zh) 2009-04-23 2009-09-16 海安县隆泰包装有限公司 一种负离子红外线除臭保鲜粉
WO2012164131A1 (fr) * 2011-06-03 2012-12-06 Nanobiomatters Research & Development, S. L. Matériaux nanocomposés à base d'oxydes de métaux à propriétés multifonctionnelles

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106096018A (zh) * 2016-06-24 2016-11-09 西安交通大学 一种在多群数据库中考虑共振弹性散射的方法
CN106096018B (zh) * 2016-06-24 2019-04-16 西安交通大学 一种在多群数据库中考虑共振弹性散射的方法
WO2020230107A1 (fr) * 2019-05-15 2020-11-19 Polyamyna Nanotech Inc. Nanoargiles antimicrobiennes comprenant des agents antimicrobiens cationiques, procédé de préparation et utilisations de celles-ci

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ES2415242A2 (es) 2013-07-24
ES2415242R1 (es) 2013-07-30
WO2013093168A9 (fr) 2014-04-17

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