[go: up one dir, main page]

WO2000053413A1 - Plastiques antimicrobiens - Google Patents

Plastiques antimicrobiens Download PDF

Info

Publication number
WO2000053413A1
WO2000053413A1 PCT/US2000/005967 US0005967W WO0053413A1 WO 2000053413 A1 WO2000053413 A1 WO 2000053413A1 US 0005967 W US0005967 W US 0005967W WO 0053413 A1 WO0053413 A1 WO 0053413A1
Authority
WO
WIPO (PCT)
Prior art keywords
antimicrobial
polymeric
resin
coating
plastic
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/US2000/005967
Other languages
English (en)
Inventor
Shantha Sarangapani
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ICET Inc
Original Assignee
ICET Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by ICET Inc filed Critical ICET Inc
Priority to AU40069/00A priority Critical patent/AU4006900A/en
Publication of WO2000053413A1 publication Critical patent/WO2000053413A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/16—Halogen-containing compounds
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
    • A01N25/10—Macromolecular compounds
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/34—Shaped forms, e.g. sheets, not provided for in any other sub-group of this main group
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/16—Heavy metals; Compounds thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/38—Packaging materials of special type or form
    • B65D65/46—Applications of disintegrable, dissolvable or edible materials
    • B65D65/466—Bio- or photodegradable packaging materials
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0058—Biocides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2949/00—Indexing scheme relating to blow-moulding
    • B29C2949/07—Preforms or parisons characterised by their configuration
    • B29C2949/0715—Preforms or parisons characterised by their configuration the preform having one end closed
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2949/00—Indexing scheme relating to blow-moulding
    • B29C2949/30—Preforms or parisons made of several components
    • B29C2949/3064—Preforms or parisons made of several components having at least one components being applied using techniques not covered by B29C2949/3032 - B29C2949/3062
    • B29C2949/3074—Preforms or parisons made of several components having at least one components being applied using techniques not covered by B29C2949/3032 - B29C2949/3062 said at least one component obtained by coating
    • B29C2949/3076—Preforms or parisons made of several components having at least one components being applied using techniques not covered by B29C2949/3032 - B29C2949/3062 said at least one component obtained by coating on the inside
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
    • B29C49/02—Combined blow-moulding and manufacture of the preform or the parison
    • B29C49/06—Injection blow-moulding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D81/00—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
    • B65D81/24—Adaptations for preventing deterioration or decay of contents; Applications to the container or packaging material of food preservatives, fungicides, pesticides or animal repellants
    • B65D81/28—Applications of food preservatives, fungicides, pesticides or animal repellants
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/0806—Silver
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/085—Copper

Definitions

  • This invention is directed to antimicrobial plastics and methods for making same, and specifically directed to antimicrobial materials for use in food packaging and medical applications.
  • Citrus and other fruit juice processing operations present an important part of the food industry in the U.S and the world.
  • Pasteurized single strength juices and frozen concentrates are two major types of products. These products are not free of microbiological spoilage problems.
  • Yeast, molds, and lactic acid bacteria have been implicated in spoilage of fruit juices. Molds may be temporarily injured by minimal heat processing, making them difficult to detect with normal quality control procedures. However, such injury to the mold may be repaired if presented with the proper temperature and moisture conditions.
  • the low pH and high sugar content of most juice concentrates create a restrictive milieu for the growth of most microorganisms, xerotolerant yeast can still grow to unacceptable levels under these conditions.
  • the main purpose of packaging is to protect food from microbial and chemical contamination, oxygen, water vapor and light.
  • the type of packaging used therefore serves an important role in determining the shelf life of the food.
  • Packaging with antimicrobial effects so-called “active packaging,” does more than simply provide a barrier to outside influences. It can control and even react to events taking place inside and outside the packaging.
  • antimicrobial packaging perform two very important functions. First, such packaging resists surface contamination by air-borne and other types of microbes which may settle on the surface of packaging materials. Second, it actively preserves the freshness of the packaged item by virtue of leaching small amounts of the antimicrobial agent onto, or in the case of a liquid item, into the item itself. The addition of preservatives to fruit juices and fruit juice beverages is common.
  • the shelf life of a product becomes an issue when large quantities such as a 4- liter bottles needs to be stored for several weeks.
  • the shelf life of such products that contain no preservatives run the risk of showing signs of spoilage when stored at ambient temperatures. Occasionally a poor seal may also allow air borne microbes to enter the surface of the fruit juice. Spoilage is more rapid between 20C and 35C and normally slows down as temperature decreases.
  • preservatives such as sodium benzoate and parabenzoate are added in concentrations of 0.1 % w/v directly to liquid fruit juices and fruit juice beverages stored in plastic or glass bottles. While the need for the antimicrobial agent to preserve freshness is well-accepted, it is much more desirable to add the smallest amount of preservatives as possible, and where possible, to the packaging material and not the perishable food item itself. It is also desired to be able to decrease the amount of preservatives required without requiring drastic and costly changes to common packaging methods, namely plastic bottles.
  • the present invention describes alternatives to the traditional practice of adding preservatives directly to foods.
  • This invention teaches coating the surfaces of plastic containers with antimicrobial additives. Some coatings that adhere very well to the surfaces of commonly employed plastic bottles and which release the additives slowly with time into the contacting media are described.
  • This invention also teaches directly incorporating one or more antimicrobial additives into the raw material polymer used to create the packaging. Both methods present useful and long-needed solutions for improving the packaging of materials used for food packaging, and for decreasing the amount of preservatives needed to inhibit microbial growth. These methods may also be readily used in many other applications, such as the fabrication of medical devices such as catheters or stents.
  • Applicant has found that a significantly smaller amount of antimicrobial agents is required to preserve the freshness of a food product when the agents are added to the packaging material and not the product itself.
  • this invention provides antimicrobial coatings for application on surfaces of plastic bottles, and other containers based on a polymeric substrate that eliminate the need to add preservatives directly into the food product.
  • the invention provides for coatings comprising various polymeric coating vehicles which adheres well to a polymeric substrate, and one or more food grade preservatives, which when applied to the polymeric substrate, becomes integrated into the structure of the substrate.
  • this invention provides compositions of antimicrobial inner coatings to packaging containers, such as polyethylene terephthalate (PET) such that microbial survival is prevented under all conditions starting from the initial filling of the container with food or other items through the extent of its storage life.
  • packaging containers such as polyethylene terephthalate (PET)
  • this invention provides solvent-based coating systems that are antimicrobial and adhere well to PET and other polymeric substrates, and are formulated with FDA approved food preservatives.
  • the invention provides for antimicrobial compositions that may be directly incorporated into polymeric resin, that results in a finished container with antimicrobial activity, and methods for making same.
  • the invention provides for plastic containers that discourage microbial growth during storage of perishable and other items, and releases small quantities of various antimicrobial reagents into the item in a time dependent manner.
  • the antimicrobial activity in plastics is dependent on the molecular diffusion of the biocide and its slow release into the juice.
  • Polymers that exhibit a low glass transition temperature usually allow this diffusion to occur fast enough to provide adequate protection against the proliferation of microbes.
  • an additive when added to these polymers, it diffuses through the thickness of the substrate polymer and "blooms" to the surface, where it comes into contact with the food medium.
  • PET polyethylene terephthalate
  • PET polyethylene terephthalate
  • current PET containers used for juice packing are quite thin and substance applied to the container needs to provide a high area of contact with the juice in order to be effective.
  • a composition of antimicrobial agents having desired properties is incorporated into a coating which is then applied to at least the inner surface of the container, either in a pre-formed state (prior to stretch blow molding) or in the finished state.
  • Application of the coating to the finished packaging article is ideal when the antimicrobial articles are temperature-sensitive, or otherwise not suited for treatment with high temperatures.
  • additive candidates include sorbates, dicarbonic esters, sulfites. carbonates, Nisin, biphenyls, Nystatin, benzoic acid, salicylic acid, parabens, and phenols.
  • the coating containing these additives may be applied to a pre-form of the polymeric resin, which is then heated to about 100-120C and stretch blow molded to its final dimensional specifications.
  • the antimicrobial ingredients are directly blended into the polymeric resin that is then melted at relatively higher temperatures to create the finished plastic container.
  • This direct blending typically takes place at or above the melting point of the polymeric resin, e.g. about 530F for PET resin.
  • Such high temperature direct blending is suitable for additives that do not generally decompose at these temperatures, such as benzoates, propionates. nanosilver. thiabendazole, silver salicylates. silver fluorides, copper carbonates, nanocopper. silver powder, or phosphates.
  • the first is a biodegradable polyester, aka biopolyester (biopolyethylene terephthalate, or BPET) sold by Eastman Chemicals. Kings Port, Tennessee, EASTSTAR Bio 14766TM which Applicant has determined is a suitable material to incorporate the various food preservatives which are compounds or combinations of compounds approved by the U.S. Food and Drug Administration as well as by regulatory agencies of various European countries.
  • a second suitable solvent-based coating vehicle is a polyester resin solution sold by Morton Adhesives and Chemical Specialties, by the trade name ADCOTE 40-3. Applicant has determined that this polyester resin is also suitable for use as a carrier for coating plastic bottles with food preservatives.
  • Applicant has found that when a coating vehicle such as BPET or polyester resin is combined with one or more preservatives and applied to a finished container, acceptable levels of biocidal activity are achieved. Furthermore, Applicant has determined that effective levels of biocidal activity may also be achieved when the preservative/coating vehicle is applied to a preform bottle prior to stretch blow molding, and also when directly incorporated into the polymeric resin raw material prior to pre-forming and stretch blow molding. In particular, direct blending of certain food preservatives with PET resin were effective when followed by fabrication of pressed films from about 500F to 550F.
  • PET and various other polymeric materials are commonly used in the food and beverage packaging industry.
  • pellets of PET or other polymeric material is melted, typically at a temperature of about 530F for PET, in single or multi-layers, comprising the same or difference polymeric materials, and injection-molded into a pre-form.
  • resin pre-forms can be created using standard equipment such as that sold by Husky of Toronto, Canada.
  • the pre-form is then stretched blow molded at a lower temperature, typically about 100-150C with hot air to expand and stretch the pre-form to its desired dimensional specifications, again using standard equipment such as blow-molding equipment sold by Sidel of France.
  • multi-layer PET-based bottles comprise a barrier layer such as nylon material, interspersed among virgin layers of PET which form the outer surfaces.
  • preservatives may be employed.
  • sulfite salts such as calcium sulfite and sodium sulfite are also possible candidates for direct incorporation into the polymeric resin used to create the packaging material. These preservatives will diffuse to the surface of the container in contact with food and are hydrolyzed to produce sulfur dioxide which is an excellent inhibitor of mold and yeast.
  • Such compounds which hydrolyze and release sulfur dioxide or carbon dioxide may be incorporated in the polymeric substrate such as PET, by a direct addition into the PET resin prior to melting or as a coating on a pre-form or stretch-molded PET container depending on their thermal stability.
  • carbon dioxide releasing chemicals may be carbonates of Ca, Mg or other non-toxic metals or dicarbonic acid esters. For instance, dimethyl esters (Sigma) and diethyl esters are well known to release carbon dioxide and ethanol at low levels.
  • additives may comprise copper salts such as carbonates or chlorides or other non-toxic anions.
  • divalent copper ions react with ascorbic acid producing hydrogen peroxide and transient -OH radicals which could prove to be of extreme value in biocidal action.
  • the -OH radicals and hydrogen peroxide have broad spectrum biocidal effects.
  • the bottles were then capped by caps subjected to the same temperature and carefully wrapped in aluminum foil heated to the same temperature.
  • the Morton's ADCOTE material which comes as a dispersion of 65%- solids in MEK (methyl ethyl ketone). the following procedure was used. The ADCOTE dispersion is diluted about 3 times, and a 3% benzoic acid solution was prepared in this dispersion. Each dried bottle was coated with 10 ml of this dispersion with and without the preservative, benzoic acid. After 24 hours, the bottles were subjected to a heat treatment for 15 minutes at 150C.
  • formulations include 2% ethyl paraben. 2% propyl paraben (Sigma Chemical) plus 0.1 % silver powder having an average particle size 1 micron (Cerac Corporation). Each bottle was coated with 10 ml of these formulation in triplicate. The bottle codes and the formulations are shown below.
  • P. roqitefortii and Zygosaccharomyces Bacilli Two cultures, a mold and a yeast (P. roqitefortii and Zygosaccharomyces Bacilli) were received from a commercial juice processing plant.
  • the P. Roqitefortii species was grown in malt extract broth (MEB) and then maintained on malt extract agar plates.
  • the yeast species was grown in potato dextrose broth (PDB) and maintained on potato dextrose agar (PDA) plates. All incubations were carried out at 25C in an incubator.
  • the media used for the microbiological tests was pasteurized apple juice commercially available off the store shelf. The sterility of this juice medium was often checked by assaying the juice.
  • a potato dextrose agar plate containing Z Bacilli, an yeast was used.
  • a loopful of yeast cells was inoculated into 5ml of sterile PBD (Difco) at 25C for 48hrs.
  • the optical density (OD) of the juice suspension was measured after gently vortexing at 550 nm against a PDB blank. OD was determined to be approximately 1.048.
  • the bottles to be inoculated, as well as the set of control bottles were filled with commercially available filtered apple juice at 170F (whose sterility was confirmed with repeated tests) and then allowed to cool to room temperature.
  • Each bottle except the control bottles) were inoculated with about 100 cells of the Penicillium mold or with Zygosaccharamyces Bacilli yeast species.
  • the inoculated bottles were gently swirled and left undisturbed in an incubator at 25C. Over the course of three weeks, the inoculated bottles were visually inspected for the appearance of mold growth on the surfaces of the apple juice samples. For the yeast, the bottles were gently removed and held against bright light to check for turbidity of the juice. The results of the visual inspection tests for two sets of tests are given below.
  • the juice media was assayed by spreading 100 microliters on a PDA plate for the yeast and MEA plate for the mold.
  • Tables III, IV, and V show microbiological challenge results of the juice contacting the various coated and uncoated bottles.
  • Table III shows the use of a coating comprising benzoic acid and BPET.
  • the benzoic acid when added to the coating at a concentration of 3.0% (all of the "A" samples), was effective at inhibiting the growth of yeast. Assuming that all of the benzoic acid in the coating dissolved instantly and diffused into the apple juice, this coating would provide 0.1% w/v concentration of benzoic acid in the juice. It is, however, possible that the benzoic acid in the coating did not come into contact with the juice at once but slowly partitioned between the juice and the coating.
  • the acidity of the juice decreases the solubility considerably (compared to the solubility of benzoic acid in water of 0.34g/100gm of water).
  • the "B" samples contain 1.5% benzoic acid in the coating.
  • the maximum concentration of benzoic acid provided in the apple juice is 0.05% benzoic acid.
  • This method has a detection limit of ⁇ 10 cfu/ml.
  • Table IV shows the ability of benzoic acid to inhibit the growth of mold when used as a coating in conjunction with BPET. The same coating concentrations were utilized as in Table III.
  • This method has a detection limit of ⁇ 10 cfu/ml.
  • Table V shows the use of benzoic acid to inhibit the growth of yeast in plastic bottles coated with a combination of benzoic acid and either BPET or ADCOTE polyester resin.
  • the bottles labeled AD contained ADCOTE-based coatings, while bottles labeled BMS and D contained BPET based coatings.
  • This method has a detection limit of ⁇ 10 cfu/ml.
  • Tables VI and VII show the release of various preservatives from BPET-based coating as a function of time.
  • Table VI Concentrations of Antimicrobials in Apple Juice of Coated Bottles as a Function of Time
  • BPET was used as the coating vehicle.
  • AD ADCOTE as coating vehicle.
  • D and BMS BPET as coating vehicle.
  • plastic bottles are fabricated in two stages.
  • the plastic resin such as PET
  • the pre-form is stretch blow molded to its final specifications at about 150C (about 330F).
  • PET Polyethylene terephthalate
  • the additives such as potassium benzoate, calcium propionate, or silver benzoate or citrate (1-5% by weight) were mixed with the PET pellets and melt pressed at 540F using a hydraulic press. Control PET films without the additive were also made under the same conditions. Small strips of 1cm by 3 cm were cut and used for the microbiological assays.
  • Table VII shows the efficacy of additive potassium benzoate that was directly added to PET resin prior to melting in inhibiting microbial growth.
  • the release rate of the additive as well as the dispersion of the additive caused some variations. It is clear from the preliminary results that the potassium benzoate is very effective in completely inhibiting the mold and yeast species.
  • both the control blanks and the control disks showed turbidity (indicating growth of microbial colonies) after 48 hours of incubation at 25C. The sample disks inhibited growth completely, reducing the cell numbers to zero, as evidenced by the plate counts.
  • 3 sterile strips were placed in 3 tubes containing 3 ml of sterile apple juice from a commercial bottle, and challenged at two levels 1 ) lOOOcells /3mL (approximately 300cells/mL) and lOOcells /3mL (30 cells/ml).
  • Each tube contained one of the following: a) additive-incorporated PET strip, b) control PET strip; c) no PET strip (control blank containing juice only).
  • Duplicate samples of the strips were also placed in tubes of sterile apple juice and inoculated with lOuL of 10 s cfu/ml or lOuL of 10 4 cfu/mL of the yeast species.
  • the mold inoculation was conducted using the same procedure, in another set of tubes containing the samples, controls, and control blanks. Both visual and plate counts were monitored for all the test tubes and carefully recorded.
  • Nanophase silver (Nanophase Technologies, Illinois) is an high surface area material with particle sizes typically ranging from 2 to 20 nanometers.
  • nanosilver refers to silver particles with a size smaller than one micron. Such dimensions are very close to molecular dimensions and several advantages can be realized by this invention.
  • the blending of the silver with the PET resin, and the high surface area of nanosilver results in a high level of activity of silver at low loading.
  • Nanotechnology is a nascent area and the uses of nanosilver as a biocide has distinct advantages, namely, greatly increased surface area of active silver per equivalent weight of silver having the same general particle geometry.
  • Nanoparticles of silver were prepared having approximate dimensions of 2 x 20 x 20 nanometers. (National Institute of Mat. Chem. Res., Tsukuba Ibaraki, Japan (1997)). These particles have volumes of approximately 800 cubic nanometers and surface areas of 500-600 square nanometers or approximately 10 34 square nanometers of surface area per milligram of silver. Because of the increased surface area, a smaller mass of silver is required to obtain greatly enhanced protection.
  • nanosilver in combination with other compounds such as bismuth subsalicylate may prevent bacterial adhesion to plastic surfaces.
  • a second, and surprising effect of nanosilver is its ability to accelerate the cure rate of certain polymers. Applicant found that the addition of nanosilver particles facilitated the curing of the polyurethane prepolymer, HYPOLTM, in the presence of phenolic compounds.
  • a formulation was prepared by blending nanosilver with terpinol or thiabendazole. Normally, these phenolic compounds inhibit or block the curing of HYPOLTM; however, the addition of nanosilver appears to overcome this problem.
  • a formulation combining different preservatives was prepared by blending 46g of thiabendazole (Sigma - Aldrich Chemical, Minnesota), 46g of sodium salicylate (Sigma - Aldrich) and lg of nanosilver (as a suspension in alpha terpinol (Nanophase Technologies. Illinois) in a 2L base of a mineral oil compound.
  • SPAN- 85.TM thiabendazole
  • sodium salicylate Sigma - Aldrich
  • nanosilver as a suspension in alpha terpinol (Nanophase Technologies. Illinois
  • Thiabendazole is an anti fungal compound fruit that is normally sprayed on citrus and other fruits. Residuals of this compound are found in various fruit juices , milk and meat. Thiabendazole is an excellent candidate for direct addition to high melting plastics such as PET due to its high melting point (about 305C) , which allows the compound to survive temperatures as high as 550F for PET bottle processing without decomposing.
  • the formulation was then metered in during the processing of the PET bottles using standard plastic bottle manufacturing equipment (Husky. Inc., Toronto, Canada) (Continental PET Technologies, New Hampshire). Pre-forms were made and then finished by stretch blow molding. No special processing changes were made and no problems were reported by the bottle manufacturer.
  • the additive incorporated plastic PET bottles were then evaluated for their biocidal properties and also analyzed for the actual additive concentrations in the plastic and the contacting juice.
  • a salicylic acid based composition was tested as well.
  • a blend of lOOg of salicylic acid (Sigma - Aldrich) and 23 g of thiabendazole was added to a base of 2L of SPAN-85. This blend was added to PET resins, and the resultant mixture was processed into a bottle by first pre-forming at a higher temperature followed by and stretch blow molding to final bottle specifications and then hot-filling heated apple juice at a lower temperature (170F).
  • the apple juice may be added in a heated, cooled, or chilled state.
  • 0.5 ppm, 1 ppm. and 2 ppm of silver salicylate was introduced into 500 ml of apple juice containing bottles followed by the inoculation of a mold or yeast species
  • Control bottles contained no added sih er salicylate but contained the same number of organisms as the test bottles
  • the silver salicylate treated samples did not show any growth w hile heavy growth was noticed in the controls after only 4o ⁇ 5 days
  • This example describes a coating composition that could be useful for a broad spectrum of applications especially for catheters, stents or for any biomate ⁇ al susceptible to microbial contamination or infection
  • a coating formulation was made as follows: lOg of HYPOL 5000TM( Dow Chemical), lg of titanium oxide (Degussa). 50mg of nanosilver (Nanophase Technologies), lg of paraben (e.g. butyl) (Sigma Company), and 0.2 g bismuth subsalicylate (Alfa -Aesar. MA).
  • the HYPOLTM was mixed with the above ingredients diluted to about 20ml . This was then coated on a TECOFLEXTM EG 80A (Thermedics , MA) tubing by a dip coating method and dried overnight. Surprisingly the coating cured rapidly overnight. This result was surprising as phenolic compounds such as the parabens typically inhibit the curing process of isocyanates. It is one theory that the activity of the nanosilver in the compound overcame the inhibition.
  • the 2" coated tubes and controls were exposed to 10 cfu/ml of S. aureus and E. coli (American Type Culture Collection) for 3 hours, followed by washing and incubation in a growth medium of phosphate-buffered solution (PBS) and 10% BHIB (Brain-Heart Infusion Broth), a very rich growth medium.
  • PBS phosphate-buffered solution
  • BHIB Brain-Heart Infusion Broth
  • control samples allowed for the adhesion and the survival of the bacteria on the HYPOLTM substrate, as evidenced by visible growth in 1 day.
  • the coated tubes resisted the bacterial adhesion and inhibited growth for up to 15 days.

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Environmental Sciences (AREA)
  • Zoology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Plant Pathology (AREA)
  • Wood Science & Technology (AREA)
  • Dentistry (AREA)
  • Toxicology (AREA)
  • Biodiversity & Conservation Biology (AREA)
  • Mechanical Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

Les bouteilles ou les récipients en polyéthylène téréphthalate ou PET sont couramment utilisés par les industries des boissons et de l'alimentation. Les bouteilles multicouche munies de couches en polyéthylène sont également utilisées. Plusieurs autres matières plastiques, utilisées dans les industries de l'alimentation, des cosmétiques et de la consommation ainsi que dans les industries médicales, sont sujettes à contamination et à formation de films biologiques par des micro-organismes. L'invention concerne un procédé qui permet d'incorporer des compositions antimicrobiennes dans des plastiques tels que le PET. En l'occurrence, elle concerne un procédé qui permet d'incorporer des formulations et compositions antimicrobiennes comme revêtements à l'intérieur de bouteilles, préformes, joints ou récipients de traitement qui libèrent lentement des conservateurs alimentaires dans les boissons ou aliments en contact afin de prévenir leur altération. L'invention concerne enfin un procédé d'incorporation directe dans la résine de PET.
PCT/US2000/005967 1999-03-06 2000-03-06 Plastiques antimicrobiens Ceased WO2000053413A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU40069/00A AU4006900A (en) 1999-03-06 2000-03-06 Antimicrobial plastics

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US12311999P 1999-03-06 1999-03-06
US60/123,119 1999-03-06

Publications (1)

Publication Number Publication Date
WO2000053413A1 true WO2000053413A1 (fr) 2000-09-14

Family

ID=22406820

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2000/005967 Ceased WO2000053413A1 (fr) 1999-03-06 2000-03-06 Plastiques antimicrobiens

Country Status (2)

Country Link
AU (1) AU4006900A (fr)
WO (1) WO2000053413A1 (fr)

Cited By (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1114583A3 (fr) * 1999-12-20 2001-09-19 Ciba SC Holding AG Concentrés biocides contenant un polyester et compositions biocides préparées à partir de ceux-ci
EP1362885A1 (fr) * 2002-05-17 2003-11-19 Kenji Nakamura Matériau ayant un traitement antibacterien et procédé pour inhiber sa coloration
WO2004056214A3 (fr) * 2002-12-23 2004-08-19 Inst Of Chemical Technology Pr Procede de preparation de materiaux d'emballage bioactifs
EP1642562A3 (fr) * 1999-06-17 2007-07-18 Bio-Gate AG Produit antimicrobien pour les soins du corps
DE102007003648A1 (de) * 2007-01-18 2008-07-24 Rebac Gmbh Kupferenthaltende Formmasse aus Polyester, ihre Herstellung und Verwendung
DE102007003662A1 (de) * 2007-01-18 2008-07-24 Rebac Gmbh Kupfer(I)enthaltende Formmasse aus Polyester, ihre Herstellung und Verwendung
DE102007003649A1 (de) * 2007-01-18 2008-07-24 Rebac Gmbh Kupfer(II)enthaltende Formmasse aus Polyester, ihre Herstellung und Verwendung
EP1972197A3 (fr) * 2007-03-12 2009-05-27 Wiberg GmbH Emballage de produits alimentaires doté de propriétés antimicrobiennes et son procédé de fabrication
FR2925264A1 (fr) * 2007-12-19 2009-06-26 Oreal Dispositif de conditionnement.
WO2009150424A1 (fr) * 2008-06-11 2009-12-17 Dupont Teijin Films U.S. Limited Partnership Film polymère antimicrobien et procédé de fabrication dudit film
US7705078B2 (en) 2004-06-25 2010-04-27 Dupont Teijin Films U.S. Limited Partnership Antimicrobial polymeric film
US7704530B2 (en) 2001-09-14 2010-04-27 Kenji Nakamura Antimicrobially treated material and methods of preventing coloring thereof
ITMI20082064A1 (it) * 2008-11-20 2010-05-21 Consiglio Naz Delle Ricerche 16 67 Metodo per la produzione di un film di materia termoplastica contenente una sostanza ad attività antimicrobica e utilizzo di tale film nella produzione di confezioni per alimenti
WO2010137015A3 (fr) * 2009-05-25 2011-03-03 Oplon B.V Récipient bioactif
CZ303531B6 (cs) * 2011-01-26 2012-11-14 Invos, Spol. S. R. O. Hygienický obal s antimikrobiální úpravou vnejší plochy a zpusob jeho výroby
WO2013149356A1 (fr) * 2012-04-02 2013-10-10 Universidad De Santiago De Chile Récipient conçu pour prolonger la durée de conservation des aliments qu'il contient, plus particulièrement des baies, par incorporation sur la surface d'un agent antifongique. en particulier des baies procédé de préparation et utilisations
WO2014001541A1 (fr) * 2012-06-29 2014-01-03 University College Cork, National University Of Ireland Cork Emballage alimentaire antimicrobien
WO2015023644A3 (fr) * 2013-08-12 2015-04-09 PurThread Technologies, Inc. Fibres polymères antimicrobiennes et antifongiques, tissus, et leurs procédés de fabrication
US20150257381A1 (en) * 2014-03-13 2015-09-17 Shenkar College Of Engineering And Design Antimicrobial polymeric film and composition
US20150291806A1 (en) * 2012-04-24 2015-10-15 At Promotions Ltd Anti-microbial drinking or eating vessel
US9856055B2 (en) 2014-04-29 2018-01-02 At Promotions Ltd Drinking or eating vessel
US9878480B1 (en) 2014-06-24 2018-01-30 PurThread Technologies, Inc. Method for making polymer feedstock usable for generation of fiber having anti-microbial properties
US10080363B2 (en) 2010-10-18 2018-09-25 PurThread Technologies, Inc. Method for generating a halogen-stable anti-microbial synthetic fiber
WO2019229495A1 (fr) 2018-05-29 2019-12-05 Copperprotek Spa. Microparticules de cuivre multicomposites microstructurées à activité antibactérienne et/ou biocide comprenant 5 différents types de composés de cuivre
FR3085105A1 (fr) * 2018-08-22 2020-02-28 Commissariat A L'energie Atomique Et Aux Energies Alternatives Nouvel agent antimicrobien a base de materiau polymerique particulaire poreux dope
US10947011B2 (en) 2014-12-22 2021-03-16 At Promotions Ltd Drinking or eating vessel
US10973349B2 (en) 2017-01-10 2021-04-13 At Promotions, Ltd Vacuum decoration of a drinking or eating vessel

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4895877A (en) * 1984-06-11 1990-01-23 Morton Thiokol, Inc. Microbiocidal compositions comprising an aryl alkanol and a microbiocidal compound dissolved therein
US5102657A (en) * 1988-10-11 1992-04-07 Morton International, Inc. Microbiocidal compositions
JPH0948094A (ja) * 1995-06-02 1997-02-18 Tootsuya:Kk 抗菌性素材及びその製造方法
JPH0957923A (ja) * 1995-08-29 1997-03-04 Toray Ind Inc 抗菌性複合延伸ポリエステルフィルム
US5614568A (en) * 1992-12-25 1997-03-25 Japan Synthetic Rubber Co., Ltd. Antibacterial resin composition
US5869073A (en) * 1993-12-20 1999-02-09 Biopolymerix, Inc Antimicrobial liquid compositions and methods for using them

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4895877A (en) * 1984-06-11 1990-01-23 Morton Thiokol, Inc. Microbiocidal compositions comprising an aryl alkanol and a microbiocidal compound dissolved therein
US5102657A (en) * 1988-10-11 1992-04-07 Morton International, Inc. Microbiocidal compositions
US5614568A (en) * 1992-12-25 1997-03-25 Japan Synthetic Rubber Co., Ltd. Antibacterial resin composition
US5869073A (en) * 1993-12-20 1999-02-09 Biopolymerix, Inc Antimicrobial liquid compositions and methods for using them
JPH0948094A (ja) * 1995-06-02 1997-02-18 Tootsuya:Kk 抗菌性素材及びその製造方法
JPH0957923A (ja) * 1995-08-29 1997-03-04 Toray Ind Inc 抗菌性複合延伸ポリエステルフィルム

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Derwent World Patents Index; AN 1997-187730 *
DATABASE WPI Derwent World Patents Index; AN 1997-208089 *

Cited By (40)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1642562A3 (fr) * 1999-06-17 2007-07-18 Bio-Gate AG Produit antimicrobien pour les soins du corps
US6475505B1 (en) 1999-12-20 2002-11-05 Ciba Specialty Chemicals Corporation Biocide-polyester concentrates and biocidal compositions prepared therefrom
US7041307B2 (en) 1999-12-20 2006-05-09 Ciba Specialty Chemicals Corporation Biocide-polyester concentrates and biocidal compositions prepared therefrom
EP1114583A3 (fr) * 1999-12-20 2001-09-19 Ciba SC Holding AG Concentrés biocides contenant un polyester et compositions biocides préparées à partir de ceux-ci
US7704530B2 (en) 2001-09-14 2010-04-27 Kenji Nakamura Antimicrobially treated material and methods of preventing coloring thereof
EP1362885A1 (fr) * 2002-05-17 2003-11-19 Kenji Nakamura Matériau ayant un traitement antibacterien et procédé pour inhiber sa coloration
WO2004056214A3 (fr) * 2002-12-23 2004-08-19 Inst Of Chemical Technology Pr Procede de preparation de materiaux d'emballage bioactifs
US7705078B2 (en) 2004-06-25 2010-04-27 Dupont Teijin Films U.S. Limited Partnership Antimicrobial polymeric film
DE102007003648A1 (de) * 2007-01-18 2008-07-24 Rebac Gmbh Kupferenthaltende Formmasse aus Polyester, ihre Herstellung und Verwendung
DE102007003662A1 (de) * 2007-01-18 2008-07-24 Rebac Gmbh Kupfer(I)enthaltende Formmasse aus Polyester, ihre Herstellung und Verwendung
DE102007003649A1 (de) * 2007-01-18 2008-07-24 Rebac Gmbh Kupfer(II)enthaltende Formmasse aus Polyester, ihre Herstellung und Verwendung
EP1972197A3 (fr) * 2007-03-12 2009-05-27 Wiberg GmbH Emballage de produits alimentaires doté de propriétés antimicrobiennes et son procédé de fabrication
FR2925264A1 (fr) * 2007-12-19 2009-06-26 Oreal Dispositif de conditionnement.
WO2009081344A1 (fr) * 2007-12-19 2009-07-02 L'oreal Dispositif de conditionnement
WO2009150424A1 (fr) * 2008-06-11 2009-12-17 Dupont Teijin Films U.S. Limited Partnership Film polymère antimicrobien et procédé de fabrication dudit film
ITMI20082064A1 (it) * 2008-11-20 2010-05-21 Consiglio Naz Delle Ricerche 16 67 Metodo per la produzione di un film di materia termoplastica contenente una sostanza ad attività antimicrobica e utilizzo di tale film nella produzione di confezioni per alimenti
WO2010057658A3 (fr) * 2008-11-20 2010-07-15 Università Degli Studi Di Foggia Procédé de fabrication d'un film de matière thermoplastique contenant une substance avec une activité antimicrobienne et utilisation de ce film dans la fabrication de conditionnement pour aliment
WO2010137015A3 (fr) * 2009-05-25 2011-03-03 Oplon B.V Récipient bioactif
US10506805B2 (en) 2010-10-18 2019-12-17 PurThread Technologies, Inc. Method for generating a halogen-stable anti-microbial synthetic fiber
US10080363B2 (en) 2010-10-18 2018-09-25 PurThread Technologies, Inc. Method for generating a halogen-stable anti-microbial synthetic fiber
CZ303531B6 (cs) * 2011-01-26 2012-11-14 Invos, Spol. S. R. O. Hygienický obal s antimikrobiální úpravou vnejší plochy a zpusob jeho výroby
WO2013149356A1 (fr) * 2012-04-02 2013-10-10 Universidad De Santiago De Chile Récipient conçu pour prolonger la durée de conservation des aliments qu'il contient, plus particulièrement des baies, par incorporation sur la surface d'un agent antifongique. en particulier des baies procédé de préparation et utilisations
US9763439B2 (en) 2012-04-02 2017-09-19 Universidad De Santiago De Chile Method of packaging food
US10125270B2 (en) * 2012-04-24 2018-11-13 At Promotions Ltd Anti-microbial drinking or eating vessel
US20150291806A1 (en) * 2012-04-24 2015-10-15 At Promotions Ltd Anti-microbial drinking or eating vessel
WO2014001541A1 (fr) * 2012-06-29 2014-01-03 University College Cork, National University Of Ireland Cork Emballage alimentaire antimicrobien
US9908987B2 (en) 2013-08-12 2018-03-06 PurThread Technologies, Inc. Antimicrobial and antifungal polymer fibers, fabrics, and methods of manufacture thereof
WO2015023644A3 (fr) * 2013-08-12 2015-04-09 PurThread Technologies, Inc. Fibres polymères antimicrobiennes et antifongiques, tissus, et leurs procédés de fabrication
US10508188B2 (en) 2013-08-12 2019-12-17 PurThread Technologies, Inc. Antimicrobial and antifungal polymer fibers, fabrics, and methods of manufacture thereof
US20150257381A1 (en) * 2014-03-13 2015-09-17 Shenkar College Of Engineering And Design Antimicrobial polymeric film and composition
US10611525B2 (en) 2014-04-29 2020-04-07 At Promotions, Ltd Drinking or eating vessel
US20180155082A1 (en) 2014-04-29 2018-06-07 At Promotions Ltd Drinking or eating vessel
US10273055B2 (en) 2014-04-29 2019-04-30 At Promotions Ltd Drinking or eating vessel
US9856055B2 (en) 2014-04-29 2018-01-02 At Promotions Ltd Drinking or eating vessel
US9878480B1 (en) 2014-06-24 2018-01-30 PurThread Technologies, Inc. Method for making polymer feedstock usable for generation of fiber having anti-microbial properties
US10947011B2 (en) 2014-12-22 2021-03-16 At Promotions Ltd Drinking or eating vessel
US10973349B2 (en) 2017-01-10 2021-04-13 At Promotions, Ltd Vacuum decoration of a drinking or eating vessel
WO2019229495A1 (fr) 2018-05-29 2019-12-05 Copperprotek Spa. Microparticules de cuivre multicomposites microstructurées à activité antibactérienne et/ou biocide comprenant 5 différents types de composés de cuivre
US10570022B2 (en) 2018-05-29 2020-02-25 Copperprotek Spa Microstructured multicomposite copper microparticle with antibacterial and/or biocidal activity that comprises in its structure 5 different types of copper compounds, all regular and crystalline
FR3085105A1 (fr) * 2018-08-22 2020-02-28 Commissariat A L'energie Atomique Et Aux Energies Alternatives Nouvel agent antimicrobien a base de materiau polymerique particulaire poreux dope

Also Published As

Publication number Publication date
AU4006900A (en) 2000-09-28

Similar Documents

Publication Publication Date Title
WO2000053413A1 (fr) Plastiques antimicrobiens
Singh et al. Role of plastics additives for food packaging
DE69701637T2 (de) Sauerstoffentfernende kondensations-copolymere für flaschen und verpackungskörper
EP2685835B1 (fr) Procédé d'obtention d'un film qui comprend l'incorporation d'agents antimicrobiens naturels dans une structure polymère
CN101313698A (zh) 果蔬纳米抗菌保鲜膜
US20120087968A1 (en) Antimicrobial Packaging Material and Methods of Making and Using the Same
CN111333888A (zh) 可降解聚乳酸抗菌膜及其制备方法
CN113234307A (zh) 一种全降解抗菌食品包装膜及其制备方法
CN115058076B (zh) 一种抗菌抗氧化色母、塑料瓶及其制备方法
CN111303525A (zh) Pe防雾抗菌保鲜收缩膜及其制备方法
EP0527903B1 (fr) Recipient et son procede de production
EP1786267B1 (fr) Film polymere antimicrobien
CN118580599A (zh) 一种防雾防霉的稀土抗菌保鲜膜及其制备方法
CN113583422A (zh) 一种抗菌功能的生物降解保鲜膜及其制备方法
EP3481197B1 (fr) Films d'emballage antimicrobiens
DE69803228T2 (de) Aktive und passive sauerstoffbarriere aus copolyamidharzen
US11566116B2 (en) Biologically active polymers prepared via reactive extrusion
Farousha et al. The future of food preservation: Active packaging with controlled release systems
US20250319640A1 (en) Active and/or intelligent packaging materials containing radical scavenging ligands
Rooney Active packaging: Science and application
AU690750B2 (en) Inhibition of the growth of micro-organisms
TWI768437B (zh) 保鮮膜結構及其製造方法
KR100600492B1 (ko) 나노 수산화알루미늄이 함유된 식품 포장재 및 그 제조방법
JP4972846B2 (ja) 防曇剤、防曇剤液、包装材料、生鮮品の鮮度保持方法、および生鮮品
Brandelli et al. Antimicrobial Packaging for Dairy Products

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AL AM AT AU AZ BA BB BG BR BY CA CH CN CR CU CZ DE DK DM EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT TZ UA UG US UZ VN YU ZA ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH GM KE LS MW SD SL SZ TZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

122 Ep: pct application non-entry in european phase