WO2015040642A1 - Procédé pour préparer une matière polymère antibactérienne pour des applications alimentaires - Google Patents

Procédé pour préparer une matière polymère antibactérienne pour des applications alimentaires Download PDF

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Publication number
WO2015040642A1
WO2015040642A1 PCT/IT2013/000254 IT2013000254W WO2015040642A1 WO 2015040642 A1 WO2015040642 A1 WO 2015040642A1 IT 2013000254 W IT2013000254 W IT 2013000254W WO 2015040642 A1 WO2015040642 A1 WO 2015040642A1
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WO
WIPO (PCT)
Prior art keywords
zinc
process according
polymer material
source
ions
Prior art date
Application number
PCT/IT2013/000254
Other languages
English (en)
Inventor
Sabrina Sangiorgi
Linda Sangiorgi
Norberto Roveri
Marco Marchetti
Marco Lelli
Francesca RINALDI
Rocco MERCURI
Rosanna CAPPARELLI
Chiara MEDAGLIA
Nunzia NOCERINO
Andrea FULGIONE
Original Assignee
B.B.S. S.P.A.
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 B.B.S. S.P.A. filed Critical B.B.S. S.P.A.
Priority to PCT/IT2013/000254 priority Critical patent/WO2015040642A1/fr
Publication of WO2015040642A1 publication Critical patent/WO2015040642A1/fr

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Classifications

    • 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

Definitions

  • the present invention relates in general terms to a process for the preparation of an antibacterial polymer material comprising Zn 2+ ions, and to the use of said material for the manufacture of products to be used in food applications, for example in the form of plates, glasses and tableware in general.
  • Zinc has also long been known as an antibacterial agent and is commonly used both in the pharmaceutical and food industries, for example in food and bone supplements to enhance the body's immune defences. Zinc has industrial application also in the preparation of antibacterial coatings for sanitary and/or medical materials and surfaces.
  • US5460644 describes the use of zinc ammonium in the preparation of an antibacterial coating for various kinds of manufactured products.
  • US2002012760 discloses a tray manufactured with a polymer material with antibacterial properties, made by using ceramic materials and, in particular, zeolites functionalized with metal ions, namely: Mg 2+ , Ag + , Zn 2+ and Cu 2+ .
  • US5102401 describes the use of polymers with antibacterial properties made by using zeolites loaded with silver ions.
  • the Applicants have found that when a starting polymer material is mixed with a source of Zn 2+ ions comprising at least the zinc salt of pyrrolidone carboxylic acid (ZnPCA), it is possible to obtain, by extrusion, an antibacterial polymer material that is particularly suitable for food-related applications, for example in the manufacture of products such as plates, cutlery and the like. Moreover, the Applicants have found that said mixing can take place both before and after the step of extruding the polymer material, making the present process highly versatile and applicable to a vast range of polymeric materials.
  • ZnPCA pyrrolidone carboxylic acid
  • the present invention relates to an extrusion process for the preparation of an antibacterial polymer material, which comprises mixing a starting polymer material with a source of Zn 2+ ions comprising at least ZnPCA, wherein said mixing can take place before or after the extrusion step.
  • the invention relates to the use of the material thus obtained for the manufacture of products for food applications.
  • the invention relates to a product for food applications manufactured from the polymer material obtained, or obtainable, with the process disclosed above.
  • Said product can be manufactured directly by extrusion or also by moulding of the extruded antibacterial polymer material.
  • the invention relates to a an extrusion process ("compounding") for the preparation of a polymer material for food applications which comprises an extrusion step that takes place at a temperature preferably comprised from 60° C to 290° C, as described in detail below.
  • the present process comprises the steps of:
  • the present process is extremely versatile, as it can be applied substantially to any type of polymer for food applications, depending, for example, on melt temperature. According to the latter, in fact, it is possible to opt for a pre-mixing of the component, or, alternatively, for mixing after the extrusion step.
  • the temperature is preferably comprised from about 80° C to about 290° C, more preferably from about 100° C to about 240° C.
  • the polymer for example in granular or powder form, is mixed with the source of ZnPCA and heated until reaching the melt temperature necessary for extrusion with a simultaneous addition of the zinc source.
  • the zinc source and the polymer material are pre-mixed dry, and the material thus obtained undergoes the extrusion process at the specified temperatures.
  • it is also possible to pre-mix the polymer and ZnPCA source in a wet state for example by preparing an aqueous solution of ZnPCA and mixing said solution with the selected polymer. In both cases, the two components (polymer and zinc source) will be intimately blended together, at the melt temperature of the polymer, leading to the formation by extrusion of the antibacterial polymer material for food applications of the invention.
  • the source of zinc ions is added at a temperature preferably comprised from about 80° C to about 220° C.
  • mixing after extrusion is particularly convenient in the event that the selected polymer has a melting point falling within the specified temperature interval.
  • extrusion in fact, can be either direct or reverse, and can be carried using apparatus used in the art, such as, for example single-screw extruders, twin screw extruders or the like.
  • the polymer material is selected from among: polyvinylchloride (PVC), polycarbonate (PC), polyethylene (PE), polypropylene (PP), polystyrene (PS), polyamide (PA), acrylonitrile butadiene styrene copolymer (ABS) , nylon, styrene acrylonitrile (SAN) , styrene butadiene (SB) , thermoplastic polyurethane (TPU) and melamine.
  • PVC polyvinylchloride
  • PC polycarbonate
  • PE polyethylene
  • PP polypropylene
  • PS polystyrene
  • PA polyamide
  • ABS acrylonitrile butadiene styrene copolymer
  • nylon nylon
  • SAN styrene acrylonitrile
  • SB styrene butadiene
  • TPU thermoplastic polyurethane
  • said material is selected from among: polyethylene (PE) , polypropylene (PP) , high- density polystyrene or transparent polystyrene, and polyamide (PA) .
  • the polymer material is preferably selected from among: polyvinylchloride (PVC) , polycarbonate (PC), polypropylene (PP) , polystyrene (PS), polyamide (PA), acrylonitrile butadiene styrene copolymer (ABS) , nylon, and styrene acrylonitrile (SAN) .
  • PVC polyvinylchloride
  • PC polycarbonate
  • PP polypropylene
  • PS polystyrene
  • PA polyamide
  • ABS acrylonitrile butadiene styrene copolymer
  • nylon styrene acrylonitrile
  • the polymer material obtained with the process of the invention has an amount of zinc ions such that it can be used as is, without there being any need to add other virgin polymer material.
  • the antibacterial material obtained with the process of the invention is in fact characterized in that it contains an amount of zinc ions comprised from about 5 ppm to 500 ppm, preferably comprised from about 20 ppm to 300 ppm. Such intervals make it possible, in practice, to use the material as obtained at the end of the present process or, optionally, as a master batch or additive to be added to another polymer for the production of a final antibacterial polymer.
  • the present process comprises the preferred use of a mixture comprising ZnPCA (zinc salt of pyrrolidone carboxylic acid) and at least one organic or inorganic zinc salt.
  • ZnPCA zinc salt of pyrrolidone carboxylic acid
  • said salt is selected from among: zinc acetate, zinc carbonate, zinc borate, zinc nitrate, zinc chloride, zinc hydroxide, zinc borate and zinc oxalate, or preferably mixtures thereof.
  • the zinc source comprises at least ZnPCA and zinc acetate, even more preferably in a percentage ratio by weight of 50:50.
  • ZnPCA is a compound that is widely used, for example, in the cosmetic industry and is readily available in the market in its dihydrate form, having the following general formula:
  • ZnPCA enables a substantially non-toxic antibacterial polymer material to be obtained without interfering with the physicochemical structure of the initial polymer. In fact, both the chemical and physical behaviour of the starting polymer, for example in relation to possible phenomena of swelling or the like, remain substantially unchanged at the end of the present process.
  • ZnPCA is present in the zinc source in amounts comprised from about 1% to 80% by weight, relative to the total weight, amounts comprised from about 5% to 50% being particularly preferred.
  • the zinc source can be added to the starting polymer material by wet mixing or, preferably, dry mixing.
  • the zinc source is added dry to the selected polymer material, for example in granular form, and the material obtained is subjected to extrusion, so that the two components are mixed hot and the formation of the antibacterial polymer material of the invention is thus obtained.
  • the zinc source is preferably added dry, for example in powder form, to the extruded material, even more preferably at a temperature comprised from 10 to 100 °C.
  • the zinc source can also be added in the form of an aqueous solution, prepared by dissolving the ZnPCA and the selected zinc salt(s) in an aqueous solvent, preferably distilled water.
  • the source of zinc ions in the form of an aqueous solution can thus be added to the polymer material during or after extrusion, using, for example, apparatus and methods known in the art.
  • the use of an aqueous solution is convenient in that it makes it possible to obtain an antibacterial material with a high degree of homogeneity of the components.
  • Said aqueous solution can have a total concentration of Zn 2+ ions preferably comprised from 10 to 15g/l, calculated considering the total weight of zinc salts relative to a litre of aqueous solution.
  • the present process makes it possible to obtain an antibacterial polymer material that is particularly suitable for the manufacture of products that can be used in food-related applications, for example in the form of plates, glasses, cutlery, tableware and the like.
  • the product obtained is a plate, an item of cutlery or a film.
  • Said product can be made to take on the desired form both by means of extrusion steps, or, alternatively, it can be shaped for example by moulding.
  • the antibacterial polymer material obtained at the end of the present process also shows high stability, so that the release over time of said zinc ions, or of other radicals or toxic by-products, is substantially avoided.
  • the polymer material obtained exhibits antibacterial properties both in bulk and superficially. This is particularly advantageous above all in the event that the product must perform its action at a surface level or its surface comes into contact with bacterial forms.
  • aqueous solutions la-lc are prepared by dissolving, in distilled water, under stirring at a temperature of about 25° C, for about 1 hour respectively:
  • the aqueous solutions obtained have a weight ratio of 12g of zinc salts per litre of distilled water.
  • aqueous solutions la-lc will then be used in the process of extruding the polymer matrix in a temperature interval comprised from 130 to 290° C.
  • the same solutions can be used in the mixing step after extrusion, at a temperature of 80-220° C.
  • Example 2 mixing of polymer grains with the Zn source in an amount such that the final amount of Zn varies from 5 to 500 ppm.
  • Grains of a polymer selected from among: PE, PPE, PET, PP, ABS, PS, SAN, SB, PUR are mixed with the source of zinc 2+ ions in the form of the aqueous solutions la-lc of example 1, or, alternatively, with the source of zinc ions in powder form comprising: ZnPCA, or ZnPCA and Zn acetate 50:50, or the zinc salts of solution lc, mixed dry.
  • the polymer compositions/source of Zn 2+ ions then undergo extrusion at the melt temperature of the polymer used, obtaining in each case an antibacterial polymer material which can be used to manufacture products for food applications.

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  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Inorganic Chemistry (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

De manière générale, l'invention concerne un procédé pour préparer une matière polymère antibactérienne comprenant des ions Zn 2+, ainsi que l'utilisation de cette matière pour la fabrication de produits pour des applications alimentaires. Le procédé selon l'invention permet d'obtenir une matière présentant des propriétés antibactériennes en vrac et superficiellement et étant stable dans le temps.
PCT/IT2013/000254 2013-09-19 2013-09-19 Procédé pour préparer une matière polymère antibactérienne pour des applications alimentaires WO2015040642A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/IT2013/000254 WO2015040642A1 (fr) 2013-09-19 2013-09-19 Procédé pour préparer une matière polymère antibactérienne pour des applications alimentaires

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/IT2013/000254 WO2015040642A1 (fr) 2013-09-19 2013-09-19 Procédé pour préparer une matière polymère antibactérienne pour des applications alimentaires

Publications (1)

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WO2015040642A1 true WO2015040642A1 (fr) 2015-03-26

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017182536A1 (fr) 2016-04-20 2017-10-26 Ineos Styrolution Group Gmbh Matières à mouler thermoplastiques non pénétrantes à effet antimicrobien

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4086297A (en) * 1975-11-28 1978-04-25 Ventron Corporation Method of making polymeric compositions and compositions therefor
US4218377A (en) * 1977-11-04 1980-08-19 Ciba-Geigy Corporation Metal salt/amine complexes
JPH03168240A (ja) * 1989-11-29 1991-07-22 Ajinomoto Co Inc 含ハロゲン樹脂組成物
JPH07179706A (ja) * 1993-12-24 1995-07-18 Aisero Kagaku Kk ポリビニルアルコール系フィルム
WO2001028556A2 (fr) * 1999-10-19 2001-04-26 The Procter & Gamble Company Compositions destinees a la prevention et au traitement du rhume et des symptomes de type grippal et procedes d'utilisation de ces dernieres
WO2009100164A2 (fr) * 2008-02-04 2009-08-13 Microban Products Company Elément d’étanchéité antimicrobien
RU128693U1 (ru) * 2011-10-13 2013-05-27 Михаил Алексеевич Попов Труба антибактериальная

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4086297A (en) * 1975-11-28 1978-04-25 Ventron Corporation Method of making polymeric compositions and compositions therefor
US4086297B1 (fr) * 1975-11-28 1988-06-28
US4218377A (en) * 1977-11-04 1980-08-19 Ciba-Geigy Corporation Metal salt/amine complexes
JPH03168240A (ja) * 1989-11-29 1991-07-22 Ajinomoto Co Inc 含ハロゲン樹脂組成物
JPH07179706A (ja) * 1993-12-24 1995-07-18 Aisero Kagaku Kk ポリビニルアルコール系フィルム
WO2001028556A2 (fr) * 1999-10-19 2001-04-26 The Procter & Gamble Company Compositions destinees a la prevention et au traitement du rhume et des symptomes de type grippal et procedes d'utilisation de ces dernieres
WO2009100164A2 (fr) * 2008-02-04 2009-08-13 Microban Products Company Elément d’étanchéité antimicrobien
RU128693U1 (ru) * 2011-10-13 2013-05-27 Михаил Алексеевич Попов Труба антибактериальная

Non-Patent Citations (5)

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Title
"AJIDEW ZN-100 (zinc salt of L-pyrrolidonecarboxylate)", 20 October 2011 (2011-10-20), Tokio, Japan, pages 1 - 2, XP055109396, Retrieved from the Internet <URL:http://www.innovadex.com/documents/1182666.pdf?bs=6835&b=238116&st=20> [retrieved on 20140324] *
DATABASE CA [online] CHEMICAL ABSTRACTS SERVICE, COLUMBUS, OHIO, US; 19 October 1995 (1995-10-19), MARUCHI, MASAHIRO ET AL: "Vinyl alcohol-type polymer films containing 2-pyrrolidone-5-carboxylic acid (salts) as plasticizer", XP002722132, retrieved from STN Database accession no. 1995:864865 *
DATABASE CA [online] CHEMICAL ABSTRACTS SERVICE, COLUMBUS, OHIO, US; 8 February 1992 (1992-02-08), TANAKA, TAKEO ET AL: "Halo-containing resin compositions with good thermal stability", XP002722133, retrieved from STN Database accession no. 1992:42613 *
DATABASE WPI Week 199135, Derwent World Patents Index; AN 1991-257268, XP002722129 *
REGLI P ET AL: "ETUDE IN VITRO DE L'ACTION ANTIFONGIQUE DES SELS DE CUIVRE ET DE ZINC DE L'ACIDE PYRROLIDONE CARBOXYLIQUE//IN VITRO STUDY ON FUNGICIDAL ACTION OF COPPER AND ZINC SALTS OF PYRROLIDONE CARBOXYLIC ACID", TRAVAUX DE LA SOCIETE DE PHARMACIE DE MONTPELLIER, SOCIETE DE PHARMACIE DE MONTPELLIER, MONTPELLIER, FR, vol. 38, no. FASC. 02, 1 January 1978 (1978-01-01), pages 135 - 146, XP009062644, ISSN: 0037-9115 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017182536A1 (fr) 2016-04-20 2017-10-26 Ineos Styrolution Group Gmbh Matières à mouler thermoplastiques non pénétrantes à effet antimicrobien

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