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111111111111111111111111111111111111111111111111111111111111111111111111111111111111111111 US 20210214223Al (19) United States (12) Patent Application Publication (lO) Pub. No.: US 202110214223 Al FERNÁNDEZ LOZANO et al. (43) Pub. Date: Jul. 15, 2021 (54) ANTIMICROBIAL COMPOSITE MATERIAL Publication Classification (51) Int. Cl. (71) Applicants:CONSEJO SUPERIOR DE C01B 25130 (2006.01) INVESTIGACIONES CIENTÍFICAS, A01N 25134 (2006.01) Madrid (ES); ENCAPSULAE, S.L., A01N 25110 (2006.01) Castellón (ES) C08K 3132 (2006.01) A01N 43178 (2006.01) (72) Inventors: José Francisco FERNÁNDEZ (52) U.S. Cl. LOZANO, Madrid (ES); Julián CPC .............. C01B 25130 (2013.01); A01N 25/34 JIMENEZ REINOSA, Madrid (ES); (2013.01); A01N 43178 (2013.01); C08K 3/32 Alberto MOURE ARROYO, Madrid (2013.01); A01N 25110 (2013.01) (ES); José Javier MENÉNDEZ MEDINA, Castellón de la Plana (ES) (57) ABSTRACT (21) Appl. No.: 15/734,264 The present invention relates to activated and ground sodium hexametaphosphate frit particles and antimicrobial (22) PCT Filed: Jun. 4, 2019 composite material comprising said activated and ground sodium hexametaphosphate frit particles embedded in a thermoplastic polymer such as low density polyethylene (86) PCTNo.: PCT/ES2019/070378 (LDPE). The invention also relates to the method for obtain § 371 (c)(l), ing the composite material of the invention and a thermal (2) Date: Dec. 2, 2020 activation method for the thermal activation of a sodium hexametaphosphate salt in order to generate the activated (30) Foreign Application Priority Data and ground sodiUlll hexametaphosphate frit particles. The antimicrobialmaterial ofthe invention is preferably used in Jun. 5, 2018 (ES) ........ ......................... P201830547 the food industry. >;iXel';;¡ .rV<H'\i{ ·· 2x10.. ·.4 txu;·.... ·t ... 500 1500 2000 2:500 Patent Application Publication Jul. 15, 2021 Sheet 1 of 8 US 2021/0214223 Al Figure 1 Patent Application Publication Jul. 15, 2021 Sheet 2 of 8 US 2021/0214223 Al Figure 2 Patent Application Publication Jul. 15, 2021 Sheet 3 of 8 US 2021/0214223 Al Fígure 3 Patent Application Publication Jul. 15, 2021 Sheet 4 of 8 US 2021/0214223 Al Time (s) Figure 4 Patent Application Publication Jul. 15, 2021 Sheet 5 of 8 US 2021/0214223 Al Figure 5 Patent Application Publication Jul. 15, 2021 Sheet 6 of 8 US 2021/0214223 Al Time(s) Fig-ure 6 Patent Application Publication Jul. 15, 2021 Sheet 7 of 8 US 2021/0214223 Al Figure 7 Patent Application Publication Jul. 15, 2021 Sheet 8 of 8 US 2021/0214223 Al Figure 8 US 2021/0214223 Al Jul. 15, 2021 1 ANTIMICROBIAL COMPOSITE MATERIAL ofpolyphosphates on Clostridium perfringens growth, spo rulation and spore outgrowth. Food Microbiology 25,6 FIELD OF THE INVENTION (2008)802-808] describes bacteria! growth inhibition pro cesses for a relevant number of bacteria for polyphosphate [0001] The present invention relates to the area of anti salt concentrations commonly used in the food industry, i.e., microbial materials. More specifically, the present invention 0.2-0.8% by weight. However, the efficacy of said poly relates to the area of antimicrobial composite materials. phosphate salts as antimicrobial agents described in the state of the art is extremely limited and does not allow the use BACKGROUND OF THE INVENTION thereof in a large number of bacteria. Another difficulty in [0002] Today, microbial infections still account for a quar the use of polyphosphate salts as antimicrobial agents is the ter of deaths worldwide. This situation is aggravated if the slow dissolution thereof in aqueous media. Furthermore, a increase in antibiotic resistance by microorganisms is taken simultaneous antimicrobial effect of polyphosphate salts in into account. Many substances can be described as antimi Gram-positive and Gram-negative bacteria has not been crobial, for example disinfectants, antibiotics, and obviously proven so far. antimicrobial agents. However, many of these compounds [0005] There is therefore a need to provide new composite can be toxic or harmful to human beings. The document by materials which exhibit antimicrobial activity against dif Kenawy et al. [E. Kenawy, S. D. Worley and R. Broughton. ferent bacteria, a high efficacy, and are free ofthe drawbacks The Chemistry and Applications ofAntimicrobial Polymers: related to toxicity phenomena. A State-ofthe-Art Review. Biomacromolecules, 85, 1359 BRIEF DESCRIPTION OF THE INVENTION 1384(2007)] propases the use ofpolymers for improving the efficacy of sorne antimicrobial agents. In particular, Kenawy [0006] The authors of the present invention have devel et al. propase the introduction of antimicrobial functional oped a composite material comprising activated and ground groups in polymer molecules, generating antimicrobial poly sodium hexametaphosphate frit particles and a polymer mers. In this manner, the residual toxicity of said functional matrix with antimicrobial properties. groups is reduced and their efficiency, selectivity, and shelf [0007] Therefore, a first aspect of the invention relates to life are increased. However, attempts at reducing the toxicity a composite material comprising: of said antimicrobial agents are far from guaranteeing their [0008] a) activated and ground sodium hexametaphos use in areas as susceptible as food and medica! applications, phate frit particles obtainable by means of a thermal among others. activation method comprising the steps of: [0003] In the food industry, sodium hexametaphosphate is [0009] i) heating a sodium hexametaphosphate salt used as a synthetic stabilizer and an acidity regulator. It can until it melts such that a molten sodium hexameta be applied in meat and fish to improve their water retention phosphate salt is obtained; capacity and to prevent fat oxidation. In emulsions, it [0010] ii) abruptly cooling the molten sodium hex increases viscosity and prevents product precipitation, ametaphosphate salt obtained in step (i) in a dry improving the texture and color of the food products. For medium to obtain activated sodium hexametaphos these reasons, it is often found in processed meat, chewing phate frit particles; and gums, sugary drinks, ready-made meals and dairy products, [0011] iii) grinding the activated sodium hexameta such as lactase-free milk or different types of cheese, sauce, phosphate frit particles obtained in step (ii) to obtain fruit jellies, frozen desserts, salad dressing, breakfast cereal, activated and ground sodium hexametaphosphate frit ice-cream, beer, and bottled drinks, among others. For particles; and example, document CN104542895A describes a water [0012] b)a polymer matrix; soluble polymer composite material for use as pork meat wherein said activated and ground sodium hexametaphos preservative. The composition of said polymer material phate frit particles are embedded in said polymer matrix. includes a commercial sodium hexametaphosphate salt in a [0013] A second aspect of the present invention relates to proportion between about 15-25% by weight to preserve the the use ofthe composite material ofthe present invention as moisture in the meat. Furthermore, by means of adding an antimicrobial agent; preferably as an antibacterial agent; specific natural bactericida! agents such as pomelo peel more preferably as an antibacterial agent against Gram polysaccharides, a bactericida! effect is generated in the positive bacteria and Gram-negative bacteria. polymer material described in said document. The polymer [0014] A third inventive aspect relates to a method for material described in document CN104542895A is used as obtaining the composite material of the present invention, preservative, although it would be limited to specific appli comprising the steps of cations and could not be used, for example, for food pack [0015] i) providing aging, due to its water-soluble nature. [0016] a) activated and ground sodium hexameta [0004] In the scientific literature, phosphate salts have phosphate frit particles obtainable by means of a been described as acting indirectly as preservatives or thermal activation method comprising the steps of: microorganism growth inhibitors. The document by Tomp [0017] i) heating a sodium hexametaphosphate salt kin [R. B. Tompkin, Indirect antimicrobial effects in foods: until it melts such that a molten sodium hexam phosphates. Journal of Food Society 6(1983)13-17] etaphosphate salt is obtained; describes the inhibitory mechanism produced by said phos [0018] ii) abruptly cooling the molten sodium hex phate salts due to interferences with the divalent cation ametaphosphate salt obtained in step (i) in a dry metabolism of the microorganisms by causing a deficiency, medium to obtain activated sodium hexameta mainly of magnesium, which inhibits cell division and phosphate frit particles; and causes the loss of cell wall. The document by Akhtar et al. [0019] iii) grinding the activated sodium hexam [S. Akhtar, D. Paredes-Sabja, M. R. Sarker. Inhibitory effects etaphosphate frit particles obtained in step (ii) to US 2021/0214223 Al Jul. 15, 2021 2 obtain activated and ground sodium hexameta [0035] FIG. 6 shows conductivity values (¡.tS/cm) with phosphate frit particles; and respect to time for activated and ground sodium hexameta [0020] b) a polymer matrix; and phosphate frit particles embedded in a low density polyeth ylene. [0021] ii) embedding said activated and ground sodium hexametaphosphate frit particles in said polymer [0036] FIG. 7 shows (a) an optical confocal microscopy matrix. image of an activated and ground