FR2797563A1 - BIOCIDAL COMPOUNDS AND THEIR USE IN THERMOPLASTIC POLYMERS - Google Patents

Abstract

The invention relates to novel bioactive compounds, comprising a dendritic polymer and at least one body based on a biocidal metal or a biocidal metal compound. The invention relates more particularly to organic-based compounds compatible with thermoplastic polymers. It also relates to thermoplastic compositions comprising an organic-based biocidal compounds.

Description

Biocidal compounds and their use in thermoplastic polymers

  The invention relates to bioactive compounds, in particular anti-bacterial, anti-

  microbials and fungicides, comprising a biocidal body. The invention also relates to

  thermoplastic compositions comprising the bioactive compound.

  For many applications, it is sought to limit the development of microorganisms in the vicinity of thermoplastic articles. In the textile fields, for example, it is sought to avoid smelly effects by limiting the development of a bacterial flora on the tissues. In the medical sectors it is of great importance to limit the development of bacteria on work tools, on building materials, on clothing. Another field of application of

  bioactive compounds is that of the prevention of dust mite allergies.

  Agents having biocidal properties have been known for a very long time and are used, for example, for cosmetic applications or for fungicidal applications. Among these agents, elements based on metals such as silver, copper

or zinc are the best known.

  Other agents are described in the literature. Patent EP 085 877 describes, for example, the use of dendrimers bearing primary amine functions, these functions being neutralized. These agents are formulated in aqueous or emulsion compositions to be applied in the form of lotions, creams, gels, spray. These agents are however not incorporated in thermoplastic polymers and

  not withstand the shaping temperatures of these.

  In order to give textile surfaces biocidal properties, many primers containing bioactive compounds have been developed. However, these primers always have a limited performance and their effects disappear after one or more washes. It is therefore in many cases more interesting to introduce the active ingredient directly

  in the article to present a bio active property.

  For this purpose, it is known to introduce a bioactive agent into spun yarns in solution.

  or spun by coagulation. The bioactive agent is then introduced into the solvent of the polymer.

  For polymers shaped in the melt phase, it is known to introduce inorganic fillers supporting a bioactive metal-based element. These fillers can be introduced during the polymerization process or during the shaping process. Many solutions are proposed for the realization of mineral fillers. These fillers must have sufficient dispersibility in the polymer, an acceptable color and they must not impair too much

the properties of the polymers.

  For example, US Pat. No. 4,775,855 describes the use of silver-bearing zeolites. US Pat. No. 5,180,585 describes mineral fillers comprising three layers, for example a titanium dioxide support, a silver-based layer and a silica-protective layer. The protective layer is described as protecting the polymer from damage caused by the presence of silver. The object of the present invention is to propose a further filler, which can in particular be introduced into thermoplastic polymers, and which can be more

  particularly be introduced during the shaping phase of the polymer.

  For this purpose, the invention provides a biocidal compound comprising at least one biocidal body based on at least one metal or biocidal metal compound, characterized in that it comprises a dendritic polymer compatible with a thermoplastic matrix, to which

is bound the biocidal body.

  Dendritic polymers are polymeric structures with numerous branches. Among the dendritic polymers, dendrimers and hyperbranched polymers are generally distinguished. These two types of structures can

be used for the invention.

  By dendrimer is meant a polymeric structure having regular branches, arborescent, generally controlled, and may have symmetry. They are for example made by tree growth of compounds having a functionality greater than 2, the growth being initiated around a

  heart molecule. Such structures are for example described in D.A. Tomalia, A.M.

  Naylor and W. A. Goddard III Angewangte Chemie, Int. Ed. Engl. 29, 138-175 (1990).

  By hyperbranched polymer is meant a branched polymeric structure obtained by polymerization in the presence of compounds having a functionality greater than 2, and whose structure is not perfectly controlled. These are often statistical copolymers. The hyperbranched polymers may for example be obtained by reaction between, in particular, multifunctional monomers, for example trifunctional and bifunctional monomers, each of the monomers carrying at least two reactive functions

different polymerization.

  The dendritic polymers generally have a substantially globular shape with a size ranging from a few nanometers to several tens of nanometers. The ramifications of the molecular construct have ends, the functionality of which can be modulated. By definition the number of ends per macromolecule is

greater than 2.

  Suitable dendritic polymers for the invention are dendritic polymers that are compatible with thermoplastic matrices, that is to say those that can be homogeneously incorporated into a thermoplastic matrix, without significant segregation, which have at least partial miscibility with the matrix.

  or which have chemical functionalities compatible with the matrix.

  Among the dendritic polymers that are suitable for the invention, mention may be made of polypropylene imines containing carboxyl functional groups, for example the compounds sold by the company DSM under the name ASTRAMOL ™, the polyamidoimines containing carboxylic ends, for example the compounds sold by the company Dendritech under the name ASTRAMOL ™. the name STARBURST, hyperbranched polyesters functionalized, for example by succinic anhydride, of the type of those

  marketed by Perstorp under the name Boltorn.

  The biocidal body based on at least one metal or biocidal metal compound is bonded to the dendritic polymer. The bond may be a covalent bond, an ionic interaction, or a chelating force. The biocidal element is preferably linked to the ends

  chains, possibly functionalized.

  The biocidal bodies may be chosen from the following list: metallic silver, its Ag + cation, its oxides, for example Ag 2 O - metallic copper, its Cu + and Cu ++ cations, its CuO and Cu 2 O oxides, its CuS sulphide, its hydroxides, hydroxycarbonates, oxycations, halides, carbonates - metallic zinc, its Zn ++ cation, its oxide ZnO and its sulphide ZnS - the other compounds and ions of groups 3 to 12 of the international classification, such as Ru, Rh, Pd, Os, Ir, Pt, Au, Hg, Cd, Cr, Ni, Pb They can be used in the compound alone or in combination. We can mention

  for example, combinations of copper and silver ions or zinc and silver ions.

  Preferred dendrimers for carrying out the invention are hyperbranched copolyesters and hyperbranched copolyamides. More particularly, the preferred copolyamides are hyperbranched copolyamides that are not totally aromatic. Such compounds are described in the patent application filed in France on May 5, 1999 under number 99/05885. They are for example obtained by reaction between: A at least one monomer of formula (I) below: (I) AR-Bf in which A is a reactive polymerization function of a first type, B is a reactive polymerization function of a second type capable of reacting with A, R is a hydrocarbon species, and f is the total number of reactive functions B per monomer: f> 2, preferably 2 <f <10; A and at least one monomer of the following formula (II): (II) A'-R'-B 'or the corresponding lactams,

  in which A ', B', R 'have the same definition as that given above.

  above for A, B, R respectively in formula (I); characterized in that the molar ratio 1/11 is defined as follows: 0.05 <1/11 and preferably 0.125 <1/11 <2; and in that at least one of the entities R or R 'of at least one of the

  monomers (I) or (II) is aliphatic, cycloaliphatic or arylaliphatic.

  According to a preferred embodiment of the invention, the hyperbranched copolyamide is characterized in that: A hydrocarbon species R, R 'monomers (I) and (II) respectively, each comprising: i at least one linear or branched aliphatic radical; and / or at least one cycloaliphatic radical; iii and / or at least one aromatic radical having one or more aromatic rings; these radicals (i), (ii), - (iii) may optionally be substituted and / or comprise heteroatoms; A, A 'is a reactive function of the amine, amine salt, or acid, ester, acid halide or amide type; A B, B 'is a reactive function of the acid, ester, acid halide type

  or amide or amine type, amine salt.

  Thus, the reactive polymerization functions A, B, A ', B' more especially retained are those belonging to the group comprising the carboxylic and amine functional groups.

  By carboxylic function is meant any COOH acid function, ester or anhydride.

  In the case where A, A 'corresponds to an amine or an amine salt, then B, B'

  represents an acid, an ester, an acid halide or an amide and vice versa.

  According to an advantageous variant, the hyperbranched polymer may consist of a mixture of several different monomers (I) and of several different monomers (11), provided that at least one of these monomers is aliphatic,

  cycloaliphatic or arylaliphatic.

  In addition to the multifunctional monomers (I) and the bifunctional monomers (II), it is conceivable to have a hyperbranched polymer according to the invention also comprising, as constituent elements, monomers mono or plurifunctional (111) type "core" (or "core") and / or monofunctional monomers

(IV) of the "chain limiter" type.

  The "core" type monomers optionally included in the copolyamide and / or hyperbranched ester according to the invention may be those of formula (III) below: (III) RI (B ") n in which: R 'is a hydrocarbon radical substituted or unsubstituted, of the silicone type, linear or branched alkyl, aromatic, alkylaryl, arylalkyl or cycloaliphatic may comprise unsaturations and / or heteroatoms; B "is a reactive function of the same nature as B or B ';

  o n> 1, preferably 1 <n <100.

  The monomers of the "chain-limiting" type optionally included in the hyperbranched copolyamide according to the invention may be those of formula (IV):

(IV) R2-A "

  in which: R 2 is a substituted or unsubstituted hydrocarbon-based radical, of the silicone, linear or branched alkyl, aromatic, arylalkyl, alkylaryl or cycloaliphatic type which can comprise one or more unsaturations and / or one or more heteroatoms.

  o and A "is a reactive function of the same nature as A or A '.

  According to an advantageous modality, at least a part of the monomers

  bifunctional (II) are in the form of prepolymer.

  It may be the same with regard to the monomers (111) of the "heart" type, or even the

  monomers (IV) of the "chain limiter" type.

  The radicals R 1 and R 2 may advantageously comprise functionalities conferring particular properties on the hyperbranched polymer. These features do not react with the functions A, B, A ', B' during the

polymerization of PAHB.

  According to a preferred embodiment, f = 2 so that the monomer (I) is trifunctional: ARB 2, A = amine function, B = carboxylic function and R = aromatic radical. The hyperbranched polymer obtained, according to the invention, from the monomers I and II can be likened to tree structures having a focal point formed by the function A and a periphery with B terminations. When they are present, the monomers (111) form nuclei. Advantageously, the hyperbranched polymer may comprise monofunctional (IV) monomers "chain limiter", located in

  periphery of the dendrimers according to the invention.

  In addition, the bifunctional monomers (II) are spacing elements in the three-dimensional structure. They allow a control of the density of branching and are in particular at the origin of the interesting properties of hyperbranched polymers

according to the invention.

  The monomers (111) and (IV) make it possible to control the molecular weight.

  Advantageously, the monomer (I) is, for example, chosen from the group comprising: 5-amino-isophthalic acid, 6-aminoundecandioic acid, 3-aminopimelic diacid, aspartic acid, acid 3,5-diaminobenzoic acid, 3,4-diaminobenzophthalic acid, lysine,

- and their mixtures.

  Advantageously and for example, the bifunctional monomer of formula (II) is: I I-caprolactam and / or the corresponding amino acid: aminocaproic acid, and / or para or metaaminobenzoic acid, and / or acid 1-amino-1-undecanoic acid, and / or lauryllactam and / or the corresponding amino acid:

amino-12-dodecanoic acid.

  More generally, the bifunctional monomers of formula (II) can be

  the monomers used for the manufacture of linear thermoplastic polyamides.

  Thus, mention may be made of oe-aminoalkanoic compounds comprising a hydrocarbon chain having from 4 to 12 carbon atoms, or the lactams derived from these

  amino acids such as ε-caprolactam.

  The preferred bifunctional monomer (II) of the invention is scaprolactam.

  By way of example, the monomers (III) may be, for their part: => saturated aliphatic dicarboxylic acids having from 6 to 36 carbon atoms such as, for example, adipic acid, azelaic acid, I sebacic acid, dodecanoic acid, => linear or branched saturated, preferably aliphatic, diamines having from 6 to 36 carbon atoms, such as, for example, hexamethylenediamine, trimethylhexamethylenediamine, tetramethylenediamine, nylenediamine, polymeric compounds such as the aminated polyoxyalkylenes marketed under the trade name JEFFAMINE, or else the amino silicone chain, eg polydimethylsiloxane mono

or diamine.

  -> aromatic or aliphatic monoamines, => aromatic or aliphatic monoacids, or

  > aromatic or aliphatic triamines or triacids.

  Preferred monomers (111), "core" are: hexamethylene diamine and

  adipic acid, JEFFAMINE T403 or 1,3,5-benzene tricarboxylic acid.

  According to another characteristic of the invention, the molar ratio of the monomers (IV) to the bifunctional monomers (I) is defined as follows:

(IV) <10

  (J) preferably (IV) (I) and even more preferably (IV) (I) As regards the molar ratio of functional monomers (III) "rings" with respect to multifunctional monomers (I), it can be defined as follows:

(III) <1

(I) preferably

<(III) 1/2

  () And more preferably still) and even more preferably (III)

0 <(<1/3

  (J) Advantageously, the hyperbranched copolyamide may be in the form of

  particle form each consisting of one or more tree structures.

  Another interesting feature of such a copolyamide is that it can be functionalized: at the focal point of the tree structure (s), by means of monomers (111) carrying the function (s) considered , O and / or at the periphery of the tree structures, via

  monomers (IV) carrying the function or functionalities considered.

  As regards the synthesis aspect, it will be pointed out that the hyperbranched copolyamides can be obtained by a process characterized in that it essentially consists in carrying out a polycondensation between monomers (I) and monomers (II) which react with each other and optionally with monomers (111)

  and / or (IV); and under appropriate temperature and pressure conditions.

  This polymerization is carried out in the melt phase, in the solvent phase or in the solid phase, preferably in the melt phase or in the solvent phase; the monomer (II) advantageously

role of solvent.

  The process for synthesizing hyperbranched polymers according to the invention can

  implement at least one polycondensation catalyst.

  The polymerization by polycondensation is carried out, for example, under conditions and according to a procedure equivalent to those used for the manufacture of the

  linear polyamide corresponding to the monomers (II).

  According to an advantageous embodiment of the invention, the biocidal body is chosen from the cations of silver, copper, zinc and their mixtures and the dendritic polymers have at least partially ends of anionic chains, for example ends carboxylate. Without wishing to be bound to any theory, it is very likely that the metal cations are bound to the dendritic polymer by

ionic interaction.

  By way of example, it is possible to use the hyperbranched copolyamides described above

  and having carboxylic ends.

  Some of these compounds, especially those with a sufficient branching rate and carboxylic ends, are soluble in basic media. The

  Solubilized compounds can be precipitated for example in ethanol.

  For the production of a compound according to the invention in powder form, the dendrimer may be solubilized in a basic solution, for example a sodium hydroxide solution, and then precipitated by adding a solution of silver nitrate or by casting. in a solution of silver nitrate. This method has no limiting character for the production of the compounds according to the invention comprising an anionic dendrimer

  and one or more metal cations.

  Other methods can be used, for example the dendritic polymer can be solubilized in an organic solvent such as DMF and then precipitated by adding a

  metal acetate, for example silver acetate.

  The compound may be stored in aqueous phase in order to enter compositions other than thermoplastic compositions, especially

compositions for cosmetic use.

  Another solution is to introduce into the polymerization medium monomers bearing an anionic charge, for example a sulfonated diacid such as sulfo-5-isophthalic acid (AISNa) or a sulfonated amino acid. Anionic function

  is not necessarily carried by a chain end.

  According to another embodiment of the invention, dendritic polymers which are functionalized at the end of the chain or within the chains are used so that they have chelating functions for metals or metal cations, for example tertiary amine functions or bi pyridines. Chelating functions

  can be located at the ends of the chains or carried within the chains.

  The invention also relates to the compositions based on a polymer

  thermoplastic and containing the compounds described above.

  The proportion by weight of the biocidal compound in the thermoplastic compositions is dependent on the activity of the compound and the level of activity desired for the use to be made thereof. It is generally between 0.01 and 10%. The proportion by weight of the biocidal body in the composition is generally understood

between 5 ppm and 10000 ppm.

  The thermoplastic polymer is advantageously chosen from polyesters, such as PET, PTT, PBT, their copolymers and mixtures, polyamides such as nylon 6, nylon 6.6, nylon 4, polyamides 6-10, 4- 6, 6-36, their copolymers and

mixtures.

  The compositions may contain any other additives which may be used, for example reinforcing fillers, flame retardants, UV stabilizers, heat stabilizers,

mattifying.

  The compositions according to the invention can be shaped into yarns, fibers and filaments by melt spinning. They can also be used in the fields

  technical plastics, for example for the production of molded articles.

  For this purpose, the biocidal compound can be added in the form of a powder in an extrusion device upstream of the spinning device. Threads, fibers and filaments, as well as

  textile articles obtained therefrom exhibit biocidal activity.

  The compositions are preferably made by introducing the compound

biocide in the molten polymer.

  According to another embodiment of the invention, the biocidal compound is used in compositions for sizing fiber and filament yarns, in formulations of primers or dyes applied to textile surfaces, or in

laundry formulations.

  Other details and advantages of the invention will become apparent from the examples given above.

  below given only as an indication.

  The antibacterial activity of the compounds, compositions containing them and fibers made from these compositions is measured according to the test called "Shake Flask Test" and described in US Pat. No. 4,708,870. The operating protocol for the test is as follows 1 g of product to be tested is brought into contact with 70 ml of phosphate buffer at pH 7.2 and 5 ml of a bacterial suspension at 1-310 5 CFU / ml in a 250 ml Erlenmeyer flask. A powderless Erlenmeyer flask is used as a control test. The bacterial strain used is Klebsiella pneumoniae. The Erlenmeyer flasks are stirred at 300 movements per minute at room temperature. A count of bacteria is made after 0, 1 and 24 hours of incubation. A reduction ratio is defined as the ratio between the difference between the number of bacteria before and after incubation and the

  number of bacteria before incubation (measured at 0 hours).

  EXAMPLE 1 Manufacture of a hyperbranched copolymer with sodium carboxylate ends A hyperbranched copolyamide is produced according to the example of the patent application filed in France on May 5, 1999 under the number 99/05885, the synthesis of a hyperbranched copolyamide with carboxylic acid terminations by copolycondensation

  in the melt phase of 1,3,5-benzene tricarboxylic acid (core molecule (iii) of type R1-

  B "3, with B = COOH), 5-aminoisophthalic acid (branching molecule (I)

  type A-R-B2, with A = NH2) and ε-caprolactam (spacer (II) of type A'-R'-B ').

  The reaction is carried out at atmospheric pressure and under light nitrogen sweep in a 7.5 l autoclave commonly used for the melt phase synthesis.

polyesters or polyamides.

  The monomers are fully charged at the beginning of the test. 1811.5 g of 5-aminoisophthalic acid (10 mol), 84 g of 1,3,5-benzene tricarboxylic acid (0.4 mol), 1131.6 g of scaprolactam (10 mol) are introduced successively into the reactor. mol) and

  1.35 g of a 50% (w / w) aqueous solution of hypophosphorous acid.

  The reaction mass is stirred (speed = 50 rpm) and heated gradually from 20 to 200 C in 100 min., Then from 200 to 250 C in 60 min. The distillation starts at a temperature of 160 ° C. and continues until the temperature of 245 ° C. At 250 ° C., the system is progressively evacuated until an absolute pressure of 5 mbar is reached after 30 minutes. The reactor is then placed under

  nitrogen overpressure and the polymer drained through the bottom valve.

  The water contained in the 221.06 g of distillate collected is titrated using a Karl Fischer coulometer. The water content of the distillate is 81.1%, which reflects a rate

overall progress of 99.3%.

  of the copolyamide obtained are solubilized at ambient temperature and with stirring in a beaker containing 570 ml of 40 g / l aqueous sodium hydroxide. The solution is then poured dropwise and with stirring into 5 liters of absolute ethanol. A white precipitate is obtained which is isolated by filtration on sintered glass n 4. The filter cake is rinsed 3 times with 100 ml of ethanol and then dried under the vacuum of a vane pump at 80 C for 16 hours. The hyperbranched copolyamide with carboxylate ends of sodium thus obtained is characterized in elemental analysis. The measured sodium level

  experimentally is 7.47% by weight.

  EXAMPLE 2 Manufacture of a Biocidal Compound Ag grams of a hyperbranched copolyamide with sodium carboxylate ends as described in Example 1 are solubilized at room temperature in 500 ml of demineralized water. The solution obtained is transferred into a dropping funnel and added dropwise to an aqueous solution of silver nitrate (68.33 g of AgNO 3 in 400 ml of water) stirred and protected from light. A pinkish white precipitate is obtained which is retained on sintered filter n 5. The filter cake is washed with demineralised water until no more Ag + cations are detected in the washing waters (precipitation test with an aqueous solution of sodium chloride). It is then dried under the vacuum of a vane pump at 80 C for 16 hours. The hyperbranched copolyamide with silver carboxylate ends thus obtained is characterized in elemental analysis. Its mass content in silver is 28.4%. he

  there is a residual sodium content of 0.87% by mass.

  Example 3 - Manufacture of a Biocidal Compound - Zn grams of a hyperbranched copolyamide with sodium carboxylate ends as described in Example 1 are solubilized at room temperature in 800 ml of demineralized water. The solution obtained is transferred into a dropping funnel and added dropwise to an aqueous solution of zinc sulphate (110 g of ZnSO.sub.4, 7H.sub.2 O dissolved in 900 ml of water) with stirring. A white precipitate is obtained which is retained on sintered filter n 4. The filter cake is washed with 3 × 500 ml of demineralised water. It is then dried under the vacuum of a vane pump at 80 C for 16 hours. The hyperbranched copolyamide with zinc carboxylate ends thus obtained is characterized in elemental analysis. Its mass content of zinc is

  9.9%. There remains a residual sodium content of 1.15% by weight.

  EXAMPLE 4 Manufacture of a biocidal compound - AqlZn grams of a hyperbranched copolyamide with sodium carboxylate ends as described in Example 1 are solubilized at room temperature in 800 ml of demineralized water. The solution obtained is transferred into a bécherplacé with magnetic stirring. An aqueous solution of silver nitrate (39.3 g of AgNO 3 in 350 ml of water) is added dropwise. We observe the fleeting formation of a white precipitate which is redissolved as and when it is formed. Once the addition of the silver nitrate solution is complete, the contents of the beaker are transferred to a dropping funnel and added dropwise to a solution of zinc sulphate (73.2 g of ZnSO 4, 7 H 2 O dissolved in 700 ml of water) stirred. Throughout these operations, solutions are protected from light. A white precipitate is obtained which is retained on sintered filter n 4. The filter cake is then dried under the vacuum of a vane pump at 80 C for 16 hours. The hyperbranched copolyamide with zinc carboxylate mixed ends and silver carboxylates thus obtained is characterized in elemental analysis. Its mass content of zinc is 6.0% and that in

  9.6% money. There is a residual sodium content of 1.8% by weight.

  Example 5 - Manufacture of a biocidal compound - Ag / Cu 114 grams of a hyperbranched copolyamide with sodium carboxylate ends as described in Example 1 are solubilized at room temperature in 456 ml of demineralized water. The solution obtained is transferred into a beaker placed under magnetic stirring. An aqueous solution of copper sulphate (17.9 g of CuSO 4, 5H 2 O in 180 ml of water) is added dropwise thereto. The formation of a blue precipitate is observed which is redissolved after a few minutes with stirring. Once the addition of the copper sulphate solution is complete, the contents of the beaker are transferred to a dropping funnel and added dropwise to a solution of silver nitrate (40.6 g of AgNO 3 in 460 ml of water) protected from light. A sky blue precipitate is obtained which is retained on sintered filter n 4. The filter cake is then dried under the vacuum of a vane pump at 80 C for 16 hours. The hyperbranched copolyamide with mixed ends of copper carboxylates and silver carboxylates thus obtained is characterized in elemental analysis. Its mass content of copper is 3.0% and that

  in silver of 15.8%. There remains a residual sodium content of 2.0% by mass.

  EXAMPLE 6 Manufacture of Polyamide-Based Compositions Polyamide 66 granules with a viscosity index of 140.6 ml / g (measured at 25 ° C. in a Hubbelhode-type viscometer with a solution containing 5 g / l of dissolved polymer in a mixture composed of 90% by weight of formic acid and 10% by weight of water). are dried at 80 ° C. under vacuum for 16 hours. Biocidal compounds according to Examples 3 to 5 are incorporated into the polyamide using a Leistriz 30.34 twin-screw extruder. The compositions obtained are crushed by cryogenic grinding into a powder

  of which 90% of the grains have a diameter of less than 850 μm.

  The characteristics of the compositions are specified in Table 1.

  Comparative Example A control sample containing no biocidal compound is made in the same

  conditions as Example 6. (DO composition).

Table 1

  Composition Biocidal compound% by weight of the compound IV (ml / g) biocide in the composition

DO / 0 145.6

  Dl Example 3 0.12 147.6 D2 Example 4 0.2 144.3 D3 Example 5 0.2 146.2 The biocidal activity of the compositions is tested according to the protocol described above. A

  Powder-free test control is performed. The results are specified in Table 2.

Table 2

  Bacteria concentration (CFU / ml) Reduction rate (%) Initial composition 1 hour 24 hours 1 hour 24 hours Test test 1.26 104 1, 69 104 1.68 10 '

OD 1.21 10 7.73 103 7.29 104 36

D1 1.2 104 1.50 10 0 88 100

D29.28 10T 0 0i 100 100

D2 1.39 104 1.28 10 4.20 103 8 70

Claims (15)

  1. Biocidal compound comprising a biocidal body based on at least one metal or biocidal metal compound, characterized in that it comprises a dendritic polymer compatible with a thermoplastic matrix to which the biocidal body is bonded. 2. Biocidal compound according to claim 1 characterized in that the biocidal body is selected from metallic silver, metallic copper, metallic zinc, their cations, their oxides and sulphides.   3. The biocidal compound according to claim 1 or 2, characterized in that the polymer dendritic is a dendrimer.   4. The biocidal compound according to claim 1 or 2, characterized in that the polymer   dendritic is a hyperbranched polymer.   5. The biocidal compound as claimed in claim 4, characterized in that the polymer   dendritic is a hyperbranched copolyamide or hyperbranched copolyester.   6. Biocidal compound according to one of the preceding claims characterized in that the   proportion by weight of the biocidal body is between 0.05 and 99.5% with respect to total weight of the compound.   7. Biocidal compound according to one of the preceding claims characterized in that the   biocidal body is selected from cations of silver, copper, zinc, or mixtures thereof, the cations being bound by ionic interaction with a dendritic polymer   having anionic groups.   8. The biocidal compound according to claim 7, characterized in that the groups   anionic are carried by chain ends of the dendritic polymer.   9. Biocidal compound according to one of claims 6 or 7 characterized in that the   Anionic groups are carboxylates.   10. Biocidal compound according to one of claims 1 to 6 characterized in that the   dendrimer has chelating chain ends.   11. Biocidal composition based on a thermoplastic polymer characterized in that it   comprises a biocidal compound according to one of claims 1 to 10.   12. The biocidal composition according to claim 11 characterized in that the proportion by weight of the biocidal compound is between 0.01 and 10%.   13. Biocidal composition according to one of claims 11 or 12, characterized in that   the thermoplastic polymer is chosen from polyesters and polyamides.   14. Fibers, fibers and filaments obtained by melt spinning from a composition one of claims 11 to 13.   Textile articles obtained from yarns and filaments according to claim 14.