AU672996B2

AU672996B2 - Antiseptic polymer

Info

Publication number: AU672996B2
Application number: AU47581/93A
Authority: AU
Inventors: Michel Bourgeois; Jean Claude Bouvier; Bernard Chabert; Roger Chatelin; Benedicte Leger; Jean Pierre Picolet
Original assignee: Institut Textile de France; Thuasne and Cie SA
Current assignee: Institut Textile de France; Thuasne and Cie SA
Priority date: 1992-09-23
Filing date: 1993-09-23
Publication date: 1996-10-24
Anticipated expiration: 2013-09-23
Also published as: FR2695800B1; EP0591024B1; CZ286597B6; ATE168241T1; DE69319686T2; AU4758193A; JPH0797409A; DE69319686D1; CZ197593A3; RU2141491C1; EP0591024A3; CA2106736A1; FR2695800A1; EP0591024A2

Abstract

Polymer with antiseptic property, obtained using, during a polymerisation reaction, a monomer of general formula: <IMAGE> in which: a) R1 and R2 are alkyl groups, CaH2a+1 for R1 and CbH2b+1 for R2, respectively, and R3 is either an alkyl group CcH2c+1 with c >/= 4 and 15 >/= a+b+c >/= 6 or an aryl group of formula -(CH2)d-C6H5 with d >/= 1 and a+b+d </= 8 b) 3 >/= n >/= 1 c) A is an ethylene functional group capable of participating in a polymerisation reaction d) X<(-)> is an anion. ng

Description

1 ANTISEPTIC POLYMER FIELD OF THE INVENTION The present invention relates to an antiseptic polymer, in particular a polymer capable of ensuring protection against bacteria, fungi and other microorganisms, for solid supports, in particular, textile materials or coatings of the varnish or paint type, or else liquid compositions, in particular, cosmetic emulsions.

TECHNOLOGICAL BACKGROUND In the present text the generic term polymer is understood 'o mean a material, the structure of which comprises repeated patterns, irrespective of the S 15 number and nature of those patterns. This definition accordingly includes products which are commonly known as homopolymers, containing a single type of pattern, products which are commonly known as copolymers, containing several different types of patterns, and also those which are designated by the term oligomers in which the number of patterns is small, ranging from a few units to ten units, designated by the term telomers, which are oligomers comprising two similar or different terminal reactive functions, and designated Sby the term prepolymers in which the number of patterns is comprised between 10 and 50 units.

cc I 5 The protection of textile supports, in particular, against external agents such as bacteria, fungi etc by fixing to said supports, products having a specific activity in relation to said agents is already well known.

t 1 SFrench Patent No. 2 511 001 relates in particular to a product for the processing of polyhydroxylated or polyaminated polymers with an N-oxiranemethane-N,N,N-trialkylaminium salt having the following general formula: *1J

R

2 -A B -CH H 2 1, X" i. 5 n 0 1 i in which: 1I 10 A denotes a nitrogen or phosphorus atom,

R

1 R, R 3 denote alkyl radicals within the C, to C, range, saturated or unsaturated, or alkenyl or aryl radicals, substituted where appropriate, B denotes an alkylene radical between C, and C 1 0 X" denotes an anion, n denotes a number having a value of 1, 2 or 3,

R

3 may also represent the radical -B-CH-CH, o S R and R 2 being capable also of forming heterocyclic compounds with 20 nitrogen.

i As indicated in this document, the process adopted in order to obtain such a processing product results in a relatively low yield of the order of At the same time the attachment of this product to the textile support is effected by reaction of the epoxide terminal group on the polymer structure of said support. Epoxides are known to be reactive compounds, but restricted in respect of polymers described as having mobile hydrogen, so that such a reaction is difficult to control; since a condensation reaction is involved, fixing is of the substitution type with a fixed pattern, thus limiting the accessibility of 30 the fixed molecule and in consequence the efficacy of the antiseptic function.

i 1 In the case of the antiseptic protection of solid supports, particularly i* t textile supports, the applicants' first aim is to propose an agent capable of conferring this protection without including an epoxide group so as to avoid the limitations referred to above.

Furthermore, the applicants have sought to propose an antiseptic protection agent which is particularly effective and the effects of which are .1 3 durable in respect of the protection afforded to a solid support in the strict sense, to a support based on a liquid, paste or gel composition which is becoming solid, or else to a liquid medium, especially in the cosmetic sector.

SUMMARY OF THE INVENTION There is disclosed herein a process for producing a polymer useful in the antiseptic protection of a solid support or a liquid medium, said process using, in a polymerisation reaction, a monomer having the following general formula:

R,

15 A (CH N R 3

,X'

20 in which i**

R

1 and R 2 are alkyl groups, respectively CaH2a+1 for R, and CQbH 2 b+ for

R

2 and R 3 is either an alkyl group CoH2+, with c 4 and 15 a+b+c 6 or an aryl group having the formula -(CHz)d-CH5 with d 1 and 25 a+b+d 8, 3 n >1, A is an ethylene functional group capable of participating in a polymerisation reaction, XO is an anion.

In the polymer according to the invention, the quaternary ammonium group, which imparts the specific activity in relation to external agents such as bacteria, fungi and other micro-organisms, is repeated as many times as there are patterns corresponding to the monomer having the general formula referred A I -4 0 c

O_^

4 to above; the repetitive mode affords a very wide range of access to the microorganisms and, ii consequence, highly effective antiseptic protection.

Furthermore the selection made in regard to the structure of the groups

R

1 R, and R 3 attached to the quaternary ammonium, which exerts an influence on the length of the carbon chains of these groups as a whole, makes a particular contribution to the access referred to above in the case of the protection afforded to a solid support by means of grafting, whereby the polymer according to the invention is present in the form of grafts attached to the support, as will be explained later in the course of the present text.

The ethylene functional group A is preferably a vinyl group or else a group having the general formula:

CH

2

B-

R4 in which R 4 is H or -CH, B is [CH 2 or [C 0] or [C NH] I I 0 0 According to a preferred embodiment, the antiseptic polymer according to the invention is obtained by polymerisation using a monomer which consists of a quaternary ammonium bromide containing a methacrylate group linked to the nitrogen atom, having the following formula:

CH,

CH

2 =C C 0 CH 2 CH, N CH,,Br-' CH, O CH, in which n is equal to 1, R, and R 2 are methyl groups and R 3 is an octyl group.

r According to another embodiment, the monomer from which the polymer according to the invention is obtained has the following general formula:

CH

3

CH

2 C -C -0 CH 2 N' CH 2 ,C1' CH3 0 CH 3 0 0 O 04 Do e 00 0 0 0 0 00 00 o 0 0 0 aoo 25 o 0 00 0 in which n, is equal to 1, R 1 and R 2 are methyl groups and R 3 is a benzyl group.

It is to be noted that the processes used to obtain the monomers used for obtaining the polymers according to the invention are simple processes which enable yields in excess of 90% to be achieved.

Furthermore, the polymerisation reactions implemented by means of the ethylene functional group are well known and easy to perform; the same applies to the specific reaction known as grafting, which ensures, at the same time as the polymerisation, that the polymer chain, known as the graft, is fixed to a main structure.

A first type of the polymer according to the invention is a homopolymer, which is obtained by polymerisation only of the antiseptic monomer having the general formula set out above.

A second type of the polymer according to the invention is a copolymer which is obtained by copolymerisation of an antiseptic monomer having the general formula set out above and a further monomer, for example ethyl acrylate or acrylamide. It is evident that the antiseptic monomer has an excellent reactivity and is in consequence capable of forming numerous polymers.

Another aspect of the invention is to claim a first process for the protection of a solid support, using the antiseptic polymer referred to above.

The process consists characteristically of developing and fixing said polymer to the support in the form of grafts, during a grafting reaction. In this case the I 1 6 polymers/grafts are fixed irreversibly to the support which it is required to protect. Such a process is particularly advantageous in the case of the antiseptic protection of textile materials.

In the case of a cotton fabric grafted with the polymer/graft according to the invention in particular, the antiseptic protection is especially effective where the fabric in question has at least 4 tig to 7 mg nitrogen per gram derived from the antiseptic quaternary ammonium group.

The applicants believe that antiseptic protection of a support is imparted by the polymer according to the invention as a result of the presence on the support of a quantity of polymer corresponding to the MIC [minimum inhibiting concentration] of the corresponding monomer in the liquid phase. It is clearly evident that, according to the applications, this rate has to be and can easily be modified by the system of grafting which is claimed.

Another aim of the invention is to claim a second process for the protection of a solid support, using the antiseptic polymer according to the invention. Characteristically, the process consists of impregnating said support with a liquid suspension containing the monomer having the general formula referred to above and iperforming the polymerisation reaction in situ, in the support. In this case stabilization of the antiseptic polymer is effected merely by its inclusion in the solid support. Such a process is particularly advantageous t in the case of the antiseptic protection of rigid and porous materials, for ll 75 example natural materials such as wood.

L. 6 Another aim of the invention is to claim a third process, using the antiseptic polymer according to the invention, for the protection of a support which becomes solid, based on an initial reticulable liquid composition.

Characteristically, the process consists of preparing a homogeneous mixture of the antiseptic polymer and of the liquid composition in such a way that, during solidification of the latter, the antiseptic polymer is stabilized in the reticulated network of the support. Such a process is used, in particular, for the antiseptic ni 15 *I $2 2 ft *F 25 k ii 2 protection of plastic films, of hot melts and of coated textiles. It is also used for the protection of surface coatings, such as a paint or varnish.

Another aim of the invention is to claim a fourth process, using the antiseptic polymer according to the invention, for the protection of a liquid medium. According to the process, the liquid medium consists of an emulsion of a cosmetic compound with which said antiseptic polymer is homogeneously mixed.

In all the cases referred to above, the fact that antiseptic protection is achieved with the polymer according to the invention has great advantages over and above the access which is gained to the micro-organisms already referred to. Its polymer structure ptrmits good stabilization of the solid supports, even without any solid fixation of the covalent type to the support; this avoids the migration phenomena which would inevitably occur with the use of an antiseptic compound such as that described in US Patent 4 829 867. Furthermore, in the case of the antiseptic protection of a cosmetic emulsion, its polymer form avoids breaking up the emulsion and rendering it less volatile.

DESCRIPTION OF PREFERRED EMBODIMENTS The present invention will be better understood by examining the following examples of the production of antiseptic polymers obtained by the use, during the course of a polymerisation reaction, of a monomer having the general formula referred to above.

Example 1. In this first example, the antiseptic monomer is a quaternary ammonium bromide, in which the groups linked with the nitrogen atom are respectively two methyl groups for R 1 and R 2 an octyl group for R 3 and an ethyl methacrylate; it has the following general formula: I i se~

CH

3 S= C C 0 C C C -CH 2 CH, N CeHBr' I I 1

CH

3 0 CH, To obtain this monomer, the bromo-octane is reacted on dimethylaminoethyl methacrylate.

In a specific example of this embodiment, 90 ml dimethylformamide are added to 47.10 g dimethylamino-ethyl methacrylate. 57.60 g bromo-1-octane are added subsequently. The reagent medium, protected from the light, is then stirred at ambient temperature with a magnetic stirrer. The duration of the reaction is 48 h.

ml chloroform is then added, cooling the mixture in an ice bath. The mixture thus obtained is poured into 500 ml ethyl ether with vigorous stirring.

A white precipitate is produced, which is filtered then dried under vacuum over

P

2 0 5 95.3 g of the dry product is recovered, corresponding to a reaction yield of 91%.

The product thus obtained conforms to the formula given above. It is pure, as may be verified by NMR of the proton, determination of the halide with silver nitrate and determination of the unsaturation phenomena by the ,r morpholine reaction in an acetic acid/dioxane medium.

The antiseptic activity of the monomer thus obtained is measured by Li L calculating the minimum inhibiting concentration (MIC) in the following way.

Successive dilution ranges of said monomer are prepared in a nutrient medium containing, at pH 7.4 and in 1 litre of distilled water, 375 g infusion of heart, 100 g biothone and 5 g sodium chloride.

T 9 A first series of dilutions, consisting of 1, 10, 100, 1000 and 10,000 [ig/ml of the antiseptic monomer, is distributed in test tubes. Each test tube is then inoculated with a bacterial suspension of Staphylococcus aurelus containing about x 10 s micro-organisms/ml. The tubes are placed in an oven at 37 1°C for 30 h. The turbidity of the nutrient medium is then noted.

This procedure enables the bracket values of the minimum inhibiting concentration (MIC) to be determined; if the nutrient medium content of a particular tube remains clear, this signifies that the antiseptic monomer concentration in the tube is greater than the MIC; a cloudy content of the tube signifies that the concentration is below the MIC, By preparing successive dilution series between the values of the last tube containing turbid nutrient medium and the first tube containing clear nutrient medium, it is possible to narrow the interval within which the MIC of the antiseptic monomer is located.

An MIC value between 70 and 80 lig/ml has been found for the antiseptic monomer in this first example.

In an application involving the antiseptic protection of a cotton fabric, a polymer has been developed and fixed to said cotton fabric in the form of grafts, tA* tusing the above antiseptic monomer under the conditions set out below.

S2: 25 Pieces of bleached cotton fabric weighing about 25 g were irradiated by electron bombardment with a radiation dose of about 20 kGy. The, were then immersed in solutions containing 25 g of the antiseptic monomer and 250 ml Swater.

Said pieces of fabric were then passed through a mangle on which the crushing cylinders were set at a pressure of the order of 7 bar. They were subsequently rinsed in distilled water after a standing time of about 45 min.

The quantity of antiseptic monomer polymerised and fixed to the cotton was obtained by measuring the nitrogen level recorded by Kjeldahl determination. Under the above conditions, the nitrogen content was 0.34 mg nitrogen per g fabric, corresponding to a relatively low grafting rate.

In order to verify the antiseptic protection offered by the antiseptic polymer referred to above, fixed in the form of grafts, a bacteriological procedure was used which consisted of bringing the fabric grafted in this way into contact for a determined time with a bacterial suspension of Staphylococcus aureus and determining, after this contact time, the number of surviving microorganisms. The Staphylococcus aureus used was of the standard ATCC 9144 type.

More specifically, the pieces of cotton fabric grafted in this way, and two non-grafted pieces of control cotton fabric, were cut into approximately 300 mg squares and placed in sterile, empty Petri dishes. Each fabric square was inoculated with 200 I.1 of a bacterial suspension containing about 10 5 microorganisms per ml.

o The inoculated fabric squares were divided into two groups. The first group was immediately put into suspension in 10 ml nutrient medium in order Oo to determine the micro-organism count at t 0. A 100 gl sample was taken 0 0 from each tube and spread on the agar in a Petri dish, which was then placed in an oven for 24 h at about 37 0 C. Since each deposited micro-organism gave rise to a circular colony having a pale yellow colour, it was possible after removal from the oven to count the number of CFUs (colony-forming units).

S* «The second group was placed in a humid atmosphere at 370° 1°C for 24 h. After this contact period, the squares were immersed in the same way in tubes containing 10 ml nutrient broth and stirred vigorously in order to it the micro-organisms into suspension. Successive 1/10 dilutions were prepared in each tube. 100 ul of each dilution was spread on the agar in a Petri dish, which was allowed to stand in the oven at 37 0 C for 24 h before counting.

The colony counts enabled the number of surviving micro-organisms present in the tubes to be calculated, taking into account the dilutions.

The results obtained for the fabrics grafted in accordance with this first example are shown in Table 1 below: i Control fabric Grafted fabric t 0 34 200 37 400 St 24 h 2.8x10 9 1400 i The minimum grafting rate required, according to the applicants, in order to obtain antiseptic protection is that corresponding to the MIC of the monomer in the liquid phase, in the present case this is 4 jg N/g fabric.

Example 2. In this second example, an antiseptic homopolymer was prepared from the same monomer as had been used in the first example. More specifically, 10 g of said monomer was dissolved in 30 ml acetonitrile, to which 23 mg AIBN [azo-bis-isobutyronitrile] was added as a primer, then heated in a water bath at 80°C for 1 h 30 min. The homopolymer thus formed was precipitated with methylethylketone, filtered and dried in the oven.

The minimum inhibiting concentrations (MIC) of this homopolymer were determined by preparing a series of dilutions between 200 and 1500 ig/ml by 4 the same procedure as that described above in Example 1, for the monomer.

The MIC found for the homopolymer in this second example was less than 200 jig/ml. In order to verify the antiseptic activity of the homopolymer when brought into contact with a textile support, this homopolymer was dissolved in Swater in a concentration of Fabric squares were impregnated with 200 pl1 of this homopolymer solution. They were then placed on agar in a Petri dish previously inoculated with 200 .tl of a bacterial suspension containing 105 microorganisms/ml. Fabric squares impregnated with 200 4l distilled water were also

I

12 placed on seeded agar by way of controls. All the Petri dishes were incubated for 24 h in an oven at 37C.

At the end of this incubation time, all the fabric squares impregnated with the homopolymer solution had substantial inhibition zones (IZ) (2-5 mm in size) and exhibited no bacterial growth on their surface, whereas the fabric squares impregnated with distilled water were contaminated with bacterial colonies and had no inhibition zones. The presence of an inhibition zone may be explained by the fact that the homopolymer is not fixed in covalent fashion.

Example 3. In this third example an antiseptic copolymer was prepared by copolymerisation of the monomer of the first example with ethyl acrylate.

More specifically, 5 g of each monomer were dissolved in 30 ml acetonitrile. 52 mg AIBN were added as primer, followed by heating at 80 0 C for 1 h 30 min in o a water bath. The copolymer thus formed was recovered by evaporation of the solvent and washing with methylethylketone. It was then dried in the oven.

o t *00a 0o The MIC of this antiseptic copolymer was determined by the same procedure as in the first example; it was found to be between 400 and 600 ig/ml.

.O .n Example 4. In this fourth example an antiseptic copolymer was prepared by copolymerisation of the monomer of the first example and o a acrylamide by the same method of operation as in Example 3, using 5 g o .°25 methacrylamide and 69 mg AIBN as primer.

The MIC of the antiseptic copolymer thus obtained was between 200 and S 400 pg/ml.

Example 5. This fifth example is intended to demonstrate the stability and efficacy of the antiseptic effect of a polymer according to the invention, grafted to a solid support, namely cotton fabric.

13 Pieces of bleached fabric weighing about 25 g were immersed in an aqueous solution containing 20 wt% of the antiseptic monomer of the first example and irradiated by electron bombardment at a radiation dose of about kGy. After 45 min standing time, the fabric pieces were rinsed with distilled water.

The quantity of antiseptic polymer fixed to the cotton was determined by measuring the quaternary ammonium function by ion exchange, using dichromate ions; the grafting rate was 0.23 mequiv/g (ie 3.22 mg N/g), corresponding to a high grafting rate. This method of determination by ion exchange reveals the accessibility of the quaternary ammonium function, unlike the Kjeldahl determination in which the material is completely mineralized.

Using the same bacteriological procedure as in Example 1, the antimicrobial activity was determined on a grafted fabric and on the same grafted fabric after 5 washing cycles at 40°C in a washing machine, with a commercial detergent used at 5 g/1.

The results obtained were as follows: *i P *5*1 4 t 30 St S Before washing After 5 washes Control Grafted Control Grafted t 0 37,250 50 37,150 24,900 t 2 h 45,300 0 51,350 11,800 t 6 h 8x10 5 0 7x10 5 600 t 24 h 2x10 8 0 108 0 The protection given to the textile support was retained even after five wash cycles.

A virtually complete absence of bacteria is to be noted on the grafted sample at what is described as zero time, before washing. This was due to the time required for performing the bacterial count, of the order of 5 to 10 min.

14 Since in the present case the grafting rate is high, this time is sufficient for the antiseptic activity of the grafts to be revealed.

Example 6. In this sixth example antiseptic protection was given to other forms of solid supports. These were non-woven fabrics in polyamide and viscose, which were grafted with the monomer of the first example under the following conditions.

Pieces of polyamide and viscose non-woven fabrics, weighing about 30 g, were immersed in an aqueous solution containing 20 wt% of the monomer of the first example and irradiated by electron bombardment with a radiation dose of about 20 kGy on each surface after being placed in a bag. After 45 min standing time, the samples of non-woven fabric were rinsed with distilled water.

The quantity of antiseptic polymer fixed was determined by determination of the quaternary ammonium function using dichromate ions; the grafting rate Swas 0.47 mequiv/g (ie 6.58 mg N/g) for the polyamide non-woven fabric and 0.32 o mequiv/g (ie 4.48 mg N/g) for the viscose non-woven fabric.

The. antimicrobial activity of the two grafted non-woven fabrics was determined by the same bacteriological procedure.

SThe results were as follows: O 9 9 25 t t Polyamide Viscose Control Grafted Control Grafted t 0 29,200 0 18,100 300 t= 2h 29,600 0 31,500 0 t 6 h 3.3x10 6 0 7x10 5 0 t 24 h 3.5x10 8 0 4.5x10 s 0 Example 7. In this seventh example, the antiseptic monomer consisted of a quaternary ammonium chloride containing, linked to the nitrogen atom, two i -I ethyl groups for R, and R 2 one benzyl group for R 3 and an ethyl methacrylate.

It had the following structural formula:

CH

3 I I SCH, C C O CH, CH, N' CH, Cl j CH 3 0 CH 3 i 10 This monomer was prepared by causing the benzyl chloride to react with dimethyl-amino-ethyl methacrylate.

More specifically, 90 ml dimethylformamide was added to 62.8 g dimethylamino-ethyl methacrylate. 56 g benzyl chloride was then added drop by drop, the reagent medium being stirred vigorously and protected from the light. It was left to react at ambient temperature for 1 h, followed by cooling of the reagent medium in an ice bath and the addition of 60 ml chloroform.

The mixture thus obtained was poured into 500 ml ethyl ether with vigorous stirring. A precipitate appeared, which was filtered and then dried under vacuum over P 2 0 5 110 g dry product was recovered, corresponding to a 97% yield.

The product thus obtained was in conformity with the formula given above. It is a pure product, as can be verified by NMR of the proton, determination of the halide vith silver nitrate and determination of the unsaturation phenomena by the action of morpholine in an acetic acid/dioxane medium.

0 OThe minimum inhibiting concentration of this antiseptic monomer was determined by the same procedure as that used in the first example. The preparation of successive dilution series revealed an MIC value for this of between 400 and 500 pg/ml.

ii 16 Grafting of this second antiseptic monomer on a cotton fabric was carried out under the same conditions as those described in the first example. The quantity of grafted polymer, measured on the basis of the nitrogen content, was 0.38 mg N/g fabric.

The antiseptic protection of the cotton fabrics, offered by the grafted polymer, was also verified by the same bacteriological procedure as that described in the first example. The results obtained are shown in the table below.

Control fabric Grafted fabric t 0 34,200 35,000 t 24 h 2.8r109 1,000 004QOf S 5 The minimum grafting rate required in order to obtain antiseptic protection is, according to the applicants, 7 jig N/g fabric.

eo o o .o 0 Example 8. In this eighth example an antiseptic homopolymer was 9 produced from the monomer of the seventh example. The operating conditions adopted for homopolymerisation were identical with those of Example 2, as were the conditions for determining the MIC. The latter was found to be within the range from 800 to 1000 pg/l.

99 The same test as that described in Example 2 was performed by :25 impregnating a fabric with a solution of this homopolymer. The fabric in question again exhibited a significant inhibition zone.

Example 9. In this ninth example an antiseptic homopolymer was produced from a monomer having the following formula:

CH

3 CH, CH C 0 CH, CH, N CH,, 1 Br' 35 o cH 0 CH i 4 17 The operating conditions of homopolymerisation, and also the conditions governing the determination of the MIC, were identical with those obtaining in Example 2. The MIC was found to be within the range from 400 to 600 ig/ml.

The present invention is not restricted to the embodiments described above, by way of non-exhaustive examples. In regard to the copolymerised form, in particular, the polymers according to the invention may be produced by the copolymerisation of an a:.tiseptic monomer having the general formula set out in Claim 1 and of many other monomers, for example polymerisable, acrylated epoxide monomers, single or multi-function acrylic esters, multifunction oligomers, polyester acrylates, urethane acrylates, polyethylene glycol diacrylate, trimethylolpropane triacrylate, vinyl acrylic derivatives, methacrylates, acrylamides or methacrylamides etc.

The polymers according to the invention may be used for the protection of any type of solid support, not only by fixing to the support in the form of grafts, or by impregnation of the support as described in the examples, but also by inclusion in the structure of the support. This also applies in particular where the polymer is mixed with a liquid composition containing the support and said polymer remains locked in the material of the support after elimination of the liquid phase. This applies in particular to inks, coating products for paper, plastics or textiles, coating materials such as paint and varnish or plastic films. In this case the polymer is stabilized in the solid support after solidification of the latter, in particular in a reticulated network.

In another case of the inclusion of the antiseptic polymer according to the invention in a solid support, the procedure is to introduce into said support, 1 i i Seg a natural material such as wood, a suspension containing the monomer having the general formula set out in one of the claims, followed by polymerisation in situ, so that the antiseptic polymer thus obtained is stabilised in the structure of said support and is accordingly more homogeneously distributed in it.

18 The polymers of the invention may be used for the antiseptic protection of liquid media, in particular cosmetic or para-pharmaceutical emulsions. In this case they are merely added to and homogeneously mixed with the other components. It is to be noted that their presence does not modify the characteristics of the emulsion which remains stable as a function of time.

Said polymers may also be used in anti-abrasive coatings, as flocculation agents in water treatment and in general for the antiseptic protection of any support capable of being grafted by radiochemical, chemical or photochemical means, irrespective of the form of the support, whether paper, cotton wool, textiles or non-woven fabrics and in particular felt. They may also be used in the agricultural sector for the antiseptic protection of crop areas, for example by fixing to or coating of fertilizers in particular. It is to be noted that the polymer of the invention comprises a nitrogenous function which is compatible S* -15 with commercial fertilizer formulations. Lastly, the protected solid support may be used as a filtration material; in this case, the antiseptic activity of the polymer according to the invention may be brought to bear on the filtered, o gaseous or liquid medium, either for the biological purification of water or during air conditioning.

I

o a e 4 4

Claims

1. Process for the antiseptic protection of a solid support characterized in that it consists of forming and fixing to said support, in the form of grafts during a grafting reaction, a polymer obtained by using, in a polymerisation reaction, a monomer having the following formula: R1 A-(CH 2 -CH 2 )n-N R3,X( R2 in which: R 1 and R 2 are alkyl groups, respectively CaH2a+l for R 1 and CbH2b+l for R 2 and R 3 is either an alkyl group CcH 2 c+l with c 4 and 15 a+b+c 6 or an aryl group having the formula -(CH 2 )d-C 6 H 5 with d 2 1 and a+b+d 8, 3 n 1, A is an ethylene functional group capable of participating in a polymerisation reaction, is an anion.

2. Process for the antiseptic protection of a solid support characterized in that it consists of developing a polymerisation reaction by means of an antiseptic monomer having the following general formula: V. R 1 i A-(CH2-CH2)n--N R 3 R2 20 in which: R 1 and R 2 are alkyl groups, respectively CaH2a+1 for R 1 and CbH2b+l for R 2 and R 3 is either an alkyl group CcH2c+l with c 4 and 15 2 a+b+c 6 or an aryl group having the formula -(CH 2 )d-C 6 H 5 with d 2 1 and a+b+d 5 8, 3n >1, A is an ethylene functional group capable of participating in a polymerisation reaction, is ar' anion. after said monomer has penetrated said support.

3. Process for the antiseptic protection of solid support, said support being obtained from a liquid composition in particular of a reticulable nature, characterized in that it consists of mixing with said liquid composition, a polymer obtained by using, in a polymerisation reaction, a monomer having the following general formula: [N:\libaa]00602:jvr R 1 A-(CH 2 -CH 2 )n-N R3,X() R2 in which: R 1 and R 2 are alkyl groups, respectively CaH2a+1 for R 1 and CbH2b+1 for R 2 and R 3 is either an alkyl group CcH 2 c+I with c 2 4 and 15 2 a+b+c 2 6 or an aryl group having the formula -(CH2)d-C 6 H 5 with d 1 and a+b+d 8, 3 2n>l, A is an ethylene functional group capable of participating in a polymerisation reaction, is an anion. the polymer being stabilized in the solid support after elimination of the liquid phase.

4. Process for the antiseptic protection of a liquid medium characterized in mixing in homogeneous fashion the said liquid medium which consists of an emulsion of a cosmetic or para-pharmaceutical compound with a polymer obtained by using, in a polymerisation reaction, a monomer having the following general formula: R 1 A-(CH 2 -CH 2 )n-N R 3 R2 in which: R 1 and R 2 are alkyl groups, respectively CaH2a+1 for R 1 and CbH2b+l for R 2 and R 3 is either an alkyl group CcH 2 c+i with c 4 and 15 a+b+c 2 6 or an aryl group having the formula -(CH2)d-C 6 H 5 with d 2 1 and a+b+d 8, 3 n>1, A is an ethylene functional group capable of participating in a polymerisation reaction, is an anion.

5. Process according to any one of claims 1 to 4 in which A is a vinyl group.

6. Process according to any one of claims 1 to 4 in which A is an ethylene group having the general formula: CH 2 =C-B- R in which R 4 is -H or -CH3, B is-[CH 2 or or [C-NH]- O O [N:\libaa00602:ivr a or o o0 e o 0 r o« *0 ar a a I 21

7. Process according to claim 6, characterized in that the monomer has the following general formula: CH 3 CH 2 C-O-C C-CH-N(-C 18 H 17 ,Br() 1 II 1 CH 3 0 CH 3

8. Process according to claim 6, characterized in that the monomer has the general formula: CH 3 CH2=C-C-O-CH 2 -CH 2 -N()-CH 2 CI, II CH 3 0 CH 3

9. Cotton fabric obtained by the process of claim 1 with a monomer having the following formula: CH 3 CH2=C- C-O-CH2-CH 2 -N 0C 8 H 17 ,Br I I0 H CH3 CH3 o1 or CH 3 CH 2 C--O-CH 2 -CH 2 C i( CH 3 0 CH 3 and containing 4ag to 7mg nitrogen per gram of fabric.

10. Process for the antiseptic protection of a solid support, substantially as hereinbefore described with reference to any one of the Examples. 15

11. Process for the antiseptic protection of a solid support characterized in that it consists of forming and fixing to said support, in the form of grafts during a grafting reaction, a polymer obtained by using, in a polymerisation reaction, a monomer substantially as hereinbefore described with reference to any one of the Examples.

12. Process for the antiseptic protection of a solid support characterized in that it 20 consists of developing a polymerisation reaction by means of an antiseptic monomer substantially as hereinbefore described with reference to any one of the Examples.

13. Process for the antiseptic protection of a solid support, said support being obtained from a liquid composition in particular of a reticulable nature, characterized in that it consists of mixing with said liquid composition, a polymer obtained by using, in a polymerisation reaction, a monomer substantially as hereinbefore described with reference to any one of the Examples.

14. Process for the antiseptic protection of a liquid medium characterized in Smixing in homogeneous fashion the said liquid medium which consists of an emulsion of a [N:\libaa]00602:jv- <[N:\libaa]00602:jvr #VR4 RA T 0ca~ 22 cosmetic or para-pharmaceutical compound with a polymer obtained by using, in a polymerisation reaction, a monomer substantially as hereinbefore described with reference to any one of the Examples. Dated 29 August, 1996 Centre technique Industriel dit INSTITUT TEXTILE D E FRANCE Patent Attorneys for the Applicant/Nominated Person SPRUSON FERGUSON [N:\libaa]00602:jvr I ABSTRACT OFTHE DISCLOSURE ANTISEPTIC POLYMER Polymer having antiseptic properties obtained. by using, in a polymerisation reaction, a monomer having the general formula: A -(CH 2 -CH 2 W"-Ral ,Xt R 2 in which: R, and R. are alkyl groups, respectively C 5 1-I 2 for R, and Q7-b,-I for R 2 and R 3 is either an alkyl group C~Ii2,, with c 4 and 15 2: a+b~c 6 or an aryl group having the formula C 6 H 5 with d I 1 arid a+b~d 3 :n >1, t it A is an ethylene futnctional group capable of participating wn a polymerisation reaction, is an anion.