METHOD FOR PRODUCING INFECTION RESISTANT MATERIALS AND INFECTION RESISTANT MATERIALS

Abstract: The present invention relates to a method for producing infection resistant materials, devices or part thereof from a molten blend of at least one polymer, in which at least a compound of the general formula (1): R1-O-((CH2)ai-O)n-R2, where: R1 is a saturated or unsaturated hydrocarbon group; ai is, for i = 1 to n, an integer greater or equal to 2; R2 is an organic group possibly substituted; and n is an integer selected so that the HLB of said compound is comprised between 12 and 20, is mixed with said polymer, said compound acting as an antioxidant, as a plasticizer and as an antiviral agent.

Description: METHOD FOR PRODUCING INFECTION RESISTANT MATERIALS AND INFECTION RESISTANT MATERIALS BACKGROUND OF THE INVENTION Field of the Invention The invention relates to a method for producing infection resistant materials from a molten blend of at least one polymer and a compound in which the compound acts as an antioxidant, as a plasticizer and as an antiviral agent. The Prior Art It is known that, for manufacturing devices from a molten blend of a polymer, it is suitable to add some additives such as plasticizer(s) and antioxidant(s). It is also known to cover devices with a layer containing an an- tibacterial agent. For covering such devices, a composition containing a polymer, a solvent of said polymer and an antibacterial agent is prepared, the composition is then applied on the surface of the device so that, after drying, the device is provided with an antibacterial polymeric layer. Such devices are expensive and have antibacterial properties only on one surface thereof. It is known to add to molten polyvinyl chloride benzoate of sodium or mercury salts for avoiding a microbial growth on said polymer. However, such additives are toxic for the health so that the use thereof has to be proscribed. Nonoxynol-9, a non-ionic surfactant of the general formula 1 , has been described as an inhibitor of the growth of several microbes such as herpes simplex virus, HTLV-III. Nonoxynol-9 has already been used in spermacides. Applicants have found that compounds of the general formula 1 : R1 - 0 - ((CH 2 ) a - 0) n - R 2 i are antiviral agents, plasticizers and antioxidants, which are stable at temperature higher than 100°C, so that they may be used in usual in¬ jection, extrusion, or other transformation processes. SUMMARY OF THE INVENTION The invention relates to a method for producing infection-resistant materials, devices or part thereof from a molten blend of at least one polymer in which at least a compound of the general formula 1 : ι - 0 - ((CH 2 ) a - 0) n - R 2 i where: R-| is a saturated or unsaturated hydrocarbon group; aj is, for i = 1 to n, an integer greater or equal to 2; R is an organic group possibly substituted; and n is an integer selected so that the HLB of said compound is comprised between 12 and 20 is mixed with said polymer, said compound acting as an antioxidant, as a plasticizer and as an antiviral agent. Said molten blend may thus, for example, be: extruded, injected or dip moulded so as to manufacture infection-resistant materials or devices; or sprayed on materials or devices so as to provide said materials or devices with an infection-resistant layer. The invention relates also to infection resistant devices for example surgical gloves, surgical clothes, surgical operative fields, finger stalls, aprons, bibs, caps, etc., manufactures for example by injecting into a mould a molten blend of a polymer mixed with a compound of formula 1 in which R-j , a\, n and R have the aforementioned meanings. The invention relates to compounds of general formula 1 and to composition of polymer(s) containing a compound of formula 1, said compounds and/or compositions being suitable for the manufacture of infection-resistant devices according to the invention. BRIEF DESCRIPTION OF THE DRAWINGS Figures 1 to 8 are chromatograms at 225, 254 and 271 nm of compounds suitable for the method according to the invention; Figure 9 is a UV spectrum of a compound suitable for the method according to the invention; Figures 10 to 12 show the stability of polyvinylchloride at 175°C; and Figures 13 and 14 show permeabilities of polyvinylchloride. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT Compounds of general formula 1 : R, - 0 - ((CH 2 ) - 0) n - R 2 a. are known as being non-ionic surfactants. Said compound may be characterized by a hydrophile-lipophile balance (HLB) as taught by Griffin, W. C, J. Soc. Cosmet. Chem.1, (1949) 311-326. Such compounds are, for example, alkylphenoxypoly (ethyleneoxy) 5 ethanol and more specifically nonylphenoxypoly (ethyleneoxy) ethanol (Antarox<_? Antarox®CO-630, Nonoxynol -9). Methods for the manufacture of such compounds are given for example, in U.S. Patent No. 1,970,578 and U.S. Patent No. 2,774,709. Compounds which are suitable are compounds of the general o formula 1 : R 1 - 0 - «CH 2 ) a - 0) n - R 2 i where R 1 is a saturated or unsaturated hydrocarbon group; a t is, for i = 1 to n, an integer greater or equal to 2; s R 2 is an organic group possibly substituted; and n is an integer selected so that the HLB of said compound is . comprised between 12 and 20. It has been found that said compounds when treated at tem¬ perature higher than 100°C have always virucide action for example o against Hepatitis A, Hepatitis B and AIDS (HTL VIII). The compounds were even stable at temperature of about 200°C. In a method according to the invention, compound of general formula 1 in which R R 2 , a j and n have the above-given meanings is mixed with a plasticizer before being added to a molten polymer. When 5 manufacturing for example disposable gloves, the compound of general formula 1 will be distributed between the surface and the polymer matrix. Therefore, the infection-resistant devices according to the invention provide an antiviral contact protection and a protection mechanism in case of pinholes or microcracks. Since the compounds of formula 1 in which R 1t R 2 , a, and n have the above-given meanings do not affect the polymer network properties, such as tensile strength, elasticity modules, etc. up to 10% or even more of said compounds may be added. Moreover, since said compounds of formula 1 have a similar plastificating effect as known plasticizers such as di iso nonyl phthalate (DINP), dialkylhexylphthalate, etc. the compounds of formula 1 may replace the plasticizers. The used compound of general formula 1 has preferably the following characteristics: ] is a possibly substituted cycloalkyl or aromatic radical ad¬ vantageously a phenyl radical substituted by at least one alkyl group and preferably a phenyl radical substituted in para position with a C^ alkyl group; a, is 2 or 3; n is an integer comprised between 6 and 20, preferably be¬ tween 8 and 15; and R 2 is a radical selected from the group consisting of hydrogen and/or alcohol. Polymers which may be used in said method are polyethylene (low density, high density), polypropylene, polyvinylchloride, polystyrene, polyamide, polycarbonate, rubber, . . . The Cg., 2 alkyl group which is used as substituent in para position of the phenyl radical may be selected from the group consisting of linear alkyl group such as n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl and n-dodecyl and branched alkyl group such as methyl pentyl, methyl heptyl, methyl octyl, methyl nonyl, methyl decyl, methyl undecyl, di-methyl hexyl, 4-(tert-octyI), ethyl propyl. Preferred alkyl groups are n-octyl, n-nonyl, 4-(tert octyl), 7- methylheptyl, 6-di methyl hexyl, 8-methyloctyl, 7-dimethylheptyl. EXAMPLES AND TESTS Example of Compounds Compounds which are suitable for the method according to the invention are compounds of formula Ri - 0 - ((CH 2 ) 2 - 0) n - H in which n is an integer comprised between 7- 8 and 15. Such compounds are given hereafter: The chromatograms of said compounds are given in figures 1 to 8. In said figures, curve A is the chromatogram at 225 nm, curve B is the chromatogram at 254 nm and curve C is the chromatogram at 271 nm. It appears from these figures that peaks appear for each compound after about 1.3, 1.6, 1.7, 1.9 and 2.1 minutes. From this chromatograms, it is clear that the products of the ANTAROX family may be considered as a mixture of various compounds, n being only a mean value. ANTAROX* CO-630 (normal grade) has been analyzed via a UV spectrum (see figure 9). In said figure 9, curves D, E, F, G and H represent the UV spectrum of the fraction of the compound ANTAROX appearing on the chromatogram at respectively 1.04, 1.26, 1.52, 1.78 and 3.78 minutes. It appears from this UV analysis that ANTAROX CO-630 contains various compounds having the following structure H 19 C 9 .C 6 H 4 -0-(CH 2 -CH 2 -0) - H and that the n value given to ANTAROX CO-630 is a mean value of the various n, Another example of non ionic surfactant of the formula 1 which is suitable for the method according to the invention is: CH, CH, H 3 C CH, - 0 -- [CH 2 -CH 2 -0] — H CH, CH, n being equal to 9 - 10. Said compound is sold by BOEHRINGER MANNHEIM LABORATORIES under the name TRITON* X - 100. It is clear that mixture of compounds of general formula 1 may be used as antivirus agent, plasticizer and antioxidant. Thermal Stability Tests The stability of blends containing compounds ANTAROX* CO-630 (normal grade) has been shown by means of the following test. A sample of polyvinyl chloride has been heated on the following manner: Figures 10 to 12 show the thermal response of PVC sample, i.e., the heat flow (mW) required for heating the sample (P) or for the melting thereof (Q) or for maintaining a temperature of 175°C (R) after a time of X minutes. If a variation of heat flow occurs while maintaining a temperature of 175°C, it means that the sample is oxidized or degradated. Figure 10 shows the termal response of a PVC sample, with the standard plasticizer (DINP) while Figure 11 and Figure 12 show the influence of replacing the standard plasticizer with an equivalent amount of ANTAROX CO-630, respectively for 5 and 10% of the formulation concentration. It appears from these figures that the addition of ANTAROX CO-630 increases the stability of the PVC sample. It means also that ANTAROX CO-630 is stable at temperature of 175°C so that said compound may be used in usual techniques such as polymer injection or extrusion without any degradation. Examples of Manufacture Ninety-five kg of liquid plastisol (a blend containing 45% of polyvinyl chloride, the rest essentially DINP) is mixed with 5 kg of ANTAROX 8 CO-630. Said composition has been cast so as to produce film samples for mechanical tests, after gelification at 175°C. During the mixing of ANTAROX* CO-630, with the plastisol, no phase separation was observed. The tensile strength of samples was estimated by tests performed with a rate of 200 mm/min. A surface migration of ANTAROX was observed for the films, the thickness of which was approximative 130 microns. In a same manner, films samples were manufactured from a composition containing 90 kg of plastisol and 10 kg of ANTAROX* CO-630. A surface migration was also observed for the gloves, the thickness of which was about 130 microns. The mechanical properties of the casted film samples are summarized in the following table. For comparison purpose said table contains also mechanical properties of samples made only from plastisol. TABLE When using gloves containing ANTAROX* CO-630, no allergic reaction of the users was observed. Further Advantage The gas permeability of polyvinylchloride with or without Antarox CO-630 has also been studied. For this study, samples are set in a measuring chamber comprising two parts, the lower of which being the circulation and sampling system while the upper part is the gassing chamber. The working gas was constituted of respectively one-third of carbon dioxide (C0 2 ), one-third of oxygen (0 2 ) and one-third of nitrogen (N 2 ), said gas flowing in the upper part. The gas passes through the PVC film and is periodically swept by helium gas (vector gas) to the detector where it is quantified. The permeabilities of the films without ANTAROX (film I, plastisol), of the film containing 5% Antarox CO-630 (film J) and of the film containing 10% Antarox CO-630 (film K) are given in figure 13 for C0 2 and in figure 14 for 0 2 , said permeabilities being expressed in cm 3 /day m 2 atm. Devices and materials obtained by the process according to the invention are thus effective for making gas barrier. The replacement of known plasticizer such as DINP by Antarox CO-630 allow to reduce the gas permeability. Therefore, it seems that devices and materials obtained by the process according to the invention have pinholes, the dimensions of which or the number of which are lower than devices and materials which do not contain a compound of formula 1 in the matrix of the polymer. In other words, materials and devices according to the invention have a low porosity. The gas barrier property of films or materials obtained by the process according to the invention are improved when the composition contains at least 1% of compound(s) of formula 1, preferably between 2 and 10% and more preferably about 5%. The viscosity of plastisol is about 800 to 1300 cps at temperature comprised between 30 and 35°C while the viscosity of plastisol containing 10% Antarox* CO-630 is about 920 cps at 32°C. Therefore, the use of compounds of formula 1, in particular of Antarox* CO-630 instead of known plasticizers such as DINP, does not require modification of the manufacture process.

Claims: What We Claim Is: ι 1. A method for producing infection-resistant materials, devices 2 or part thereof from a molten blend of at least one polymer, in which at 3 least a compound of a general formula 1 : R 1 - O - ((CH 2 ) a - 0) n - R 2 5 where: 6 R 1 is a saturated or unsaturated hydrocarbon group; 7 a j is, for i = 1 to n, an integer greater or equal to 2; β R 2 is an organic group possibly substituted; and 9 n is an integer selected so that the HLB of said compound is ιo comprised between 12 and 20 ιι is mixed with said polymer, said compound acting as an antioxidant, as a 12 plasticizer and as an antivirus agent, and/or as agent improving the gas 13 barrier. ι 2. A method according to claim 1, in which a compound of 2 general formula 1 , the radical R., of which is a radical selected from the 3 group consisting of substituted cycloalkyl and substituted aromatic radical, is used as an antioxidant, as a plasticizer and as an antiviral agent. ι 3. A method according to claim 1, in which a compound of 2 general formula 1 , the radical R, of which is a substituted phenyl radical, 3 is used as an antioxidant, plasticizer and as an antiviral agent. ι 4. A method according to claim 1, in which a compound of 2 general formula 1 , the radical R, of which is a phenyl radical substituted 3 by at least one alkyl group, is used as an antioxidant, a plasticizer and as 4 an antiviral agent. 5 5. A method according to claim 1, in which a compound of 6 general formula 1 , the radical R, of which is a phenyl radical substituted in 7 para position with a C^ alkyl group, is used as an antioxidant, a β plasticizer and as an antiviral agent. ι 6. A method according to claim 1, in which a compound of 2 general formula 1 , the integers a, and n of which are respectively equal to 3 2 or 3 and comprised between 6 and 20, is used as an antioxidant, a plasticizer and as an antiviral agent. ι 7. A method according to claim 1, in which a compound of 2 general formula 1 , the integers aj and n of which are respectively equal to 3 2 or 3 and comprised between 8 to 15, is used as an antioxidant, a 4 plasticizer and as an antiviral agent. ι 8. A method according to claim 1 , in which a compound of 2 general formula 1 , the radical R 2 of which is selected from the group 3 consisting of hydrogen and alcohol, as an antioxidant, a plasticizer and as an antiviral agent. ι 9. A method according to claim 1 , in which the molten blend is 2 extruded, injected or moulded so as to manufacture resistant devices or 3 parts thereof. ι 10. A method according to claim 1, in which devices or part(s) 2 thereof which have to be infection resistant are soaked in a bath 3 containing a blend or plastisol of at least one polymer, mixed with at least 4 a compound of a general formula 1 : R 1 - O - ((CH 2 ) - 0) n - R 2 6 where: 7 R t is a saturated or unsaturated hydrocarbon group; s ^ is, for i = 1 to n, an integer greater or equal to 2; 9 R 2 is an organic group possibly substituted; and ιo n is an integer selected so that the HLB of said compound is ιι comprised between 12 and 20. 1 11. A method according to claim 1, in which the blend or 2 plastisol is sprayed on the device or part thereof which have to be in- 3 fection resistant. ι 12. A method according to claim 1, in which the polymer is 2 selected from the group consisting of polyethylene, polypropylene, 3 polyvinyl chloride, polystyrene, polyamide. ι 13. Infection resistant devices or part thereof manufactured 2 according to the method according to claim 1 , said devices or part thereof 3 being made from a molten blend of at least one polymer of at least a 4 compound of the general formula 1 : 5 R t - O - ((CH 2 ) a - 0) n - R 2 i 6 where: 7 R, is a saturated or unsaturated hydrocarbon group; 8 β j is, for i = 1 to n, an integer greater or equal to 2; 9 R 2 is an organic group possibly substituted; and ιo n is an integer selected so that the HLB of said compound is ιι comprised between 12 and 20. ι 14. Infection resistant devices or part thereof according to claim 2 13, in which the compound of formula 1 is a compound in which: 3 R 1 is a radical selected from the group consisting of substituted 4 cycloalkyl and substituted aromatic radical 6 n is an integer comprises between 6 and 20, and 7 R 2 is selected from the group consisting of hydrogen and alco- β hoi. ι 15. Compound used as an antioxidant, as a plasticizer and as 2 an antiviral agent and/or as agent improving the gas barrier in the method 3 according to claim 1 , the formula of said compound being: R 1 - 0 - ((CH 2 ) a - 0) n - R 2 5 where: 6 R, is a saturated or unsaturated hydrocarbon group; 7 a, is, for i = 1 to n, an integer greater or equal to 2; β R 2 is an organic group possibly substituted; and 9 n is an integer selected so that the HLB of said compound is o comprised between 12 and 20. ι 16. Compound according to claim 15, having the general 2 formula 1 in which: 3 R, is a radical selected from the group consisting of substituted 4 cycloalkyl and substituted aromatic radical; 5 a j is 2 or 3; 6 n is an integer comprises between 6 and 20; and 7 R 2 is selected from the group consisting of hydrogen and alco- 8 hoi. ι 17. Composition containing at least one polymer for the method 2 for producing infection resistant and/or gas proof devices or part thereof 3 according to claim 1 , said composition containing also at least a 4 compound of the general formula 1 : R 1 - O - ((CH 2 ) 'a a . - 0) n - R 2 where: 7 R t is a saturated or unsaturated hydrocarbon group; β a, is, for i = 1 to n, an integer greater or equal to 2; 9 R 2 is an organic group possibly substituted; and ιo n is an integer selected so that the HLB of said compound is ιι comprised between 12 and 20, 12 said compound acting as an antioxidant, as a plasticizer and as an 13 antiviral agent and/or as an agent improving the gas barrier. ι 18. Composition according to claim 17, said composition 2 containing at least a compound of formula 1 in which: 3 R, is a radical selected from the group consisting of substituted 4 cycloalkyl and substituted aromatic radical; 5 βj is 2 or 3; 6 n is an integer comprises between 6 and 20; and 7 R 2 is selected from the group consisting of hydrogen and alco- β hoi. ι 19. Composition according to claim 17, said composition 2 containing at least 1 % of compound(s) of formula 1. ι 20. Composition according to claim 17, said composition 2 containing from 2 to 10% of compound(s) of formula 1. ι 21. Composition according to claim 17, said composition 2 containing about 5% of compound(s) of formula 1.

Inventors: DELMOTTE YVES A, KERSTEIN JEAN, DELMOTTE, YVES, A., KERSTEIN, JEAN
Applicants: BAXTER INT, BAXTER INTERNATIONAL INC.
Application year: 1991
Main classification: A61K31
IPC codes: A61L31, C08K5