Infection resistant products

The present invention relates to infection resistant materials and or products made from a molten blend of at least one polymer and a compound having antioxidant, plasticizer and antiviral activity. Additionally, this compound has a hydrophilic lipophilic balance of between 12 and 20. The preferred polymer, polyvinyl chloride, is blended with the antioxidant, plasticizer, antiviral compound NONOXYNOL-9 (.alpha.-nonylphenyl-w-hydroxypoly(oxy-1, 2-ethanediyl) to form the infection resistant material.

The invention relates therefor also to infection resistant devices obtained 
by said method or process, to a compound used as antioxidant, plasticizer 
and as antiviral agent and to a composition of polymer(s) for said method 
or process. 
THE PRIOR ART 
It is known that, for manufacturing devices from a molten blend of a 
polymer, it is suitable to add same additives such as plasticizer(s) and 
antioxidant(s) 
It is also known to cover devices with a layer containing an antibacterial 
agent. For covering such devices, a composition containing a polymer, a 
solvent of said polymer and an antibacterial agent is prepared, said 
composition being 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 (.alpha.-(nonylphenyl)-w-hydroxypoly(oxy-1,2,ethanediyl), 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 (.alpha.-(nonylphenyl)-w-hydroxypoly(oxy-1,2, 
ethanediyl)-9 has already been used in spermicides. 
Applicant s have found that compounds of the general formule 1 
EQU R.sub.1 --O--((CH.sub.2).sub.ai --O).sub.n --R.sub.2 ( 1) 
are antiviral agents, plasticizers and antioxidants, which are stable at 
temperature higher than 100.degree. C., so that they may be used in usual 
injection, extrusion, or other transformation processes. 
BRIEF DESCRIPTION OF THE INVENTION 
The invention relates to a method for producting 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: 
EQU R.sub.1 --O--((CH.sub.2).sub.a.sbsb.i --O).sub.n --R.sub.2 
where 
R.sub.1 is a saturated or unsaturated hydrocarbon group; 
a.sub.i is, for i=1 to n, an integer greater or equal to 
R.sub.2 is an organic group possibly substituted, and 
n is an integer selected so that the Hydrophilic Lipophilic Balance 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 a 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.sub.1, a.sub.i, n and R.sub.2 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 or/and 
compositions being suitable for the manufacture of infection-resistant 
devices according to the invention. 
DESCRIPTION OF THE INVENTION 
Compounds of general formula 1: 
EQU R.sub.1 --O--((CH.sub.2).sub.a.sbsb.i --O).sub.n --R.sub.2 
are known as being non-ionic surfactants. 
Said compound may be characterized by a hydrophile-lipophile balance (HLB) 
as teached by GRIFFIN, W.C. (1949), J. Soc. Cosmet. Chem.1, 311-326. 
Such compounds are, for example, alkylphenoxypoly (ethyleneoxy) ethanol and 
more specifically nonylphenoxypoly (ethyleneoxy)ethanol ANTAROX CO-630 
(nonylphenoxypoly (ethyleneoxy)ethanol) and NONOXYNOL 
(.alpha.-(nonylphenyl)-w-hydroxypoly(oxy-1,2,ethanediyl). 
Methods for the manufacture of such compounds are given for example, in 
U.S. Pat. No. 1,970,578 and U.S. Pat. No. 2,774,709. 
Compounds which are suitable are compounds of the general formula 1: 
EQU R.sub.1 --O--((CH.sub.2).sub.a.sbsb.i --O).sub.n --R.sub.2 ( 1) 
where 
R.sub.1 is a saturated or unsaturated hydrocarbon group; 
a.sub.i is, for i=1 to n, an integer greater or equal to 2; 
R.sub.2 is an organic group possibly substituted, and 
n is an integer selected so that the Hydrophilic Lipophilic Balance of said 
compound is comprised between 12 and 20. 
It has been found that said compounds when treated at temperature higher 
than 100.degree. C. have always virucide action for example against 
Hepatitis A, Hepatitis B and AIDS (HTL VIII). The compounds were even 
stable at temperature of about 200.degree. C. 
In a method according to the invention, compound of general formula 1 in 
which R.sub.1, R.sub.2, a.sub.i and n have the above given meanings is 
mixed with a plasticizer before being added to a molten polymer. When 
manufacturing for example disposable gloves, the compound of general 
formula 1 will be distributed between the surface and the polymer matrix. 
Therefor, 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.sub.1, R.sub.2, a.sub.i and n 
have the above given meanings does 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: 
R.sub.1 is a possibly substituted cycloalkyl or aromatic radical 
advantageously a phenyl radical substituted by at least one alkyl group 
and preferably a phenyl radical substituted in para position with a 
C.sub.6-12 alkyl group; 
a.sub.i is 2 or 3; 
n is an integer comprised between 6 and 20, preferably between 8 and 15, 
and 
R.sub.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, and rubber. 
The C.sub.6-12 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-octyl) and, ethyl propyl. 
Preferred alkyl groups are n-octyl, n-nonyl, 4-(tert octyl), 
7-methylheptyl, 6-dimethylhexyl, 8-methyloc-tyl and, 7-dimethylheptyl.

EXAMPLES AND TESTS 
Example of Compounds 
Compounds which are suitable for the method according to the invention are 
compounds of formula 
EQU R.sub.1 --O--((CH.sub.2).sub.2 --O).sub.n --H 
in which 
##STR1## 
and n is an integer comprised between 7-8 and 15. 
Such compounds are given hereafter: 
______________________________________ 
Hydrophilic 
Lipophilic 
TRADEMARK n Balance FIGS. 
______________________________________ 
ANTAROX .RTM. CO-610 
7-8 12.2 1 
nonylphenoxypoly- 
(ethyleneoxy) 
ethanol 
(sold by GAF CHEMICAL 
CORP., U.S.A.) 
ANTAROX .RTM. CO-620 
8-9 12.6 2 
nonylphenoxypoly 
(ethyleneoxy) 
ethanol 
ANTAROX .RTM. CO-630 
9 13.0 3 
nonylphenoxypoly and 
(ethyleneoxy) 4 
ethanol 
ANTAROX .RTM. CO-660 
10 13.2 5 
nonylphenoxypoly- 
(ethyleneoxy) 
ethanol 
ANTAROX .RTM. CO-710 
10-11 13.6 6 
nonylphenoxypoly 
(ethyleneoxy) 
ethanol 
ANTAROX .RTM. CO-720 
12 14-2 7 
nonylphenoxypoly 
(ethylenoxy) 
ethanol 
ANTAROX .RTM. CO-730 
15 15 8 
nonylphenoxypoly 
(ethyleneoxy) 
ethanol 
______________________________________ 
The chromatograms of said compounds are given in FIGS. 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 
nonylphenoxypoly(ethyleneoxy) ethanol family may be considered as a 
mixture of various compounds, n being only a mean value. 
ANTAROX.RTM. CO-630 nonylphenoxypoly(ethyleneoxy) ethanol (normal grade) 
has been analyzed via a UV spectrum (see FIG. 9). In said FIG. 9, curves 
D, E, F, G and H represent the UV spectrum of the fraction of the compound 
ANTAROX nonylphenoxypoly(ethyleneoxy) ethanol 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 
nonylphenoxypoly(ethyleneoxy) ethanol contains various compounds having 
the following structure H.sub.19 C.sub.9 --C.sub.6 H.sub.4 --O--(CH.sub.2 
--CH.sub.2 --O).sub.n.sbsb.i --H and that the n value given to ANTAROX 
CO-630 nonylphenoxypoly(ethyleneoxy) ethanol is a mean value of the 
various n.sub.i. 
Another example of non ionic surfactant of the formula 1 which is suitable 
for the method according to the invention is: 
##STR2## 
n being equal to 9-10. 
Said compound is sold by BOEHRINGER MANNHEIM LABORATORIES under the name 
TRITON.RTM. X-100 nonylphenoxypoly(ethyleneoxy) ethanol. 
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.RTM. CO-630 
nonylphenoxypoly(ethylereoxy) ethanol (normal grade) has been shown by 
means of the following test. 
A sample of polyvinyl chloride has been heated on the following manner: 
0 to 3 minutes the sample is heated at 55.degree. C. under nitrogen, 
from 3 minutes to 6 minutes the temperature of the sample under nitrogen is 
increased at a rate of 40.degree. C. per minutes, 
from 6 minutes to 46 minutes (end of the test) the temperature of the 
sample is maintained at 175.degree. C. and a flow of oxygen is applied on 
the sample, the thermal response of which is studied by means of a Perkin 
Elmer Thermal Analysis System. 
FIGS. 10 to 12 show the thermal response of polyvinylchloride 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.degree. C. (R) after a 
time of X minutes. 
If a variation of heat flow occurs while maintaining a temperature of 
175.degree. C., it means that the sample is oxidized or degradated. 
FIG. 10 shows the termal response of a polyvinylchloride sample, with the 
standard plasticizer (DINP) while FIG. 11 and FIG. 12 show the influence 
of replacing the standard plasticizer with an equivalent amount of Antarox 
CO-630 polyoxyethylated nonylpenol, respectively for 5 and 10% of the 
formulation concentration. 
It appears from these figures that the addition of ANTAROX CO-630 
nonylphenoxy-poly(ethyleneoxy) ethanol increases the stability of the PVC 
sample. It means also that ANTAROX CO-630 nonylphenoxypoly(ethylencoxy) 
ethanol is stable at temperature of 175.degree. C. so that said compound 
may be used in usual techniques such as polymer injection, extrusion, . . 
. without any degradation. 
Examples of manufacture 
95 kg of liquid plastisol, (a blend containing 45% of polyvinyl chloride, 
the rest essentially DINP) is mixed with 5 kg of ANTAROX.RTM. CO-630 
nonylphenoxypoly(ethyleneoxy) ethanol. Said composition has been cast so 
as to produce film samples for mechanical tests, after gelification at 
175.degree. C. 
During the mixing of ANTAROX.RTM. CO-630 nonyl phenoxy poly(ethyleneoxy) 
ethanol, 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 nonyl phenoxypoly(ethyleneoxy) ethanol 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.RTM. CO-630 
nonylphenoxypoly(ethyleneoxy) ethanol. 
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 
______________________________________ 
plastisol Plastisol 
+ 5% + 10% 
plastisol ANTAROX ANTAROX 
______________________________________ 
Tensile Strength 
8.1 6.94 5.9 
N/mm.sup.2 
Elongation % 
217 241 243 
______________________________________ 
When using gloves containing ANTAROX.RTM. CO-630, 
nonylphenoxypoly-(ethyleneoxy) ethanol, no allergic reaction of the users 
was observed. 
Further advantage 
The gas permeability of polyvinylchloride with or without Antarox CO-630 
nonylphenoxypoly(ethyleneoxy) ethanol 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 
(CO.sub.2), one third of oxygen (O.sub.2) and one third of nitrogen 
(N.sub.2), said gas flowing in the upper part. 
Said 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 
nonylphenoxypoly(ethyleneoxy) ethanol (film I, plastisol), of the film 
containing 5% ANTAROX CO-630 nonylphenoxypoly(ethyleneoxy) ethanol (film 
J) and of the film containing 10% Antarox CO-630 
nonylphenoxypoly(ethyleneoxy) ethanol (film K) are given in FIG. 13 for 
CO.sub.2 and in FIG. 14 for O.sub.2, said permeabilities being expressed 
in cm.sup.3 /day m.sup.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 
nonylphenoxypoly(ethyleneoxy) ethanol allow to reduce the gas 
permeability. Therefor 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.degree. and 35.degree. C. while the viscosity of 
plastisol containing 10% ANTAROX.RTM. CO-630 
nonylphenoxypoly-(ethyleneoxy) ethanol is about 920 cps at 32.degree. C. 
Therefor, the use of compounds of formula 1, in particular of Antarox.RTM. 
CO-630 nonylphenoxypoly(ethyleneoxy) ethanol instead of known plasticizers 
such as DINP does not require modification of the manufacture process.