Cleaning compositions for solid surfaces – auxiliary compositions – Cleaning compositions or processes of preparing – With halogen – nitrogen – oxygen – or phosphorus containing...
Reexamination Certificate
2000-03-31
2002-10-15
Boyer, Charles (Department: 1751)
Cleaning compositions for solid surfaces, auxiliary compositions
Cleaning compositions or processes of preparing
With halogen, nitrogen, oxygen, or phosphorus containing...
C510S130000, C510S131000, C510S235000, C510S238000, C510S289000, C510S286000, C510S356000, C510S384000, C510S385000, C510S386000, C510S387000, C510S388000, C510S391000, C510S504000, C510S466000, C510S319000
Reexamination Certificate
active
06465409
ABSTRACT:
The present invention relates to an aqueous system based on a biocide and on a polyorganosiloxane containing polyether functions, as well as to its use for the long-lasting disinfection of hard surfaces by slow, gradual release of the said biocide after application, by contact with water on the treated surface.
Aqueous biocidal compositions for treating hard surfaces generally have the drawback of rapidly losing their efficacy after they have been applied, in particular when the surfaces treated are then washed.
To overcome this drawback, it has been proposed to use film-forming organic polymers in these compositions in order to form, after application, a physical barrier which prevents the biocide from being released too quickly.
It has thus been suggested (WO 97/06675 from Rhône-Poulenc Chemicals Ltd.) to combine with a biocide a terephthalic copolyester having polyoxyethylene or polyoxyethylene terephthalate units in its polymer chain.
The Applicant has found a high-performance aqueous biocidal system.
A first subject of the invention is an aqueous biocidal system comprising
at least one water-soluble or water-dispersible biocidal agent, and
at least one polyorganosiloxane containing water-soluble or water-dispersible polyether functions, of formula (I)
R
1
R
2
R
3
SiO(R
4
R
5
SiO)
p
(R
6
QSiO)
q
SiR
3
R
2
R
1
(I)
in which formula
the symbols R
1
, R
2
, R
4
, R
5
and R
6
, which may be identical or different, represent a phenyl or a C
1
to C
6
alkyl radical, preferably methyl,
the symbols R
3
, which may be identical or different, represent
a phenyl or C
1
to C
6
alkyl radical, preferably methyl,
or the symbol Q,
the symbol Q represents a polyoxyalkylene ether residue of formula
—R—O—(R′O)
n
R″
where
R represents
a linear C
3
to C
15
, preferably C
3
to C
10
, alkyl group, most particularly trimethylene,
a branched C
4
to C
15
, preferably C
4
to C
10
, alkyl group, most particularly 2-methyltrimethylene,
the unit (R′O)
n
represents a poly(ethylenoxy) and/or poly(propylenoxy) group,
n is an average value ranging from 5 to 200, preferably from 5 to 100
R″ represents H or a C
1
to C
6
, preferably C
1
, alkyl group
p is an average value ranging from 10 to 200, preferably from 10 to 100
q is
a value q1 equal to 0, R
3
in this case representing the symbol Q
or, preferably, an average value q2 ranging from 1 to 100, preferably from 5 to 50, irrespective of R
3
.
It has been observed, advantageously, that the polyorganosiloxane structure of the polymer of formula (I) not only allows adhesion and wetting of the biocidal system to the support to be treated, but also creates a preferential interaction between the biocide and the polyether functions, by virtue of the high mobility of the polyorganosiloxane skeleton due to the low glass transition temperature of the polymer (Tg less than room temperature).
Among the biocidal agents which may be present in the said system of the invention, mention may be made of cationic, amphoteric, amino, phenolic and halogen-containing biocides. Systems based on cationic biocides are particularly advantageous.
As examples of biocides, mention may be made of:
cationic biocides such as quaternary monoammonium salts such as
cocoalkylbenzyldimethylammonium, C
12
-C
14
alkyl-benzyldimethylammonium, cocoalkyldichlorobenzyl-dimethylammonium, tetradecylbenzyldimethylammonium, didecyldimethylammonium and dioctyldimethylammonium chlorides
myristyltrimethylammonium and cetyltrimethyl-ammonium bromides
monoquaternary heterocyclic amine salts such as laurylpyridinium, cetylpyridinium and C
12
-C
14
alkyl-benzylimidazolium chlorides
triphenylphosphonium fatty alkyl salts such as myristyltriphenylphosphonium bromide
polymeric biocides such as those derived from the reaction
of epichlorohydrin and of dimethylamine or diethylamine
of epichlorohydrin and of imidazole
of 1,3-dichloro-2-propanol and of dimethylamine
of 1,3-dichloro-2-propanol and of 1,3-bis(dimethylamino)-2-propanol
of ethylene dichloride and of 1,3-bis(dimethylamino)-2-propanol
of bis(2-chloroethyl)ether and of N,N′-bis(dimethylaminopropyl)urea or -thiourea
biguanidine polymer hydrochlorides, such as Vantocil IB
amphoteric biocides such as derivatives of N-(N′-C
8
-C
18
alkyl-3-aminopropyl)glycine, of N—(N′—(N″—C
8
-C
18
alkyl-2-aminoethyl)-2-aminoethyl)glycine, of N,N-bis(N′—C
8
-C
18
-alkyl-2-aminoethyl)glycine, such as (dodecyl) (aminopropyl) glycine and (dodecyl) (diethylenediamine) glycine
amines such as N-(3-aminopropyl)-N-dodecyl-1,3-propanediamine
phenolic biocides such as para-chloro-meta-xylenol, dichloro-meta-xylenol, phenol, cresols, resorcinol, resorcinol monoacetate, and their derivatives or water-soluble salts
halogenated biocides such as iodophores and hypochlorite salts, such as sodium dichloroisocyanurate
Among the polyorganosiloxanes containing polyether functions which can be used in the system of the invention, mention may be made most particularly of those of formulae
Me
3
SiO(SiMe
2
O)
x
(SiMeQ
1
O)
y
SiMe
3
and
Me
2
Q
1
SiO(SiMe
2
O)
x
(SiMeQ
1
O)
y
SiQ
1
Me
2
in which formulae
x is an average value ranging from 10 to 200, preferably from 10 to 100,
y is an average value ranging from 1 to 100, preferably from 5 to 50
Q
1
represents the radical
—(CH
2
)
3
O(CH
2
CH
2
O)
z
(CH
2
CH(CH
3
)O
z
,H
or
—(CH
2
)
3
O(CH
2
CH
2
O)
z
(CH(CH
3
)CH
2
O)
z
,H
z is an average value ranging from 5 to 200, preferably from 5 to 100
z′ is an average value ranging from 0 to 100, preferably from 0 to 50 with z and z′ranging from 5 to 200, preferably from 5 to 100.
The biocidal agent and the polyorganosiloxane containing polyether functions represent the main constituents of the aqueous biocidal system forming the subject of the invention.
The biocide is preferably present in the aqueous biocidal system at a concentration of about 0.1% to 20% by weight, preferably of about 0.5% to 5% by weight.
The polyorganosiloxane containing polyether functions of formula (I) is preferably present in the aqueous biocidal system at a concentration of about 0.01% to 20% by weight, preferably of about 0.05 to 5% by weight.
The relative amounts of biocide and of polyorganosiloxane containing polyether functions can correspond to a biocide/polyorganosiloxane containing ether functionality weight ratio of about 0.1 to 50, preferably of about 0.5 to 25.
A first specific embodiment of the invention consists of an aqueous biocidal system in the form of an aqueous solution, in which system the biocidal agent and the polyorganosiloxane containing polyether functions are water-soluble.
According to the invention, along with the biocide and the polyorganosiloxane containing polyether functions, the main constituents of the aqueous biocidal system of the invention, other constituents, such as surfactants, chelating agents (such as aminocarboxylates, (ethylenediaminetetra-acetates, nitrilotriacetates, N,N-bis(carboxymethyl)-glutamates, citrates), alcohols (ethanol, isopropanol, glycols), detergency adjuvants (phosphates, silicates), dyes, fragrances, etc., may advantageously be present.
A second specific embodiment of the invention consists of a biocidal system containing, besides the biocide and the polyorganosiloxane containing polyether functions, at least one surfactant, particularly a nonionic, amphoteric, zwitterionic or anionic surfactant; these may be present in a proportion of from 1 to 25%, preferably from about 2 to 10%, of the weight of the said aqueous biocidal system.
Among the surfactants which may be present, mention may be made in particular of:
nonionic surfactants such as ethylene oxide/propylene oxide block polymers, polyethoxylated sorbitan esters, fatty esters of sorbitan, ethoxylated fatty esters (containing from 1 to 25 units of ethylene oxide), polyethoxylated C
8
-C
22
alcohols (containing from 1 to 25 units of ethylene oxide), polyethoxylated C
6
-C
22
alkylphenols (containing from 5 to 25 units of ethylene oxide), alkylpolyglycosides, amine oxides (such as C
10
-C
18
alkyldimethylamine oxides, C
8
-C
22
alk
Carr John Frederic
Davis Brian
Mignani Gerard
Vergelati Caroll
Vovelle Louis
Boyer Charles
Rhodia Chimie
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