Cleaning and liquid contact with solids – Processes – Miscellaneous
Reexamination Certificate
2003-05-27
2004-07-27
Del Cotto, Gregory R. (Department: 1751)
Cleaning and liquid contact with solids
Processes
Miscellaneous
C510S180000, C510S181000, C510S237000, C510S238000, C510S426000, C510S427000, C510S499000, C510S503000, C510S504000, C510S433000, C510S476000
Reexamination Certificate
active
06767410
ABSTRACT:
The present invention relates to the cleaning of public, domestic or industrial hard surfaces, in particular of ceramic, tile or glass type, which is aimed at giving these surfaces hydrophilic properties.
The invention relates more particularly to the use of polymers having both properties of interaction with the hard surface and hydrophilic properties to give this surface long-lasting hydrophilic properties so as to avoid the subsequent presence of marks due in particular to the drying of droplets of water deposited on said surface.
Commercial detergent formulations clean public, domestic or industrial hard surfaces efficiently. They generally consist of an aqueous solution of surfactants, in particular of nonionic and anionic surfactants, of alcohol(s) to facilitate drying, and optionally of sequestering agents and bases to adjust the pH. A major defect of these detergent formulations is that the subsequent contact of the hard surface with the skin can lead to the presence of marks on drying. This contact with water after applying detergent can originate, for example, from rainwater in the case of windows, mains water on a bathroom tile, or rinsing water when the cleaning requires a rinsing. They can also originate from the air-drying of washing-up crockery in the case of detergent formulations for washing up by hand, or from the drying of washing-up crockery in an automatic machine when it is a case of dishwasher detergent. In the case of doing the washing up in an automatic machine, said formulation can either be used in the cleaning cycle (detergent formulation) or during the rinsing cycle (rinsing liquid).
The presence of marks or stains left on hard surfaces by water which comes into contact with them is due to the phenomenon of contraction of the drops of water on contact with the hard surface, which, during the subsequent drying, leave marks on the surface which reproduce the original shapes and dimensions of the drops.
No satisfactory solution to this problem exists at the present time.
To solve the problem posed by the retraction and drying of drops of water, the solution consists in increasing the hydrophilicity of the surface in order to obtain the smallest possible contact angle between the hard surface to be treated and the drop of water.
The inventors' studies which led to the present invention have determined that this problem can be solved in an effective and long-lasting manner by incorporating a water-soluble or water-dispersible organic polymer compound which has both a function of interaction with the surface to be treated and a function giving this surface a hydrophilic nature into conventional compositions for cleaning hard surfaces.
EP 522 756 describes ampholytic terpolymers comprising, as polymer units:
a cationic monomer, in particular dimethyldiallylammonium chloride (DADMAC for diallyldimethylammonium chloride);
an anionic monomer, in particular acrylic acid;
a nonionic monomer, in particular acrylamide.
These terpolymers have moisturizing and protective properties on the skin and the nails and are provided in compositions intended to be applied to the skin, such as aftershaves, sunscreens, hand lotions, liquid soaps, bath products and shaving foams. The document also describes a composition for doing the washing up by hand, this composition being particularly suitable for protecting and moisturizing the skin.
WO 97/22 640 describes aqueous dispersions of polymers with surfactant properties and more particularly foaming properties.
The polymers are prepared by polymerization of vinyl monomers (a) containing at least one quaternary nitrogen atom with vinyl monomers (b) containing at least one amide group and vinyl monomers (c) containing both hydrophilic and hydrophobic groups, so as to give the terpolymer detergent properties.
A monomer (a) which is mentioned in particular is DADMAC.
A monomer (b) which is mentioned in particular is (meth)acrylamide.
The monomers (c) are polyethoxylated and polypropoxylated derivatives of a carboxylic acid, such as acrylic acid.
EP 835 925 describes a detergent composition for doing the washing up in an automatic dishwasher, comprising a lipolytic enzyme and a copolymer obtained by polymerization of 50 mol % to 99 mol % of anionic monomer units, in particular of acrylic acid, with 1 mol % to 50 mol % of cationic monomers, in particular DADMAC and 0 mol % to 25 mol % of an anionic, cationic, amphoteric or nonionic monomer or a mixture thereof, in particular acrylic acid esters.
The combination of the lipolytic enzyme with the polymer avoids the deposition of calcium soap on the washing-up crockery without having harmful effect on the grease-removing action by the lipases.
It has been proposed (JP 09-169 995-A) to use, in compositions for treating toilet pans against soiling, a cationic polymer for increasing the hydrophilicity of the surface to be treated. Examples of cationic polymers which are mentioned are DADMAC homopolymers and copolymers of DADMAC and of acrylamide, as well as copolymers of DADMAC and of acrylic acid; the polymers mentioned as being preferred are the copolymers of DADMAC and of acrylic acid with a DADMAC/acrylic acid weight ratio of 8/2 and most preferably the DADMAC homopolymers.
The Applicant has found, contrary to what the above document suggests, that a markedly higher permanent hydrophilicity of the treated surface is found when higher levels of anionic monomer are present.
The studies by the inventors which have led to the present invention have determined that the copolymers obtained by copolymerization of monomers containing a quaternary ammonium function and two groups containing ethylenic unsaturation with monomers containing a group capable of ionizing in the application medium to form anionic units, with a ratio of the first monomers to the second monomers which is within a given range, give hard surfaces noteworthy hydrophilic properties.
A first subject of the invention consists in using a water-soluble or water-dispersible copolymer comprising, in the form of polymerized units:
(a) at least one monomer compound of general formula I:
in which:
R
1
and R
4
, independently of each other, represent a hydrogen atom or a linear or branched C
1
-C
5
alkyl group;
R
2
and R
3
, independently of each other, represent an alkyl, hydroxyalkyl or aminoalkyl group in which the alkyl group is a linear or branched C
1
-C
5
chain, preferably a methyl group;
n and m are integers between 1 and 3;
X, which may be identical or different, represent counterions which are compatible with the water-soluble or water-dispersible nature of the polymer;
(b) at least one hydrophilic monomer bearing a function of acidic nature which is copolymerizable with (a) and capable of ionizing in the application medium,
(c) optionally, at least one hydrophilic monomer compound containing ethylenic unsaturation and of neutral charge, bearing one or more hydrophilic groups, which is copolymerizable with (a) and (b),
in which the a/b molar ratio is between 60/40 and 5/95,
to give a hard surface hydrophilic properties.
Preferably,
R
1
represents hydrogen,
R
2
represents methyl,
R
3
represents methyl,
R
4
represents hydrogen, and
m and n are equal to 1.
The ion X
−
is advantageously chosen from halogen, sulfate, hydrogen sulfate, phosphate, citrate, formate and acetate.
The monomer (a) gives the copolymer properties of interaction with the surface to be treated, in particular allowing anchoring of the copolymer to this surface.
The monomer (b) and optionally the monomer (c) give the copolymer hydrophilic properties which, after anchoring the copolymer to the surface to be treated, are transmitted to this surface.
This hydrophilic property of the surface moreover reduces the formation of mist on the surface; this benefit can be exploited in particular in cleaning formulations for glass panels and mirrors, in particular in bathrooms.
The copolymer according to the invention advantageously has a molecular mass of at least 1000, advantageously of at least 10,000; it can be up to 20,000,000, advantage
Aubay Eric
Yeung Dominic
Del Cotto Gregory R.
Rhodia Chimie
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