Cleaning and liquid contact with solids – Processes – Carbon removal
Reexamination Certificate
2000-06-19
2003-05-27
Kopec, Mark (Department: 1751)
Cleaning and liquid contact with solids
Processes
Carbon removal
C134S038000, C134S040000, C134S042000, C510S229000, C510S238000, C510S240000, C510S241000, C510S243000, C510S244000, C510S475000, C510S480000, C510S504000
Reexamination Certificate
active
06569261
ABSTRACT:
A subject-matter of the present invention is a cleaning or rinsing composition intended for the treatment of industrial, domestic or communal hard surfaces, in particular of glass, window, ceramic, tiling, hard organic polymer, metal or wood type and the like, targeted at conferring on the latter hydrophilic properties and properties of protection (corrosion resistance) of glass, of dishes and of designs by washing media during repeated washing operations in an automatic dishwasher.
A more particular subject-matter of the invention is a cleaning composition intended for the treatment of a hard surface which is capable of conferring persistent hydrophilic properties on the latter, so as to prevent the subsequent presence of marks due in particular to the drying of drops of water deposited on said surface.
Commercial detergent formulations make it possible to efficiently clean industrial, domestic or communal hard surfaces. They are generally composed of an aqueous solution of surfactants, in particular of nonionic and anionic surfactants, of alcohol(s), in order to facilitate drying, and optionally of sequestering agents and of bases, in order to adjust the pH. A significant failing in these detergent formulations is that subsequent contact of the hard surface with water can result in the presence of marks during drying. This contact with water after application of detergent can originate, for example, from rainwater, in the case of windows, from mains water on bathroom tiling, or from rinsing water when the cleaning requires rinsing. It can also originate from the drying of the dishes in the open air, in the case of detergent formulae for cleaning dishes by hand, or from the drying of dishes in an automatic device when the detergent is intended for a dishwasher. In the case of the cleaning of dishes in an automatic device, said formula can either be used in the cleaning cycle (detergent formula) or during the rinsing (rinsing liquid).
The presence of marks or stains left on the hard surfaces by the water coming into contact with the latter is due to the phenomenon of contraction of the water drops on contact with the hard surface, which, during subsequent drying, leave marks on the surface which reproduce the original shapes and sizes of the drops.
Until now, no satisfactory solution to this problem existed.
To solve the problem posed by the retraction and the drying of the drops of water, the solution consists in increasing the hydrophilicity of the surface in order to obtain a contact angle between the hard surface to be treated and the drop of water which is as small as possible.
The studies of the Inventors which have led to the present invention have made it possible to determine that this problem can be solved in an efficient and lasting way by incorporating, in conventional cleaning compositions for hard surfaces, a water-soluble or water-dispersible organic polymer compound having both a function of interaction with the surface to be treated and a function conferring a hydrophilic nature on this surface.
A first subject-matter of the invention is a cleaning or rinsing composition comprising at least one 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
is a hydrogen atom or a methyl or ethyl group;
R
2
, R
3
, R
4
, R
5
and R
6
, which are identical or different, are linear or branched C
1
-C
6
, preferably C
1
-C
4
, alkyl, hydroxyalkyl or aminoalkyl groups;
m is an integer from 0 to 10, preferably from 0 to 2;
n is an integer from 1 to 6, preferably 2 to 4;
Z represents a —C(O)O— or —C(O)NH— group or an oxygen atom;
A represents a (CH
2
)
p
group, p being an integer from 1 to 6, preferably from 2 to 4;
B represents a linear or branched C
2
-C
12
, advantageously C
3
-C
6
, polymethylene chain optionally interrupted by one or more heteroatoms or heterogroups, in particular O or NH, and optionally substituted by one or more hydroxyl or amino groups, preferably hydroxyl groups;
X, which are identical or different, represent counterions;
(b) at least one hydrophilic monomer carrying a functional group with an acidic nature which is copolymerizable with (a) and which is capable of being ionized in the application medium;
(c) optionally at least one monomer compound with ethylenic unsaturation with a neutral charge which is copolymerizable with (a) and (b), preferably a hydrophilic monomer compound with ethylenic unsaturation with a neutral charge, carrying one or more hydrophilic groups, which is copolymerizable with (a) and (b).
The monomer (a) can be prepared, for example, according to the following reaction schemes:
The monomer (a) confers, on the copolymer, characteristics of interaction with the surface to be treated, making possible in particular anchoring of the copolymer to this surface.
The monomer (b) and optionally the monomer (c) confers hydrophilic characteristics on the copolymer which, after anchoring of the copolymer to the surface to be treated, are passed on to the surface.
This property of rendering the surface hydrophilic furthermore makes it possible to reduce the formation of condensation on the surface; this advantage can be made use of in cleaning formulae for windows and mirrors, in particular in bathrooms.
The copolymer according to the invention advantageously exhibits a molecular mass of at least 1000, advantageously of at least 10,000; it can range up to 20,000,000, advantageously up to 10,000,000.
Except when otherwise indicated, when the term molecular mass is used, it will refer to the weight-average molecular mass, expressed in g/mol. The latter can be determined by aqueous gel permeation chromatography (GPC) or measurement of the intrinsic viscosity in a 1N NaNO
3
solution at 30° C.
The copolymer is preferably a random copolymer.
Preferably, in the general formula (I) of the monomer (a),
Z represents C(O)O, C(O)NH or O, very preferably C(O)NH;
n is equal to 2 or 3, very particularly 3;
m ranges from 0 to 2 and is preferably equal to 0 or 1, very particularly to 0;
B represents
with q from 1 to 4, preferably equal to 1;
R
1
to R
6
, which are identical or different, represent a methyl or ethyl group.
The preferred monomer (a) is Diquat of following formula:
X
−
representing the chloride ion.
Other particularly advantageous monomers (a) are:
The X anions are in particular a halogen, preferably chlorine, sulfonate, sulfate, hydrogensulfate, phosphate, phosphonate, citrate, formate and acetate anion.
The monomers (b) are advantageously C
3
-C
8
carboxylic, sulfonic, sulfuric, phosphonic or phosphoric acids with monoethylenic unsaturation, their anhydrides and their salts which are soluble in water.
Mention may be made, among the preferred monomers (b), of acrylic acid, methacrylic acid, &agr;-ethacrylic acid, &bgr;,&bgr;-dimethylacrylic acid, methylenemalonic acid, vinylacetic acid, allylacetic acid, ethylidineacetic acid, propylidineacetic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, N-(methacroyl)alanine, N-(acryloyl)hydroxyglycine, sulfopropyl acrylate, sulfoethyl acrylate, sulfoethyl methacrylate, styrenesulfonic acid, vinylsulfonic acid, vinylphosphonic acid, phosphoethyl acrylate, phophonoethyl acrylate, phosphopropyl acrylate, phophonopropyl acrylate, phosphoethyl methacrylate, phophonoethyl methacrylate, phosphopropyl methacrylate, phophonopropyl methacrylate and the alkali metal and ammonium salts thereof.
Mention may be made, among the monomers (c), of acrylamide, vinyl alcohol, C
1
-C
4
alkyl esters of acrylic acid and of methacrylic acid, C
1
-C
4
hydroxyalkyl esters of acrylic acid and of methacrylic acid, in particular ethylene glycol and propylene glycol acrylate and methacrylate, polyalkoxylated esters of acrylic acid and of methacrylic acid, in particular the polyethylene glycol and polypropylene glycol esters, esters of acrylic acid or of methacrylic acid and of polyethylene glycol or polypropylene glycol C
1
-C
25
monoalkyl ethers,
Aubay Eric
Yeung Dominic
Kopec Mark
Mruk Brian P.
Rhodia Chimie
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