Cleaning compositions for solid surfaces – auxiliary compositions – Cleaning compositions or processes of preparing – Specific organic component
Reexamination Certificate
2000-07-14
2004-03-16
Mruk, Brian P. (Department: 1751)
Cleaning compositions for solid surfaces, auxiliary compositions
Cleaning compositions or processes of preparing
Specific organic component
C510S361000, C510S434000, C510S475000, C510S477000, C424S070110, C424S078180, C424S401000
Reexamination Certificate
active
06706679
ABSTRACT:
This application is an application under 35 U.S.C. Section 371 of International Application Number PCT/FR99/00091 filed on Jan. 19, 1999.
The present invention relates to copolymers in which one of the monomers is an unsaturated acid or diacid, or a derivative, as a foam protector in detergent or cosmetic formulations.
The appearance of a large amount of long-lasting foam is a phenomenon which is very important to have in detergent or cosmetic formulations, more particularly those which are used by hand. The reason for this is that it is clearly recognized that this foaming phenomenon is synonymous, for the user, with the efficacy of the cleaning undertaken. Consequently, even though this phenomenon does not really have any effect on the quality of the cleaning, a particular objective of formulators is to prepare formulations which give a large amount of foam.
However, the appearance and especially the durability of the foam are highly dependent on the other compounds present in the bath, and mainly greases. In other words, once the washing bath contains greasy substances, the foam is more or less rapidly eliminated.
One aim of the present invention is to propose detergent and cosmetic formulations which generate large amounts of foam, and especially which conserve this foam, in particular under unfavorable conditions, such as in the presence of greases, and possibly of divalent cations such as calcium.
Thus, a subject of the present invention is the use, as a foam protector in detergent or cosmetic formulations, of a copolymer or a mixture of copolymers comprising:
at least one monomer (I) chosen from C
3
-C
5
unsaturated acids, diacids or anhydrides, or
at least one monomer (II) chosen from ethylene oxide and propylene oxide, or
at least one monomer (III) chosen from linear or branched C
4
-C
8
hydrocarbons comprising at least one ethylenic unsaturation, or
at least one monomer (IV) of the following formula:
R
1
—COO—
R
2
,
in which:
R
1
represents a linear or branched, optionally substituted C
1
-C
4
hydrocarbon-based radical;
R
2
represents a linear or branched C
1
-C
4
hydrocarbon-based radical optionally substituted with an anionic group which can be in the form of an acid or of an alkali metal salt or ammonium salt of —N(R
3
)
3
+
type, with R
3
, which may be identical or different, representing hydrogen atoms or C
1
-C
4
hydrocarbon-based radicals, or optionally substituted with a hydroxyl group;
the monomer (IV) comprising at least one ethylenic unsaturation.
It should be noted that the term “foam protector”means a compound which conserves this foam, at least partly, under unfavorable conditions, such as in the presence of greases or of divalent cations. It should be noted that the foamability of the polymer used as a foam protector in the present invention is not a criterion that is considered as truly essential. However, the compound used should not excert a harmful effect on the ability of the foaming agents moreover present in the formulation.
The term “greases” refers more particularly to any liquid and/or solid hydrophobic hydrocarbon-based medium having, for example, a solubility in water of less than 5 g/l, preferably less than 1 g/l.
This grease can be provided by the external medium and/or can be a constituent of the detergent or cosmetic formulation. Thus, it can be either a hydrophobic soiling or a hydrophobic active compound of said formulation, for example.
Greases which may be mentioned as examples are:
aliphatic or aromatic hydrocarbons (alkanes (for example such as hexadecane), paraffins, mineral oils, liquid paraffins, kerosene, petrol, fuel, perhydrosqualane, squalene, etc.);
alkylmonoglycerides, alkyldiglycerides, triglycerides, such as the oils extracted from plants and vegetation (palm oil, coconut oil, cotton seed oil, soybean oil, sunflower oil, olive oil, grape seed oil, sesame oil, ground nut oil, castor oil, hazlenut oil, etc.) or oils of animal origin—tallow, fish oils), derivatives of these oils such as hydrogenated oils, and lanolin derivatives;
natural or non-natural essential oils, such as eucalyptus oil, lavender oil, hybrid lavender oil, vetiver oil, lemon oil, orange oil, sandalwood oil, rosemary oil, camomile oil, savory oil, nutmeg oil, cinnamon oil, bergamot oil, cade oil, geraniol oil, etc.,
fatty alcohols such as cetyl alcohol, stearyl alcohol or oleyl alcohol;
fatty esters such as isopropyl palmitate, 2-ethylhexyl cocoate, myristyl myristate, lactic acid esters, stearic acid esters, behenic acid esters, or isostearic acid esters;
polyorganosiloxane oils, gums or resins such as linear or cyclic polydimethylsiloxanes, &agr;,&ohgr;-hydroxylated polydimethylsiloxanes, &agr;,&ohgr;-trimethylsilyl polydimethylsiloxanes, polyalkylmethylsiloxanes, polymethylphenylsiloxanes, polydiphenylsiloxanes, amino derivatives of silicones and silicone waxes;
organic soiling (sebum, etc.).
Thus, the use of these copolymers in detergent or cosmetic formulations gives initial foaming properties that are at least as good as those of conventional formulations. In addition, and this constitutes a noteworthy advantage of these copolymers, the use of these copolymers in detergent and cosmetic formulations makes it possible to conserve a foam volume which is 10%, preferably 15% or even up to 30% greater than that of formulations from which they are absent, and allows this in the presence of greases possibly combined with divalent cations.
However, other aims and advantages of the present invention will emerge more clearly on reading the description and the examples which follow.
As has just been stated, the foam protector used in the present invention is a copolymer or a mixture of several copolymers comprising at least one of the monomers (I) to (IV) mentioned previously.
More specifically, the copolymer or mixture of copolymers comprises at least one monomer of at least two monomers of types (I) to (IV), of at least two monomers of the type (IV) and optionally of at least one monomer of type (I) to (III), or mixtures thereof.
It should be noted that the copolymer used as foam protector is more particularly soluble at the time of use of the formulation into which it is introduced, i.e. soluble in aqueous media.
More particularly, the copolymer is such that it is soluble in an aqueous solution of basic pH. Such conditions are conventional in particular in the washing up of kitchenware and in the washing of laundry.
In addition, the copolymer used according to the invention advantageously has both a hydrophilic part and a hydrophobic part. Thus, it lowers the interface tension between the aqueous solution and the greases, which improves the dispersion of these greases in the aqueous solution.
Generally, the copolymers used according to the invention have a weight-average molar mass of between 10
3
and 10
7
g/mol, more particularly between 10
4
and 10
6
g/mol and preferably between 10
4
and 5×10
5
g/mol. According to an even more advantageous embodiment, the copolymers have a weight-average molar mass of between 1.5×10
4
and 5×10
5
g/mol. The molar mass is determined by steric exclusion chromatography in aqueous phase. As an example of a method for measuring the molar mass of the copolymers used in the context of the invention, a TSK-gel column, with an eluent comprising water, 0.1 mol/l of NaO
3
and 200 ppm of NaN
3
, was used. The detection of the molar mass is based on the refractive index, using polyethylene oxide as standard.
As more particularly regards the monomer (I), this monomer is chosen from C
3
-C
5
unsaturated acids, diacids or anhydrides.
The most suitable representatives of these monomers are acrylic acid and methacrylic acid. As regards the diacids and anhydrides, mention may be made, inter alia, of maleic acid, fumaric acid, itaconic acid, maleic anhydride, furmaric anhydride and itaconic anhydride.
The monomer (II) is chosen from ethylene oxide and propylene oxide.
The monomer (III) is chosen from linear or branched hydrocarbons comprising at least one C
4
-C
8
ethylenic unsaturation. As examples
Bergeron Vance
Schoonbrood Harold
Mruk Brian P.
Rhodia Chimie
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