Cleaning compositions for solid surfaces – auxiliary compositions – Cleaning compositions or processes of preparing – For cleaning a specific substrate or removing a specific...
Reexamination Certificate
2000-08-15
2002-01-29
Hardee, John (Department: 1751)
Cleaning compositions for solid surfaces, auxiliary compositions
Cleaning compositions or processes of preparing
For cleaning a specific substrate or removing a specific...
C510S475000
Reexamination Certificate
active
06342472
ABSTRACT:
The present invention relates to low-concentration, highly viscous liquid detergents which, as a result of using a thickening system, are storage- and viscosity-stable under very diverse climatic conditions, do not undergo phase separation, and have color stability even on exposure to light.
Highly viscous detergents and cleaners, and also cosmetics have been increasingly offered in recent years, those products having a “gel”-like consistency being widely accepted by the consumer. In the field of liquid detergents, highly viscous gel products have the advantage that fewer nonaqueous solvents can be used and the product can be applied in a targeted manner to stains without running. In this connection, conventional liquid detergents are customarily converted into highly viscous products by the use of thickening agents, such as agar agar, carrageen, tragacanth, gum arabic, alginates, pectins, polyoses, guar flour, carob seed grain, starch, dextrins, gelatin, casein, carboxymethylcellulose and also cellulose ethers, hydroxyethyl- and -propylcellulose and the like, seed grain ethers, polyacrylic and polymethacrylic compounds, vinyl polymers, polycarboxylic acids, polyethers, polyimines, polyamides, polysilicic acids, clay minerals, such as montmorillonites, zeolites and silicas. The use of these thickeners for increasing the viscosity in a very wide variety of liquids has belonged to the prior art for some time. The use of polymers in liquid detergents is also well-known.
The incorporation of said thickeners in cases of liquid detergents only leads to stable gels above certain surfactant contents. A gel will usually only form at surfactant contents above 35% by weight. Liquid detergents with surfactant contents below 35% by weight exhibit, after a few days, phase separation or agglomerate formation, which is evident from the formulation becoming opaque (“cloud formation”). Additionally, the viscosity of such products sometimes drops drastically during storage. Since highly viscous liquid detergents are usually offered in transparent bottles to highlight the esthetic features, it is also a requirement that the thickeners used are stable toward light since otherwise free-radical decomposition of the polymers arises, which manifests itself in the destruction of the product color and undesired “cloud formation”.
Liquid detergents with viscosities between 500 and 20,000 mPas, preferably from 2000 to 10,000 mPas, in which lamellar surfactant droplets are dispersed in an aqueous electrolyte phase, are described in European Patent Application EP-A 691 399 (Colgate). These compositions comprise 10 to 45% by weight of surfactant(s), at least one builder, and 0.01 to 5% by weight of a mercapto-terminally-capped polymer having an average molecular weight between 1500 and 50,000 gmol
−1
.
The use of boron compounds in aqueous liquid detergents is described in EP-A 381 262 (Unilever). These liquid detergents comprise the boron compounds, and a polyol as enzyme-stabilizing system for a mixture of proteolytic and lipolytic enzymes, preferred stabilizing systems consisting of a sorbitol/borax mixture. Information about viscosity and stability of the liquid detergents is not given in this specification.
Liquid, aqueous detergent concentrates which retain or increase their viscosity upon dilution with water are described in EP-A 724 013 (Colgate). This effect is achieved by the use of two surfactants having varying stability toward electrolytes and the addition of a dissolved electrolyte, where the concentrate has a viscosity of less than 2500 mPas and, upon dilution with water, loses its micellar structure at the expense of the formation of a lamellar phase.
The International Patent Application WO 96/01305 (Unilever) describes an aqueous cleaner and liquid detergent which, upon dilution with at least twice the amount of water, forms a microemulsion which has particle sizes from 10 to 100 nm. The composition comprises 20 to 70% by weight of water, 15 to 40% by weight of a surfactant system which comprises at least one nonionic surfactant from the group of alkoxylated alcohols and not more than 20% by weight of anionic, cationic, amphoteric or zwitterionic surfactants, 5 to 30% by weight of solvents and 5 to 20% by weight of water-insoluble oil.
None of said specifications deals with the problem of providing low-concentration and highly viscous liquid detergents which guarantee a stable viscosity, do not lead to agglomerate formation (so-called “cloud formation”) or phase separation, and do not have a decrease in color stability on exposure to light. The solution to this problem was the object of the present invention.
It has now been found that liquid detergents with said profile of properties can be prepared if a thickening system comprising polyurethanes or modified polyacrylates, a boron compound and complexing agents is incorporated into the compositions.
The present invention therefore provides aqueous, highly viscous liquid detergents comprising surfactant(s) and other customary ingredients of detergents and cleaners, where the compositions comprise, as thickening system, in each case based on the total composition,
a) 0.2 to 5% by weight of a polyurethane or a modified polyacrylate,
b) 0.5 to 7% by weight of a boron compound, and
c) 1 to 8% by weight of a completing agent.
By using the thickening system according to the invention it is possible to prepare highly viscous liquid detergents which are free from said disadvantages. According to the invention, it is possible also to prepare concentrated highly viscous liquid detergents which have surfactant contents above 35% by weight. Since, however, said problems arise particularly in the case of low-concentration products, for the purposes of the present invention, preference is given to aqueous, highly viscous liquid detergents whose content of surfactant(s) is below 30% by weight.
The first component of the thickening system is a polyurethane or a modified polyacrylate which, based on the total composition, is used in amounts of from 0.2 to 5% by weight.
Polyurethanes (PUR) are prepared by polyaddition from di- and polyhydric alcohols and isocyanates and can be described by the general formula I
in which R
1
is a low molecular weight or polymeric diol radical, R
2
is an aliphatic or aromatic group, and n is a natural number. R
1
is preferably a linear or branched C
2-12
-alk(en)yl group, but can also be a radical of a polyhydric alcohol, by means of which crosslinked polyurethanes are formed which differ from the formula I given above by virtue of the fact that further —O—CO—NH groups are bonded to the radical R
1
.
Industrially important PUR are prepared from polyesterdiols and/or polyetherdiols and, for example, from toluene 2,4-diisocyanate or 2,6-diisocyanate (TDI, R
2
=C
6
H
3
—CH
3
), methylene 4,4′-di(phenylisocyanate) (MDI, R
2
=C
6
H
4
—CH
2
—C
6
H
4
) or hexamethylene diisocyanate [HMDI, R
2
=(CH
2
)
6
]. Commercially available thickeners based on polyurethane are available, for example, under the names Acrysol® PM 12 V (mixture of 3-5% of modified starch and 14-16% of PUR resin in water, Rohm&Haas), Borchigel® L75-N (nonionogenic PUR dispersion, 50% strength in water, Borchers), Coatex® BR-100-P (PUR dispersion, 50% strength in water/butyl glycol, Dimed), Nopco® DSX-1514 (PUR dispersion, 40% strength in water/butyl triglycol, Henkel-Nopco), thickener QR 1001 (20% strength PUR emulsion in water/diglycol ether, Rohm&Haas) and Rilanit® VPW-3116 (PUR dispersion, 43% strength in water, Henkel).
Preferred liquid detergents comprise 0.2 to 4% by weight, preferably 0.3 to 3% by weight and in particular 0.5 to 1.5% by weight, of a polyurethane.
Modified polyacrylates which can be used for the purposes of the present invention are derived, for example, from acrylic acid or from methacrylic acid, and can be described by the general formula II
in which R
3
is H or a branched or unbranched C
1-4
-alk(en)yl radical, X is N—R
5
or O, R
4
is an optionally alkoxylated, branched or unbranched, optio
Legel Dieter
Penninger Josef
Voelkel Theodor
Hardee John
Henkel Kommanditgesellschaft Auf Aktien (KGaA)
Jaeschke Wayne C.
Murphy Glenn E. J.
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