Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
21S2465
WO 94/14908 PCT/EP93/03486
A neutral self-shine emulsion for the care of floor~ (II)
This invention relates to a floor-care formulation
in the form of a dispersion which dries leaving a shine
on the floor. Formulations such as these are also known
as self-shine emulsions.
Nowadays, new previously untreated floors and floors
which have been subjected to thorough cleaning are mainly
treated with self-shine emulsions to protect them against
soiling and damage. These emulsions, which contain wax
and/or film-forming polymers in varying amounts, form
continuous, glossy and soil-repellent films on the floors
after drying. Films with a high percentage wax content
can easily be polished and, when necessary, are also easy
to remove from the surfaces whereas films consisting pre-
dominantly or completely of film-forming polymers are
particularly resistant to mechanical stressing. A prob-
lem affecting all self-shine emulsions, which has not yet
been completely solved, is that the emulsions or disper-
sions have to dry extremely uniformly on the surfaces if
a completely continuous protective film is to be formed.
It is very often found that the initially continuous film
of the aqueous dispersion breaks up on drying and, in
some cases, even contracts to form individual droplets so
that the floor-care film formed is patchy in appearance.
This effect is particularly noticeable in the case of the
dispersions with a substantially neutral pH value which
are preferred today. One of the problems addressed by
the present invention was to provide an improvement in
this regard. Another problem addressed by the invention
was to improve the stability of the dispersions, above
all during storage at low temperatures.
The present invention relates to an aqueous self-
shine emulsion for the care of floors which, in undiluted
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form, has a pH value of 5 to 9 and which contains an at
least partly water-insoluble polymer compound with a
minimum film forming temperature of 0 to 70C or a
mixture of several polymer compounds with this property
and a monoalkyl diethylene glycol ether containing l to
4 carbon atoms in the alkyl moiety or a mixture of such
ethers. Polymer dispersions with a pH value in undiluted
form of 6 to 9 are particularly preferred.
The new self-shine emulsions are distinguished by
high stability in storage, particularly at low tempera-
tures. A particularly noteworthy feature is their
extremely uniform drying behavior characterized by the
virtual absence of cracks in the film, so that uniform
floor-care films of satisfactory appearance are obtained.
Another surprising feature of the formulations according
to the invention is that they are resistant to microbial
contamination so that there is no need for typical
preservatives to be added.
The polymer compounds present in the self-shine
emulsions are those which are at least partly insoluble
in water at a neutral pH value and which have a minimum
film forming temperature in the range from about 0 to
about 70C. The polymer compounds in question are
preferably polymers prepared from ethylenically unsatura-
ted monomers. Examples of such monomers are styrene,acrylates or methacrylates of aliphatic alcohols contain-
ing l to 8 carbon atoms, acrylonitrile, vinyl acetate,
acrylic acid and methacrylic acid. Particularly prefer-
red polymers are poly(meth)acrylates of two or more of
these monomers which may even contain other monomers in
small quantities. Most particularly preferred polymers
contain l to 30 parts by weight of monomers containing
carboxylic acid groups, 30 to 70 parts by weight of
monomers which form homopolymers with glass temperatures
below 20C, preferably esters of acrylic acid with Cl8
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Wo 94/14908 3 PCT/EP93/03486
alcohols and/or methacrylic acid with C4-8 alcohols, and
30 to 70 parts by weight of monomers which form homopoly-
mers having glass temperatures above room temperature,
preferably methacrylates of C13 alcohols or styrene.
Where several different polymer compounds of the type
mentioned above are used in the form of a mixture in the
polymer dispersion, the film forming temperature deter-
mined for the mixture should be in the range from 0 to
70C. The film forming temperatures mentioned apply to
the plasticizer-free system, i.e. to the polymers with no
further additives. Examples of such film-forming poly-
mers are the following commercial products available as
dispersions: Licomer A 41 (Hoechst), Neocryl A 349 (ICI)
and Primal B 527 (Rohm and Haas).
Where necessary, heavy metal ions, for example zinc
ions, which lead to particularly resistant films after
drying, may be added to polymers containing carboxylate
groups. Examples of commercially available polymer
dispersions containing metal salts are Ubatol TS 85
(Stapol), Neocryl SR 267 (ICI), Primal B 1604 (Rohm and
Haas).
Film-forming polymers of another type, which may be
used together with poly(meth)acrylates, are polyurethanes
which are also commercially available for this purpose.
Examples of suitable polyurethane dispersions are Alber-
dingk U 210 W (Alberdingk Boley) and Neorez 986 (Poly-
vinyl).
The polymers are present in the formulations accord-
ing to the invention in quantities of preferably 10 to
50% by weight and, more preferably, 11 to 20% by weight.
These figures apply to the pure polymers. If the disper-
sions according to the invention are produced from
dispersed polymers of the type often available on the
market, the dispersions in question have to be used in
correspondingly larger quantities in the production of
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WO 94/14908 4 PCT/EP93/03486
the formulations according to the invention. Polyure-
thanes may be present in the formulations in quantities
of up to 15% by weight and preferably in quantities of 2
to 8% by weight.
In addition to the film-forming polymers mentioned
above, which make up the predominant part of the solids
in the formulation according to the invention, the
formulations may contain waxes in dispersed form. The
wax component is intended to make the floor-care films
formed polishable to a certain extent. Suitable waxes
are both natural waxes and synthetic waxes which may be
of natural origin or even fully synthetic. Examples are
polyethylene waxes, oxidized polyethylene waxes, montan
ester waxes, paraffin waxes, candellila wax and carnauba
wax. Of these waxes, polyethylene waxes are preferred
for the formulations according to the invention. The wax
content may be up to 20% by weight of the formulation, at
least 1% by weight of wax preferably being used. The wax
content is preferably between 1 and 10~ by weight,
particularly where polyethylene waxes are used.
The second characteristic component of the self-
shine emulsion according to the invention are monoalkyl
diethylene glycol ethers containing 1 to 4 carbon atoms
in the alkyl moiety which may be used individually or in
admixture with one another. Methyl diglycol, ethyl
diglycol and n-butyl diglycol are preferably used. In
conjunction with the film-forming polymers in the aqueous
neutral emulsion, the ethers appear to be responsible for
the unexpected properties of the new formulations men-
tioned above. Small quantities of the ethers are gener-
ally sufficient. Their percentage content in the formu-
lations according to the invention is from 0.05 to 11% by
weight and preferably from 3 to 8% by weight.
In addition to the ingredients mentioned above, the
self-shine emulsions according to the invention may con-
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tain other active substances and auxiliaries in relative-
ly small quantities, including for example plasticizers,
emulsifiers, wetting agents and flow control agents,
wetting resins, preservatives and perfume oils.
Plasticizers are intended to modify the consistency
of the film, a distinction being drawn between temporary
plasticizers and permanent plasticizers. Temporary
plasticizers are volatile hydrophilic solvents which
promote the coalescence of the polymer particles during
film formation. Examples are ethylene glycol, diethylene
glycol and glycol ethers. Their percentage content in
the formulations according to the invention is generally
not more than 15% by weight and is preferably between 0.5
and 10~ by weight. Permanent plasticizers are liquids
which are not volatile under normal conditions so that
the character of the floor-care film can be lastingly
influenced with their assistance. Examples of such
plasticizers are dibutyl phthalate, tributyl phosphate,
tributoxyethyl phosphate and N-methyl caprolactam.
Permanent plasticizers also are generally present in the
suspensions according to the invention in quantities of
not more than 15% by weight and preferably in a quantity
of 0.5 to 10% by weight.
Wetting agents and flow control agents are intended
to improve the wetting of the treated surface during
application of the self-shine emulsion. In addition,
they make the emulsion easier to dilute with water, for
example for application to wet floors. Suitable wetting
and flow control agents are any of the usual surfactants,
more particularly nonionic and anionic surfactants, for
example ethoxylates of long-chain alcohols or alkyl
benzene sulfonates and fatty alcohol sulfates. Fluorine
surfactants are also used in many cases and produce a
particularly marked reduction in surface tension. The
content of wetting and flow control agents is generally
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WO 94/14908 6 PCT/EP93/03486
not more than 5% by weight, based on the total weight of
the self-shine emulsion, and is preferably between o.l
and 2% by weight. Surface wetting during application can
also be improved with wetting resins. Wetting resins are
preferably styrene/maleate resins or clear polyacrylates.
Their content in the formulations is generally not more
than 5% by weight and is preferably from 0.1 to 2% by
weight.
The formulations may be prepared by standard mixing
processes. They are generally prepared from a commer-
cially available, preformed polymer dispersion. Alterna-
tively, a dispersion of the polymer in water may be
prepared by methods known per se. If the self-shine
emulsion is also to contain wax, the wax may first be
separately processed to form an emulsion in water,
optionally with addition of suitable wax emulsifiers, and
subsequently added in that form to the polymer disper-
sion. The remaining ingredients may then be introduced
with stirring into the resulting mixture. If necessary,
the pH of the formulation is adjusted to the required
value in the neutral range (pH 5 to pH 9) by addition of
alkalis or acids.
The self-shine emulsions according to the invention
are generally applied in undiluted form. The emulsions
are applied to the surface and uniformly distributed
thereon in the required quantity using a soft object, for
example a sponge or a cloth. After evaporation of the
water, an extremely uniform, glossy film is left on the
surface in this floor-care process.
Example~
The formulations described in the following were
prepared from preformed polymer dispersions by mixing of
the components listed in Tables 1 and 2. Unless other-
wise indicated, the figures in the Tables are percentages
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WO 94/14908 7 PCT/EP93/03486
by weight, based on the pure active substances. Self-
shine emulsions 1 to 4 thus prepared were then tested for
their stability during storage at low temperatures and
for their flow control properties.
To evaluate stability at low temperatures, the
samples were stored for 12 weeks at 0 to 3C. Over this
period, the samples were removed weekly from the freezer
and visually evaluated on reaching room temperature.
Visible signs of instability were flocculation, sediment,
deposits and changes in viscosity. Evaluation was based
on the following scale:
0 uniform, homogeneous sample
1 slight deposits or sediment after 12 weeks
2 slight deposits or sediment after 3 weeks
3 medium deposits or sediment after 3 weeks
4 heavy deposits or sediment after 3 weeks
very heavy deposits or sediment after 3 weeks
The flow control properties were determined by
application to black untreated PVC sheets under condi-
tions which meet practical requirements. To this end, 10
ml of the suspension to be tested were uniformly applied
by hand applicator to a 30 x 60 cm PVC tile in each test.
The applicator consisted of an upholstery velvet stretch-
ed over a frame with an effective surface area of 20 x
5.5 cm. After drying, the appearance of the surface was
visually evaluated on the following scale:
0 streak-free
1 faintly visible uniform streaks
2 distinctly visible streaks
3 distinct, uneven streaks
4 heavy uneven residues.
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WO 94/14908 8 PCT/EP93/03486
Table 1
Example 1 2
Na benzoate 0.05
Chloroacetamide 0.1
Tributoxyethyl phosphate 2.2 2.2
Phthalic acid dibutyl ester 1.2 1.2
Polyacrylate MFT 72C * 7.5 7.5
Polyurethane (Neorez 986) 5.0 5.0
Polyethylene dispersion 1.0 1.0
Acrylonitrile/styrene 8.5 8.5
copolymer MFT 55C *
Zonyl FSJ (fluorine surfactant) 0.02 0.02
Ethylene glycol 1.0 1.0
Perfume 0.2 0.2
Diethylene glycol - 10.0
mono-n-butyl ether
Water ad 100 ad 100
p~ value 8.7 8.7
Stability in storage at 0-3C 3 0
Flow control properties 4
*MFT = minimum film forming temperature
Table 2
Example 3 4
Na benzoate 0.05
Chloroacetamide 0.1
Tributoxyethyl phosphate 1.6 1.6
Phthalic acid dibutyl ester 1.0 1.0
Polyacrylate MFT 53C 14 14
Polyethylene dispersion 3.5 3.5
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WO 94/14908 9 PCT/EP93/03486
Example 3 4
Zonyl FSJ 0.02 0.02
Ethylene glycol 1.0 1.0
Perfume 0.2 0.2
Diethylene glycol - 10.0
mono-n-butyl ether
Water ad 100 ad 100
pH value 8.7 8.7
Stability in storage at 0-3C 3 0
Flow control properties 4
The test results clearly reflect the extremely
advantageous properties of self-shine emulsions 2 and 4
according to the invention in relation to comparison
formulations 1 and 3.
