Note: Descriptions are shown in the official language in which they were submitted.
WO 94/14907 215 2 4 6 9 pCT/EP93/03485
A neutral self-shine emulsion for the care of floors (I)
Field of the Invention
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. _
Background of the Invention
Nowadays, new previously untreated floors and floors
which have been subj ected 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.
Sununary of the Inventior_ '
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 70°C or a
mixture of'several polymer compounds with this property
and an alcohol from the group consisting of benzyl
alcohol, 2-phenyl ethanol, 2-phenoxyethanol and mixtures
thereof. Polymer dispersions with a pH value in un-
diluted 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.
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 70°C. 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 1 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 1 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 20°C, preferably esters of acrylic acid with C1_8
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 C1_3 alcohols or styrene.
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WO 94/14907 -3- PCT/EP93/03485
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 determined
for the mixture should be in the range from 0 to 70°C. 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 polymers are the following
commercial products available as dispersions: Licomer TM A 41
(Hoechst), Neocryl TM 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 TM TS 85 (Stapol TM) , Neocryl TM SR 267 (ICI) ,
Primal TM 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 Alberdingk TM U 210 W
(Alberdingk Boley) and Neorez TM 986 (Polyvinyl).
The polymers are present in the formulations according to
the invention in quantities of preferably 10 to 50~ by weight
and, more preferably, 11 to 20o by weight. These figures
apply to the pure polymers. If the dispersions 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 the formulations according to the invention.
Polyurethanes may be present in the formulations in quantities
of up to 15o by weight and preferably in quantities of 2 to
8s by weight.
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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 is an aromatic
alcohol from the group consisting of benzyl alcohol, 2-
phenylethanol and 2-phenoxyethanol. Mixtures of these
alcohols may of course also be used. In conjunction with
the film-forming polymers in the aqueous neutral emul-
sion, these alcohols appear to be responsible for the
unexpected properties of the new formulations mentioned
above. Small quantities of these alcohols are generally
sufficient. Their percentage content in the formulations
according to the invention is from 0.05 to 11% by weight
and preferably from 1 to 5% by weight.
In addition to the ingredients mentioned above, the
self-shine emulsions according to the invention may con
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
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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 also glycol and polyglycol 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
not more than 5% by weight, based on the total weight of
the self-shine emulsion, and is preferably between 0.1
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.
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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.
Detailed Description of the Invention
Examples
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
by weight, based on the pure active substances. Self-
shine emulsions 1 to 8 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
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samples were stored for 12 weeks at 0 to 3°C. 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
5 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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Table 1
Example 1 2 3 4
Na benzoate 0.05 - - -
Chloroacetamide 0.1 - - -
Tributoxyethyl phosphate 2.2 2.2 2.2 2.2
Phthalic acid dibutyl ester 1.2 1.2 1.2 1.2
Polyacrylate MFT 72C * 7.5 7.5 7.5 7.5
Polyurethane (Neorez 986) 5.0 5.0 5.0 5.0
Polyethylene dispersion 1.0 1.0 1.0 1.0
Acrylonitrile/styrene 8.5 8.5 8.5 8.5
copolymer MFT 55C
TM
Zonyl FSJ (fluorine surfactant) 0.02 0.02 0.02 0.02
Ethylene glycol 1.0 1.0 1.0 1.0
Perfume 0.2 0.2 0.2 0.2
2-Phenoxyethanol - 2.0 - -
2-Phenylethanol - - 1.0 -
Benzyl alcohol - - - 1.0
Water ad 100 ad 100 ad 100 ad 100
pH value 8.7 8.7 8.7 8.7
Stability in storage at 0-3C 3 0 0 0
Flow control properties 4 0 0 0
*MFT = minimum film forming temperature
Table 2
Example 5 6 7 8
Na benzoate 0.05 - - -
Chloroacetamide 0.1 - - -
Tributoxyethyl phosphate 1.6 1.6 1.6 1.6
Phthalic acid dibutyl ester 1.0 1.0 1.0 1.0
Polyacrylate MFT 53C 14 14 14 14
Polyethylene dispersion 3.5 3.5 3.5 3.5
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WO 94/14907 9 PCT/EP93/03485
Example 5 6 7 8
Zonyl FSJ 0.02 0.02 0.02. 0.02
Ethylene glycol 1.0 1.0 1.0 1.0
Perfume 0.2 0.2 0.2 0.2
2-Phenoxyethanol - 2.0 - -
2-Phenylethanol - _ - 1.0 -
Benzyl alcohoi - - - 1.0
Water ad 100 ad 100 ad 100 ad 100
pH value
Stability storage at 0-3C 3 0 0 0
in properties 4 0 0 0
Flow control
The test results clearly reflect the unusually favorable
properties of self-shine emulsions 2 - 4 and 6 - 8 according
to the invention in relation to comparison formulations 1 and
5.
It should be understood that the detailed
description and specific examples which indicate the
presently preferred embodiments of the invention are
given by way of illustration only since various changes
and modifications within the spirit and scope of the
appended claims will become apparent to those of ordinary
skill in the art upon review of the above description.