Note: Descriptions are shown in the official language in which they were submitted.
- 1043~L94
This invention relates to a process for rendering building
materials hydrophobic.
There are two basic types of processes for renderlng
building materials hydrophobic. In one type of process, the compound
imparting hydrophobic properties to the building material (hereinafter
called the hydrophobic agent) is mixed into the building material,
e.g. cement, before shaping and hardening. In the other type of pro-
cess, the hydrophobic agent is applied to the surface of the building
material after shaping and hardening to at least an advanced degree,
which may take place with either hydraulically or non-hydraulically
hardening building materials, or to the surface of, for example, natural
marble. The hydrophobic agent may be applied, for example, to a
facade.
The present invention in its broadest aspect is concerned
with processes of the latter type, in which the hydrophobic agent is
applied to the surface of the building material in the form of a solu-
tion. Such processes have previously been described in, for example,
E.G. Grunauj Fassade und Wasserhaushalt der Wand, K~ln-Braunsfeld 1967,
page 42. They have the advantage over processes in which the hydro-
phobic agent is applied in the form of aqueous or organic emulsionsor suspensions, that there is no substantial, or considerably less,
demixing (as may occur on the surface of the building material due to
breaking of the emulsion or suspension). This means that the hydro-
phobic agent can penetrate more deeply into the building material with
the result that a longer-lasting repellency of liquid water is obtained
while the water vapour
- 2 _
1043~94
permeability of the building material is maintained. Organosilicon
compounds are particularly suitable hydrophobic agents; solutions of
these compounds in organic solvents have the advantage that they can
be applied to building materials that have previously been treated
with such compounds.
In ~resent processes for rendering building materials hydro-
phobic, it is often necessary to clean the surface of the building
material, with, for example, water vapour or acid, or by sandblast,
prior to treating it with the hydrophobic agent. This is particularly
so when the building material has been exposed to the atmosphere for
some time and thus has been rendered dirty by, for example, dust or
waste gases. Building materials that have been cleaned with aqueous
cleaning agents have to be left to dry before hydrophobic agents in
organic solution can be applied.
In order to achieve a sufficiently great penetration depth
with presently used hydrophobic agent solutions it is often necessary
to apply several coatings of the solution, which makes the process r
more expensive. A further disadvantage of using present solutions,
emulsions, and suspensions, is that because of their great mobility it '-
is often difficult to prevent the agent spreading onto places, such
as, for example, windows and doors, where it is not intended to be
applied. I ;~
The presen-t inven-tion in its broad aspect provides a
process for simultaneously cleaning and rendering a preformed
building material hydrophobic, which comprises: tl) applying
to the surface of the building material selected from the
group consisting of concrete, bric~s, glazed ceramic tiles
and plaster, a composition comprising (a) a hydrophobic agent;
(b) a solvent for the hydrophobic agent in which the hydrophobic
30 agent is presen-t in an amount of from 0.2 to 50 percent by
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~43~
weiyht based on the weight of the hydrophobic ayent and solvent and (c) a
residue forming filler having a surface area of at least 50 m /g, in an
amount of from 1 to 25 percent by weigh-t based on the total weight of the
hydrophobic agent and solvent, (2) removing the solvent by evaporation to
form a filler residue on the surface of said building material and there-
after (3) removing the filler residue from said surface simultaneously to
clean and to render said building material hydrophobic.
By one aspect thereof the hydrophobic agent is selected from
the group consisting of organopolysiloxanes having siloxane units of the
general formula R H SiO , silanes of the formula R SiX and
n m (4-m-n)/2 n 4-n
partial hydrolsates thereof, alkali metal hydrocarbon siliconates of the
formula R'Si(OH)2CM and polymers having units of the formula R'SiO(OM) and r
mlxtures thereof, wherein R is selected from the group consisting of alkyl
and aryl radicals having up to 18 carbon atoms, R' is selected from the
group consisting of a monovalent hydrocarbon radical having up to 5 carbon
atoms and a phenyl radical, ~ represents an alkali metal atom, X represents
a hydrolyzable radical, n denotes 0, 1, 2 or 3 and m denotes 0 or 1, and in
the polysiloxane the average value of n is from 0.9 to 1.8, and n is 1 in
at least 50 percent of the number of siloxane units.
By one variant thereof, n represents 2 or 3 in up to 30 mole
percent of the units of the given organopolysiloxane formula, while in
another variant, the organopolysiloxane has a viscosity up to 1000 cSt,
measured at 25C. in a 50 percent by weight solution in toluene.
By another aspect, the hydrophobic agent is selected from he
group consisting of polymethacrylates, polyacrylates, epoxy resins, unsatura-
ted alkali resistant polyester resins, chlorinated polyolefins, chlorinated
rubber, vinyl chloride copolymers soluble in organic solvents and a satura-
ted aliphatic hydrocarbon having a boiling point of at
~ - 3 a -
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1~43~94
least 360C. at 760 mm Hg.
By other variants, the solvent for the hydrophobic agent is
selected from the group consisting of water, an organic solvent, and a mix- _
ture of water and a water-mixcible organic solvent, and may be an organic
solvent substantially free of water; or an alcohol; or may be selected from
the group consisting of water, an organic solvent, and a mixture of water
and a water-mixcible organic solvent and wherein said organic solvent is
selected from the group consisting of an alkane having a boiling point in
the range of from 120C. to 180C. at 760 mm Hg, an aromatic hydrocarbon, a
; 10 chlorohydrocarbon, an alcohol, a ketone, and an ester.
By another variant, the amount of hydrophobic agent is fr~m 5 to
20 percent by weight, based on the total ~eight of hydrophobic agent and
solvent.
By a further v æ iant, the mixture of the filler and the hydro~
phobic solution is a visible suspension.
By still a further v æ iant, the filler is silicon dioxide and in
another v æ iant, the filler contains on its surface chemical bonded organo- r-
siloxy groups.
By a further v æ iant, the amount of filler is from 1 to 25 per-
cent by weight based on the total weight of hydrophobic agent and solventpreferably being from 5 to 15 percent by weight based on the total weight of
hydrophobic agent and solvent.
By yet another v æ iant, the composition containing the hydro-
phobic agent, solvent and filler is applied to the surface of the building ~
material in an amount of fr~m 0.1 to 2.0 kg/m2, preferably in an amount of
from 0.4 to 0.7 kg/m2.
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1043~L9~
It has heen founcl that Ihe process of broad aspects of this
invention has the advantage over previous processes that the applica-
tion of the hydrophobic solution simultaneously cleans the surface of
the building material, thus rendering any previous cleaning step _
superfluous and saving the expense of such a step. A greater pene-
tration depth is achieved using the process of broad aspects of this
invention which saves the expense of repeated application of the
hydrophobic solution. A further advantage of this process is thai- the ~'
solutions are not so mobile as the previously used solutions and that
it is easier to avoid the solution running onto areas where it is not
intended to be applied.
The hydrophobic agents used according to broad aspects of
the process of the present invention may be the same as those previously
used for application to building materials in the form of solutions.
Organosilicon compounds are preferably used for this purpose because
they give a particularly high degree of water-repellency. Preferred
organosilicon compounds are organopolysiloxanes consisting essentially
of units of the general formula
(4 m n)/2
- in which R denotes an optionally halogenated alkyl or aryl group having
up to 18 carbon atoms, n denotes 0, 1, 2, or 3, and m denotes O or 1.
In the polysiloxane, the average value of n should be from 0.9 to 1.8
.and the average value of m
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I
-
1~43~i94
should be from 0.0 to 1.0, and n should denote 1 in at least 50% of the
number of units. Preferably, _ should be 2 or 3 in not more than 30 nDle
of the units; the preferred viscosity of these organopolysiloxanes is not
more than 1000 cSt, measured at 25C in a 50~ by weight solution in toluene.
other preferred organosilicon compounds are silanes of the general formula
RnSiX4_n
in which R and _ are defined as above and X denotes a hydrolysable atom or
group. The partial hydrolysates, soluble in organic solvents, of these
silanes, are also preferred organosilicon compounds. All these compounds
are preferred because they are easily obtainable.
The radicals denoted by R in the above formulae may be alkyl
radicals, for example, met hyl, ethyl, propyl, isopropyl, and octadecy~
radicals, or halogenated alkyl radicals, for example, an , , ,-trifluoro-
propyl radical. Alternatively, R may denote an aryl radical, the most im~
portant example of which is phenyl radical, or a halogena~ed aryl radical,
for example a ~chlorophenyl radical. secause they are more easily ob,
tained, atlleast 50% of the nu~ber of radicals R are preferably methyl radi- r
cals, any remaining radicals R preferably being phenyl radicals.
Further preferred organosilicon compounds are alkali metal hydro-
carbon siliconates, which are preferably monomeric co~pounds of the generalformula
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~43~.94
R~r~si(~H)2oM
or polymeric compounds comprising units of the general formula 1
R'SiO)OM)
in which formulae R' denotes a monovalent aliphatic hyclrocarbon radical
hav-ng up to 5 carbon atoms or a phenyl radical, and M denotes an
alkali metal atom. An n-propyl radical is particularly preferred as
the radical R' because of its high alkali resistance. Other suitable
aliphatic hydrocarbon radicals R; are other alkyl radicals, for example,
methyl, ethyl, isopropyl, n-butyl, sec-butyl, and amyl radicals, and
alkenyl radicals, for example, vinyl radicals. The alkali metal atom
M may be a lithium, sodium, potassium, rubidium, or caesium atom,
but sodlum and potassium atoms are preferred because they are more
easily obtained.
The above-mentioned organosilicon compounds are preferred
because they are all fairly readily obtainable. Mixtures of different
organopolysiloxanes and/or organosilanes, or of different alkali metal
organosiliconates can be used.
~. - . . .
Other hydrophobic agents that can be used in the process of i -
aspects of the present invention are,for example, organic resins, e.g., i~
polymethacrylates, polyacrylates, vinyl chloride copolymers soluble in
organic solvents (particularly lacquer solvents), epoxy resins,
unsaturated alkali-resistant polyester resins, highly chlorinated
polyolefins, and chlorinated rubber. Saturated aliphatic hydrocarbons
having a boiling point of at least 360C at 760 mm Hg can also be used
as hydrophobic agents. Ilydrophobic agents that are not organosilicon
compounds can, if desired, be used in admixture with organosilicon
compounds.
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~L043~i~94
The solvents used in the process according to aspects of the
present invention may be the same as those previously used for the
application of hydrophobic agents in solution to the surfaces of
building materials. The actual solvent used will of course depend on
the solubility of the particular hydrophobic agent. The solvent may
be water, an organic solvent (either water-immiscible or water-miscible),
or a mixture of water and a water-miscible organic solvent. Examples
of suitable water-miscible solvents are alcohols, e.g., methanol,
ethanol, n-propanol, and isopropanol, and ketones, e.g., acetone, and
methyl ethyl ketone.
Water and mixtures of water and solvents are primarily used
with alkali metal organosiliconates, whereas organic solvents
substantially free of water are used primarily with other organosilicon
compounds and with hydrophobic agents other than organosilicon com-
pounds. Examples of organic solvents suitable for use with the
.
organopolysiloxanes and silanes mentioned above and with hydrophobic
agents other than organosilicon compounds are alkanes having boiling
points in the range of from 120 to 180C at 760 mm Hg; aromatic
hydrocarbons, e.g. toluene, xylenes, and trimethylbenzenes; chloro-
hydrocarbons, e.g. trichloroethylene; alcohoIs, e.g. ethanol,isopropanol, and diacetone alcohol; ketones, e.g. acetone, methyl
ethyl ketone, and cyclohexanone; and esters, e.g. ethyl acetate.
Mixtures of organic solvents can be used.
In order to achieve good penetration, of the hydrophobic
solutions into the building materials even at relatively high air
temperatures, it is advantageous to use a solvent that
1043~4
does not evaporate too quickly, that is to say one that evaporates at
least five times more slowly than diethyl ether. Moreover, if the
building material is moist with water, it is advantageous to use a
water-miscible solvent, either as the solvent or as a component of
the solvent, in order to achieve better penetration.
The amount of hydrophobic agent used should advantageously
be at least 0.2% by weight, relative to the total weight of solvent and
hydrophoblc agent, in order to give a sufficiently high degree of
water-repellency. Moreover, advantageously the a~ount of hydrophobic
agent should not exceed 50% by weight, relative to the weight of solvent
and hydrophobic agent , first because it is preferred that the hydro-
phobic agent should achieve its effect not by the formation of a film
on the surface of the building material but by causing an increase in
the surface tension of water, and secondly because it is preferred that
the coating or residue of filler remaining on the surface of the
building material after evaporation of the solvent should not, or
should only loosely, adhere to the building material so that it may
fairly easily be removed. It is found that the best results are
generally obtained using from 5 to 20% by weight of the hydrophobic
agent, relative to the total weight of solvent and hydrophobic agent.
The fillers used according to the process of an aspect of
this invention have a surface area of at least 50 m2/g, as determined
by the nitrogen adsorption method described in ASTM Technical Bulletin
No. 51, 1941, pages 95 ff., generally known as the BET method.
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They are preferably colourless in order to avoid undesired colouring
of the building material. Advantageously the fillers should be present
in the hydrophobic solutions as a visible suspension, that is to say
they should not be colloidally soluble in the water or organic solvent,
otherwise their removal from the building material is more difficult.
Suitable fillers, satisfying these requirements, are, for example,
various forms of silicon dioxide, for example, pyrogenically produced
silicon dioxide (fume silica), silicon dioxide aerogels (that is
silicon dioxide hydrogels that have been dehydrated while retaining
their structure), precipitated silicon dioxide; and pyrogenically
produced titanium dioxide. Mixtures of fillers can be used.
The fillers used according to the process of aspects of this
invention, and fillers having a surface area of less than 50 m2/g
which may conjointly be used as described below, are advantageously
"coated", that is to say that the fillers may carry organic or silicon-
organic compounds adhering, and generally chemically bonded, to their
surrace, or may contain organic or silicon-organic groups, especially
organosiloxy groups, e.g. trimethylsiloxy or dimethylsiloxy groups.
Fillers of this kind may be produced, for example, by reacting pyro-
genically produced silicon dioxide with organosilicon compounds, e.g.
trimethylethoxysilane; this reaction may be carried out in a grinding - -
device, for example a ball mill or edge runner, as described in German
Offenlegungsschrift No. 2 211 377.
The filler is admixed with the solution of the hydrophobic
agent prior to application of said solution to the surface of
1~43~L~4
the building material~ In order that the solutions shall be in a suitable
thickened form, that is preferably in the form of pastes or spreadable li-
quids, in order that the water-repellent effect is obtained by an increase
in the surface tension of water and not by film formation, and in order that
the filler may be easily removed from the building material after evaporation
of the solvent, the amount of filler used should preferably be at least 1%
by weight, relative to the total weight of solvent and hydrophobic agent.
On the other hand, in order to achieve a good degree of water repellency,
the amount of filler should preferably not exceed 25% by weight, relative
10 to the total weight of solvent and hydrophobic agent. It has been found
that the best results are generally obtained when using from 5 to 15% by
weight of fillers, relative to the total weight of solvent and hydrophobic
agent.
In addition to being admlxed with the fillers, the hydrophobic
solutions can be admlxed with various auxiliary substances, for example,
agents for increasing the alkali resistance, agents for increasing the water
repellency, hardening catalysis for organosilicon compounds, agents for in-
creasing the effectiveness of the hydrophobic agents (e.g. metal compounds,
e.g. aluminium stearate, aluminium alcoholates, zirconium com~ounds, zinc
20 octoate, and titanium alcoholates), and fillers having a surface area of
less than 50 m2/g (e.g. diatamaceous earth), and pigments (e.g. iron oxide).
The amount of hydrophobic solutions incorporating fillers applied
to the surface of the building material is from 0.1 to 2.0 kg, more prefera-
bly from 0.4 to 0.7 kg, of these spreadable
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liquids or pastes per m2 of the surface of the building material.
Building materials that can be rendered water-repellent by
the process of aspects of the present invention are those that could
be rendered water-repellent by previous processes in which a hydro-
phobic agent was applied to the building material in the form of a
soIution. The process of aspects of the present invention is of parti-
cular importance for the treatment of glazed ceramic tiles, and of the
exposed surfaces of sand and lime mortar or sand and cement mortar
as used in mortar joints of walls built of bricks or built of natural
and/or synthetic stones. The process can also be used for the treat-
ment of, for example, plaster, that is wall coatings based on a mixture
of sand and hydraulically or non-hydraulically binding inorganic
materials, e.g. lime, cement, and gypsum. Walls and other structures
of concrete, slag stones, calciferous sandstones, or asbestos cement,
are further examples of building materials that can be treated by
the process of aspects of the present invention.
The hydrophobic solutions incorporating the fillers can be
applied to the surfaces of the building materials in any desired
manner suitable for the application of pastes or spreadable liquids,
for example by spreading, spraying, or trowelling. When the hydro-
phobic solutions incorporating the fillers have been applied and the
solvent has evaporated, the filler remains on the surface of the
building material. This filler may loosely adhere to the building
- material forming a coating, or most of it may fall off if the surface
~is perpendicular or at an angle of more than 45~ to the horizontal.
It may
-- 11 --
.:
1~43194
however, easily be removed either by brushing it off or by blowing it
off with compressed air.
The following Examples and Comparison Example were carried
out to illustrate the process of aspects of the present invention and
to compare it with a previously known process.
Gla~ed ceramic tiles were fixed by means of cement mortar
onto concrete slabs of size 50 cm x 50 cm x 10 cm, and the joints
were filled with cement mortar. The slabs were then exposed to
weathering for seven months during which time, dir~ settled on the
joints and on the tiles.
Various solutions consisting of (a) 2 parts by weight of an
organopolysiloxane consisting essentially of monomethylsiloxane units
and a few dimethylsiloxane units, having the average unit formula
(CH3)1 1osi(oc2H5)o.02(OH)o.04l.92
and having a viscosity of 40 to 60 cSt at 25C measured in a 50% by
weight toluene solution (12 secs in the DIN cup with an aperture of
4 mm), (b) 2 parts by weight of an organopolysiloxane resin consisting
of C6H5SiO3/2~ CH3SiO3/2, and (CH3)2SiO units in a molar ratio of
1:1:1, having a viscosity of 110 cSt at 25C (measured as above), and
(c) 1 part by weight of aluminium stearate, in (d) 95 parts by weight
of toluene, thickened with (e) various fillers as stated in the follow-
ing Table (except in the case of the Comparison Example where no
filler was used), were subsequently applied to the tiles and joints
in a thickness of from 2 to 3 mm by means of a brush. The solutions
were left to dry, and with the slabs in an inclined position,
- 12 -
. .
the majorlty of the fll~er ~e~ ~off the surface after evaporation of the
solvent; the remainder of the filler Was brushed off.
The dirt deposited during weathering was found to have been re-
moved in the case of the slabs treated with the thickened solutions, but
not in the case of that treated with the unthickened solution. The pene-
tration depth of the hydrophobic aa,ent was determined by breaking open the
treated slabs and ap~lying water to the fracture surface : the surface re-
mained light as far as the hydrophobic agent had penetrated, but the remain- ~
der of the surface was darkened with the water.
The results are shown in the Table.
Table
Filler Surface Parts by weight Penetration
are~ of filler depth (mm) r
(m2/g)
.
None - - 1 - 2
(a~ Silicon dioxide 130 15 3 - 4
produced
pyrogenically
in the gas
phase ~-
(b) As (a), but 130 15 5
containing
trimethylsiloxy
groups on the
surface
; (c) As (b) 300 15 7
(d) Precipitatedmore 10 2 - 3
silicic acidthan 50
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~43~94
The silicon dioxiae produced pyrogenically in the gas phase and containing
trimethylsiloxy groups on the surface was obtained by mixing 10 kg of sili-
con dioxide produced pyrogenically in the gaseous phase with 2.5 kg of tri- .
methylethoxysilane and storing for 5 days in a closed polyethylene bag
at room tem~erature.
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