EMULSIONS OF ORGANOSILICON COMPOUNDS FOR IMPARTING WATER REPELLENCY TO BUILDING MATERIALS

EMULSIONS DE COMPOSES ORGANOSILICIES PERMETTANT DE RENDRE HYDROFUGES DES MATERIAUX DE CONSTRUCTION

English Abstract

Aqueous emulsions contain the components
(A) organosilicon compounds which are selected from
(A1) C1-C20-hydrocarbon-C1-C6-alkoxysilanes and
(A2) branched organopolysiloxanes containing C1-C6-alkoxy groups,
(B) organosilicon compounds which are selected from
(B1) C1-C6-alkoxysilanes containing aminoalkyl groups and
(B2) branched organosiloxanes containing aminoalkyl groups and
(C) an emulsifier.
The aqueous emulsions are suitable for imparting water repellency to porous
mineral building materials and building coatings and to wood.

French Abstract

Émulsions aqueuses renfermant des composés organosiliciés (A), choisis parmi (A1) des hydrocarbyl(C1-C20)alcoxy(C1-C6)silanes et des organopolysiloxanes (A2) ramifiés contenant des groupes alcoxy C1-C6, (B) des composés organosiliciés, choisis parmi des (B1) alcoxysilanes C1-C6 contenant des groupes aminoalkyle, et (B2) des organosiloxanes ramifiés contenant des groupes aminoalkyle, et (C) un émulsifiant. Les émulsions aqueuses permettent de rendre hydrofuges des matériaux minéraux poreux et des revêtements pour la construction, ainsi que le bois.

Claims

-33-
What Is Claimed Is:
1. An aqueous emulsion which contains the components
(A) organosilicon compounds which are selected from
(A1) C1-C20-hydrocarbon-C1-C6-alkoxysilanes and
(A2) branched organopolysiloxanes containing C1-C6-alkoxy groups;
(B) organosilicon compounds which are selected from
(B1) C1-C6-alkoxysilanes containing aminoalkyl groups and
(B2) branched organosiloxanes containing aminoalkyl groups; and
(C) an emulsifier.
2. The aqueous emulsion as claimed in claim 1, wherein the
C1-C20-hydrocarbon-C1-C6-alkoxysilanes (A1) have 1 or 2 identical or different,
optionally halogen-substituted, monovalent C1-C20-hydrocarbon radicals bonded via
SiC, and the other radicals are identical or different C1-C6-alkoxy radicals.
3. The aqueous emulsion as claimed in claim 1, wherein the
organopolysiloxanes (A2) are composed of units of the general formula (I)
<IMG>
in which
R is an identical or different monovalent optionally halogen-substituted
C1-C20-hydrocarbon radical bonded via SiC,
R1 is an identical or different monovalent C1-C6-alkyl radical,
x is 0, 1, 2 or 3, on average 0.8 to 1.8,
y is 0, 1, 2 or 3, on average 0.01 to 2.0, and
z is 0, 1, 2 or 3, on average 0.0 to 0.5, with the proviso that the sum of x,
y and z is on average not more than 3.5,

-34-
the organopolysiloxanes (A2) having at least one unit of the general formula (I) in
which the sum of x, y and z has the values 0 or 1.
4. The aqueous emulsion as claimed in claim 2, wherein the
organopolysiloxanes (A2) are composed of units of the general formula (I)
<IMG>
in which
R is an identical or different monovalent optionally halogen-substituted
C1-C20-hydrocarbon radical bonded via SiC,
R1 is an identical or different monovalent C1-C6-alkyl radical,
x is 0, 1, 2 or 3, on average 0.8 to 1.8,
y is 0, 1, 2 or 3, on average 0.01 to 2.0, and
z is 0, 1, 2 or 3, on average 0.0 to 0.5, with the proviso that the sum of x,
y and z is on average not more than 3.5,
the organopolysiloxanes (A2) having at least one unit of the general formula (I) in
which the sum of x, y and z has the values 0 or 1.
5. The aqueous emulsion as claimed in claim 1, wherein the
C1-C6-alkoxysilanes (B1) containing aminoalkyl groups have the general formula (II)
R2a R3b Si(OR4)4-a-b (II),
in which
R2 is an identical or different monovalent, optionally halogen-substituted,
SiC-bonded C1-C20-hydrocarbon radical,
R3 is an identical or different monovalent, optionally halogen-substituted,
SiC-bonded aminoalkyl radicals having 1 to 30 carbon atoms,
R4 is identical or different and is a hydrogen atom or a C1-C6-alkyl radical,

-35-
a is 0, 1 or 2 and
b is 1, 2 or 3,
with the proviso that the sum of a and b is less than or equal to 3.
6. The aqueous emulsion as claimed in claim 2, wherein the
C1-C6-alkoxysilanes (B1) containing aminoalkyl groups have the general formula (II)
R2a R3b Si(OR4)4-a-b (II),
in which
R2 is an identical or different monovalent, optionally halogen-substituted,
SiC-bonded C1-C20-hydrocarbon radical,
R3 is an identical or different monovalent, optionally halogen-substituted,
SiC-bonded aminoalkyl radicals having 1 to 30 carbon atoms,
R4 is identical or different and is a hydrogen atom or a C1-C6-alkyl radical,
a is 0, 1 or 2 and
b is 1, 2 or 3,
with the proviso that the sum of a and b is less than or equal to 3.
7. The aqueous emulsion as claimed in claim 3, wherein the
C1-C6-alkoxysilanes (B1) containing aminoalkyl groups have the general formula (II)
R2a R3b Si(OR4)4-a-b (II),
in which
R2 is an identical or different monovalent, optionally halogen-substituted,
SiC-bonded C1-C20-hydrocarbon radical,
R3 is an identical or different monovalent, optionally halogen-substituted,
SiC-bonded aminoalkyl radicals having 1 to 30 carbon atoms,
R4 is identical or different and is a hydrogen atom or a C1-C6-alkyl radical,
a is 0, 1 or 2 and

-36-
b is 1, 2 or 3,
with the proviso that the sum of a and b is less than or equal to 3.
8. The aqueous emulsion as claimed in claim 4, wherein the
C1-C6-alkoxysilanes (B1) containing aminoalkyl groups have the general formula (II)
R2a R3b Si(OR4)4-a-b (II),
in which
R2 is an identical or different monovalent, optionally halogen-substituted,
SiC-bonded C1-C20-hydrocarbon radical,
R3 is an identical or different monovalent, optionally halogen-substituted, SiC-bonded aminoalkyl radicals having 1 to 30 carbon atoms,
R4 is identical or different and is a hydrogen atom or a C1-C6-alkyl radical,
a is 0, 1 or 2 and
b is 1, 2 or 3,
with the proviso that the sum of a and b is less than or equal to 3.
9. The aqueous emulsion as claimed in claim 1, wherein the
branched organosiloxanes (B2) containing aminoalkyl groups are composed of
units of the general formula (IV)
<IMG> ,
in which
R7 has the meanings of R,
R8 has the meanings of R3,
R9 has the meanings of R1,
c is 0 or 1,
d is 0, 1, 2 or 3, and

-37-
e is 0, 1, 2 or 3,
with the proviso that the sum of c, d and e is not more than 3 and the
organopolysiloxanes (B2) have at least one unit of the general formula (IV) in
which the sum of c, d and e has the values 0 or 1.
10. The aqueous emulsion as claimed in claim 2, wherein the
branched organosiloxanes (B2) containing aminoalkyl groups are composed of
units of the general formula (IV)
<IMG> ,
in which
R7 has the meanings of R,
R8 has the meanings of R3,
R9 has the meanings of R1,
c is 0 or 1,
d is 0, 1, 2 or 3,and
e is 0, 1, 2 or 3,
with the proviso that the sum of c, d and e is not more than 3 and the
organopolysiloxanes (B2) have at least one unit of the general formula (IV) in
which the sum of c, d and e has the values 0 or 1.
11. The aqueous emulsion as claimed in claim 3, wherein the
branched organosiloxanes (B2) containing aminoalkyl groups are composed of
units of the general formula (IV)
<IMG> ,
in which

-38-
R7 has the meanings of R,
R8 has the meanings of R3,
R9 has the meanings of R1,
c is 0 or 1,
d is 0, 1, 2 or 3, and
e is 0, 1, 2 or 3,
with the proviso that the sum of c, d and e is not more than 3 and the
organopolysiloxanes (B2) have at least one unit of the general formula (IV) in
which the sum of c, d and e has the values 0 or 1.
12. The aqueous emulsion as claimed in claim 5, wherein the
branched organosiloxanes (B2) containing aminoalkyl groups are composed of
units of the general formula (IV)
<IMG> ,
in which
R7 has the meanings of R,
R3 has the meanings of R3,
R9 has the meanings of R1,
c is 0 or 1,
d is 0, 1, 2 or 3, and
e is 0, 1, 2 or 3,
with the proviso that the sum of c, d and e is not more than 3 and the
organopolysiloxanes (B2) have at least one unit of the general formula (IV) in
which the sum of c, d and e has the values 0 or 1.

-39-
13. The aqueous emulsion as claimed in claim 8, wherein the
branched organosiloxanes (B2) containing aminoalkyl groups are composed of
units of the general formula (IV)
<IMG> ,
in which
R7 has the meanings of R,
R8 has the meanings of R3,
R9 has the meanings of R1,
c is 0 or 1,
d is 0, 1, 2 or 3, and
e is 0, 1, 2 or 3,
with the proviso that the sum of c, d and e is not more than 3 and the
organopolysiloxanes (B2) have at least one unit of the general formula (IV) in
which the sum of c, d and e has the values 0 or 1.
14. The aqueous emulsion as claimed in claim 5, wherein the
radical R3 denotes a radical of the general formula (III)
R5 2NR6- (III),
in which
R5 is identical or different and is hydrogen or a monovalent, optionally
substituted C1-C10-hydrocarbon radical, or a C1-C10-aminohydrocarbon
radical, and
R6 denotes a divalent C1-C15-hydrocarbon radical.
15. The aqueous emulsion as claimed in claim 9, wherein the
radical R3 denotes a radical of the general formula (III)

-40-
R52NR6 (III),
in which
R5 is identical or different and is hydrogen or a monovalent, optionally
substituted C1-C10-hydrocarbon radical, or a C1-C10-aminohydrocarbon
radical, and
R6 denotes a divalent C1-C15-hydrocarbon radical.
16. The aqueous emulsion as claimed in claim 1, wherein the
total amount of components (A) and (B) is 1 to 80% by weight.
17. The aqueous emulsion as claimed in claim 2, wherein the
total amount of components (A) and (B) is 1 to 80% by weight.
18. The aqueous emulsion as claimed in claim 5, wherein the
total amount of components (A) and (B) is 1 to 80% by weight.
19. A process for imparting water repellency to porous mineral
building materials and building coatings and to wood, in which said building
materials, building coatings, and wood are treated with the emulsion as claimed in
claim 1.
20. A process for imparting water repellency to porous mineral
building materials and building coatings and to wood, in which said building
materials, building coatings, and wood are treated with the emulsion as claimed in
claim 2.

Description

CA 02249~2 1998-10-0~
WAS 0281 PCA -1-
EMULSIONS OF ORGANOSILICON
COMPOUNDS FOR IMPARTING WATER
REPF,~,~,F,NCY TO BUILDING MATERIALS
Technolo~ical Field
The invention relates to aqueous emulsions of organosilicon
compounds cont~ining alkoxy groups and organosilicon compounds cont~ining
aminoalkyl groups, and to a process for imparting water repellency to porous
mineral building materials, building coatings, and to wood.
Description Of The Related Art
Aqueous emulsions of organosilicon compounds are used in building
protection, especially because of their outst~n-ling action against impregnation by
water and dirt, their envilol.ll.elllal compatibility, and their physiological safety.
US-A-4,757,106 describes the impregnation of neutral mineral
building materials with an aqueous emulsion of polyorganosiloxanes having
ammonium groups and polyorganosiloxanes having ethoxy groups. The water
repellent effect is smaller on ~lk~lin~ building materials since the ammonium
groups are neutralized and the emulsion breaks. The polyorganosiloxane then
scarcely penetrates into the building material.
Emulsions which contain, as an active ingredient, resin-like
polyorganosiloxanes having alkoxy groups penetrate readily into porous building
materials and impart good surface water repellency to them. However, dense
building materials are only superficially and temporarily protected.
Although emulsions of alkylalkoxysilanes penetrate readily into
building materials, these emulsions do not have a long shelf life. US-A-4,877,654
describes buffered emulsions of alkylalkoxysilanes which, although exhibiting a

CA 02249~2 1998-10-0~
WAS 0281 PCA -2-
long shelf life, are deposited too slowly, in particular in neutral building materials,
and therefore impart water repellency poorly. This poor water repellency is noted
particularly in the zone close to the surface.
Emulsions which contain resin-like polyorganosiloxanes having
5 alkoxy groups and low molecular weight alkylalkoxysiloxanes or
alkylalkoxysilanes as active ingredients are disclosed in US-A-5,039,724. These
emulsions are a compro,llise between a long shelf life and a water repellent action
at the surface.
US-A-5,196,054 describes an emulsion which, in addition to
10 siloxanes and silanes cont~ining alkyl and alkoxy groups, also contains a mixture
or a reaction product of a silane cont~ining aminoalkyl groups and o~,~-
hydroxypolydialkylsiloxane. Although these components result in more rapid
formation of the hydrophobic character on the surface of the building material,
they impede the penetration of the other active components into the deep pores of
15 the building material.
Sl-mm~ry Of The Invention
It is the object of the invention to provide aqueous emulsions of
organosilicon compounds for imparting water repellency to porous mineral
building materials and building coatings, these emulsions exhibiting a long shelf
20 life, and to provide a process for hll~a,ling water repellency to porous mineral
building materials and coatings, a process which is particularly effective in the case
of neutral and basic building materials and coatings, and which does not have the
disadvantages of the emulsions described above. These objects are achieved by
employing aqueous emulsions of organosilicon compounds cont~ining alkoxy
25 groups and organosilicon compounds cont~ining aminoalkyl groups.

CA 02249~2 1998-10-0~
WAS 0281 PCA -3-
Description Of The Preferred Embodiment
The invention relates to an aqueous emulsion which contains the
components
(A) organosilicon compounds which are selected from
(A1) Cl-C20-hydrocarbon-CI-C6-alkoxysilanes and
(A2) branched organopolysiloxanes cont~ining Cl-C6-alkoxy groups,
(B) organosilicon compounds which are selected from
(B1) Cl-C6-alkoxysilanes cont~ining aminoalkyl groups and
(B2) branched organosiloxanes cont~inin~ aminoalkyl groups, and
10 (C) an emulsifier.
Preferably, the C,-C20-hydrocarbon-CI-C6-alkoxy-silanes (A1) have
1 or 2 identical or dirrelelll, optionally halogen-substituted, monovalent Cl-C20-
hydrocarbon radicals bonded via SiC, and the other radicals are identical or
dirÇ~Ient Cl-C6-alkoxy radicals.
Examples of Cl-C20-hydrocarbon radicals are alkyl radicals such as
the methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl,isopentyl, neopentyl, and tert-pentyl radicals; hexyl radicals such as the n-hexyl
radical; heptyl radicals such as the n-heptyl radical; octyl radicals such as the n-
octyl radical and isooctyl radicals such as the 2,2,4-trimethylpentyl radical; nonyl
20 radicals such as the n-nonyl radial; decyl radicals such as the n-decyl radical; and
dodecyl radicals such as the n-dodecyl radical; cycloalkyl radicals such as
cyclopentyl, cyclohexyl, 4-ethylcyclohexyl, and cycloheptyl radicals, norbornyl
radicals and methylcyclohexyl radicals; alkenyl radicals such as the vinyl, allyl,
n-5-hexenyl, 4-vinylcyclohexyl and 3-norbornenyl radicals; aryl radicals such as25 the phenyl, biphenylyl, naphthyl, anthryl, and phenall~ l radicals; alkaryl
radicals such as o-, m-, and p-tolyl radicals, xylyl radicals and ethylphenyl
radicals; aralkyl radicals such as the benzyl radical and the o~- and ~-phenylethyl

CA 02249~2 1998-10-0~
WAS 0281 PCA -4-
radicals. The unsubstituted C~-C12-alkyl radicals and the phenyl radical are
particularly preferred.
Examples of halogen-substituted C1-C20-alkyl radicals are alkyl
radicals substituted by fluorine, chlorine, bromine and iodine atoms, such as the
3,3,3-trifluoro-n-propyl radical, the 2,2,2,2' ,2',2'-hexafluoroisopropyl radical and
the heptafluoroisopropyl radical.
Examples of C1-C6-alkoxy radicals are the methoxy, ethoxy, n-
propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy and tert-butoxy radical;
pentyloxy radicals such as the n-pentyloxy radical, and hexyloxy radicals such as
the n-hexyloxy radical. The ethoxy radicals are particularly plerelled. The alkoxy
radicals may be substituted by halogen atoms, but this is not plefelred.
The emulsion may contain a branched organopolysiloxane (A2)
cont~ining C~-C6-alkoxy groups or a llli~lure of a plurality of organopolysiloxanes
(A2). The organopolysiloxanes (A2) may additionally contain hydroxyl groups,
which facilitate binding to the building materials.
The organopolysiloxanes (A2) are preferably composed of units of
the general formula (I)
RXSi(OR l)y(OH)zO4~~~~, (I),
in which
20 R denotes identical or dirrerellL monovalent optionally halogen-substituted C1-
C20-hydrocarbon radicals bonded via SiC,
R1 denotes identical or different monovalent C1-C6-alkyl radicals,
x denotes the values 0, 1, 2 or 3, on average 0.8 to 1.8,
y denotes the values 0, 1, 2 or 3, on average 0.01 to 2.0, and
z denotes the values 0, 1, 2 or 3, on average 0.0 to 0.5, with the proviso that
the sum of x, y and z is on average not more than 3.5,

CA 02249~2 1998-10-0~
WAS 0281 PCA -5-
the organopolysiloxanes (A2) having at least one unit of the general formula (I) in
which the sum of x, y and z has the values O or 1.
The organopolysiloxane (A2) preferably has a viscosity of 5 mm2/s
to 50,000 mm2/s, in particular 10 mm2/s to 5000 mm2/s, at 25~C.
Examples of the C,-C20-hydrocarbon radicals are the examples of
C,-C20-hydrocarbon radicals mentioned above in the case of the Cl-C20-
hydrocarbon-C,-C6-alkoxysilanes (A1).
Although not shown in the above formula, some of the radicals R
may be replaced by hydrogen atoms bonded directly to silicon atoms. However,
this is not pref~lled.
Examples of the radicals OR' are the C,-C6-alkoxy radicals
mentioned above for C1-C20-hydrocarbon-C,-C6-alkoxysilanes (A1).
Preferably, x has an average value of 0.9 to 1.1. Preferably, y has
an average value of 0.4 to 1.2. Preferably, z has an average value of 0.0 to 0.2.
Since the organopolysiloxanes (A2) are branched, they have at least
one unit of the general formula (I) in which the sum of x, y and z has the values
O or 1. Preferably, the organopolysiloxanes (A2) have at least 10 mol%, and in
particular at least 30 mol % of units of the general formula (I) in which the sum of
x, yandzhasthevaluesOor 1.
Examples of organosiloxanes (A2) are those which are obtainable
by reacting methyltrichlorosilane and optionally a C,-C8-alkyltrichlorosilane orphenyltrichlorosilane with ethanol in water, such as the organopolysiloxanes of the
empirical formulae
CH3si(oc2Hs)o 8~l 1 or
C6HsSi(OC2Hs)o.72ol ,4 or
(CH3)0 7 (i-octyl)0,3 si(ocH3), 3~o 8s

CA 02249~2 1998-10-0~
WAS 0281 PCA -6-
Preferably, the C1-C6-alkoxysilanes (B1) cont~ining aminoalkyl
groups have the general formula (II)
R2aR3bSi(oR4)4 a b (II),
in which
5 R2 denotes identical or dirrelent monovalent, optionally halogen-substituted,
SiC-bonded C1-C20-hydrocarbon radicals,
R3 denotes identical or different monovalent, optionally halogen-substituted,
SiC-bonded aminoalkyl radicals having 1 to 30 carbon atoms,
R4 may be identical or dirrerelll and denotes hydrogen atom or C1-C6-alkyl
radicals,
a is 0, 1 or2 and
b isl,2Or3,
with the proviso that the sum of a and b is less than or equal to 3.
Examples and plerelled examples of the radical R2 are mentioned
above in the case of radical R. The methyl radical is particularly plefelled.
Radical R3 is preferably a radical of the general formula (III)
R52NR6 (III),
in which
R5 may be identical or dirre~lll and denotes hydrogen or a monovalent,
optionally substituted C1-C10-hydrocarbon radical or C1-C10-
aminohydrocarbon radical and
R6 denotes a divalent C1-C15-hydrocarbon radical.
Examples of radical R5 are the examples of hydrocarbon radicals
given for radical R and hydrocarbon radicals substituted by amino groups, such as
25 aminoalkyl radicals, the aminoethyl radical being particularly plel~lled.

CA 02249~2 1998-10-0~
WAS 0281 PCA -7-
Preferably, at least one hydrogen atom is bonded to each nitrogen
atom in the radicals of the general formula (III).
Radical R6 is preferably a divalent hydrocarbon radical having 1 to
10 carbon atoms, particularly preferably 1 to 4 carbon atoms, in particular the n-
5 propylene radical.
Examples of radical R6 are the methylene, ethylene, propylene,butylene, cyclohexylene, octadecylene, phenylene and butenylene radicals.
Preferred examples of radicals R3 are
H2N(CH2)3-
~
H2N(CH2)2NH(CH2)2-,
H2N(CH2)2NH(CH2)3-
H2N(CH2)2-,
H3CNH(CH2)3-~
C2H5NH(CH2)3-~
15 H3CNH(CH2)2-~
C2HsNH(CH2)2-,
H2N(CH2)4-~
H2N(CH2)5-~
H(NHCH2CH2)3-~
C4H9NH(CHz)2NH(CH2)2~~
cyclo-C6HllNH(CH2)3~,
cyclo-C6H,lNH(CH2)2-,
(CH3)2N(CH2)3-~
(CH3)2N(CH2)2-,
(C2H5)2N(CH2)3- and
(C2H5)2N(CH2)2-
The examples of alkyl radicals R' are also fully applicable to the
radical R6.

CA 02249~2 1998-10-0~
WAS 0281 PCA -8-
Examples and pler~lled examples of the radical R4 are mentioned
above in the case of radical R'. The methyl and the ethyl radical are particularly
preferred.
The branched organosiloxanes (B2) cont~ining aminoalkyl groups
5 are preferably composed of units of the general formula (IV)
RC7Rd(OR9)eSiO4 ~ d ~ (IV),
in which
R7 has the m~aning.c of R,
Rg has the mP~ning~ of R3 and
10 R9 has the me~ning~ of R1 and
c denotes the values 0 or 1,
d denotes the values 0, 1, 2 or 3 and
e denotes the values 0, 1, 2 or 3,
with the proviso that the sum of c, d and e is not more than 3 and the
organopolysiloxanes (B2) have at least one unit of the general formula (IV) in
which the sum of c, d and e has the values 0 or 1.
Preferred mP~nings of R7 are mentioned above for R, and in
particular R7is a methyl radical.
Plefelled mP~nings of R8 are mentioned above for R3, and in
particular R8 is an aminopropyl or (aminoethyl)aminopropyl group.
Preferred mP~nings of R9 are mentioned above for R1, and in
particular R9is a methyl or ethyl radical.
The plefelled average value for c is 0 to 1, in particular 0.1 to 0.9.
d preferably denotes the values 0 or 1. The preferred average value
for d is 0.1 to 1, in particular 0.2 to 0.8.
e preferably denotes the values 0, 1 or 2. The plef~lled average
value for e is 0.2 to 2, in particular 0.4 to 1.6.

CA 02249~2 1998-10-0~
WAS 0281 PCA -9-
The branched organosiloxanes (B2) cont~ining aminoalkyl groups
preferably have a viscosity of 5 mm2/s to 5000 mm2/s, in particular of 10 mm2/s
to 3000 mm2/s at 25~C.
The organosiloxanes (B2) preferably have at least 10 mol%, in
5 particular at least 30 mol %, of units of the general formula (I) in which the sum
of a, b and c has the values 0 or 1.
Organosiloxanes (B2) can be pfepaled in a known manner, for
example by equilibration or condensation of silanes having amino functional
groups with organopolysiloxanes which contain alkoxy groups and/or hydroxyl
10 groups and which are free of basic nitrogen.
The aqueous emulsion contains emulsifiers (C) known per se.
Particularly suitable anionic emulsifiers are:
1. Alkylsulfates, in particular those having a chain length of 8 to 18
C atoms, alkyl ether sulfates and alkaryl ether sulfates, each having 8 to 18 C
15 atoms in the hydrophobic radical and 1 to 40 ethylene oxide (EO) or propylene oxide (PO) units;
2. Sulfonates, in particular alkylsulfonates having 8 to 18 C atoms,
alkylarylsulfonates having 8 to 18 C atoms, taurides, esters and half-esters of
sulfosuccinic acid with monohydric alcohols or alkylphenols having 4 to 15 C
20 atoms; these alcohols or alkylphenols may optionally also be ethoxylated with 1 to
40 EO units;
3. Alkali metal and ammonium salts of carboxylic acids having 8 to 20
C atoms in the alkyl, aryl, alkaryl or aralkyl radical; and
4. Partial esters of phosphoric acid and the alkali metal and ammonium
25 salts thereof, in particular alkyl and alkaryl phosphates having 8 to 20 C atoms in
the organic radical, alkyl ether or alkaryl ether phosphates having 8 to 20 C atoms
in the alkyl or alkaryl radical and 1 to 40 EO units.
Particularly suitable nonionic emulsif1ers are:

CA 02249~2 1998-10-0~
WAS 0281 PCA -10-
5. Polyvinyl alcohol which still has 5 to 50%, preferably 8 to 20%, of
vinyl acetate units, having a degree of polymerization of 500 to 3000;
6. Alkyl polyglycol ethers, preferably those having 8 to 40 EO units
and alkyl radicals of 8 to 20 C atoms;
7. Alkylaryl polyglycol ethers, preferably those having 8 to 40 EO
units and 8 to 20 C atoms in the alkyl and aryl radicals;
8. Ethylene oxide/propylene oxide (EO/PO) block copolymers,
preferably those having 8 to 40 EO and PO units;
9. Adducts of alkylamines having alkyl radicals of 8 to 22 C atoms
with ethylene oxide or propylene oxide;
10. Fatty acids having 6 to 24 C atoms;
11. Alkyl polyglycosides of the general formula R*-O-Zo~ in which R*
denotes a linear or branched saturated or unsaturated alkyl radical having on
average 8 - 24 C atoms and ZO denotes an oligoglycoside radical with on average
o = 1 - 10 hexose or pentose units or mixtures thereof;
12. Natural substances and derivatives thereof, such as lecithin, lanolin,
saponins, cellulose; cellulose alkyl ethers and carboxyalkyl celluloses whose alkyl
groups each have up to 4 carbon atoms; and
13. Linearorgano(poly)siloxanescont~iningpolargroups, inparticular
those organo(poly)siloxanes with alkoxy groups having up to 24 C atoms and/or
up to 40 EO and/or PO groups.
Particularly suitable cationic emulsifiers are:
14. Salts of primary, secondary and tertiary fatty amines having 8 to 24
C atoms with acetic acid, sulfuric acid, hydrochloric acid and phosphoric acids;15. Quaternary alkyl- and alkylbenzeneammonium salts, in particular
those whose alkyl groups have 6 to 24 C atoms, in particular the halides, sulfates,
phosphates and acet~tes; and

CA 02249~2 1998-10-0~
WAS 0281 PCA -11-
16. Alkylpyridinium, alkylimicl~7olinium and alkyloxazolinium salts,
in particular those whose alkyl chain has up to 18 C atoms, especially the halides,
sulfates, phosphates and acetates.
Particularly suitable ampholytic emulsifiers are:
17. Amino acids substituted by a long-chain radical, such as N-alkyl-
di(aminoethyl)glycine or N-alkyl-2-aminopropionic acid salts;
18. Betaines, such as
N-(3-acylamidopropyl)-N,N-dimethylammonium salts having a C8-CI8-acyl radical,
and alkylimidazolium betaines.
Preferred emulsifiers (C) are nonionic emulsifiers, in particular the
alkyl polyglycol ethers mentioned above under 6., the alkylaryl polyglycol ethers
mentioned under 7., the adducts of alkylamines with ethylene oxide or propylene
oxide, mentioned under 9., the alkylpolyglycosides mentioned under 11. and the
polyvinyl alcohol mentioned above under 5. Particularly preferred are polyvinyl
alcohols still cont~ining 5 to 20%, in particular 10 to 15%, of vinyl acetate units
and preferably having a degree of polymerization of 500 to 3000, in particular
1200 to 2000.
The total amount of the components (A) and (B) in the aqueous
emulsions is preferably 1 to 80% by weight, in particular 5 to 75% by weight.
The ratio of the components (A): (B) in parts by weight in the
aqueous emulsions is preferably 200: 1 to 5: 1, in particular 100: 1 to 10: 1.
The amount of the emulsifier (C) is preferably 0.1 to 30% by
weight, in particular 0.5 to 10 % by weight, of the total amount of the components
(A) and (B).
The emulsions may furthermore contain solid silicone resins which
are composed of monofunctional R3SiOo s units and SiO2 (so-called MQ resins),
where the molar ratio of the R3SiOos and SiO2 units may be 0.4 to 1.2. R are
preferably unsubstituted alkyl radicals, in particular the methyl radical. These MQ
radicals result in rapid formation of the hydrophobic character in particular in the

CA 02249~2 1998-10-0~
WAS 0281 PCA -12-
case of very highly absorptive building materials. If such silicone resins are used
in the emulsions, their amount is preferably not more than 10% by weight, in
particular not more than 5% by weight, based on the total amount of the
components (A) and (B).
Furthermore, the emulsion may also contain organic polymers, such
as, for example, fluorine-cont~ining polymers and polyolefin waxes, in addition
to the components (A), (B) and (C). Instead of the polyolefin waxes, silicone
waxes may also be used.
These polymers impart particular properties to the emulsions
according to the invention. With the fluorine-cont~ining polymers, such as, for
example, fluorinated acrylates or polyule~llalles, the emulsions not only have awater repellent effect but also an oil-repellent effect. Polyolefin and silicone waxes
influence the appearance of the building material surfaces treated with the
emulsions, in such a way that they produce a certain deepening of color or a
specific surface gloss. If such organic polymers or waxes are used in the
emulsions, their amount is preferably not more than 10% by weight, in particularnot more than 5 % by weight, based on the total amount of the components (A) and(B).
The emulsions may additionally contain customary fillers and
thickeners, in particular reinforcing fillers, i.e. fillers having a BET surface area
of more than 50 m2/g, such as silica prepared by a pyrogenic method, precipitated
silica and mixed silicon-~lnminl~m oxides having a large BET surface area. Finely
divided silica is particularly suitable. It is possible to use one type of filler as well
as a mixture of at least two fillers. The amount of fillers is preferably not more
than 5% by weight, and in particular not more than 2% by weight of the total
amount of the components (A) and (B).
The emulsions may also contain buffer substances which stabilize
the pH in the range from 5 to 9, in which the alkyltrialkoxysilanes are very stable
to hydrolysis. All organic and inorganic acids and bases which are chemically inert

CA 02249~2 1998-10-0~
WAS 0281 PCA -13-
with respect to the other components of the emulsions are suitable, in particular the
alkali metal, ~lk~lin~ earth metal and ammonium salts of carboxylic acids,
phosphoric acid, carbonic acid and sulfuric acid. Sodium carbonate, sodium
bicarbonate, sodium hydrogen phosphate and a mixture of acetic acid and aqueous
5 ammonia solution are particularly preferred. The amount of buffer substances is
preferably not more than 3 weight percent, in particular not more than 1 weight
percent of the total amount of the components (A) and (B).
In addition to the components described above, the emulsions may
contain fungicides, bactericides, algicides, microbicides, odor substances,
10 corrosion inhibitors and antifoams as additives. The preferred amount of additives
is not more than 2 weight percent, in particular not more than 0. 5 weight percent
of the total amount of the components (A) and (B).
The aqueous emulsions according to the invention are prepared by
conventional processes for the preparation of aqueous emulsions. Preferably, first
15 only a part of the water is mixed with emulsifier (C), the component (B) is then
added and finally the component (A) is incorporated into the emulsion until a
viscous oil phase ("stiff phase") forms, and then the rem~ining water is
incorporated to form a less viscous emulsion. The components (A) and (B) may
also be mixed and added to an emulsion comprising emulsifier and water. The
20 mixing is preferably carried out in pressure emulsification machines or colloid
mills and in particular in high-speed stator-rotor stirring appalalus according to
Prof. P. Willems.
The invention also relates to a process for imparting water
repellency to porous mineral building materials and building coatings and to wood,
25 in which the building materials, building coatings and the wood are treated with
the above aqueous emulsion. The treatment also comprises the addition to materials
which are processed to give building materials and building coatings.
The emulsions are suitable for inll)al lillg water repellency to mineral
building materials such as natural or artificial stone, concrete, cement, lime
........ . . .

CA 02249~2 1998-10-0~
WAS 0281 PCA -14-
sandstone and porous concrete; building materials comprising clay minerals such
as bricks; and wood; and as an additive acting as water repellent and optionally as
a binder, to plaster, renders, and building coatings such as mineral paints, silicone
resin emulsion paints and renders, silicate emulsion paints, emulsion paints,
5 brushable fillers, leil~lcillg materials, and primers.
The emulsions are also suitable for imparting water repellency to
finely divided inorganic substances, such as perlite, vermiculite and heat insulating
materials.
Emulsions which have both alkoxysilanes (A1) and organosiloxanes
(A2) preferably in the ratio alkoxysilanes (A1): organosiloxanes (A2) of 0.5: 1
to 20: 1, in particular 1: 1 to 10: 1, are preferably used for hl~alLil1g water
repellency to highly absorptive mineral building materials and building coatings.
The emulsions are particularly suitable for imparting water
repellency to mineral-bound, preferably cement-bound fibrous building materials
whose fibers consist of natural fibers or synthetic fibers. Suitable natural fibers are
mineral fibers, such as rockwool, quartz fibers, or ceramic fibers; or plant fibers,
such as cellulose. Suitable synthetic fibers are, for example, glass fibers, plastics
fibers and carbon fibers. The use of the emulsion for hllpa~ lg water repellencyto cement-bound cellulose fiber components is particularly preferred. The cellulose
fibers may be, for example, jute, coconut or hemp fibers or may originate from
paper, cardboard or waste paper.
The emulsions are suitable for use in the bulk material, i.e. the
emulsion is added to a hydraulic mixture for the production of components prior
to setting, or for imparting water repellency to components after setting.
Before they are used as water repellents and optionally binders, the
emulsions according to the invention can be diluted with water. In the case of the
surface impregnation of building materials after setting, dilution up to a totalcontent of the components (A) and (B) of 1% by weight is advantageous.

CA 02249~2 1998-10-0~
WAS 0281 PCA -15-
In the following examples, all stated parts and percentages relate to
weight, unless stated otherwise. Unless stated otherwise, the examples below arecarried out at a pressure of the surrounding atmosphere, i.e. at about 0.10 MPa,and at room temperature, i.e. at about 20~C, or at a temperature which is
5 established on combining the reactants at room temperature without additional
heating or cooling. All viscosity data mentioned in the examples relate to a
temperature of 25~C. The solids content of the emulsions denotes the sum of all
components, with the exception of water.
Examples
The following are used as component (A):
H1: isooctyltriethoxysilane
H2: organopolysiloxane of the empirical formula CH3Si(OC2H5)0 8~l I having
an average molecular weight of about 650 g/mol and a viscosity of about
20 mm2/s
15 H3: methylsilicone resin present as a highly viscous liquid and comprising
CH3SiO3,2 units, with about 20 mol% of (CH3)2SiO2,2 units and about 10
mol% of C2H5OSiO3,2 units and a molecular weight of about 5000 g/mol
H4: methylsilicone resin present in powder form and comprising CH3SiO3,2
units, with about 3 mol% of (CH3)2SiO2,2 units and about 4 mol% of
C2H5OSiO3,2 units, a molecular weight of about 5000 g/mol and a softening
point of about 50~C
H5: organopolysiloxane of the empirical formula
(CH3)0 7(isooctyl)0 3Si(OcH3)l 3Oo 85~ having an average molecular weight
of about 760 g/mol and a viscosity of about 17 mm2/s
The following are used as component (B):
Nl: N-(2-aminoethyl)-3-aminopropyltrimethoxysilane

CA 02249~2 1998-10-0~
WAS 0281 PCA -16-
N2: condensate of H2 and N-(2-aminoethyl)-3-aminopropyltrimethoxysilane in
the presence of KOH with an amine number of about 3.0, a viscosity of
about 500 mm2/s at 25~C and a residual methoxy content of less than 5
mol %, based on the methoxy groups initially present in the N-(2-
aminoethyl)-3-aminopropyltrimethoxysilane
The following are used as component (C):
E1: Arlypon~ IT 16 from Chemische Fabrik Grunau GmbH, Illertissen, an
isotridecyl alcohol-(16)-polyglycol ether
E2: Polyviol~ W 25/140 from Wacker-Chemie GmbH, Munich, a polyvinyl
alcohol having a degree of polymerization of about 1600 and still having
11-14% of acetoxyethylene units
Preparation of the emulsions
The aqueous emulsions according to the invention are prepared by
first mixing some of the water with em~ ifier (component (C)) and emulsifying
silane or siloxane having amino functional groups (component (B)), followed by
silane and/or polysiloxane (component (A)). Both the first-mentioned mixing and
the emulsification are carried out in a high-speed rotor-stator stirring apparatus
from Prof. P. Willems. The compositions are shown below in Table I. The
comparative emulsions are prepared in an analogous manner. The compositions are
likewise shown in Table I.

CA 02249~2 1998-10-0~
WAS 0281 PCA -17-
TAsLE I
' Silane/ ~ ' F ' ~ Water
siloxane. . ' (A) aminosiloxane (C)
. ~, (B)
Fmlllcil~nc Icco,di,lg to the invention
EMl 66.5%H1 2%N1 2.6%E1 29.7%
EM2 34.1 %Hl 2%N1 1.8%E1 49.8%
12.3 %H2
EM3 43.4%H1 6.8%N2 1.8%E1 48.0%
EM4 40.0%H1 0.5%N1 2.2%E1 47.7%
10.0%H5
EM5 39%H1 2.7%N2 1.8%E1 47.0%
5.8%H2
3.7%H4
EM6 40.2%H1 0.5%N1 2.2%E1 48.2%
6.9%H2
2.0%MQ resin*
EM7 9.2%H1 4.9%N1 3.7%E2 46.1 %
36.1%H3
COll)ld~dliV~ emnlcir~nc
EM8 47.8%H1 - 2.2%E1 50.0%
EM9 36.1%H1 - 1.8%E1 49.8%
12.3 %H2
EM10 39.2%Hl - 2.2%E1 48.9%
8.8%H2
0.9%
filler**
EMll 63.5%H1 5.0% 2.6%E1 28.9%
amino-
silu~ *~*
* MQ resin: solid col-~;cli"g of Me3SiOOs and SiO2 units in the ratio 1:1
** finely divided silica having a specific surface area of about 150 m2/g
*** condensate of ~,~-dihydroxypolydi",~,~l,ylsiloxane and N-(2-al"i"o~;ll,yl)-3-
dlllinO~JlV~~ oxy-silane~ having a viscosity of about 1500 mm2/s (at 25~C) and an
amine number of about 0.6
None of the emulsions shows any phase separation either after
storage for 14 days at 50~C or after 6 months at room tempelalule. They therefore
have a long shelf life. The same applies to dilutions prepared therefrom and having
active ingredient contents of 25 to 5%. At even lower concentrations, i.e. for

CA 02249~2 1998-10-0~
WAS 0281 PCA -18-
example 1% active ingredient content, slight c.eal~ g may occur but no proper
phase separation takes place.
Example 1
Im~ water repellency to mineral cQ~in~
Emulsions according to the invention and not according to the
invention are diluted with water to 10% active ingredient content and then applied
with a brush to lime sandstone coated with mineral paint (silicate paint
Purkristallat~ from Keim-Farben GmbH, Diedorf) (amount applied about 450
g/m2). After storage for 14 days at room temperature, the discoloration and the
water repellency of water dripped on the coated lime sandstones rendered water
repellent are assessed by measuring the contact angle. Contact angles of > 90~
denote good water repellency and those of < 90~ denote wetting and therefore
tend to represent poor water repellency. The results are listed in Table II below.
TABLE II
Emulsion Discoloration Water repellency Contact angle
EM 1 none good 110~
EM 2 none very good 130~
EM 3 very slight very good 125~
EM 4 none very good 140~
EM 5 slight very good 140~
EM 6 slight very good 140~
EM 8 none poor 30~
EM 9 none moderate 70~
EM 10 white spots very good 135~
EM 11 strong very good 130~

CA 02249~2 1998-10-0~
WAS 0281 PCA -19-
As is evident from Table II, the emulsions according to the
invention do not discolor the substrate and produce out~t~n-ling water repellency.
Slight discoloration of the substrate in this test is equivalent to good penetration
behavior of the relevant products. The comparative emulsions E M 8 to E M 10
penetrate well but white spots are found on dark silicate paint in the case of E M
10. Owing to the lack of an amine component, the water repellency of the
comparative emulsions E M 8 and E M 9 is substantially poorer than that of the
emulsions according to the invention. In the case of E M 11, the aminosiloxane has
good water repellency but also leads to a dramatic darkening of the coated lime
10 sandstone.
Example 2
Imparting water repell~ncy to uncoated lime sandstone
Emulsions according to the invention and not according to the
invention are diluted with water to the active ingredient contents stated in Table
III. Lime sandstone plaques (about 10 x 10 x 2.5 cm3) are then immersed therein
for 5 ~ les (about 5 cm liquid cover). After storage for 14 days at room
temperature, the test specimens treated in this manner and ul~Lleat~d reference test
specimens are placed in water (5 cm water cover) and their water absorption is
deLel~ ed as relative weight increase after 24 hours. The test specimens are then
dried and broken and the thickness of the hydrophobic zone (equal to the depth of
penetration of the active ingredients imparting water repellency) is determined by
dripping water onto the fracture surface. The water repellency is characterized, as
in Example 1, by measuring the contact angle. The results of these experiments are
summarized in Table III.

CA 02249~2 1998-10-0~
WAS 0281 PCA -20-
TABLE m
Fm~ )n Active Water Depth of Water Contact
Ingredient Absorption Penetration Repellency Angle
Content
EM 1 5% 2.5% 1.5-2.5 mm good 110~
10% 1.2% 2-4 mm good 105~
EM 2 5% 1.4% 1-2 mm good 115~
10% 0.6% 1.5-3 mm very good 125~
EM 4 5% 1.1% 1-2 mm very good 130~
10% 0.5% 2-3 mm very good 130~
EM 6 5% 1.3% 1-2 mm very good 135~
10% 0.7% 2.5-3 mm very good 140~
EM 8 5% 7.5% 1-3 mm poor 30~
10% 4.1% 2-4 mm poor 25~
EM 9 5% 6.7% 1-2 mm poor 60~
10% 3.5% 2-3 mm moderate 50~
EM 10 5% 5.2% 0.5-1.5 mm good 120~
10% 3.4% 1.5-3 mm very good 140~
EM 11 5% 2.7% 0-0.5 mm good 115~
10% 0.9% 0.5-1 mm verygood 130~
Untreated - 12.3%
It is evident from Table III that the emulsions according to the
invention give signific~ntly better water repellency than the comparative emulsions
EM 8 and EM 9. The component having functional amino groups thus has, even
15 in very low concentration, such as, for example, in EM 4, a substantial effect on
the adhesion of the silicone resins to the surface or to that region of the substrate
which is close to the surface.
In a similar manner, the water absorption of the lime sandstones
treated with the emulsions according to the invention is advantageously affected,
20 i.e. re~ ce~l. In the case of the comparative emulsions EM 8 to EM 10, the water
, ... . ... .

CA 02249~2 1998-10-0~
WAS 0281 PCA -21-
absorption is high even two weeks after the application. In the case of EM 11,
water repellency and water absorption are comparable with the emulsions
according to the invention but the depth of penetration is small. A small depth of
penetration is undesired since it reduces the long-term stability of a water repellent
5 treatment exposed to weathering. EM 10 gives good water repellency comparable
with that of the emulsions according to the invention but the initially large contact
angle of water dripped on rapidly decreases until wetting occurs. In the water
absorption test, this effect is evident from the fact that the pale lime sandstones
appear dark and wet after only a short time in water. This undesired effect does not
10 occur in the case of the emulsions according to the invention; the stones do not
change their appearance even after storage in water for 24 hours.
FYq-np'q 3
Im~ g water repell~ncy to clay bricks
Emulsions according to the invention and not according to the
15 invention are diluted with water to 10% active ingredient content. Clay bricks
(about 22 x 10 x 7 cm3) are then immersed therein for 1 minute (about 5 cm liquid
cover). After a drying time of 14 days, water absorption, water repellency or
contact angle and depth of penetration are determined analogously to Example 2.
The results of these investigations are summarized in Table IV.

CA 02249~2 1998-10-0~
WAS 0281 PCA -22-
TABLE IV
Emulsion Water Depthof Water Contact
Absorption Penetration Repellency Angle
EM 1 1.4% 15 - 20 rnm moderate 75~
EM 2 0.8% % 12 -17 rnm good 110~
EM 4 0.3% 10 - 15 mm very good 125~
EM 8 4.8% 14 - 20 mm none 10~
EM 9 3.5% 11 - 14 mm poor 30~
EM 11 0.5% 8 - 12 mm good 110~
untreated 17.6%
Only those emulsions according to the invention which also contain
a siloxane component in addition to silane, i.e. for example EM 2 and EM 4, givevery good water repellency on the highly absorptive clay bricks, whereas the
purely silane-cont~ining EM 1 does not. However, a comparison of EM 1, EM 2
and EM 4 with EM 8 and EM 9 shows how the amino component advantageously
15 influences both the water repellency and the water absorption. A particularly good
pelrollllance is produced by EM 4 which, in addition to ethoxysilane, also contains
siloxane having methoxy functional groups, which react substantially more rapidly
than comparable components having ethoxy functional groups. Owing to its
aminosiloxane content, EM 11 also gives good results but penetrates rather more
20 poorly than the other emulsions and darkens the stone surface.
Example 4
Imparting water repçll~n~y to COIl~.. ete
The ~cses~ment of the quality of water repellants for concrete
impregnation is carried out according to the technical testing specifications for
25 surface protection systems of ZTV-SIB 90 of the B-ln~lesmini~terium fur Verkehr,
[Federal German Ministry for Traffic], Bonn. The water absorption and stability
.. . , . , .. ~

CA 02249~2 1998-10-0~
WAS 0281 PCA -23-
in an ~lk~lin~ environment are tested using mortar disks, which are produced
according to DIN EN 196 T1 (water/cement ratio 0.5). The disks have a diameter
of 10 cm and a height of 2 cm. Before the test, the test specimens must have been
stored for at least 90 days under standard climatic conditions (DIN 50 014,
5 23~C/50% relative hllmidity). The test is carried out according to the following
scheme:
Production of 10 mortar disks
Age of the mortar disks min. 90 days; storage under standard climatic
conditions according to DIN 50014 23/50-2 (Standard climatic weight I)
before the beginning of the test
Brushing with coarse scrubbing brush, storage for 28 days in delllinefalized water,
determination of water absorption (WA)
Selection of 5 mortar disks which come closest to the mean value of the
WA of the 10 mortar disks
15 Storage in the drying oven at 75~C until the standard climatic weight I is reached
Storage for 3 days in a standard climate according to DIN 50014-23/50-2
Storage in water for 2 min
Storage for 24 hours at 23/95, storage for 2 hours in a standard climate
according to DIN 50014-23/50-2
20 Imparting of water repellency by immersion for 1 min.
Delellllillalion of the absorption of impregnating agent
Storage for 14 days in a standard climate according to DIN 50014-23/50-2

CA 02249~2 1998-10-0~
WAS 0281 PCA -24-
Storage for 48 hours in 0.1 M KOH solution, determination of the amount of liquid
absorbed
Storage in a drying oven at 75~C until the standard climatic weight I is reachedStorage for 3 days in a standard climate according to DIN 50014-23/50-2
5 Determination of the water absorption (2 days, 28 days)
Drying for 24 hours at 75~C
Determination of the depth of penetration
A water repellant is classified as suitable for hlll)al~ g water
repellency to concrete if the water absorption on storage in water for 28 days is
10 reduced by at least 50% . Furthermore, the effect of the emulsions according to the
invention with regard to increasing the resistance to freezing and deicing salt
according to the technical testing specifications for surface protection systems of
ZTV-SIB 90 was investigated. For this purpose, concrete cubes (10 cm edge
length) of strength class B 25 according to DIN 1045 (water/cement ratio 0.6) were
15 produced as test specimens. Before the test, the test specimens were stored for at
least 90 days in a standard climate (DIN 50 014, 23~C/50% relative humidity).
The cubes are impregnated by complete immersion in the water repellent emulsion
for a duration of one minute. Thereafter, the test specimens are stored for 14 days
in a standard climate (DIN 50 014, 23~C/50% relative humidity). Thereafter, the
20 concrete cubes are immersed for 24 hours in 3 % strength NaCl solution and then
subjected to the freezing and thawing cycles (1 cycle comprises storage for 16
hours at -15~C and thawing for 8 hours to +20~C). After 5 cycles in each case,
the mass of the test specimens is d~le,lllilled and the relative mass loss is
calculated. A water repellant meets the requirements if the concrete cubes
25 impregnated therewith with.~t~n~l 15 cycles more than untreated reference test
specimens without ~urrelillg damage.

C A 02249~2 1998-lO-0
WAS 0281 PCA -25-
All emulsions used for the experiments were diluted to 20% active
ingredient content.
The results of the test for water absorption and stability in an
~lk~lin-o enviro~ lellt are summarized in Table V and the resistance to freezing and
5 deicing salt is summarized in Table VI.
TABLE V
Emulsion Absorption of Water Absorption Depth of Penetration
Impregn~ting
Agent
EM 1 129g/m2 2.3% 2-4mm
EM 2 121 g/m2 2.7% 1.5 - 3 mm
EM 11 103 g/m2 3 9% 0.5 - 2 mm
untreated - 5.7%
TABLE VI
Fmlllci~n Absorption Relative change in mass
of
Illll)l~,~,ll~lillg
Agent
P r e I i m - 1 Cycle 5 Cycles 10 Cycles 15
i n a r y Cycles
storage
E M 1 175 g/m2 + 0.5 % + 2.0 % + 4.2 % + 4.5 % + 2.1 %
E M 2 161 g/m2 + 1.2 % + 3.1 % + 4.4 % + 2.7 % + 0.5 %
E M 11 148 g/m2 + 1.6 % + 2.2 % + 3.5 % + 0.9 % -4.7 %
untreated - +2.7 % + 3.4 % -1.1 % -4.5 % -17.5 %
As is evident from Tables V and VI, the emulsions EM 1 and EM
2 according to the invention show out~t~n-ling penetration into the concrete, which

CA 02249~2 1998-10-0~
WAS 0281 PCA -26-
is a precondition for fi1lfilling the criteria of water absorption (less than 50%,
based on u~ eal~d) and resistance to alternate freezing and thawing (at least 15cycles without suffering damage). In the case of the comparative emulsion EM 11,the amino-functional polydimethylsiloxane illlelr.,les with the penetration to such
5 an extent that the criteria with regard to water absorption and resi~t~n~e to freezing
and deicing salt are not fulfilled.
Example 5
Imparting water repellPnry to wood
Sprucewood boards (15 x 7.5 x 0.5 cm3) are immersed for three
10 minutes in the water repellent emulsions. The test specimens are then dried for 14
days at room temperature, and the capillary water absorption is then determined
in a so-called floating test. For this purpose, the boards are floated on water on
each of the two flat sides for 15 minlltes, and the weight increase is recorded. The
test specimens are then weathered in an accelerated weathering apparatus (model
QUV/se from Q-Panel Lab Products, Cleveland, OH 44145, USA) for 2000 hours.
The weathering cycle is adjusted so that exposure to UV(B) radiation is carried out
for 8 hours, spraying is then carried out for 10 minutes and condensation is then
effected for 4 h in moisture-saturated air at a temperature of 50~C. Thereafter,spraying is again carried out for 10 minutes and the next cycle is started with
20 exposure to radiation.
After the weathering, the test specimens are dried for one week at
room temperature and again subjected to the floating test described above. In
addition, the water repellency of the wood is qualitatively assessed. The results are
summarized in Table VII.
.... . .

CA 02249~2 1998-10-0~
WAS 0281 PCA -27-
TABLE VII
Fm~,lciOnActive sefore Weatherin~ After We~thPri
Ingredient
Content
water water water water repellency
absorption repellency absorption
EM 4 5 % 11 % moderate 6 % good
10% 8% moderate 4% good
EM 4 5 % 7 % very good 3 % very good
+ wax* 10% 4.5% very good 1.5% very good
EM 7 5% 4% very good 2.5% very good
10% 2% very good 1.5% very good
EM 8 5% 17% poor 14% average
10% 13% poor 9.5% moderate
untreated - 21 % none 27 % none
* 9 parts by weight of the emulsion EM 4 were mixed with I part by weight of a 3s%
strength emulsion of a silicone wax. The active hlgledielll content of the wax is taken into
account in the total active hlgledi~.ll content in column 2 of Table VII.
From the results in Table VII, it may be concluded that in particular
the emulsions EM4 and EM7 give good results on wood whereas the comparative
emulsion EM8 performs rather moderately. The reason for this is that, on the
15 substantially neutral substrate wood, an emulsion EM8 consisting only of silane
reacts extremely slowly to give the actual active ingredient, the silicone resin. A
not inconsiderable part of the generaliy volatile silane will consequently evaporate,
which is reflected in a poor reduction of the water absorption. EM7 predomin~ntly
comprises the less reactive resin H3, which rapidly produces good water
20 repellency on the surface of the wood. In the case of EM 4, the siloxane
component results in good early water resistance which however can still be
considerably improved by suitable silicone wax (EM 4 + wax). In contrast to
conventional organic polymer waxes, the silicone wax used is weather-resistant and
has a long life.

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WAS 0281 PCA -28-
Example 6
Water repPIlent ~ ..els for mineral co~'in~s on mineral l)~ in~ materials
a) Emulsion EM 2 diluted to a solids content of 10% by weight is
applied in 400 g/m2 to lime sandstone. After storage for 14 days at room
5 temperature, the following properties of the lime sandstone which has been
rendered water repellent are measured:
Water repellency: very good
Contact angle: 130~
Depth of penetration: 3 mm
w value: 0.073 kg/m h
sd value: 0.02 m
The water absorption is evaluated by measuring the water absorption
coefficient w according to DIN 52617. Values of w < 0.1 kg/m2hl'2 denote an
extremely low water absorption.
The sd value is measured according to DIN 52615; sd values < 0.1
m indicate high water vapor permeability, sd values > 0.1 m in~licate low water
vapor permeabilities.
The lime sandstone stored for 14 days is coated with silicone resin
emulsion paint according to DIN 18363 (the content of organic resins does not
20 exceed the content of organopolysiloxanes). The adhesive strength of the coating
according to ISO 4624 is determined as 2.8 N/mm2. Without the water repellent
priming with 10% strength emulsion EM 2, the adhesion of this silicone resin paint
to lime sandstone is determined only as 1.5 N/mm2.
b) Emulsion EM 3 diluted to a solids content of 10% by weight is
25 stored for 14 days at 50~C, after which it shows no visual change. Thereafter, this
dilute emulsion is applied by means of a brush to a fiber cement slab coated 2 mm

CA 02249~2 1998-10-0~
W AS 0281 PCA -29-
thick with brittle lime-cement render and then stored for 14 days at room
temperature.
In the case of untreated lime-cement render, a w value of 1.3
kg/m2hl~2 is found.
The following properties of the lime-cement render made water
repellent in this manner are found:
water repellency: very good
contact angle: 125~
depth of penetration: 2 mm
w value: 0.068 kg/m h
What is striking is the improved surface strength of the lime-cement
render after application of 10% strength EM 3.
The substrate treated in this manner can be coated with silicone
resin emulsion paints. All preparations coated in this manner exhibit, after Q-UV
accelerated weathering for 1000 h, absolutely no flaking or color changes while
retaining very good water repellency.
Example 7
Water repellPnt additive for aqueous m~onry paints and renders having a
high filler content
Masonry paints which have a high filler content and high capillary
water absorption and tend to have a low binder content, such as emulsion silicate
paints and renders, emulsion-based coatings having a high filler content, emulsion
lime paints, brushable fillers and reinforcing materials, mineral paints, mineral
renders, lime paints, etc., are considered here. The pigment volume concentration
(PVC) of the coatings is typically above 50%. Usually, the water absorption of the

CA 02249~2 1998-10-0~
WAS 0281 PCA -30-
abovementioned coating materials is at least 3 kg/m2 after 24 hours, determined by
the accelerated test described below.
The addition of only 1 % of the un-lilutecl emulsions according to the
invention as water repellent additive to the coating materials shown below in Table
5 VIII dr~m~tic~lly reduces this capillary water absorption. The water absorption is
determined after the accelerated test described below.
The suction effect of lime sandstone or that of the composite lime
sandstone/coating system is measured. The measurement of the capillary water
absorption is described in DIN 52617. The procedure used here is performed as
10 an accelerated test based on the above method. The paint substrates used are lime
sandstone panels (115 x 70 x 20 mm with a surface area of 0.008 m2). During
coating of the paint substrates, 6.5 g are poured onto the surface as a first coat and
distributed uniformly with a flat brush, the lateral surfaces also being coated. The
second coat is applied after 24 hours. The amount of paint applied is 4.5 g. The15 coated test specimens are stored for 24 hours at room temperature and then for 24
hours at 50~C. For further conditioning, storage is carried out for an additional 24
hours at room temperature.
The test specimens prepared in this manner are introduced into
dishes which are lined with foam and filled with water, so that the coated surface
20 remains constantly in contact with the water-saturated foam surface. The weight
increase is measured as a function of time (after 2, 6 and 24 hours) and is
compared with that of the untreated test specimen.

CA 02249~2 1998-10-0~
WAS 0281 PCA -31-
TABLE VIII
Coating material Water absorption Addition 1% by weight each
[kglm2]
Emulsion silicate paint 6.4
0.28 EM3
Pit lime render 7.4
0. 35 EM4
Filler-containing 3.4
emulsion paint (PVC 70) 0.62 EM2
F,Yn~nple 8
Water repellent additive for mortar mixtures
A mixture of 1350 g of sand and 450 g of Portland cement is stirred
with a mixture of 225 g of water and 5.2 g of emulsion (one experiment with EM
1, and a second experiment with EM 11) to give a mortar. This is then introducedinto polytetrafluoroethylene rings having a ~ m~ter of 10 cm and a height of 2 cm.
After a drying time of 4 weeks, the rings are removed from the samples of the
latter and are placed 5 cm deep in water for 28 days, and the water absorption is
15 dele~ ed gravimetrically.
In addition, the mortar mixtures are poured into rectangular
polytetrafluoroethylene molds having the dimensions 15 cm (length) x 4 cm (width)
x 4 cm (height). After a setting time of, likewise, 4 weeks, the test specimens are
removed from the mold and used for de~e~ g compressive strength and
20 bending strength.
The results of the water absorption and compressive strength and
bending strength are summarized in Table IX below.

CA 02249~2 1998-10-0~
WAS 0281 PCA -32-
TABLE IX
Emulsion Waterabsorption Compressive strength Bending strength
EM 1 2.2% 41 N/mm2 7.8 N/mm2
EM 11 2.4% 28 N/mm2 6.0 N/mm2
ul,tledted 5.5% 43 N/mm2 7.6 N/mm2
It is evident from Table IX that both the emulsion EM 1 according
to the invention and the comparative emulsion EM 11 significantly reduce the
water absorption of the mortar samples. In contrast to EM 1, however, EM 11,
owing to its polydimethylsiloxane content, impairs the mechanical properties of
10 compressive strength and bending strength to a considerable extent, whereas they
remain virtually unrh~nged as a result of the addition of EM 1.
... .