Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – At least one aryl ring which is part of a fused or bridged...
Reexamination Certificate
1999-05-24
2001-09-04
Moore, Margaret G. (Department: 1712)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
At least one aryl ring which is part of a fused or bridged...
C524S837000, C427S387000
Reexamination Certificate
active
06284834
ABSTRACT:
BACKGROUND OF THE INVENTION
The present invention relates to novel aqueous preparations for the treatment of mineral building materials comprising (I) an aqueous emulsion of at least one polyfunctional carbosilane and/or carbosiloxane (A) and/or the (partial) condensation product thereof, (II) an emulsion of at least one organo(poly)siloxane (B), (III) at least one organic polymer (C) dispersible or emulsified in water, (IV) inorganic nanoparticles (D) dispersed or dispersible in water, and (V) optionally other additives (E).
The construction and building materials industry is searching for aqueous treatment agents for mineral building materials that impregnate or waterproof the materials well, that increase resistance to chemicals in order to protect against environmental influences, and that at the same time impart good easy to clean properties to the building material. In so doing, the appearance of the mineral building material must not be changed, for example, in order to protect monuments, natural stone facades, or terracotta materials from environmental influences or from graffiti.
Aqueous emulsions of organosilicon compounds have been successful as impregnating, waterproofing, and building protective agents for mineral building materials.
DE-A 19,517,346 describes, for example, aqueous emulsions of organosilicon compounds for waterproofing porous mineral building materials and building coatings. On mineral building materials, aqueous emulsions of organosilicon compounds produce only inadequate easy to clean properties.
DE-A 3,702,542 describes graft copolymers of (meth)acrylic acid derivatives and alkoxy-functional silicone resins for impregnation purposes, especially in buildings protection. Although those graft copolymers are good impregnating agents and, especially as a pigmented formulation, impart good easy to clean properties to mineral building materials, they contain organic solvents and change the visual appearance of the substrate.
WO 97/12,940 discloses aqueous preparations which comprise an emulsion of an alkoxysilane that is insoluble or only slightly soluble in water and a polymer containing alkoxysilane groups that is dispersible or emulsified in water.
In addition, coating compositions based on multifunctional carbosilanes are known, see U.S. Pat. Nos. 5,378,790, 5,621,038 and 5,686,523. The preparation of such hybrid materials is mostly carried out in dilute organic solution, generally by means of a sol/gel process, which is disadvantageous for many applications because, for example, with the known hybrid materials, a high molecular weight network is built up in a sol/gel process. Those high molecular weight polymers are not able to permeate the mineral building material very well and consequently result in a change in the surface of the mineral building material, which mostly becomes shiny. Moreover, relatively large amounts of solvent are necessary in sol/gel processes. That is undesirable because of the toxicological properties and the fire risk of the solvents, and existing VOC guidelines.
Accordingly, the object of the present invention was to provide an aqueous preparation that effectively impregnates or waterproofs mineral building materials, that imparts to the mineral building material adequate chemical resistance and good easy to clean properties, and that at the same time does not change the outward appearance of the mineral building material.
Surprisingly, it has now been found that that object is achieved by aqueous preparations that comprise an emulsion of at least one polyfunctional carbosilane and/or carbosiloxane (A), an emulsion of at least one organo(poly)siloxane (B), at least one organic polymer dispersed or emulsified in water (C), inorganic nanoparticles dispersed or dispersible in water (D), and optional other additives (E).
SUMMARY OF THE INVENTION
The present invention, therefore, relates to aqueous preparations comprising
(I) an emulsion of a polyfunctional carbosilane and/or carbosiloxane (A),
(II) an emulsion of at least one organo(poly)siloxane (B),
(III) at least one organic polymer (C) dispersed or emulsified in water,
(IV) inorganic nanoparticles (D) dispersed or dispersible in water, and
(V) optional other additives (E).
DETAILED DESCRIPTION OF THE INVENTION
The polyfunctional carbosilanes and/or carbosiloxanes (A) are preferably silanes or siloxanes that contain at least two units of the formula (1)
—(CH
2
)
m
SiR
1
n
X
3−n
(1)
wherein
m is from 1 to 6 (preferably 2 or 3),
n is from 0 to 2,
R
1
is an unsubstituted C
1
-C
18
-hydrocarbon (preferably methyl or ethyl) or a hydrocarbon that contains at least O, N, S, and/or P, each R
1
within the molecule being identical or different, and
X is a radical selected from the group OH, C
1
-C
4
alkoxy, C
6
-C
20
aryloxy, C
1
-C
6
acyloxy, and hydrogen (preferably OH or C
2
alkoxy).
These compounds can be prepared, for example, by reacting silanes or siloxanes having Si—H bonds with appropriately functionalized silanes having vinyl, allyl, or higher alkenyl groups, or by reacting silanes or siloxanes having vinyl, allyl, or higher alkenyl groups with appropriately functionalized silanes having Si—H bonds.
In a further embodiment of the invention, the polyfunctional carbosilanes and/or carbosiloxanes (A) are silanes of the formula (2)
R
2
4−p
Si[—O
t
(CH
2
)
m
SiR
1
n
X
3−n
]
p
(2)
or the partial condensation products thereof,
wherein
t is 0 or 1,
p is 4, 3, or 2,
R
2
is C
1
-C
18
alkyl and/or C
6
-C
20
aryl, and
m, n, R
1
, and X are as defined above.
In a further embodiment of the invention, the polyfunctional carbosiloxane (A) is a siloxane that is composed of at least two structural units selected from monofunctional units R
3
3
SiO
½
, difunctional units R
4
2
SiO
{fraction (2/2)}
, and trifunctional units R
5
SiO
{fraction (3/2)}
and optionally, in addition, tetrafunctional units SiO
{fraction (4/2)}
and/or the condensation product and/or partial condensation product thereof, wherein R
3
, R
4
and R
5
are each independently of the others H, C
1
-C
18
alkyl, C
2
-C
18
alkenyl and/or C
6
-C
20
aryl or units of the general formula (1).
Suitable siloxanes are, for example, siloxanes containing Si—H groups or vinyl, allyl, or higher alkenyl groups, which are prepared according to known processes, such as, for example, by hydrolysis and condensation of the corresponding chlorosilanes and, optionally, subsequent equilibration.
The underlying siloxanes preferably have a molecular weight (number average) of from 300 to 5000.
In a further preferred embodiment of the invention, the polyfunctional carbosiloxane (A) is a compound of formula (3)
or the partial condensation product thereof, wherein a is from 3 to 6 (preferably 4) and R
1
, R
2
, X, m, and n are as defined above.
The polyfunctional carbosilanes (A) are very especially preferably the compounds of formula (4) and/or (5)
or the partial condensation products thereof.
Compounds of formulas (3), (4), and (5) can be prepared, for example, according to the process described in DE-A 19,603,241 or in DE-A 19,711,650.
Within the context of the invention, condensation products and partial condensation products are to be understood as being compounds which, for example, are formed wholly or partially by the reaction of two radicals of the general formula (1) with the removal of water or alcohol.
The emulsion is preferably aqueous or water in admixture with pure alcohol and preferably contains from 5 to 70 wt. % (especially from 10 to 50 wt. %) of the poly-functional carbosilane and/or siloxane.
The organo(poly)siloxane (B) is preferably at least one hydroxy- and/or alkoxy-functional organo(poly)siloxane that forms an emulsion with water, emulsifiers, that is to say, for example, anionic, cationic, and non-ionic emulsifiers, such as, for example, polyoxyethylene triglyceride, ethoxylated tridecyl alcohol, and, optionally, other auxiliary substances, such as, for example, protective colloids, anti-aging agents, bactericides, fungicides, and the like. The hydro
Kasler Karl-Heinz
Kirchmeyer Stephan
Mechtel Markus
Bayer Aktiengesellschaft
Gil Joseph C.
Henderson Richard E. L.
Moore Margaret G.
Roy Thomas W.
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