Title of Invention

LIGHT-PERMEABLE HEAT PROTECTION ELEMENT WITH ALUMINATE-MODIFIED OR BORATE-MODIFIED SILICON DIOXIDE

Abstract The invention relates to a light-permeable heat-protection element comprising at least one support element and at least one protective coating containing a reaction product which comprises an aqueous alkali silicate solution and aluminate-modified or borate-modified silicon dioxide. The invention also relates to a method for producing said element.
Full Text Light permeable heat protection element with aluminate-
modified or borate-modified silicon dioxide
The invention relates to a transparent heat protection
element having at least one support element and at
least one protective layer comprising a reaction
product containing aqueous alkali metal silicate
solution and aluminate- or borate-modified silicon
dioxide and also a process for producing it.
DE-A 2 414 575 describes fire-shielding glass panes
containing a fire-resistant layer comprising a polymer
membrane which on at least one side has a layer
containing a barrier-forming material. This material
may be an aluminate or an alkali metal silicate. The
purpose of this material is to make the layer(s) more
opaque to infrared radiation on heating, since this
material forms thermally insulating barriers.
US 4,190,698 describes transparent fire protection
panes containing at least one dried layer comprising
hydrated alkali metal silicates and one or more
auxiliaries such as urea, polyhyriric alcohols,
colloidal silica or sodium aluminate. When colloidal
silica and sodium aluminate are used, a modulus of less
than 4 is achieved. The purpose of the addition of the
auxiliaries is to improve the resistance of the layer
and thus the fire protection pane in the case of fire.
A disadvantage in the production of these fire
protection panes is that evaporation of water from the
original formulation is necessary, which is complicated
from a production engineering point of view. The dried
fire protection layer is formed by casting onto an open
surface and subsequent drying and cannot be formed in
closed hollow spaces. It is also known that the
addition of sodium aluminate to the protective layer
leads to precipitates and thus, as a further
disadvantage, to the protective layer rapidly becoming
cloudy.
WO-A 2004/014813 describes the production of heat protection
elements based on a solution comprising water glass and an
aluminate, with the aluminate having to be partially
neutralized using organic acids such as citric acid before
addition to the silicate solution. If partial neutralization of
the aluminate is not carried out, a stable solution of water
glass and aluminate is not obtained. A disadvantage in the
production of these heat protection elements is that
evaporation of water from the original formulation for the heat
protection elements is necessary, which is complicated in terms
of production engineering.
WO-A 94/04355 describes the production of a transparent heat
protection element having at least one support element and a
protective layer composed of water-containing alkali metal
silicate. Such transparent heat protection elements are
employed, for example, for the production of fire protection
glasses. A significant constituent of the heat protection
elements is the protective layer of water-containing alkali
metal silicate which is produced by reaction of an alkali metal
silicate and a silica aqua sol in such a mixing ratio that the
molar ratio of silicon dioxide to the total amount of alkali
metal oxide, known as the modulus, is greater than 4:1. The
silica sol component is in this case used as hardener for the
alkali metal silicate. Curing by means of silica sols enables
the evaporation of water from the original formulation of the
layer, which is necessary in other known protective layers and
is complicated in terms of production engineering, to be
dispensed with.
However, a disadvantage of protective layers composed of water-
containing alkali metal silicate and silica sol as hardener, as
described in WO-A 94/04355, is their tendency to become cloudy
35during use. This applies particularly in the case of prolonged
exposure to temperatures above 20°C, which can be prolonged
during the summer months and can accelerate the clouding
process.
Electron micrographs confirm that the clouding of the aqueous
alkali metal silicate protective layer is caused by a
crystallization process. The additions of oxides of the
elements of main group III of the Periodic Table, in particular
boron oxide or aluminum oxide, are known to promote
crystallization processes in glasses and should accordingly be
expected to accelerate the clouding of glasses.
There is therefore a need for transparent heat protection
elements and also materials for use as protective layer in such
heat protection elements, which have a high transparency and
aging resistance. In addition, the starting composition for the
protective layer should be flowable and be suitable for casting
into hollow spaces and subsequently harden over an appropriate
period of time to form the protective layer.
It was therefore an object of the present invention to provide
such heat protection elements and also materials for use as
protective layer in these heat protection elements.
This object has surprisingly been achieved by the protective
layer comprising a reaction product containing aqueous alkali
metal silicate solution and aluminate- or borate-modified
silicon dioxide, with this reaction product having a modulus of
from 4 to 7. An addition of organic acids as described in
WO-A 2004/014813 is not necessary here.
The present invention accordingly provides a transparent heat
protection element having at least one support element and at
least one protective layer comprising a reaction product
containing aqueous alkali metal silicate solution and
aluminate- or borate-modif ied silicon dioxide, characterized in
that the reaction product has a modulus of from 4 to 7.
As aqueous alkali metal silicate solution, it is possible to
use water glass, preferably potassium water glass.
The silicon dioxide which is suitable for the purposes of the
invention can, for example, be introduced in the form of
precipitated silicon dioxide, silica gel, pyrogenic silicon
dioxide or silica sols into the protective layers or be
produced therefrom. Preference is given to using pyrogenic
silicon dioxide or silica sols, particularly preferably silica
sols. The water-containing silicon dioxide is preferably
produced from stable suspensions, sols or gels or colloidal or
colloidally disperse solutions, for example silica sols, of
such forms of silicon dioxide. Silica sols and their production
are known to those skilled in the art. Silica sols are
commercially available; mention may here be made by way of
example of the products obtainable under the trade name Levasil
from H. C. Starck GmbH.
Silica sols are colloidal solutions of amorphous silicon
dioxide in water, which are also referred to as silicon dioxide
sols but usually as silica sols for short. In these, the
silicon dioxide is present in the form of spherical particles
which are hydroxylated on the surface. The particle diameter of
the colloidal particles is generally from 1 to 200 nm, with the
specific BET surface area (determined by the method of G. N.
Sears, Analytical Chemistry Vol. 28, No. 12, 1981-1983,
December 1956), which correlates with the particle size, being
from 15 to 2000 m2/g. The surface of the SiO2 particles has a
charge which is compensated by an appropriate counterion,
leading to stabilization of the colloidal solution.
Silica sols which are suitable for the purposes of the
invention have a pH of from 7 to 11.5 and contain, for example,
small amounts of Na2O, K2O, Li2O, ammonia, organic nitrogen
bases, tetraalkylammonium hydroxides or alkali metal aluminates
or ammonium aluminates as alkalizing agent. The pH values
quoted are, unless indicated otherwise, pH values determined at
25°C. The solids concentrations of suitable silica sols are
preferably from 5 to 60% by weight of SiO2.
For the purposes of the invention, aluminate-modified silicon
dioxide, in particular aluminate-modified silica sol, can be
prepared, for example, by addition of a suitable amount of
aluminate ions, Al(OH)4-, to silicon dioxide with stirring. The
solution of aluminate ions is appropriately a dilute sodium
aluminate or potassium aluminate solution. The silicon dioxide
particles appropriately have from about 0.05 to about 2,
preferably from about 0.1 to about 2, Al+ atoms/nm2 of surface
area of the silicon dioxide particles. The aluminate-modified
silicon dioxide particles comprise inserted or exchanged
aluminate ions, producing aluminosilicate sites having a fixed
negative surface charge. The aluminate-modified silicon dioxide
particles retain their high negative surface charge up to a pH
of 3, in contrast to conventional unmodified silicon dioxide.
In the case of unmodified silicon dioxide, the negative surface
charge decreases when the pH is reduced, normally to a pH of
about 2, which represents the zero-charge point for unmodified
silicon dioxide. Thus, the surface charge for unmodified
silicon dioxide particles at a pH below about 8 is smaller than
for aluminate-modified silicon dioxide. The pH of the
aluminate-modified silicon dioxide can appropriately be set to
a pH in the range from 3 to 11, preferably from about 4 to 10,
preferably by means of an ion-exchange resin. The aluminate-
modified silicon dioxide can then be concentrated so that it
has a silicon dioxide content of from about 1 to 60% by weight.
The process for preparing the aluminate-modified silicon
dioxide is also described in "The Chemistry of Silica" by Ralph
K. Ilcr, pp. 407-409, John Wiley & Sons, 1979 and in US
5,368,833.
An analogous production process can be employed for borate-
modified silicon dioxide, in particular borate-modified silica
sol.
The production of aluminate- or borate-modified silica sols
comprises carrying out essentially the production steps of
dealkylation of water glass by means of ion exchange, setting
and stabilization of the desired particle size (distribution)
of the SiO2 particles, setting of the desired SiO2 concentration
and aluminate- or borate-modification of the SiO; particles. In
none of these steps do the SiO2 particles leave the colloidally
dissolved state. This explains the presence of the discrete
primary particles.
The aluminate- or borate-modified silicon dioxide preferably
has an aluminate or borate content of from 0.01 to 1.5% by
weight, particularly preferably from 0.05 to 1.0% by weight,
based on the total weight of SiO2 in the unmodified silicon
dioxide.
The term modulus is known. To a person skilled in the art, the
modulus of a siliceous binder is the molar ratio, which can be
determined by analysis, of silicon dioxide (SiO2) and alkali
metal oxide M2O (M = boron, lithium, sodium or potassium) in the
solid of the binder.
The aluminate- or borate-modified silicon dioxide preferably
has a modulus of from 4.2 to 6.5.
The reaction product can preferably additionally contain an
agent for lowering the freezing point; the agent for lowering
the freezing point can be a monofunctional and/or
polyfunctional alcohol selected from the . group consisting of
glycerol, glycol, sugar, diethylene glycol and polyethylene
glycol.
The heat protection element of the invention is preferably a
fire protection composite glass.
In preferred embodiments of the present invention, the
protective layer(s) is/are in each case located between at
least two support elements. Sandwich structures having a
protective layer between two support elements or else multiple
sandwich structures having an alternating sequence of support
elements and protective layers can be obtained in this way.
Support elements are preferably present on the outside.
Suitable support elements for the transparent heat protection
elements of the invention are glass elements, in particular
glass plates or glass panes, but also other materials having
the desired optical properties, as long as they satisfy the
technical and physical requirements, for example heat
resistance. However, support elements made of glass are
particularly preferred. It is also possible to use fully or
partially, thermally or chemically prestressed glass as support
material.
The transparent heat protection elements of the invention can,
according to the invention, be produced using a reaction
product containing aqueous alkali metal silicate solution and
aluminate- or borate-modified silicon dioxide, with the
reaction product having a modulus of from 4 to 7, by
introducing this reaction product into a mold cavity between
two support elements or applying it to a support element,
subsequently hardening it to form a solid silicate layer while
retaining the water content and setting the molar ratio of
silicon dioxide to alkali metal oxides (modulus) in the
hardened silicate to a ratio of from 4:1 to 7:1.
The process of the invention thus makes it possible to produce
composite elements which comprise a plurality of support
elements arranged with a spacing between them and subsequently
fill the intermediate space between the support elements with
the reaction product and, if appropriate, one or more further
hardeners such as silica sol, inorganic or organic acids,
esters, acid amides, glyoxals, alkylene carbonates, alkali
metal carbonates and hydrogencarbonates, borates, phosphates or
para-formaldehyde. As a result of the high water content, the
composition flows very well and can be poured without
difficulty even into the intermediate ispaces of composite
elements having a small distance between the support elements.
Since the reaction product hardens to form a finished silicate
layer without drying, i.e. without removal of water, a drying
operation can be dispensed with, which considerably simplifies
the production of such heat protection elements. The reaction
or hardening time can be reduced in a known manner by heating.
The pot life of the castable reaction product at room
temperature is in any case sufficiently long to make a normal
production procedure possible. In the production of the heat
production elements, the castable reaction product can, as
described, be introduced or poured into a mold cavity between
at least two support elements. However, it is also possible to
apply the castable reaction product to a support element and
subsequently place a second support element on top of the still
unhardened protective layer or adhesively bond the second
support element onto the protective layer in a known manner
after hardening of said protective layer. In the production of
multiple sandwich structures by the variant of application of
the castable reaction product to a support element, the latter
process would have to be repeated a number of times. The
variant of pouring into appropriate hollow spaces therefore
offers advantages for such structures.
The reaction product is preferably degassed before processing.
This ensures that no gas inclusions which could adversely
affect the optical quality of the heat protection element of
the invention are present in the hardened silicate layer.
However, degassing can also be carried out only after filling
of the hollow spaces. To increase the adhesion of the silicate
layer to the support elements, an auxiliary in the form of
anionic or nonionic surfactants can be added to the reaction
product before processing and/or the surfaces of the support
elements can be pretrcated with such an agent. The surfaces of
the support elements can preferably also be pretreated with a
bonding agent, in particular an organofunctional silane and/or
wax dispersions.
The protective layer of hardened silicate produced according to
the invention has good intrinsic strength and displays good
adhesion to the adjoining support elements, preferably in the
form of glass plates or other transparent components. The
reaction product used as starting composition is flowable and
readily castable. The hardened protective layer is of high
optical quality and transparency and has good aging resistance.
The particular properties of the protective layer in the form
of the hardened silicate are achieved by the silicate layer
having a content of silicon dioxide in the range from 30 to 55%
by weight. The content of alkali metal oxide in the form of
sodium oxide, potassium oxide or lithium oxide or a mixture
thereof is not more than 16%. The hardened silicate layer
contains up to 60% of water. As a result, heat protection
elements of the invention having such a protective layer
achieve a very high fire resistance value since a relatively
large amount of water is available for the vaporization
process. According to the invention, the use of aluminate- or
borate-modified silicon dioxide leads to an improvement in the
aging resistance of the protective layer.
In a transparent heat protection element, the protective layer
or silicate layer is advantageously arranged between two glass
plates and together with these forms a composite element. To
achieve higher heat resistance values, heat protection elements
in which the heat protection element comprises a plurality of
silicate layers arranged in each case between two glass plates
and the glass plates and the polysilicate layers form a
composite element are constructed. In these arrangements
according to the invention, the silicate layers are in direct
contact with the adjoining glass plates which form the support
elements.
The use of a reaction product containing aqueous alkali metal.
silicate solution and aluminate- or boriate-modified silicon
dioxide in protective layers of transparent heat protection
elements has hitherto not been described in this form in the
literature.
The present invention accordingly further provides such a use
of a reaction product containing aqueous alkali metal silicate
solution and aluminate- or borate-modified silicon dioxide in
at least one protective layer of a heat protection element,
characterized in that the reaction product has a modulus of
The preferred ranges for the transparent heat protection
element of the invention apply analogously here.
Such a use is surprising, in particular, because for the reason
mentioned at the outset aluminate- or borate-modification of
silica sols in such a use would be expected to lead to earlier
crystallization and thus to clouding of the protective layer
rather than delay such crystallization.
The following examples serve merely to illustrate the invention
by way of example and are not to be construed as a limitation.
Examples
Reaction products, hereinafter referred to as fire protection
layer composition, are produced by reaction of potassium water
glasses with aluminate- or borate-modified silica sols.
Potassium water glasses having a specific modulus and solids
content are commercially available but can also be prepared as
described below by reaction of silica sols with potassium
hydroxide.
Example 1: Preparation of potassium water glass having a
modulus of 2.25 and a solids content of 55% by weight
2460 g of commercial potassium hydroxide pellets having a KOH
content of about 86.5% by weight were placed together with
429 g of deionized water in a 6 liter three-neck stirred flask
provided with condenser and dropping funnel. The three-neck
flask was located in a water bath. While cooling, 5127 g of
Levasil 50/50% (specific surface area: about 50 m2/g; solids
content: about 50.5% by weight; manufacturer: H. C. Starck
GmbH) were added at such a rate that a temperature in the range
from 60 to 80°C was maintained.
After the addition of the silica sol, the mixture was stirred
at 70°C for another 3 hours.
After sedimentation of the precipitate formed as by-product of
the reaction, the solution was decanted off:.
Example 2: Aluminate- or borate-modification of silica sols
having a specific surface area of about SO m2/g and a solids
content of about 50.5% by weight
The aluminate or borate content is repotted in % by weight
calculated as Al2O3 or B.-O3 based on the solids content of the
unmodified silica sol.
For example, sols containing a) 0.64 and b) 0.32% by weight of
Al2O3 and c) 0.22% by weight of B2O3 were produced as follows:
1000 g of Levasil3 50/50% were placed in a three-neck flask
provided with stirrer, heating mantle, dropping funnel and
distillation bridge, a) 60 ml or b) 120 ml of a solution of
25 g of commercial sodium aluminate in 500 ml of water or c) 79
ml of a solution of 5 g of commercial scjdium tetraborate and
6.6 g of 10% strength sodium hydroxide solution in 250 ml of
water were slowly added dropwise.
After the addition was complete, the mixtures were heated and
water was distilled off in such an amount (in ml) that the
original solids content was regained.
The distillation bridge was then replaced by a reflux condenser
and the mixture was refluxed for a total boiling time of 3
hours.
Insoluble material formed was allowed to settle for a period of
3524 hours and separated off by subsequent decantation.
Example 3: Production of a fire protection layer composition
having a modulus of 4.7 from potassium water glass and an
aluminate-modified silica sol containing 0.32% by weight of
Al2O3
170.4 g of a potassium water glass characterized as in example
1 together with 13.5 g of commercial ethylene glycol were
placed in a 250 ml multineck stirred flask with gas outlets.
The mixture was heated to 20°C by means of a heatable water
bath.
116 g of a silica sol produced as described in example 2a) and
containing 0.32% by weight of Al2O3 and having a specific
surface area of 50 m2/g and a solids content of 50.5% were added
over a period of 30 minutes.
The reaction mixture was stirred at 20°C for a further
1.5 hours. It was then heated to 40°C over a period of 30
minutes and maintained at this temperature for 30 minutes.
The reaction mixture was cooled to 20°C over a period of 15
minutes by replacement of water in the heating bath. The
mixture was stirred for a further SO minutes at this
temperature. During the last 20 minutes, a; water pump vacuum of
about 110 mbar was applied via the gas outlet.
About 60 ml of this reaction mixture were transferred by means
of a glass piston-type pipette into a 100 ml glass bottle which
was closed by means of a crown seal.
The bottled sample was heated at 80°C in a drying oven for
about 20 hours.
The absence of a sediment was then visually confirmed as a
criterion for complete reaction and a turbidity of 1.6 TU/F
(turbidity units based on formazine) was measured by means of a
suitable turbidity photometer (e.g. model LTP 5 from Lange).
The storage of the sample at 80°C was then continued with
regular measurement of the turbidity until 3.5 TU/F was reached
after 63 days, i.e. turbidity could be observed visually.
Example 4: Production of a fire protection layer composition
having a modulus of 4.7 from potassium water glass and an
aluminate-modified silica sol containing 0.64% by weight of
Al2O3
A silica sol produced as described in example 2b) and
containing 0.64% by weight of Al2O3 and having a specific
surface area of 50 m2/g and a solids content of 50.5% was
reacted by the reaction procedure described in example 3.
After heating for 20 hours as described in example 3, the
sample had a turbidity of 4.5 TU/F. After the reaction was
complete, the turbidity was reduced to 2.1 TU/F after 3 days.
After 83 days, a renewed increase in the turbidity to 3.5 TU/F
was observed.
Example 5: Production of a fire protection layer composition
having a modulus of 4.7 from potassium water glass and a
borate-modified silica sol containing 0.22% of B2O3
A silica sol produced as described in example 2c) and
containing 0.22% by weight of B2O3 and having a specific surface
area of 50 m2/g and a solids content of 50.5% was reacted by the
reaction procedure described in example 3.
After heating for 20 hours as described in example 3, the
sample showed a sediment and had a turbiditjy of 2.2 TU/F.
The increase in turbidity to 3.5 TU/F was found after 25 days.
Comparative example: Production of a fire protection layer
composition from potassium water glass andj an unmodified silica
sol
An unmodified silica sol having a specific surface area of 50
m2/g and a solids content of 50.5% was reacted by the reaction
procedure described in example 3.
After heating for 20 hours as described in example 3, the
sample showed a sediment and had a turbiditjy of 1.5 TU/F.
The increase in the turbidity to 3.5 TU/F was observed after 20
days.
CLAIMS
1. A transparent heat protection element; having at least one
support element and at least one protective layer
comprising a reaction product containing aqueous alkali
metal silicate solution and aluminate- or borate-modified
silicon dioxide, characterized in that the reaction
product has a modulus of from 4 to 7.
2. The transparent heat protection element as claimed in
claim 1, characterized in that the silicon dioxide is
selected from the group consisting of silica sol,
precipitated silicon dioxide, silica gel and pyrogenic
silicon dioxide.
3. The transparent heat protection element as claimed in
claim 1 or 2, characterized in that the silicon dioxide is
silica sol.
4. The transparent heat protection element as claimed in at
least one of claims 1 to 3, characterized in that the
silicon dioxide has an aluminate or borate content of from
0.01 to 2.0% by weight, based on the total weight of the
SiO2 in the unmodified silicon dioxide.
5. The transparent heat protection element as claimed in
claim 4, characterized in that the silicon dioxide has an
aluminate or borate content of from 0.01 to 1.5% by
weight, preferably from 0.05 to 1.0% by weight, based on
the total weight of SiO2 in the unmodified silicon dioxide.
6. The transparent heat protection element as claimed in
claim 1, characterized in that the aqueous alkali metal
silicate solution is water glass.
7. The transparent heat protection element as claimed in at
least one of claims 1 to 6, characterized in that the
reaction product has a modulus of from 4.2 to 6.5.
8. The transparent heat protection elemeht as claimed in any
of claims 1-7, characterized in that the reaction product
additionally contains an agent for lowering the freezing
point.
9. The transparent heat protection element as claimed in at
least one of claims 1 to 8, characterized in that the heat
protection element is a fire protection composite glass.
10. The transparent heat protection element as claimed in at
least one of claims 1 to 9, characterized in that the
protective layer(s) is/are in each case located between at
least two support elements.
11. A process for producing a transparent heat protection
element as claimed in any of claims 1 to 10, characterized
in that the reaction product is introduced into a mold
cavity between two support elements or applied to a
support element, subsequently hardened to form a solid
silicate layer with retention of the water content and the
molar ratio of silicon dioxide to alkali metal oxides in
the hardened silicate is set to a ratio of from 4:1 to
7:1.
12. The process as claimed in claim 11, characterized in that
the surfaces of the support elements are pretreated with a
bonding agent in the form of an organofunctional silane
and/or wax dispersions.
13. The use of a reaction product containing aqueous alkali
metal silicate solution and aluminate- or borate-modified
silicon dioxide in at least one protective layer of a heat
protection element, characterized in that the reaction
product has a modulus of from 4 to 7.
14. The use as claimed in claim 13, characterized in that the
silicon dioxide is selected from the group consisting of
silica sol, precipitated silicon dioxide, silica gel and
pyrogenic silicon dioxide.
15. The use as claimed in claim 13 or 14, characterized in
that the modified silicon dioxide is silica sol.
16. The use as claimed in at least one of claims 13 to 15,
characterized in that the reaction product has a modulus
of from 4.2 to 6.5.
17. The use as claimed in at least one of claims 13 to 16,
characterized in that the silicon dioxide has an aluminate
or borate content of from 0.01 to 2.0% by weight, based on
the total weight of SiO2 in the unmodified silicon dioxide.
18. The use as claimed in claim 17, characterized in that the
silicon dioxide has an aluminate or birate content of from
0.01 to 1.5% by weight, preferably from 0.05 to 1.0% by
weight, based on the total weight of SiO2 in the unmodified
silicon dioxide.
19. The use as claimed in at least one of claims 13 to 18,
characterized in that the heat projection element is a
fire protection composite glass.
20. The use as claimed in at least one of claims 13 to 19,
characterized in that the protective layer(s) is/are in
each case located between at least two support elements.

The invention relates to a light-permeable heat-protection element comprising at least one support element and at
least one protective coating containing a reaction product which comprises an aqueous alkali silicate solution and aluminate-modified
or borate-modified silicon dioxide. The invention also relates to a method for producing said element.

Documents:

http://ipindiaonline.gov.in/patentsearch/GrantedSearch/viewdoc.aspx?id=9Q07tmeCmA/B6vJmzaTtFQ==&loc=wDBSZCsAt7zoiVrqcFJsRw==


Patent Number 280045
Indian Patent Application Number 3250/KOLNP/2010
PG Journal Number 06/2017
Publication Date 10-Feb-2017
Grant Date 08-Feb-2017
Date of Filing 02-Sep-2010
Name of Patentee VETROTECH SAINT-GOBAIN (INTERNATIONAL) AG
Applicant Address STAUFFACHERSTRASSE 128, CH-3000 BERN 22 SWITZERLAND
Inventors:
# Inventor's Name Inventor's Address
1 MELZER, HARTMUT WEBERSTR. 27, 40789 MONHEIM GERMANY
2 SCHWANKHAUS, NORBERT VON REUSCHENBURGSTRASSE 21, 52499 BAESWEILER GERMANY
3 GELDERIE, UDO BERGSTRASSE 33C, 52136 WÜRSELEN GERMANY
4 PANTKE, DIETRICH EISENHÜTTENSTR. 30, 40882 RATINGEN GERMANY
5 PUPPE, LOTHAR AM WEIHER 10A, 51399 BURSCHEID GERMANY
6 SCHMITZ, PETER-NIKOLAUS WUPPERSTR. 25A, 40764 LANGENFELD GERMANY
PCT International Classification Number C04B 28/26
PCT International Application Number PCT/CH2009/000080
PCT International Filing date 2009-02-26
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 354/08 2008-03-10 Switzerland