rexresearch.com
Sascha SCHWINDT
Spray-On Glass
http://www.nanopool.eu/en/core-competence/core-competence
Liquid Glass is probably the world’s most versatile
new technology ?
“SiO2- ultra thin layering” is the technical term for Liquid
Glass. Apart from a select group of professionals, few people in
the UK know about this stunning technology. If you walk around
Ataturk’s Mausoleum in Ankara you are walking on it; if you visit
certain hospitals in the UK you are touching it. If you see an
unusually clean train you are probably looking at it, and if you
wonder how your white settee looks so clean, you may be sitting on
it. All of these surfaces have been coated with invisible glass.
The flexible and breathable glass coating is approximately 100
nanometres thick (500 times thinner than a human hair), and so it
is completely undetectable. It is food safe, environmentally
friendly (winner of the Green Apple Award) and it can be applied
to almost any surface within seconds . When coated, all surfaces
become easy to clean and anti- microbially protected (Winner of
the NHS Smart Solutions Award ). Houses, cars, ovens, wedding
dress or any other protected surface become stain resistant and
can be easily cleaned with water ; no cleaning chemicals are
required. Amazingly a 30 second DIY application to a sink unit
will last for a year or years, depending on how often it is used.
But it does not stop there - the coatings are now also recognised
as being suitable for agricultural and in-vivo application. Vines
coated with SiO2 don’t suffer from mildew, and coated seeds grow
more rapidly without the need for anti-fungal chemicals. This will
result in farmers in enjoying massively increased yields . Trials
for in-vivo applications are subject to a degree of secrecy, but
Neil McClelland, the UK Project Manager for Nanopool GmbH,
describes the results as “stunning”.
“Items such as stents can be coated, and this will create anti
sticking features - catheters , and sutures which are a source of
infection, will also cease to be problematic.”
When asked about how the technology works, Neil, said “In essence,
we extract molecules of SiO2 (the primary constituent of glass)
from quartz sand, and then we add the molecules to water or
ethanol. Unfortunately, as they say in the movies , if I told you
any more …..”. Neil comments further, “The really clever part is
that there are no added nano-particles , resins or additives- the
coatings form and bond due to quantum forces. Our research informs
us that in all probability, we offer the most versatile coating in
the world. We are happy to hear about any other technology which
offers the same range of applications. Very soon almost every
product that you purchase will be protected with some form of easy
-to -clean coating. It just so happens that we offer something
that everyone finds fascinating . The concept of spray -on glass
is just mind -boggling”.
This technology is now available for domestic use in Germany. Full
scale retail availability in the UK will commence in early 2010
http://www.treehugger.com/files/2010/02/spray-on-liquid-glass-sio2-nanopool.php
Potentially Amazing Technology: Is Spray-On Liquid
Glass About to Make Everything Greener?
by
Michael Graham Richard
liquid-glass-nanopool-image-01.jpg
"The fissure was induced in order present an image which shows the
characteristics of the coating. The image shows the SiO2 coating
on a filament of a microfibre." Image: Nanopool
If it Works and is Safe, It Could
Change the World
A special coating technically known as "SiO2 ultra-thin layering",
but more memorably called "spray-on liquid glass", has been
invented in Turkey at the Saarbrücken Institute for New Materials
(the patent is owned by Nanopool). It is non-toxic promises to
"protect virtually any surface against almost any damage from
hazards such as water, UV radiation, dirt, heat, and bacterial
infections [...] the coating is also flexible and breathable,
which makes it suitable for use on an enormous array of products."
How Does it Work?
The details are still secret, but based on the information that is
available, it seems like a pretty simple process. They purify
silicon dioxide (SiO2, which is basically what you find in regular
glass) from quartz sand, add water or ethanol molecules, and then
through an unknown process are able to spray this on surfaces and
get a very thin film of glass (100 nanometers, or 15-30 molecules)
to stick. "The really clever part is that there are no added
nano-particles, resins or additives- the coatings form and bond
due to quantum forces." They also claim that it is very safe
(these is already a lot of these types of inert molecules out in
the wild, though I think it stills needs to be rigorously tested
for toxicity).
An Almost Unbelievable List of
Applications
Nanopool writes:
The flexible and breathable glass coating is approximately 100
nanometres thick (500 times thinner than a human hair), and so it
is completely undetectable. It is food safe, environmentally
friendly (winner of the Green Apple Award) and it can be applied
to almost any surface within seconds . When coated, all surfaces
become easy to clean and anti- microbially protected (Winner of
the NHS Smart Solutions Award ). Houses, cars, ovens, wedding
dress or any other protected surface become stain resistant and
can be easily cleaned with water ; no cleaning chemicals are
required. Amazingly a 30 second DIY application to a sink unit
will last for a year or years, depending on how often it is used.
But it does not stop there - the coatings are now also recognised
as being suitable for agricultural and in-vivo application. Vines
coated with SiO2 don't suffer from mildew, and coated seeds grow
more rapidly without the need for anti-fungal chemicals. This will
result in farmers in enjoying massively increased yields . Trials
for in-vivo applications are subject to a degree of secrecy, but
Neil McClelland, the UK Project Manager for Nanopool GmbH,
describes the results as "stunning". "Items such as stents can be
coated, and this will create anti sticking features - catheters ,
and sutures which are a source of infection, will also cease to be
problematic."
Physorg has a few more details: "Food processing companies in
Germany have already carried out trials of the spray, and found
sterile surfaces that usually needed to be cleaned with strong
bleach to keep them sterile needed only a hot water rinse if they
were coated with liquid glass. The levels of sterility were higher
for the glass-coated surfaces, and the surfaces remained sterile
for months. [...] A year-long trial of the spray in a Lancashire
hospital also produced "very promising" results for a range of
applications including coatings for equipment, medical implants,
catheters, sutures and bandages. The war graves association in the
UK is investigating using the spray to treat stone monuments and
grave stones, since trials have shown the coating protects against
weathering and graffiti. Trials in Turkey are testing the product
on monuments such as the Ataturk Mausoleum in Ankara. "
Promising, but Let's Wait and See
I'm still waiting for more tests (real-world and lab) before
getting too excited. But if it works as promised, this could be a
new super-material like graphene, with multiple applications in
tons of different fields. And if it really makes things more
durable and reduces or removes the need for strong chemicals to
clean something, it could have a pretty significant positive
environmental impact. But it could also have unforeseen effects,
so let's not rush to put this everywhere.
http://www.physorg.com/news184310039.html
Spray-on liquid glass is about to revolutionize
almost everything
February 2nd, 2010
The fissure was induced in order present an image which shows the
characteristics of the coating. The image shows the SiO2 coating
on a filament of a microfibre.
Spray-on liquid glass is transparent, non-toxic, and can protect
virtually any surface against almost any damage from hazards such
as water, UV radiation, dirt, heat, and bacterial infections. The
coating is also flexible and breathable, which makes it suitable
for use on an enormous array of products.
The liquid glass spray (technically termed “SiO2 ultra-thin
layering”) consists of almost pure silicon dioxide (silica, the
normal compound in glass) extracted from quartz sand. Water or
ethanol is added, depending on the type of surface to be coated.
There are no additives, and the nano-scale glass coating bonds to
the surface because of the quantum forces involved. According to
the manufacturers, liquid glass has a long-lasting antibacterial
effect because microbes landing on the surface cannot divide or
replicate easily.
Liquid glass was invented in Turkey and the patent is held by
Nanopool, a family-owned German company. Research on the product
was carried out at the Saarbrücken Institute for New Materials.
Nanopool is already in negotiations in the UK with a number of
companies and with the National Health Service, with a view to its
widespread adoption.
The liquid glass spray produces a water-resistant coating only
around 100 nanometers (15-30 molecules) thick. On this nanoscale
the glass is highly flexible and breathable. The coating is
environmentally harmless and non-toxic, and easy to clean using
only water or a simple wipe with a damp cloth. It repels bacteria,
water and dirt, and resists heat, UV light and even acids. UK
project manager with Nanopool, Neil McClelland, said soon almost
every product you purchase will be coated with liquid glass.
Food processing companies in Germany have already carried out
trials of the spray, and found sterile surfaces that usually
needed to be cleaned with strong bleach to keep them sterile
needed only a hot water rinse if they were coated with liquid
glass. The levels of sterility were higher for the glass-coated
surfaces, and the surfaces remained sterile for months.
Other organizations, such as a train company and a hotel chain in
the UK, and a hamburger chain in Germany, are also testing liquid
glass for a wide range of uses. A year-long trial of the spray in
a Lancashire hospital also produced “very promising” results for a
range of applications including coatings for equipment, medical
implants, catheters, sutures and bandages. The war graves
association in the UK is investigating using the spray to treat
stone monuments and grave stones, since trials have shown the
coating protects against weathering and graffiti. Trials in Turkey
are testing the product on monuments such as the Ataturk Mausoleum
in Ankara.
The liquid glass coating is breathable, which means it can be used
on plants and seeds. Trials in vineyards have found spraying vines
increases their resistance to fungal diseases, while other tests
have shown sprayed seeds germinate and grow faster than untreated
seeds, and coated wood is not attacked by termites. Other vineyard
applications include coating corks with liquid glass to prevent
“corking” and contamination of wine. The spray cannot be seen by
the naked eye, which means it could also be used to treat clothing
and other materials to make them stain-resistant. McClelland said
you can “pour a bottle of wine over an expensive silk shirt and it
will come right off”.
In the home, spray-on glass would eliminate the need for scrubbing
and make most cleaning products obsolete. Since it is available in
both water-based and alcohol-based solutions, it can be used in
the oven, in bathrooms, tiles, sinks, and almost every other
surface in the home, and one spray is said to last a year.
Liquid glass spray is perhaps the most important nanotechnology
product to emerge to date. It will be available in DIY stores in
Britain soon, with prices starting at around £5 ($8 US). Other
outlets, such as many supermarkets, may be unwilling to stock the
products because they make enormous profits from cleaning products
that need to be replaced regularly, and liquid glass would make
virtually all of them obsolete.
http://www.nanopool.eu/en/downloads
Videos
http://uk.reuters.com/news/video?videoId=47835540
http://svtplay.se/v/1909578/rapport/flytande_glas_skyddar_omtaliga_ytor
http://www.nanopool.eu/images/stories/Nanopool_EN.WMV
http://www.nanopool.eu/images/stories/NEXPT_klein.wmv
http://www.nanopool.eu/images/stories/NP_KORK_DT.wmv
http://www.56.com/u80/v_NDk3MzkwNzc.html
Nanopool GmbH
http://www.nanopool.eu
Zum Felsacker 76
D - 66773 Hülzweiler
phone: +49 (0) 6831 - 890 2712
fax: +49 (0) 6831 - 890 2715
E-Mail: presse@nanopool.eu
DE102007034724
[0001] The invention relates to a method for preparing a
composition, is dispersed in an aqueous solution in which at
least one gel-forming substance. The invention also relates to
a composition, in particular for coating surfaces, which
consists at least from an aqueous solution and at least one
gel-forming substance.
[0002] Sol-gel processes are wet processes, which are for
example the deposition of homogeneous, nano-crystalline
ceramic oxide coatings or keramischorganischer used. The
special feature of sol-gel process is that the production of
coating each of a liquid sol state proceeds, which is
converted by a sol-gel transformation into a solid gel
state.As brine dispersions of solid particles in the size
range be used between 1 nm to 100 nm, which are dispersed in
water or organic solvents. Sol-gel process usually go out of
brines based on organometallic polymers. The transition from a
liquid sol is then used for coating each of the gel state,
where there is a three-dimensional network of nanoparticles in
the solvent, so that the gel is replaced by solid state
properties.The transfer of the gel into a solid oxide coating
is controlled by a heat treatment in air.
[0003] Sol-gel coatings influence the properties of surfaces.
Depending on the nature of the brine and its impurities, hard
and scratch-resistant surfaces are generated by such a
coating. Sol-gel coatings can be performed on metals, glasses,
synthetic and natural polymers.There exist in this area a
number of patents and publications, both of which are only
mentioned a few examples (HK Schmidt, Organically modified
silicates as inorganic-organic polymers, RM Laine (Ed.),
Inorganic and Organometallic Polymers with special properties,
297-317 , 1992 Kluwer Academic Publishers, Netherlands; CJ
Brinker and G. Scherer, Sol-Gel Science. The Physics and
Chemistry of Sol-Gel Processing, Academic Press, Boston, MA
(1990); H. Böttcher, K.-H.Kallies, T. Textor, E. Schollmeyer,
T. Bahners, DE 197 56 906 A (1999); H. Böttcher, J. Trepte,
K.-H. Kallies, DE 19839292 (2000).
[0004] The simultaneous hydrolysis of inorganic salts and
organic silanes gives coatings with an adjustable flexibility
to each other depending on the ratio of the inorganic and
organic components (T. Textor, D. Knittel, T. Bahners,
E.Schollmeyer, Inorganic-organic hybrid polymers for coating
textile materials, Current Trends in Polymer Science, Vol 8,
2003, page 127-133).
[0005] The chemical compounds that are capable of volatile and
other organic compounds bind to, are known cyclodextrins.
These are macrocyclic molecules, which are constructed from
six, seven or eight [alpha]-D-glucose units. There are
ring-shaped molecules that possess a hydrophobic cavity.In
this cavity a number of organic molecules is deposited. This
changes the physical and chemical properties of the embedded
molecules. The embedded molecules possess, for example,
compared to the free molecules, a much lower vapor pressure
and an improved stability against degradation by light or
oxygen. For this reason, cyclodextrins have been used for many
years in the field of cosmetics and pharmaceuticals
(J.Szejtli, Cyclodextrin Technology, Kluwer, Dordrecht, 1988).
[0006] A permanent fixation of cyclodextrins on various
textile materials is known (for BH-J Buschmann, D. Knittel, E.
Schollmeyer, DE 4036328;. DE 40 35 378 A and DE 100 60 710 A).
The binding of the cyclodextrins by chemical bonds or physical
interactions, so that their removal by washing processes is
not possible.
[0007] The removal of odors andthe fragrance of textile
materials with the aid of cyclodextrins or cyclodextrin
derivatives is also known (eg, T. Trinh, JM Gardlik, TJ Banks
and F. Benvegnu U.S. 5,094,761, JM Gardlik, T. Trinh, TJ Banks
and F. Benvegnu 5.23461 million U.S., T . Trinh, JM Gardlik,
TJ Banks and F. Benvegnu EP 0392607 and JM Gardlik, T. Trinh,
TJ Banks and F. Benvegnu, EP-A-0 392 606).The used
cyclodextrins have no affinity for the fiber material so that
they do not adhere to the textile materials.
[0008] The adsorptive accumulation of cyclodextrins with
substituted polyethylene glycols of various materials, such as
hair and textile materials is well known (A. Schmidt, O.
Lammerschop and H. Küster, DE 103 44 967 A). These
cyclodextrin derivatives can partlybe a normal household
washing process removed from the surface of materials.
[0009] The object of the invention to provide cyclodextrins
for sol-gel process and available to provide an improved
method and an alternative composition for coating surfaces.
[0010] This object is inventively achieved by a method for
preparing a composition of the aforementioned kind in which
the dispersion is at least one cyclodextrin added.
[0011] In an advantageous embodiment of the inventive method
provides that the cyclodextrin at a final concentration of 0.1
to 20 wt -%, preferably 0.1 to 15 wt -%, more preferably 0.1
to 10 wt -%, especially 0.1 to 5 wt-% Is added.
[0012] In an alternative advantageous embodiment of the
inventive method provides that the cyclodextrin derivative in
a final concentration of 1 to 20 wt -%, preferably 5 to 20 wt
-%, preferably 10 to 20 wt -%, especially 15 to 20 weight -%
is added.
[0013] In an alternative advantageous embodiment of the
inventive method provides that the cyclodextrin at a final
concentration of 0.1 to 15 wt-%, Preferably 5 to 10 wt -%,
particularly preferably from 1 to 5 wt -%, especially 2 to 4
wt -% is added.
[0014] According to the invention it is particularly
advantageous when the partially methylated cyclodextrin
[beta]-cyclodextrin and / or hydroxypropyl-[beta]-cyclodextrin
is added to /.
[0015] Here, the cyclodextrin in the dispersion may be
dissolved or dispersed.
[0016] To cyclodextrins for use in a sol-gel method to make
use of, d.h. the cyclodextrins to embed in a coating is
advantageously provided that a cyclodextrin is prepared by
reacting with polyvinylamines, polyethyleneimines
aminosiloxanes, alkylamines with 3 to 12 carbon atoms in the
alkyl group, chitosan, polyvinyl alcohols and / or
Perfluoroalkylaminen.
[0017] The novel cyclodextrin derivatives can be fixed in the
coating, such as a silicon oxide coating, by their
substituents, which act almost as anchor molecules. Due to the
inventive derivatization or modification of cyclodextrins is
also advantageously able to handle these useful materials in a
sol-gel process and permanently integrate into an ultra-thin
coating.
[0018] In a further advantageous embodiment of the inventive
method is provided that can be stored in the
Cyclodextrinderivatmoleküle organic substances. It may be, for
example to insecticides, fungicides, biostatic or biocidal
agents, fragrances and / or therapeutic agents.
[0019] In an advantageous embodiment of the inventive method
is further provided that is dispersed as a gel-forming
material at least one metal oxide or a mixture of metal oxides
in aqueous solution, preferably SiO2, Al2O3, ZrO2, TiO2 and /
or R VerSiOn with R = H , alkyl, aryl, epoxy-alkyl,
aminoalkyl, and n = 1.5 or 1
[0020] According to the invention the object is also achieved
by following the methods described above prepared
composition.Such a composition is advantageously used for
coating surfaces in a sol-gel method.
[0021] The object is further achieved by a composition of the
type that includes at least one cyclodextrin. Such a
composition is also advantageously used for coating surfaces
in a sol-gel method.
[0022] In an advantageous embodiment of the inventive
composition is provided that the cyclodextrin at a final
concentration of 0.1 to 20 wt -%, preferably 0.1 to 15 wt -%,
more preferably 0.1 to 10 wt -%, especially 0.1 to 5 wt -% is
included.
[0023] In an alternative embodiment of the inventive
composition is provided that the cyclodextrin derivative in a
final concentration of 1 to 20 wt-%, Preferably 5 to 20 wt -%,
preferably 10 to 20 wt -%, especially 15 to 20 wt -% is
included.
[0024] In an alternative embodiment of the inventive
composition is provided that the cyclodextrin at a final
concentration of 0.1 to 15 wt -%, preferably 5 to 10 wt -%,
particularly preferably from 1 to 5 wt -%, especially 2 to 4
weight -% is included.
[0025] Preferably, the cyclodextrin derivative according to
the invention a partially methylated [beta]-cyclodextrin or
hydroxypropyl-[beta]-cyclodextrin.
[0026] In an advantageous manner can be stored more organic
substances in the novel cyclodextrin derivative, preferably
insecticides, fungicides, biostatic or biocidal agents,
fragrances and / or therapeutic agents.As therapeutic agents,
for example, anti-inflammatory and / or wound-healing agents.
[0027] In an advantageous embodiment of the inventions
according to the composition is further provided that the
gel-forming substance is at least one metal oxide or a mixture
of metal oxides, preferably SiO2, Al2O3, ZrO2, TiO2 and / or R
VerSiOn with R = H, alkyl, aryl , epoxy-alkyl, aminoalkyl, and
n = 1.5 or 1
[0028] The invention also relates to a method for coating
surfaces, in which a sol is applied from an aqueous solution,
at least one gel-forming substance and at least one
cyclodextrin derivative to a surface and then dried. This
method is particularly advantageous when the coating is at
least partly from the composition of the invention is or has
been made of this.The cyclodextrin derivatives according to
the invention are derivatized so that they can be processed in
a sol-gel process and permanently incorporated into a coating
produced in this process.
[0029] Preferably the sol is sprayed onto either the surface
or the surface immersed in the sol. In both cases,
advantageously produces an ultra-thin coating that uniformly
covers the so-coated article.
[0030] The sol can be applied for example to a textile
material, a nonwoven fabric made of natural or synthetic
polymers or mixtures of these polymers. Alternatively, the sol
can also be applied to an inorganic fiber material, preferably
glass fibers, carbon fibers and / or ceramic fibers, or
metallic, ceramic, glass-like and / or cellulosic materials.In
a particularly preferred embodiment of the invention, the sol
also on plastics or plastic-like materials are applied.
[0031] The inventive composition is particularly suitable for
coating of textile materials and / or leather, preferably
clothing, shoes, diapers, wound dressings or office equipment,
interior trim and other interior fittings of motor vehicles,
trains and airplanes.In these applications, in particular, the
odor-binding properties of the composition and the ability to
store active substances in the cyclodextrin advantage of
[0032] Also advantageous is the use of the composition for
coating plastics, preferably sanitation or interior trim and
other interior fittings of motor vehicles, trains and
airplanes.Examples are toilet lids and seats and plastic
components in motor vehicles, the latter being bound in a
coated form not only smell, but no self-interference, due to
production have more odor. Is also particularly advantageous
to coat the plastic housings of mobile phones with coatings
that are embedded in the antimicrobial substances and / or
fragrances.
[0033] The invention also includes any object with a nonstick
surface, which was prepared by the method of the invention and
/ or in which the coated surface comprises the composition of
the invention.
[0034] The invention relates for example, ultra-thin coatings
that are produced by a sol-gel process and have the addition
to the known properties still an odor-reducing
properties.Likewise, a storage of insecticides, fungicides or
other agents into the possible in the sol-gel coating located
Cyclodetrinderivate. The embedding of the active ingredients
in the cyclodextrin their stability to degradation by exposure
to light and oxygen is greatly increased. For drugs that have
a higher vapor pressure, evaporation is prevented by the
incorporation in the cavities of the cyclodextrin.
[0035] According to the invention has been shown that some of
cyclodextrin so in a sol-gel matrix can be stored, that the
cavities of the cyclodextrins remain still accessible. This
can produce sol-gel coatings that have both a protective
layer, or another functional layer formed on the surfaces of
textile materials, woven fabrics, glass fibers, metals,
ceramics or wood and have the same odor-reducing properties.In
addition, a variety of organic compounds are incorporated into
the cyclodextrins, which are released only by moisture and get
back to the surface of the coating.
[0036] Known brine based on pure aqueous solutions or mixtures
of water and alcohols. It can be used preferably metal oxide
xerogels of SiO 2, R VerSiOn, Al2O3, ZrO2, TiO2 or mixtures
thereof, where R = H, alkyl, aryl, epoxy-alkyl, aminoalkyl,
and can be n = 1.5 or 1.As unsuitable for incorporation into
the starting sols has been shown [beta]-cyclodextrin. Its
solubility in the brine is too low. Sols in alcoholic form
[alpha] -, [beta] - and [gamma]-cyclodextrin precipitation.
Such solutions are not suitable for the sol-gel process.
[0037] The invention therefore relates to the production
example, cyclodextrin-salt, which can be in a conventional
sol-gel process as thin or very thin coating is applied
uniformly to different materials.
[0038] The invention also relates, for example brine
containing 0.1 weight -% contained, a cyclodextrin derivative
-% to 10 wt -%, preferably 1 wt -% to 5 wt.These solutions can
be applied both in a dipping process as well as by spraying
onto the desired substrate. After drying, a coating has formed
on the basis of polymerized SiO2.
[0039] are in principle the following cyclodextrin derivatives
for incorporation in the composition of the invention:
partially methylated [beta]-Cyclodextrin (CAVASOL <(R)>
W7 M, Wacker-Chemie) and hydroxypropyl-[beta]-Cyclodextrin
(CAVASOL <(R) > W7 HP, Wacker-Chemie).Starting with a
cyclodextrin derivative with a reactive group, such as
monochlortriazinsubstituiertes [beta]-cyclodextrin (CAVATEX
W7MCT, Wacker Chemie GmbH, Burghausen) or other cyclodextrin
derivative with a reactive group (A. Schmidt, H.-J. Buschmann,
E . Schollmeyer, DE 101 55 781 A) or the reaction product of
acrylic acid or an acrylic acid derivative with an
unsubstituted cyclodextrin, for example, thispolyvinylamine
(ZD1168/69-3, BASF, Ludwigshafen, Germany), polyethylenimine
(Chemos GmbH), amino siloxane (DMS-A12, ABCR), alkylamines
(Merck), dialkyl amines (Fluka), chitosan (Sigma-Aldrich),
polyvinyl alcohol (Fluka) , Perfluoralkylamin
(Perfluorononylamin, Fluka), amino acids such as glycine
(Fluka), implemented. Among cyclodextrins [alpha] are - to
understand and [gamma]-cyclodextrin -, [beta]. The
above-mentioned reactive derivatives formed, for exampleby
reaction of [alpha] -, [beta] - and [gamma]-cyclodextrin with
cyanuric chloride and acrylic acid or acrylic acid
derivatives.
[0040] The reaction products are water-soluble cyclodextrin
derivatives mentioned above can be added to the sol as a
concentrated solution or as a pure substance. After a
homogeneous solution is formed, it can go no further
preparations for the application.Of the non-water-soluble
cyclodextrin derivatives, is produced using ultrasound, a
dispersion. This is mixed with the corresponding sol and
applied to a homogenisation of the surface to be equipped.
[0041] The inventive method has the advantage that the sol-gel
process is combined with equipment to adsorb odors and other
organic substances.Through the use of cyclodextrin derivatives
described the effect of odor control is permanent. These
cyclodextrin derivatives are anchored by their substituents at
the silicon oxide coating. On the other hand, the
accessibility of the cyclodextrin cavities is guaranteed,
leaving the complex-forming properties of the cyclodextrins.
[0042] The cyclodextrin-salt can be applied to metallic and
ceramic surfaces by a dipping or spraying. After drying, a
thin layer has formed on the surface that is mechanically
stable against external influences.
[0043] The cyclodextrin composition is also suitable for the
impregnation of porous inorganic materials.By immersion of
these materials into suitable brine, they reach into all the
pores by capillary forces. After centrifugation, excess sol
from the pores are removed. After drying, the surfaces of the
pores are coated by the sol, the pores of the material has
been preserved.
[0044] Natural materials such as wood and paper can be
impregnated by dipping into the corresponding
cyclodextrin-Sole.In this cause the brine one
hydrophobicisation the surface. In addition, the cyclodextrins
can be chemical agents against pests are stored. This leads to
an improved wood preservation.
[0045] Insulating materials that are made from mineral or
natural fiber materials can be impregnated by immersion in a
brine cyclodextrin. After drying, the cyclodextrin cavities
with organic substances, such asInsecticides and fungicides
are loaded. By coating with the sol, the combustibility of the
insulating material is reduced from natural fiber materials.
The loading of the cyclodextrins with insecticides and / or
fungicides reduce the pest infestation and / or infestation by
fungi. Another advantage is that do not evaporate at high
temperatures, the active ingredients from the cyclodextrin
cavities.This ensures that occurs does not pollute the air by
these substances.
[0046] Flexible materials such as films, nonwovens and textile
fabrics, can be fitted by spraying or by a dipping process
with the cyclodextrin-sols. Depending on the amount of the sol
is applied to the flexible structure of the material received.
The sol in fixed cyclodextrins are able to store chemical
substances from the air. They may, for example by sprayingAs
with perfumes and other fragrances are loaded.
[0047] A load of other organic substances such as
insecticides, fungicides, bactericide or biostatically acting
substances or pharmaceutical active substances is possible. By
deposition of insecticides and fungicides, for example, a
parasitic infestation of the materials is prevented.
[0048] After the finishing of nonwovens and / or textile
fabrics with cyclodextrin brines can be loaded onto the
cyclodextrin derivatives with pharmaceutical and / or cosmetic
agents. Come such a finished textile materials in contact with
human skin, so the stored substances are released by the
moisture on the skin surface of the skin.The sol-gel coating
prevents their hydrophobic properties, the growth of skin
cells, if such fabrics are used as wound dressings. By the
release of substances that have been stored in the
cyclodextrins, the healing process of wounds is accelerated.
[0049] The embedding of the cyclodextrin derivatives in a
sol-gel coating ensures that the cyclodextrins can be removed
by washing processes or similar processes from the surface of
the treated materials. It is therefore considered a permanent
modification of the surface of the corresponding materials.
[0050] The invention is further illustrated by the following
embodiments as an example.
Example 1
[0051] To a mixture of 50 ml of tetraethoxysilane, 15 ml of
3-glycidyloxypropyltrimethoxysilane and 40 ml of ethanol are
added 10 ml of 0.01 N HCl and stirred at room temperature for
10 hours. Then 20 ml of a 10 wt -% solution added to the
polyvinylaminsubstituierten cyclodextrin and stirred an
additional hour. The result is a water-clear sol. To this sol,
a 10 wt -% solution of ZrOCl 2 * 8H2O in 50 weight -% ethanol
added.This sol is applied to a polypropylene film and dried.
[0052] By applying a drop of an alkaline phenolphthalein
solution on the surface, the accessibility of the cavity of
[beta]-cyclodextrin can be detected. They observed a
discoloration of the drop, which occurs only in the presence
of cyclodextrin (K. Beermann, H.-J. Buschmann, D. Knittel,
E.Schollmeyer, methods of determination of cyclodextrins in
textile materials, textile finishing, 37 (2002) 17).
Example 2
[0053] To a mixture of 30 ml of tetraethoxysilane,
diethoxysilane dimethyl-30 ml, 20 ml of
3-glycidyloxypropyltrimethoxysilane, 60 ml of ethanol are
added dropwise 15 ml of 0.01 N HCl in 50 ml ethanol and
stirred at room temperature for 10 hours. Then 20 ml of a 15
wt -% solution added to the polyethyleniminsubstituierten
cyclodextrin and stirred an additional hour.The result is a
water-clear sol. % Ethanol added - to this sol, a solution of
10 wt -% Al 2 (OH) 2-3H2O in 5Cl * 90 wt. The resulting sol is
using a padding applied to a wool fabric (wet pickup 80 weight
-%) and the tissue dried.
[0054] The proof is the accessibility of the cyclodextrin
cavities with an alkaline phenolphthalein.
Example 3
[0055] To a mixture of 70 ml of tetraethoxysilane, 30 ml of
methyl triethoxysilane, 400 ml of ethanol are added 20 ml of
0.01 N HCl in portions and [deg.] Stirred at 25 C for several
hours. To this sol after which a solution of 10 weight -% Al 2
(OH) 2-3H2O in 5Cl * 80 weight -% ethanol and 30 ml of an
aqueous dispersion (20 wt -%) added to the
aminosiloxansubstituierten cyclodextrin.The resulting
dispersion is applied to a cotton fabric using a sprayer and
dried.
[0056] The proof is the accessibility of the cyclodextrin
cavities with an alkaline phenolphthalein.
Example 4
[0057] To a mixture of 30 ml of tetraethoxysilane,
diethoxysilane dimethyl-30 ml, 20 ml of
3-glycidyloxypropyltrimethoxysilane, 60 ml of ethanol are
added dropwise 15 ml of 0.01 N HCl in 50 ml ethanol and
stirred at room temperature for 10 hours. Then 20 ml of a 15
wt -% solution added to the partially methylated
[beta]-cyclodextrin and stirred an additional hour. The result
is a water-clear sol. To this sol, a solution of 10 weight -%
Al 2 (OH) 2-3H2O * 5Cl in 90 wt- Added% ethanol. By dipping a
piece of wood in the resulting sol is impregnated them. After
drying, the piece of wood at room temperature, the sample is
sprayed with a Permethrinlösung in acetone. After drying, the
wood is dipped briefly in acetone to remove adsorbed
permethrin. Evidence of complex formation of cyclodextrin with
permethrin is done by an aqueous extraction of the wood
piece.In the extract permethrin by GC-MS analysis is proven.
QUOTES INCLUDED IN THE
DESCRIPTION
[0058] This list of documents cited by the applicant was
automatically generated and is included solely to better
inform the reader. The list is not part of the German patent
or utility model application. The DPMA is not liable for any
errors or omissions.
Patent literature cited
[0059]
- DE 19756906 A [0003]
- DE 19839292 [0003]
- DE 4036328 [0006]
- DE 4035378 A [0006]
- DE 10060710 A [0006]
- U.S. 5094761 [0007]
- U.S. 5234610 [0007]
- EP 0392607 [0007]
- EP 0392606 A [0007]
- DE 10344967 A [0008]
- DE 10155781 A [0039]
Non-patent literature cited
[0060]
- HK Schmidt, Organically modified silicates as
inorganic-organic polymers, RM Laine (Ed.) Inorganic and
Organometallic Polymers with special properties, 297-317, 1992
Kluwer Academic Publishers, Netherlands [0003]
- CJ Brinker and G. Scherer, Sol-Gel Science: The Physics and
Chemistry of Sol-Gel Processing. Academic Press, Boston, MA
(1990) [0003]
- T. Textor, D. Knittel, T. Bahners, E. Schollmeyer,
Inorganic-organic hybrid polymers for coating textile
materials, Current Trends in Polymer Science, Vol 8, 2003,
Page 127-133 [0004]
- J.Szejtli, Cyclodextrin Technology, Kluwer, Dordrecht, 1988
[0005]
- K. Beermann, H.-J. Buschmann, D. Knittel, E. Schollmeyer,
methods of determination of cyclodextrins in textile
materials, textile finishing, 37 (2002) 17 [0052]
WO 2009033635
SOL-GEL COATING OF SUBSTRATE
MATERIAL SURFACES WITH ODOR-ABSORBING PROPERTIES
The invention relates to sol-gel
coatings, which additionally has known about the properties
still an odor-reducing properties. Likewise, a storage of
insecticides, fungicides or other agents in the in the sol-gel
coating located cyclodextrins possible.The embedding of the
active ingredients in the cyclodextrins their stability to
degradation by exposure to light and oxygen is greatly
increased. For drugs that have a higher vapor pressure,
evaporation is prevented by the incorporation in the cavities
of the cyclodextrins.
The production and application of sol-gel coatings on
different materials is discussed below.
Sol-gel coatings influence the properties of surfaces.
Depending on the nature of the brine and its impurities, hard
and scratch-resistant surfaces are generated by such a
coating. Sol-gel coatings can be performed on metals, glasses,
synthetic and natural polymers. There exist in this field a
number of patents and publications, both of which are only
mentioned a few examples (HKSchmidt, Organically modified
silicates as inorganic-organic polymers, RM Laine (Ed.),
Inorganic and Organometallic Polymers with special properties,
297 - 317, 1992 Kluwer Academic Publishers, Netherlands; CJ
Brinker and G. Scherer, Sol-gel Science: The Physics and
Chemistry of Sol-Gel Processing. Academic Press, Boston, MA
(1990); H. Böttcher, K.-H. Kaili, T. Textor, E. Schollmeyer,
T. Bahners, DE 19756906 (1999); H. Böttcher, J. Trepte, K.-H.
Kaili, DE 19839292 (2000).By the simultaneous hydrolysis of
inorganic salts and organic silanes gives coatings with an
adjustable flexibility to each other depending on the ratio of
the inorganic and organic components (T. Textor, D. Knittel,
T. Bahners, E. Schollmeyer, Inorganic-organic hybrid polymers
for coating textile materials, Current Trends in Polymer
Science, Vol.8, 2003, Page 127-133;. Bahners T., T. Textor,
E.Schollmeyer, Surface functionalization of textile fibers
with reactive silanes, in KL Mittal (Ed.), Silanes and Other
Coupling Agents, Vol 4 "s. 141-152, VSP, Leiden (2007)).
Coatings by the sol-gel method with a deodorizing effect can
be produced by the installation of catalytic additives (T.
Benthien, P. Faber, G. Jonschker, p. Sepeur, H. Schmidt, P.
Stossel, DE 19,915,377 (1999)).These catalysts are able to
decompose organic substances at high temperatures.
As chemical compounds that are able to bind and other volatile
organic compounds, cyclodextrins are known. These are
macrocyclic molecules, which are constructed from six, seven
or eight [alpha]-D-glucose units. There are ring-shaped
molecules that possess a hydrophobic cavity. In this cavity a
number of organic molecules is deposited.This changes the
physical and chemical properties of the embedded molecules.
The embedded molecules possess as compared to the free
molecules, a much lower vapor pressure and an improved
stability against degradation by light or oxygen. For this
reason, cyclodextrins have been used for many years in the
field of cosmetics and pharmaceuticals (J. Szejtli,
Cyclodextrin Technology, Kluwer, Dordrecht, 1988).
Permanent fixation of cyclodextrins on various textile
materials is known (eg H.-J. Buschmann, D. Knittel, E.
Schollmeyer, DE 4036328 and DE 4035378 and DE 10.06071
million). The binding of the cyclodextrins by chemical bonds
or physical interactions, so that their removal by washing
processes is not possible.
The removal of odor or fragrance of textile materials with the
aid of cyclodextrins orCyclodextrin is also known (eg, T.
Trinh, JM Gardlik, TJ. Benvegnu F. Banks and U.S. 5,094,761,
JM Gardlik, T. Trinh, TJ. Benvegnu F. Banks and 5.23461
million U.S., Trinh T., JM Gardlik, TJ. Banks and F. Benvegnu
EP 0392607 and JM Gardlik, T. Trinh, TJ. Benvegnu F. Banks and
EP 0392606). The used cyclodextrins have no affinity for the
fiber material so that they do not adhere to the textile
materials.
Adsorptive accumulation of cyclodextrins with substituted
polyethylene glycols of various materials, such as hair and
textile materials is well known (A. Schmidt, O. and H. Küster
Lammerschop DE 10,344,967). These cyclodextrin derivatives can
be partly through normal household washing process removed
from the surface of materials.
The use of cyclodextrins in the preparation of sol-gel
coatings is described in the literature on principle.Thus, the
embedding of native [alpha] -, ss-and [gamma]-cyclodextrins
described in a matrix of amorphous silicon dioxide (F.
Mizukami, M. Toba and S. Niwa U.S. 4,781,858 (1988) The
embedding of the cyclodextrins. the matrix improves the
thermal stability of cyclodextrins. coatings by the sol-gel
method can also include cyclodextrins, which act as carriers
for active ingredients (M. Dreja, W. Rybinski of DE 10,126,966
(2001)).Here, the drug-loaded cyclodextrins are already used
in the manufacture of coatings. These agents can be
re-released from the cyclodextrin cavities. It is, however,
described no release mechanism. According to current
knowledge, one must assume, however, assume that the described
in the application of the matrix, drying the water molecules
are removed almost quantitatively.Small amounts of water are
required to produce drugs and other substances such as
perfumes, from the cyclodextrin cavities release (J. Szejtli,
Cyclodextrin Technology, Kluwer (1988), pages 188-190).
According to the invention has been shown that some of
cyclodextrin derivatives, egwith one or two substituents such
as polyvinyl amine, polyallylamine, polyethyleneimine,
polyethylene glycol and polyvinyl alcohols so in a sol-gel
matrix can be stored, that the cavities of the cyclodextrins
remain still accessible.These substituted cyclodextrins are
almost infinitely soluble in water or aqueous alcoholic
solutions, so that the disadvantages of low solubility of
ss-cyclodextrin in water and the native cyclodextrins ([alpha]
-, ss-and [gamma]-CD) in aqueous alcoholic solutions no longer
exist.It is possible to produce coatings, sol-gel, both a
protective layer or other functional layer formed on the
surfaces of textile materials, woven fabrics, glass fibers,
metals, wood or wood-like products such as paper, cardboard,
etc., leather or ceramics and have the same odor-reducing
properties . The coatings are formed even at room temperature.
A thermal treatment at temperatures above 40 [deg.] C is not
required, which allows the use even in very thermally
sensitive materials. Since the coatings formed are porous, can
subsequently a variety of organic compounds in the
cyclodextrins are stored, which are released only by moisture
and then get back onto the surface of the coating.Since the
accessibility of the cyclodextrin cavities in the sol-gel
coatings is given, the cyclodextrins in the matrix chemical
compounds bind in the air. Thus, the coating has an
odor-reducing properties. By treatment with an aqueous
solution can remove all the odor molecules from the
cyclodextrin, whereby the odor-reducing effect of the coating
with the cyclodextrin is restored.
Since the charge of cyclodextrins after formation of the
sol-gel coating is applied, is an influence of the sol-gel
process through the use of cyclodextrin avoided. In aqueous
and aqueous ethanolic solutions dissociate the cyclodextrin
used, so that by the previously may be adversely affected in
the cyclodextrins bound substances and active ingredients of
the sol-gel process.This drawback is not with the approach
described in this application given.
The used cyclodextrin derivatives have an effect biostatic.
Therefore, the use of additional chemical substances are not
required to obtain a biostatic or biocidal effect of the
coating. This makes it possible to produce sol-gel coatings,
which have simultaneously a biostatic or biocidal and an
odor-reducing effect.Known brine based on pure aqueous
solutions or mixtures of water and alcohols. Here are
preferably made of Si metal-oxide xerogels [theta] 2, R-SiON,
Al2O3, ZrO2, Ti [theta] 2 [theta] using the mixtures thereof,
where R = H, alkyl, aryl, epoxy-alkyl, aminoalkyl, and n can
be 1, 5 or 1. As unsuitable for incorporation into the
starting sols has proven ss-cyclodextrin. Its solubility in
the brine is too low.Sols in alcoholic form [alpha] -, ss-and
[gamma]-cyclodextrin precipitation. Such solutions are not
suitable for the sol-gel process.
The invention therefore relates to the provision of a coating
on a substrate, which is produced by the sol-gel method from a
cyclodextrin and brine can be as thin or very thin coating is
applied uniformly to different materials.
This problem is solved by a cyclodextrin-salt, are used in the
specific cyclodextrin in a special weight percent interval in
which the cyclodextrin is dissolved in the sol or dispersion.
The invention therefore relates to a coating of a substrate by
the sol-gel process by cyclodextrin-salt, which is
characterized in that the 0.1 wt -% to 10 wt-% Containing a
cyclodextrin derivative that is dissolved or dispersed in the
sol.
These solutions / dispersions can be applied either in an
immersion process and by spraying or similar methods to the
desired substrate. After drying, a coating has formed on the
basis of polymerized SiO2.
According to a preferred embodiment, the coating is
characterized in that the cyclodextrin derivatives are
prepared by reaction with polyvinylamine, polyallylamine,
polyethyleneimine, aminosiloxanes, alkylamines with 3 to 12
carbon atoms in the alkyl group, chitosan, polyvinyl alcohols
and / or Perfluoroalkylamine.In principle, the following
cyclodextrin derivatives suitable for incorporation in brine:
partially methylated ss-cyclodextrin (CAVASOL (R) W7 M,
Wacker-Chemie) and hydroxypropyl-ss-cyclodextrin (CAVASOL (R)
W7 HP, Wacker-Chemie). Starting with a cyclodextrin derivative
with a reactive group, such as monochlortriazinsubstituiertes
ss-cyclodextrin (CAVATEX W7MCT, Wacker Chemie GmbH,
Burghausen) or other cyclodextrin derivative with a reactive
group (A. Schmidt, H.-J. Buschmann, E.Schollmeyer, DE
10155781) or the reaction product of acrylic acid or an
acrylic acid derivative with an unsubstituted cyclodextrin, is
this example, with polyvinyl (ZD1168/69-3, BASF, Ludwigshafen,
Germany), polyethylenimine (Chemos GmbH), amino siloxane
(DMS-A12, ABCR) , alkylamines (Merck), dialkyl amines (Fluka),
chitosan (Sigma-Aldrich), polyvinyl alcohol (Fluka),
Perfluoralkylamin (Perfluorononylamin, Fluka), amino acids
such as glycine (Fluka), implemented.Among cyclodextrins
[alpha] are - to understand, and ss-[gamma]-cyclodextrin. The
above-mentioned reactive derivatives are formed for example by
reaction of [alpha] -, ss-and yCyclodextrin with cyanuric
chloride and acrylic acid or acrylic acid derivatives.
The reaction products are water-soluble cyclodextrin
derivatives mentioned above can be added to the sol as a
concentrated solution or as a pure substance.After a
homogeneous solution is formed, it can go no further
preparations for the application. Of the non-water-soluble
cyclodextrin derivatives, is produced using ultrasound, a
dispersion. This is mixed with the corresponding sol, and
applied to a homogenisation of the surface to be equipped.
The erf [iota] ndungsmässe advantage of the described coating
or finish is that the sol-gel process is combined with
equipment to adsorb odors and other organic substances.
Through the use of cyclodextrin derivatives described the
effect of odor control is permanent. These cyclodextrin
derivatives are permanently anchored by their substituents at
the silicon oxide coating.On the other hand, the accessibility
of the cyclodextrin cavities is guaranteed, leaving the
complex-forming properties of the cyclodextrins. According to
a preferred embodiment, the coating is characterized by the
fact that this 1 wt -% to 5 wt -%, contains a cyclodextrin
derivative that is dissolved or dispersed in the sol.
According to a preferred embodiment, the coating is
characterized in that the formation of the sol-gel matrix
[deg.] At temperatures between 15 <0> C and 40 C takes
place.
According to a preferred embodiment, the coating is
characterized in that the cyclodextrin permanently in the
sol-gel matrix is ??anchored.
According to a preferred embodiment, the coating is
characterized in that the sol-gel matrix in the cyclodextrin
molecules subsequently incorporated 0.1 weight -% of organic
substances are stored - up to 10% by weight.
According to a preferred embodiment, the coating is
characterized in that the sol-gel matrix in the cyclodextrin
molecules subsequently incorporated 0.1 weight - up to 10% by
weight-% Insecticides, fungicides and / or biostatic and
biocidal substances are stored.
According to a preferred embodiment, the coating is
characterized in that the carrier material is a textile
material, a nonwoven fabric made of natural or synthetic
polymers or mixtures of these polymers.
According to a preferred embodiment, the coating is
characterized in that the carrier material consists of
inorganic substances.
According to a preferred embodiment, the coating is
characterized in that the carrier material contains glass
fibers, carbon fibers and / or ceramic fibers. According to a
preferred embodiment, the coating is characterized in that the
carrier material includes metal, ceramic, glass-like and / or
cellulosic materials.
According to a preferred embodiment, the coating is
characterized in that the carrier material, wood and / or wood
chip plant substances.
According to a preferred embodiment, the coating is
characterized in that the carrier material has a surface of
plastics or plastic-like materials.
According to a preferred embodiment, the coating wherein the
coating has a thickness of 1 x 10 <"6> m to 50 x 10
<"> ^ m (very thin) or a thickness of 100 x 10
<"6> m to 1000 x 10 <"6> m (thin) has.
The cyclodextrin-salt can be applied to metallic and ceramic
surfaces by a dipping or spraying.After drying at room
temperature, a thin layer has formed on the surface that is
mechanically stable against external influences.
The cyclodextrin-salt are also used for impregnation of porous
inorganic materials. By immersion of these materials into
suitable brine they reach into all the pores by capillary
forces. After centrifugation, excess sol is removed from the
pores.After drying at room temperature, the surfaces of the
pores are coated by the sol, the pores of the material has
been preserved. The coating is permanent.
Natural materials such as wood and paper can be impregnated by
dipping into the corresponding cyclodextrin-Sole. In this
cause the brine one hydrophobicisation the surface. In
addition, the cyclodextrins can be chemical agents against
pests are stored.This leads to an improved wood preservation.
In the manufacture of wood particle materials of different
sizes of wood chips with a binder are pressed together. After
manufacture the fittings by dipping or spraying with a
cyclodextrin-salt impregnated. This causes a hydrophobization
the surface. Simultaneously, the cyclodextrin molecules
capable of chemical components that can be released from the
binders are too complex.Thus, the emission of substances that
can cause an odor nuisance is reduced considerably.
Insulation, made from mineral or natural fiber materials can
be impregnated by immersion in a brine cyclodextrin. After
drying, the cyclodextrin cavities with organic substances such
as insecticides and fungicides are loaded.The coating with the
sol, the combustibility of the insulating material is reduced
from natural fiber materials. The loading of the cyclodextrins
with insecticides and / or fungicides reduce the pest
infestation and / or infestation by fungi. Another advantage
is that vaporize at high temperatures, the active ingredients
are not from the cyclodextrin cavities, since the formed
cyclodextrin complexes are thermally stable.This ensures that
occurs does not pollute the air by these substances.
Flexible materials such as films, nonwovens and textile
fabrics, can be fitted by spraying or by dipping process with
the cyclodextrin-sols. Depending on the amount of the sol is
applied to the flexible structure of the material received.
The sol in fixed cyclodextrins are able to store chemical
substances from the air. They may also, by spraying, egwith
perfumes and other fragrances that are loaded. A load of other
organic substances such as insecticides, fungicides,
bactericide or biostatically acting substances or
pharmaceutical active substances is possible. By deposition of
such insecticides and fungicides, a parasitic infestation of
the materials is prevented.
After the finishing of nonwovens and / or textile fabrics with
cyclodextrins, the cyclodextrin-sols with pharmaceutical and /
or cosmetic active ingredients are loaded. Come such a
finished textile materials in contact with human skin, so the
stored substances are released by the moisture on the skin
surface of the skin.The sol-gel coating prevents their
hydrophobic properties, the growth of skin cells, if such
fabrics are used as wound dressings. By the release of
substances that have been stored in the cyclodextrins, the
healing process of wounds is accelerated.
By the incorporation of cyclodextrin into a sol-gel coating
ensures that the cyclodextrins can not be removed by washing
processes or similar processes from the surface of the treated
materials. It is therefore considered a permanent modification
of the surface of the corresponding materials.
The invention further relates to the use of a
cyclodextrin-brine as equipment / impregnation of support
materials.
This invention concerns such as the use of a sol-gel method
for the cyclodextrin-produced brine containing 0.1 to 10 wt -%
containing a cyclodextrin derivative that is dissolved or
dispersed in the sol according to the type as described above
equipment / impregnation of inorganic or organic support
materials.
The present invention is explained by examples.
Example 1
To a mixture of 50 ml of tetraethoxysilane, 15 ml of
3-glycidoxypropyltrimethoxysilane and 40 ml of ethanol are
added 10 ml of 0.01 N HCl and stirred at room temperature for
10 hours. Then 20 ml of a 10 wt -% solution added to the
polyvinylaminsubstituierten cyclodextrin and stirred an
additional hour. The result is a water-clear sol. To this sol,
a 10 wt -% solution of H2O ZrOCI2 x 8 in 50 weight -% ethanol
added.This sol is applied to a polypropylene film and dried at
room temperature. By applying a drop of an alkaline
phenolphthalein solution on the surface, the accessibility of
the cavity of ss-cyclodextrin can be detected. They observed a
discoloration of the drop, which occurs only in the presence
of cyclodextrin (K. Beermann, H.-J. Buschmann, D. Knittel, E.
Schollmeyer, methods of determination of cyclodextrins in
textile materials, textile finishing, 37 (2002) 17).
Example 2
To a mixture of 30 ml of tetraethoxysilane, diethoxysilane
dimethyl-30 ml, 20 ml of 3 -
glycidyloxypropyltrimethoxysilane, 60 ml of ethanol are added
dropwise 15 ml of 0.01 N HCl in 50 ml ethanol and stirred at
room temperature for 10 hours. Then 20 ml of a 15 wt -%
solution added to the polyethyleniminsubstituierten
cyclodextrin and stirred an additional hour. The result is a
water-clear sol. To this sol, a solution of 10 weight -% AI2
(OH) 5ci x 2-3 H2O in 90 wt- Added% ethanol. The resulting sol
is using a padding applied to a wool fabric (wet pickup 80
weight -%) and the tissue dried at room temperature.
The proof of the accessibility of the cyclodextrin cavities is
carried out using an alkaline phenolphthalein.
Example 3
To a mixture of 70 ml of tetraethoxysilane, 30 ml of methyl
triethoxysilane, 400 ml of ethanol are added 20 ml of 0.01 N
HCl in portions and [deg.] Stirred at 25 C for several
hours.To this sol, then a solution of 10 wt% Al 2 (OH) 5ci x
2-3 H2O in 80 wt% ethanol and 30 ml of an aqueous dispersion
(20 wt -%) added to the aminosiloxansubstituierten
cyclodextrin. The resulting dispersion is applied to a cotton
fabric using a sprayer and then [deg.] At 30 C dried.
The proof of the accessibility of the cyclodextrin cavities is
carried out using an alkaline phenolphthalein.Example 4
To a mixture of 50 ml of tetraethoxysilane, 15 ml of
3-glycidoxypropyltrimethoxysilane and 40 ml of ethanol are
added 10 ml of 0.01 N HCl and stirred at room temperature (20
<0> C) for 10 hours. Then 20 ml of a 10 wt -% solution
added to the polyvinylaminsubstituierten cyclodextrin and
stirred an additional hour. The result is a water-clear sol.
To this sol, a 10 wt -% solution of H2O ZrOCI2 x 8 in 50
weight -% ethanol added.The resulting sol is using a padding
applied to a cotton fabric (wet pickup 80 weight -%) and the
fabric is dried at room temperature.
The cotton fabric is coated with the Formazantests (mp Altman
Prog Histochem Cytochem 9 (1976;.. W. Oppermann, R. Gutmann,
S. Schmitt, E.-held hair dryer, textile finishing, 37, 19
(2003)) on his biostatic / biocidal efficacy investigated. The
efficacy is 99%, iethere is no metabolism by microorganisms in
the tissue determined.
Example 5
From the fitted cotton fabric in Example 4 is a 2 x 2 cm
<2> large piece in a petri dish on a given nutrient agar
standardization. After the inoculation, with half a milliliter
of E. coli culture is a storage of the sample at 37 [deg.] C
for 24 hours. A visual inspection shows that no growth of
microorganisms on the finished textile sample has taken
place.It has formed around the sample and no yard. This shows
that the cyclodextrin biostatic not diffused out of the
sol-gel matrix.
Example 6
From the fully equipped in Example 4 is a round piece of
cotton fabric with a diameter of 5 cm placed on a watch glass
and placed in a desiccator. In the desiccator is a petri dish
with approximately 20 ml benzyldimethylamine.After 7 days, the
textile sample is released some time in order to remove
adsorbed benzyldimethylamine, and then into a sample vial for
headspace gas chromatography transferred. After the addition
of a few microliters of water, the sample is at 80 [deg.] C
water bath. Subsequently, the gas is analyzed by gas
chromatography. The benzyldimethylamine can be clearly
demonstrated.
Example 7
From the fully equipped in Example 4 is a round piece of
cotton fabric with a diameter of 5 cm placed on a watch glass
and placed in a desiccator. In the desiccator is a petri dish
with approximately 20 ml of hexanal. After 3 days, the textile
sample is released some time in order to remove adsorbed
hexanal, and then into a sample vial for headspace gas
chromatography transferred. After the addition of a few
microliters of water sample at 80 [deg is.] C water bath.
Subsequently, the gas is analyzed by gas chromatography. The
hexanal can be clearly demonstrated.
Example 8
From the fully equipped in Example 6 is a round piece of
cotton fabric with a diameter of 5 cm placed on a watch glass
and placed in a desiccator. In the desiccator is a petri dish
with approximately 20 ml benzyldimethylamine. After 5 days of
the textile sample is released some time in order to remove
adsorbed benzyldimethylamine.It is given a 2 x 2 cm <2>
large piece in a petri dish on a standard 1 nutrient agar.
After the inoculation, with half a milliliter of E. coli
culture is a storage of the sample at 37 [deg.] C for 24
hours. A visual inspection shows that no growth of
microorganisms on the finished textile sample has taken place.
However, over the textile sample formed a courtyard, in which
there are no microorganisms.By the existing water obviously a
release of benzyldimethylamine has taken place. Example 9
Of the vessel equipped in Example 2 is a circular piece of
wool fabric with a diameter of 5 cm placed on a watch glass
and placed in a desiccator. In the desiccator is a petri dish
containing about 5 ml of lemongrass oil. After 2 days the
textile sample is released some time in order to remove
adsorbed Lemon grass oil.After a slight moistening
significantly, the smell of lemon grass can be perceived.
Example 10
From the fitted wool fabric in Example 2 is a round piece with
a diameter of 5 cm placed on a watch glass and placed in a
desiccator. In the desiccator is a petri dish containing about
5 ml of lavender oil. After 2 days the textile sample is
released some time to adsorbed lavender oil. to remove.After a
slight moistening of the smell of lavender can clearly be
seen.
Example 11
To a mixture of 30 ml of tetraethoxysilane, diethoxysilane
dimethyl-30 ml, 20 ml of 3 -
glycidyloxypropyltrimethoxysilane, 60 ml of ethanol are added
dropwise 15 ml of 0.01 N HCl in 50 ml of ethanol and at room
temperature (20 <0> C) 10 hours stirred. Then 20 ml of a
15 wt -% solution added to the partially methylated
ss-cyclodextrin and stirred an additional hour. The result is
a water-clear sol.% AI2 (OH) 5ci x 2-3 H2O in 90 wt - - To
this sol, a solution of 10 wt% ethanol added. By dipping a
piece of wood in the resulting sol this is impregnated. After
drying, the piece of wood at room temperature, the sample is
sprayed with a Permethrinlösung in acetone. After drying, the
wood is dipped briefly in acetone to remove adsorbed
permethrin.Evidence of complex formation of cyclodextrin with
permethrin is done by an aqueous extraction of the wood piece.
In the extract permethrin by GC-MS analysis is proven.
Example 12
The sol prepared in Example 4 is used to a piece of wood
floors (36 x 17 cm) to be sprayed. For comparative purposes,
an equally large piece of wood parquet with a 10 wt -%
solution of cyclodextrin polyvinylaminsubstituierten
sprayed.After drying, both samples dropped onto a drop of
water using a pipette. In the case of the sample sprayed with
the sol is no wetting of the surface. Contrast, one observes a
complete wetting in a short time, in the sample with the
sprayed polyvinylaminsubstituierten cyclodextrin.
The complexation of substances leached from the wood floor is
determined according to DIN ISO 16006-3.This is quantitatively
measured in a test chamber after a day the concentration of
formaldehyde in the air. It gives the following values: a)
wood flooring (untreated): 0.24 [ppm] b) wood floor (sol with
cyclodextrin): 0.07 [ppm] c) Holparkett (only with
cyclodextrin): 0.03 [ppm]
PT
1826248
CONTAINER FASTENING COATING COMPOSITION, CONTAINER
FASTENING COATING, ITS MANUFACTURE AND APPLICATION
CA 2709191
WO
2009/074124
PROTECTIVE LAYER FOR PLANTS AND
TREES, THE PRODUCTION THEREOF AND USE THEREOF
2009-06-18
Inventor(s): SCHWINDT SASCHA [DE] +
(SCHWINDT, SASCHA)
Applicant(s): STIFTUNG NANO INNOVATIONS
[CH]; SCHWINDT SASCHA [DE] + (STIFTUNG NANO INNOVATIONS, ;
SCHWINDT, SASCHA)
Classification: - European:
A01N25/04; A01N25/34; A01N43/16
The invention relates to a method for producing a protective
layer on a surface of a plant, a protective coating for a
surface of a plant, a plant coated with this protective layer,
a composition for carrying out the process and the production
of the protective layer and uses of that composition.
Background of the Invention
Every year the world's agriculture caused billions in damage
by plant pests such as fungi or Frassschädlinge that infect
the leaves of crops and damage. Previously, these pests were
controlled by herbicides, pesticides, according to the
directory (Federal Office for Consumer Protection and Food
Safety, as of 01.11.2007) to the areas
Herbicides to control weeds,
Insecticides against insect pests,
Fungicides to control fungal pathogens,
Rodenticides against rodents,
Nematicides against nematodes (roundworms)
Acaricides against mites / spiders,
Molluscicides against slugs,
Bactericidal against bacteria,
Agents against viroids,
Agents against viruses
Resources for the processing of Obstund Rebveredelung and
ornamental trees,
Tool for preventing wildlife damage
Means forWound closure / wound treatment,
Growth regulator,
Seeds and Propagating Material for the treatment of seed
potatoes and
Means of soil decontamination
belong. All means and substances in common is that they are
either the protected plant to encourage appropriate defensive
measures or kill the pests. The plant leaf is next to the stem
axis and the root of one of three basic institutions of higher
plants and is known as a body type Phyllom.Leaves are lateral
outgrowths of the node (nodes) of the stem. The original
functions of leaves photosynthesis (structure of organic
materials with the aid of light) and transpiration (water
evaporation, important for nutrient uptake, and - transport).
Leaves occur only in plants sprout, that is, at fern-like
plants (Pteridophyta) and seed plants (Spermatophyta).However,
they are absent in mosses and algae, at the <"> phallus,
however, may experience leaf-like structures, but these are
provided as an analogy of the leaves. The variety of leaf
shapes is enormous. In some cases, in the course of evolution
were also leaf organs, the with the original function of the
leaf, namely, photosynthesis and transpiration, have nothing
to do more: for example, petals, leaf spines and leaf
tendrils, and bud scales.
The sheet includes the outside with a final tissue from the
epidermis, which consists of only one cell layer. The
epidermis has a waterproof layer of wax to the outside cuticle
that prevents unregulated evaporation. The cells of the
epidermis usually have no chloroplasts (the cell components,
in which photosynthesis takes place).Exceptions are the
epidermis of hygro, HeIound hydrophytes and partially shade
leaves, especially the guard of the stomata (stomata), which
always contain chloroplasts. The stomata are the regulation of
gas exchange, primarily of water vapor. After the distribution
of stomata, a distinction is hypo-matic (stomata on the leaf
base, most common form), amphistomatische (stomata on both
sides of the leaf) and epistomatische leaves (stomata on the
leaf surface, suchExample, in floating leaves). The
attachments are formed by the epidermis hairs (trichomes)
called. Are involved in the formation and subepidermal cell
layers, it is called Emergence: Examples are spikes or
glandular. When mesophyll tissue called the Assimilation. It
is usually in the structured under the upper epidermis and
palisade parenchyma located below it spongy.The palisade
parenchyma consists of an elongated or three layers,
perpendicular to the leaf surface vertical,
chloroplastenreicher cells. In the palisade, whose main task
is to photosynthesis, there are about 80 percent of
chloroplasts. The spongy parenchyma is composed of irregularly
shaped cells that form the basis of their form large
intercellular spaces. The main task of the spongy parenchyma
is to ensure the ventilation of the parenchymatous tissue.The
cells are relatively poor in chloroplasts. The vascular
bundles are often located on the border between the upper
Palisadenund spongy spongy. The structure resembles that of
the vascular bundles in the shoot axis and is usually
collateral. The vascular bundles branch off from the shoot
axis and pass by without turning the petiole into the blade.
This includes the xylem to leaf surface, the phloem to the
leaves.Large vascular bundles are often surrounded by an
endodermis, which is here called bundle sheath. The bundle
sheath controls the material exchange between vascular bundles
and mesophyll. The vascular bundles end blindly in the
mesophyll. Here, the vascular bundles is reduced still more,
that is, the first sieve tubes become less and fall out, then
remain in the xylem only part Schraubentracheiden ending
ultimately blind.The entire leaf is usually so dense
interspersed with vascular bundles, leaf cell is that no more
than seven cells from a vascular bundle. The resulting small
fields between the vascular bundles are called areoles or
intercostal fields. The function of the vascular bundles is
the delivery transport of water and minerals into the leaves
(through the xylem) and the transport of photosynthates from
the leaf (through the phloem).
So far, no methods are known which generate as protection
against fungi and a Frassinsekten whatsoever layer on the
surface of the plant or leaf surface. So far, it was expected
to affect the physiology of a coating plant leaf and thereby
harm the plant would. A coating plant leaf as a protective
layer must therefore meet two conditions.Had a sufficiently
large translucency is required to provide the information
contained in the plant leaf chloroplasts with radiation in the
range of 320 to 700 nm. A in this wavelength range adsorptive
or reflective coating acts would affect the energy supply of
the plant cell. Inside the chloroplasts located as plasmatic
phase of the stroma.This is interspersed with stroma thylakoid
membranes (Membraneinstülpungen), the multi-roll-like
superimposed is the Granum. This may in the membranes as a
pigment chlorophyll is now embedded in turn absorb light from
the above-mentioned wavelength range and use this energy for
the production of ADP (adenosine triphosphate) from ADP
(adenosine diphosphate) and phosphate.
The second requirement is to meet a nanoscale protective layer
must plant leaf, the orderly functioning of the stomata.
Through the stomata (Greek stoma, mouth) or stomata, gas
exchange is a plant. The stomata are usually of two
bean-shaped cells called guard-formed, which enclose an
opening, the gap. Counting the cells that surround the guard
around, add more, we speak of stomatal apparatus (stomatal
complex).The pores themselves are, strictly speaking, the
actual gap openings. Guard-are usually in the lower epidermis
of plant leaves, the grasses on both sides of the leaf, and
floating leaf plants only at the top. The gas exchange with
the surrounding air is especially important for the supply of
CO2. Carbon dioxide is absorbed by plants through the
processes of photosynthesis from the air.Thus, the diffusion
through the cell walls function optimally, it must be as thin
or permeable. Such cells evaporate but plenty of water, land
plants would wither quickly with such leaves. About the
separation of the intercellular space in the Journal of the
dry outside air through the stomata, the plant receives
control over the water loss.Through the pores by evaporation
(stomatal transpiration or evaporation) instead, which creates
a suction transported by water from the roots to the leaves:
further points are important for the stomata. With the water
are transferred from the soil and nutrients are concentrated
in the leaves.In addition, the evaporation cools the leaves,
this overheating in bright sunshine and not the specific
temperature optimum, the enzymes in the leaf tissues, are not
exceeded....
SI1825752
Coating compound made of an
agent which generates SiO2 with at least two antibacterial
agents
Inventor: JURGENS RALF [DE]; SCHWINDT SASCHA [DE]
[0001] The invention relates to an antibacterial coating
composition, on base of a silicon dioxide-producing means, an
application set, a nanoskalige coating on the base of polymerized
SiO2, the preparation of the coating, the subsequent treatment of
the coating as well as a multiplicity of uses, like appended more
near explained.
State of the art
[0002] DE 102004014483 A1 concerns a porous inorganic oxide layer
with at least a cationic polysaccharide contained in it. Here
chitosan, becomes Chitosansalze, a cationic Chitosanderivat with
amino and ammoniumfunkunktionellen groups and an alkyl or a
acylmodiziziertes chitosan mentioned as biozider active
ingredient. From the present invention this document differs by
the different one surface structure, those non porous is and and.
A. deacetylierte Chitosanderivate begins.
[0003] US 6306835 A1 describes
3-Trimethylammonium-2-hydroxypropyl-N-chitosan (CHI-Q188) as
antimicrobial active ingredient. It becomes described that to the
preparation more homogeneous, transparent layers the use is pure
aqueous nano-brine of advantage, since in these the antimicrobial
cationic polysaccharides are good soluble. Around the fact it is
provided that the first formed alcoholic nano-brine by careful
removal of the alcohol in aqueous nano-brine converted become.
[0004] DE 20 2004 019,687 A1 concerns the use of particles, whose
at least partly consist surface of metallic silver, with a
diameter of less than 100 Nm, and, which as clearcoat formed is in
accordance with claims. With the described layers it essentially
acts around substantial thicker lacquer layers within the range of
1 m to 100 m.
[0005] DE 20 2005 006,784 A1 describes, a porous Sol gelcoating
with antimicrobial effective substances/compounds those, prepared
after the Sol gelprocess, selected is from the group, existing
from Ag, Zn, cu, SN, I, width unit, Gr, CR, their ions as well as
their compounds and mixtures of it, in particular silver-organic
compounds, silver-inorganic compounds, zinc-organic compounds,
zinc-inorganic compounds as well as their salts and oxides. These
compounds are not subject-matter of the present invention.
Furthermore this Patent Laid open describes the presence of carbon
in detectable amount in the Sol gellayer, when case of planar is
not desired here.
[0006] The disadvantage of the before described antimicrobial
substances in the state of the art is in case of the cationic
polysaccharides in only the effect limited to negative charged
surfaces of bacteria, to cationic or nonionic microorganisms
becomes only insufficient because of the growth hindered and/or.
killed. After newest studies a resistance adjusts itself against
silver ions, the effectiveness of the antimicrobial component
diminishes thus after few weeks, from a durable antimicrobial
effect cannot thus not the speech be with certain microbial
organisms.
[0007] Disadvantages in DE 20 2005 006,784 A1 described
organometallic compounds are their strong polluti ng effect, since
excluded due to the porous structure of the Sol gelcoating an
erosion and thus an entry are not into the environment. These
active ingredients are found increased in the food chain up to the
humans and are to a considerable degree harmful for the humans and
the environment, thereby. Tributylzinn is erbgutschädigend.
[0008] It is already known, antibacterial and/or. antimicrobial
active ingredients to the destruction and/or. Growth inhibition of
bacteria, funguses, to use algae and viruses and to the protection
of materials and foods against microbial impurity. The
environmental, microbial contamination through approx. 2 to 3
billion different microorganisms, of it alone approx. a steady
increasing health Gefährdungspotenzial represents 15.000, which
can spread over the air and settle thus almost any surface. In the
following the term becomes “antimicrobial” used, thus is in
particular the biocides and/or for the effect of the substances.
biostatic effect on microorganisms meant.
[0009] It is known to produce Sol gellayers by means of a Sol
gelprocess. Metallic oxide xerogels become preferably from SiO2,
R-SiOn, R2SiOn, Al2O3, ZrO2, TiO2 or their mixtures used, whereby
R = H, alkyl, aryl, Epoxi alkyl, Aminoalkyl and n = 1.5 or 1 can
be. One by the hydrolysis and condensation reactions receive these
gels from silicon alkoxides. The molecules become connected with
one another due to the polymerization taken place during the
process. The total volume of the sols becomes polymerized thereby.
The polymerized silicon oxides form a SiO2-Gel (see. J.C. Brinker,
G.W. Sheared one, sol gel Science, Academic press, London 1990).
[0010] The continuous condensation bottom alcohol splitting off
leads to spherical increasing of the particles, which itself
starting from a thickness of approx. 70 Nm due to the light
scattering at the particles (Tyndall effect) to prove leave. By a
procedure referred as gelation sols can change into gels. The
particles continue to grow, until they touch themselves and
network by other condensation. Finally thereby a solid phase is
formed which is penetrated with a liquid phase. As gels
formbeständige, light deformable disperse systems rich at liquid
become referred, which of a solid, irregular three-dimensional
network and a liquid to consist.
The functionalization become the sol from tetraethoxysilanes
aliphatic and aromatic aldehydes, carbonic acids or aminocarbonic
acids an added. Alternative one becomes organic modified by
changed substituents at the Precursor (R'Si (OC2H5) 3) the
SiO2-Netzwerk. Likewise for it the synthesis of various
Alkyltriethoxysilane with Azomethinbindung becomes by the
conversion of aminopropyltriethoxysilanes with
Benzaldehydderivaten and/or. Acetylacetone used.
Inorganic-oxidic gels become frequent by conversion of element
alkoxides with alcohol-water mixtures or in pure water prepared.
The alcohol serves here the generation of an homogeneous reaction
mixture and can become by other per tables or aprotic solvents
replaced. The flexibility and porosity of the Sol gellayers can be
changed by modification of the prescriptions. A higher portion of
R-SiOn and/or R2SiOn improves the flexibility of the layers, by
the formation of composite oxides such as Al2O3, ZrO2, TiO2 can
the abrasion stability and specific hardness amplified become.
Invention
Antibacterial coating composition
[0011] An object of the invention is it first to make a novel
antibacterial coating composition available.
[0012] This object becomes by the combination of the Si02 of
producing means as well as particular portions of particular
antimicrobial agents dissolved, those from a selection of two by
three different material classes made.
[0013] The invention relates to so an antibacterial coating
composition, contained 50 Gew % to 99.9 Gew %, preferably 80 Gew %
to 99 Gew %, a SiO2-erzeugenden of means, whereby the coating
composition contains 0.1 Gew % to 50 Gew %, preferably 1 Gew % to
20 Gew %, related to the total composition, at least an
antibacterial active ingredient in the form of cationic, anionic
or nonionic deacetylierten chitosans and Chitosanderivaten and/or
phenols of the group of the halogenated Dihydroxydiphenylmethane,
- sulfides, and - ether and/or substituted quaternary ammonium
salts of the alkylated phosphoric acid, whereby the antibacterial
active ingredient selected from at least 2 compounds of the 3
appended connecting classes in the form of cationic, anionic or
nonionic deacetylierten chitosans and Chitosanderivaten and/or
phenols of the group of the halogenated Dihydroxydiphenylmethane,
- sulfides, and - ether and/or substituted quaternary ammonium
salts of the alkylated phosphoric acid.
[0014] An other prefered embodiment of the present invention
concerns a composition of the before-described type, with that the
SiO2-erzeugenden means selected is out
0 to 100 Gew %, preferably to Gew % tetraethoxysilanes,
0 to 100 Gew %, preferably to Gew % Trimethoxymethylsilan, and
0 to 100 Gew %, preferably to Gew % Dimethoxydimethylsilan.
[0015] An other prefered embodiment of the present invention
concerns a composition of the before-described type, with which
means producing the SiO2 contains Al2O3, TiO2, ZrO2, MgO and/or
V2O5 further up to 20 Gew %, whereby these additives are in
arbitrary mixing ratios present, preferably in mixing ratios
between 0,1 Gew % and 50 Gew % from the group of the Al2O3, TiO2,
ZrO2, MgO and V2O5, particularly prefered in mixing ratios between
1 Gew % and 20 Gew % from the group of the Al2O3, TiO2 and ZrO2.
[0016] An other prefered embodiment of the present invention
concerns a composition of the before-described type, with that the
active ingredient as halogenated Dihydroxydiphenylmethan, -
sulfide and - ether selected is hydroxy more diphenylether from
5,5 ' - Dichlor-2,2' diydroxy diphenylmethan, 3.5.3 ', 5 ' -
Tetrachlor-4,4' diydroxy diphenylmethan, 3.5.6.3 ', 5 ', 6 ' -
Hexchlor-2,2' diydroxy diphenylmethan, 5.5 ' - Dichlor-2,2'
dihydroxy diphenylsulfid, 2.4.5.2 ' 4 ', 5 '
Hexachlordihydroxydiphenylsulfid, 3.5.3 ', 5 ' - Tetrachlor-2,2'
Dihydroxy diphenylslfid, 4.4 ' -
Dihydroxy-2,2'dimethyl-diphenylmethan, 2 '
2-Dihydroxy-5',5-diphenylether or 2.4.4 ' Trichlor-2'.
[0017] These phenols are available as 5.5 ' - Dichlor-2,2'
diydroxy diphenylmethan (Preventol of dd, Bayer AG), 3.5.3 ', 5 '
- Tetrachlor-4,4' diydroxy diphenylmethan (Monsanto corporation),
3.5.6.3 ', 5 ', 6 ' - Hexchlor-2,2' diydroxy diphenylmethan
(Hexachlorophen), 5.5 ' - Dichlor-2,2' dihydroxy diphenylsulfid
(Novex, Boehringer Mannheim), 2.4.5.2 ' 4 ', 5 ' hexadecimal
chlorine dihydroxy diphenylsulfid, 3.5.3 ', 5 ' - Tetrachlor-2,2'
Dihydroxydiphenylslfid (Actamer, Monsanto), 4.4 ' -
Dihydroxy-2,2'dimethyl-diphenylmethan, 2 '
2-Dihydroxy-5',5-diphenylether (Unilever), 2.4.4 ' Trichlor-2'
hydroxy more diphenylether (Irgasan DP 300, Ciba-Geigy).
[0018] An other prefered embodiment of the present invention
concerns a composition of the before-described type, with which it
concerns with the phenol 2,4,4 ' Trichlor-2' hydroxy more
diphenylether.
[0019] An other prefered embodiment of the present invention
concerns a composition of the before-described type, with which it
concerns with the active ingredients cationic, anionic or nonionic
deacetylierten chitosans and Chitosanderivate, preferably around
Trimethylchitosaniumchlorid, the Dimethyl-N-C2. to
C12-alkylchitosaniumiodid, quaternary Chitosansalze with anions of
the phosphoric acid, O-Carboxymethylchitin-sodium salts,
O-Acylchitosan, N, O-Acylchitosan,
N-3-Trimethylammonium-2-hydroxypropyl-chitosan and
O-TEAE-Chitiniodid.
[0020] An other prefered embodiment of the present invention
concerns a composition of the before-described type, with which
the chitosans and Chitosanderivate are low molecular chitosans and
Chitosanderivate, whereby the molecular weights between 1,0 x
10< 5> g/mol and 3.5 x 10< 6> g/mol, preferably
between 2,5 x 10< 5> g/mol and 9.5 x 10< 5> g/mol lie.
[0021] An other prefered embodiment of the present invention
concerns a composition of the before-described type, with which
the active ingredients are quaternary ammonium salts of the
alkylated phosphoric acid, whereby each of the alkyl radicals
exhibits, independently 1 to 12 carbon atoms and/or halogenated
ammonium salts, preferably the Cetyltrimethylammoniumbromid, the
Didecyldimethylammoniumchlorid, the Hexadecylpyridiniumchlorid and
the Polyoxyalkyltrialkylammoniumchlorid. With these substituted
quaternary ammonium salts of the alkylated phosphoric acid, their
biostatic effect is in numerous publications documented. Paths of
the very good water solubility of these salts their integration is
particularly favourable into the SiO2-Matrix. Also halogenated
quaternary ammonium salts like the Cetyltrimethylammoniumbromid,
knew its antimicrobial effect bottom evidence provided and into
the SiO2-Matrix to the use to come.
[0022] An other prefered embodiment of the present invention
concerns a composition of the before-described type, with which
the microbial active ingredients in mixing ratios between 0,1 Gew
% to 99.9 Gew %, preferably 1 Gew % to 99 Gew %, in particular 5
Gew % to 95 Gew % are present.
[0023] The mixing ratio of the antimicrobial active ingredients
chitosan, 2.4.4 ' Trichlor-2' hydroxy more diphenylether
(triclosan) and quaternary ammonium salts in the sols among
themselves should become set as follows. In sum the antimicrobial
active ingredients between 0,1 Gew % and 50 Gew % can constitute,
preferably 1 to 20% related to the total composition of the sols.
The portion of the respective antimicrobial active ingredients can
be thereby between 1 volume % and 98 volume %. By different
prescriptions (quantities) the antimicrobial effect can become on
the respective microbe population the purpose of the highest
effect set.
[0024] An other prefered embodiment of the present invention
concerns a composition of the before-described type further
contained conventional auxiliary and additives, in particular
acidic and basic polycondensation catalysts and/or Flouridionen.
[0025] The invention the object continues to be the basis, an
application set to make available, which finds both with
industrial application as well as in the DO it yourself range
application.
[0026] This object becomes dissolved by the selection of the
coating composition as well as particular application means.
[0027] The invention relates to therefore an other application
set, the contained composition of the before-described type as
well as application means for the purification and preparation of
the substrates which can be coated, as well as in the form of
individual packaged Sachet cloths. The aforementioned application
means can cover bundle-large between 0,25 I to 800 I
Nanoskalige coating on carriers
[0028] The invention is the basis the other object, a nanoskalige,
and antimicrobial, to create in particular biocides coating on
base of an inorganic polymerized SiO2-Schicht on arbitrary organic
or inorganic supports which different than the layers in the state
of the art porous are not and besides both hydrophobic as well as
oleophob is.
[0029] This object becomes by the combination of the SiO2 of
producing means as well as particular portions of particular
antimicrobial agents dissolved, those from three different
material classes alone or preferably as combination of at least
two material classes made.
[0030] The invention relates to therefore further nanoskalige, in
particular 50 Nm an antibacterial coating thick to 500 Nm,
preferably between 120 Nm and 250 Nm, a contained not porous
inorganic polymerized SiO2-Schicht, applied on a support material,
whereby the coating 0.1 Gew % to 50 Gew %, preferably 1 Gew % to
20 Gew %, related to the total composition, at least an
antibacterial active ingredient in the form of cationic, anionic
or nonionic deacetylierten chitosans and Chitosanderivaten and/or
phenols of the group of the halogenated Dihydroxydiphenylmethane,
- sulfides, and - ether and/or substituted quaternary ammonium
salts of the alkylated phosphoric acid, whereby the antibacterial
active ingredient selected from at least 2 compounds of the 3
appended connecting classes in the form of cationic, anionic or
nonionic deacetylierten chitosans and Chitosanderivaten contains
and/or Phenols of the group of the halogenated
Dihydroxydiphenylmethane, - sulfides, and - ether and/or
substituted quaternary ammonium salts of the alkylated phosphoric
acid.
[0031] The layers can become in varying thickness from 50 Nm to
500 prepared, preferably however in layers between 120 Nm and 250
Nm, there the SiO2-Nanopartikel used in the spraying method on the
not-lung-common size of > 100 Nm set become.
[0032] Also prefered is a coating of the before-described type,
with which the SiO2-Schicht at least partly consists of R-SiOn,
and/or R2-SiOn, whereby R = H, alkyl, aryl, Epoxy alkyl or
Aminoalkyl and n = 1.5 is larger or.
[0033] Also prefered is a coating of the aforementioned type, with
which the SiO2 contains layer Al2O3, TiO2, ZrO2, MgO and/or V2O5
in arbitrary mixing ratios, preferably in mixing ratios between
0,1 Gew % and 50% Gew % from the group of the Al2O3, TiO2, ZrO2,
MgO and V2O5, particularly prefered in mixing ratios between 1 Gew
% and 20 Gew % from the group of the Al2O3, TiO2 and ZrO2.
[0034] The advantages of the antimicrobial coating according to
invention and/or. Surface refinement essentially consist of the
subsequent points:
1. Very high hydrophobie and Oleophobiewerte, more comparable with
the values of coatings, which become generated by means of
fluorine carbon resins. Thus an extreme strong antiadhesive
effect, which still exceeds those of the ptfe, goes it becomes
contact angles of 139,5 deg. achieved (Institut high stone). This
is favourable, in order to prevent the Erstbesiedlung of the
surfaces by microorganisms, which test before the settlement of
the substrate by the delivery of a tacky secretion quasi whether
the surface for a settlement is suitable. Since this secretion on
the oleophoben surface remains hardly clinging, it does not come
only at all in many cases to a settlement and into sequence to a
colony formation.
2. The very good adhesive coating can be laid on because of the
very good ductile properties on substrates of most different
geometry and nature.
3. The SiO2-Matrix (glass) is very abrasion-stable and is
characterised by not measurable abrasion and one much high
hardness. Due to the ultradünnen layers of < the glass layer
their very good flexible properties keeps 250 Nm.
4. The immobilization of the antimicrobial active ingredients the
prevented elution and dilution of the active ingredients and thus
removing the antibacterial activity.
5. The coating composition consists of non-toxic compounds, which
are more degradable biological. Silicates like the SiO2 are the
most frequently occurring compounds of the earth's crust.
6. With most different fabrics Waschversuche became the
determination of the permanence of the coating performed. A
requirement of the textile industry became after a resistance to
washing of > 50 laundries continuous achieved, provided that
the substrate is not likewise after this number of washing
processes degradiert.
7. By the mixture of most different antimicrobial substances a
broadband Antimikrobiotikum can become prepared that suitable is
to fight also strong heterogeneous populations. The prescription
can become the respective ambienten requests adapted. Like that it
is possible, particular prescriptions for fabrics, for
hygiene-sensitive surfaces in hospitals to manufacture for
breathing air filters or for aquatic environments and to obtain
thus the optimum growth blockade. Training of resistances becomes
more other (e.g. MRSA) prevented.
[0035] Other subject-matter of the invention is a coating of the
aforementioned type as coating for hard surfaces, in particular as
Antifouling means.
[0036] Object of the invention is it likewise to make a novel
Antifouling coating available which overcomes the disadvantages
comparable coatings to the state of the art, hydraulic and
oleophobe properties exhibits, so that an effective protection of
endangered surfaces before adhesion of biopolymers and
microorganisms, with simultaneous indulgence of the environment
is, ensured and the abrasion-stable for a lasting protection and
thus is wasserunbelastend.
[0037] This object becomes according to invention dissolved by the
fact that the surfaces a polymerized SiO2 - matrix exhibits into
which antimicrobial active ingredients and/or metal oxides are
storable, whereby these active ingredients not eluierbar and
immobilized is applicable into the SiO2-Matrix.
[0038] The coating is due to their polymerized SiO2 matrix
glass-similar. With use in moved waters from this an high
hydrodynamic efficiency, which leads to an effective self
cleaning, results. By the SiO2 matrix is the coating furthermore
abrasion-stable, scratching and scheuerfest.
[0039] This is the use of the coating composition of the
aforementioned type as Antifouling means for with water, in
particular with sea and sea water in compound standing surfaces.
[0040] An other object of the invention concerns therefore the use
of the coating for with water, in particular with sea and sea
water in compound standing surfaces to the protection before
Biofouling causing biopolymers and/or microorganisms as well as a
method to the preparation of a such coating.
[0041] Surfaces in aquatic habitats are the formation of tacky
biopolymers exposed, which introduce a Biofoulingprozess. Bottom
Biofouling understands one the deposition of living organisms on
material surfaces in aqueous environment, which their physical
surface properties negative affect. Each Foulingprozess in the
water starts with the attachment of organic molecules at a
surface. Its solidification the possible other settlement of
bacteria, Diatomeen, shells and cancers etc. In marine environment
experiences each surface Biofouling, which leads to one of the
largest problems with the surfaces in the marine technology.
Particular surface coatings, “Antifouling coatings so mentioned”,
are to prevent the vegetation at hulls, sea water constructions,
oil platforms, harbor facilities and tubes, as well as at other
artificial underwater structures. It is known, hulls, to provide
oil platforms and harbor facilities with Antifouling coatings.
[0042] The TRGS516 (technical rules for dangerous materials,
Antifouling, output 1996) shows the conditions of the
safety-relevant, as well as ergonomical requests according to
industrial medicine and hygienic to dangerous materials regarding
Inverkehrbringen and handling. It regulates the use of very toxic,
toxic and Antifouling colors injurious to health. Known
Antifouling coatings are based either on forms of the mechanical
purification or on the discharged one of toxic biocides from
matrix coatings or on a combination of both. The mechanical
purification strong slippery surfaces become generated by the use
of Teflons or silicone in the coating, which prevent the
attachment of Foulingstoffen.
[0043] In addition one differentiates between insoluble and
soluble coatings. The insoluble Antifouling coatings exhibit an
high abrasion resistance, soluble Antifouling coatings are eroding
and become from flowing water slow removed. Known Antifouling
coatings prevent the settlement phase of the Foulingprozesses by
their biocides.
[0044] In that DE 101 17 945 becomes a Antifouling coating a
without biocide described, which biomimetisch as dual
Kompositsystem, constructed with cleaning, an hydrodynamic very
smooth, a nano-structured surface pore size defined in form of of
a pore-formed component with, which I after the particle size of
tacky dirt particles arranges, and a pore-filling component, which
exhibit gel-formed desert hydrophobic, the adhesive properties of
the adhesive biopolymers adapted properties.
[0045] EP 1,446,011 A1 describes a Antifouling composition on the
base of 4-Bromo-2 (4-Chlorophenyl) - 5 (Trifluoromethyl) - 1
H-Pyrrole-3-Carbonitril.
[0046] EP 1,457,531 A1 describes likewise a Antifouling
composition on the base of a metalliferous copolymer and the
active ingredient 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one.
[0047] EP 65 10 34 A1 describes a rot-preventing painting
composition, which contains a copper oxide or a Kupferthiocyanat
and a copper salt of 2-Pyridinthiol-1 as effective compound.
[0048] EP 64 66 30 describes a coating composition, which contains
several Antifouling means as essential components or and or
several copolymers, the available is from a monomer mixture,
comprising monomer A of the formula (1)
<EMI ID=1.0>
[0049] Where R< 1> and R< 3> in each case a group is,
selected from alkyl groups, cycloalkyl groups and aryl groups, and
which can be identical or from each other various, and X is a
Aryloyloxygruppe, a Methacryloyloxylgruppe, a Maleinoyloxylgruppe
or a Fumaroyloxygruppe and a monomer B of the formula (2)
Y (CH2CH2O) NR< 4> (2)
where R< 4> an alkyl group, a cycloalkyl group or aryl group
is, Y a Aryloyloxygruppe, a Methacryloyloxylgruppe, a
Maleinoyloxylgruppe or a Fumaroyloxygruppe and a n is a whole
number from 1 to 25, and the amount of the Antifoulingmittels
amounts to 0.1 to 80 Gew % on base of the weight of the solid
content of the coating composition.
With the biocides one differentiates between “metal-organic
biocides”, like arsenics, coppers and Tributylzinn, and “natural
biocides”, with which many marine organisms themselves protect
their surface from Biofouling. They can antialgalen as biogenous
active ingredients antibacterially, work antifungisch and
makrofoulingverhindernd. However the need grows at altogether
non-toxic vegetation protection methods due to stricter
legislation
[0050] The antimicrobial active ingredients, like chitosan, 2.4.4
' Trichlor-2' hydroxy more diphenylether and quaternary ammonium
salts prevent the effective settlement of surfaces of the support
material by bacteria, funguses, viruses, algae, Diatomeen, shells
and cancers in air environment, aqueous environment and air water
systems, work thus antibacterially, antifungal, fungicidal,
algizid and virozid.
[0051] The Antifouling coating is water and environmentalneutral.
It is simple in the processing and can by spraying (aerosol) or
capers on the surfaces applied become. By storing the active
ingredients into the SiO2-Matrix they cannot be washed dissolved
or. Furthermore it is favourable that your effectiveness does not
decrease over the time.
[0052] Further it is of advantage to bring metal oxides for
example to Al2O3 and/or TiO2 into the SiO2 matrix. This
Antifouling coating according to invention is characterised with
it by a strong hydrophobische and oleophobische effect.
[0053] One with the Antifouling coating according to invention
treated surface represents a very poor clamping coat situation for
polymers and/or for microorganisms, so that hardly colonies can
form, biostatic active ingredients is antimicrobial acting
substances, with whose contact the microorganisms adjust their
growth. Beyond that it exhibits a thickness within the nanometer
range and is acidic one and caustic solutions opposite very
stable. Teflonhaltige and/or fluorcarbonhaltige or silikonhaltige
coatings, which are to cause an attaching of microorganisms due to
their smooth surface, are only hydrophobic ones, not however
oleophob, partially even oleophilic, so that microorganisms on the
oil-wetted surfaces can quite settle and take place
Biofoulingprozesse. Beyond that these coatings are not
abrasion-stable and are subject therefore to strong wear. In the
processing these coatings likewise critical are to be evaluated,
since they contain alcohol-based solvents.
[0054] Metal-organic coatings, which contain arsenics, coppers, or
Tributylzinn, are water-getting biocide dirty, strong and thus
strong polluting. Furthermore Tributylzinn haltige colors are in
the USA since 01.06.2005 even forbidden. Beyond that these not
abrasion-stable coatings are eroding and become by flowing water
removed. The active ingredients increased in the food chain are
found to biocides up to the humans and are to a considerable
degree harmful for the humans and the environment, thereby.
[0055] The nanoskalige Antifouling coating on SiO2-Basis however
the satisfied requirement after both hydrophobic and oleophober
effect. Microorganisms cling only very heavier on this surface and
can form so hardly colonies. By the complexation of the
polymerized SiO2-Schicht by means of antibacterial chemicals a not
eluierbares Antifouling becomes generated, which is water-neutral.
Cardboard box coating
[0056] Other subject-matter of the invention is a coating of the
aforementioned type in form of a packing coating.
[0057] An other object of the invention is it to make available a
coating as well as methods to the protection before moisture of
packages, like cardboard boxes on paper and sticking basis, like
also on base of fabrics and tissues of most different type, before
rains, snows, condensed water, sea water, extreme high relative
humidity and microorganisms, with simultaneous retention of the
breathing activity (diffusible) on the base of ultradünnen
SiO2-Beschichtungen and simultaneous antimicrobial protection, as
well as a method for this.
[0058] Packages, like cardboard boxes serve all type as waterproof
package of goods and goods, in order to ensure as safe a transport
of the cargo as possible, i.e. one strives to a Antifouling
coating to reach.
[0059] Here the package is not only to protect the content against
damages mechanical type, but the package is to protect the cargo
also against impairment by waters or moisture. The cargoes are
moisture of most different type, like e.g. Rain, snow, condensed
water, sea water, extreme high relative humidity or wet pile
documents, exposed. Moisten or wet-damaged cardboard boxes e.g.
suffer depreciations. by linear deformations, twist features,
changes in evenness and color, reduction of the mechanical tear
strength and. With the storage in the stack a
Feuchtigkeitsüberschuss leads to swelling the fibers in the edge
portions thereby among other things in their edges the wavy can.
These damages are irreversible, there it with the later drying
process to forgiven due to internal stresses with uneven
distribution of the moisture within the sheet and for spotting
(edges of drying) come. Charge sweat can particularly with travels
from cold to warm and/or. with the deletion in tropical ports
develop, if the good did not become sufficient heated during the
journey and e.g. when opening the hatchways and/or. Container
doors of the warm ambient air exposed becomes. A certain breathing
activity is quite desired with some packages, if e.g. Products
packaged become, which deliver moisture after packing still. In
the range of the Pharma and medical technology industry some
products e.g. become. warm and wet packaged. It exists thus the
need at packages, which are in the layer, to deliver moisture from
the inside outward simultaneous however from the outside inward
waterproof is.
[0060] It is thus provided cardboard boxes on the outside with PL
coatings (PE) too known, packages, in order to prevent the
penetration of water in the form of rains, snows, condensed water,
sea water, extreme high relative humidity or wet pile documents
into the package. Simultaneous one however the prevented PL
coating the diffusion of moisture, z. B. that residual moisture of
the product which can be packed arrives, from the inside outward.
From the outside applied PL coating works the moisture in and at
the cardboard box condensed in this place like a vapor barrier. By
the moisture absorption the stability of the carton, in particular
from the inside becomes significant affected in the first 3-5
days. During this time the frequency of the TUL processes in such
a way specified (transport, envelope, storage) is highest. Damages
at the carton are preprogrammed thereby which has immense costs
for remedy to the sequence.
[0061] Condensed water molecules are approx. 700-mal larger as
vaporous water molecules, is called water vapor is in the layer by
the coating to be diffused. Condensed molecules are substantial
larger and become thus at the surface retained. The coating is
glassy due to the polymerized SiO2-Matrix and favourable-proves
thereby very abrasion-stable, acid and caustic solution-stable as
well as scratch-proof.
[0062] Object of the invention is it to create a novel packing
coating those the disadvantages of the polyethylene coating (vapor
barrier) prevented, simultaneous wasserundurchlässige and
breathe-active properties exhibits, hydrophobic and simultaneous
oleophob and antimicrobial is and the so inexpensive number of the
damages reduced and but ensures that packages even multiple used
to become to be able.
[0063] This object becomes dissolved by the use of the coating
composition of the before-described type on/in packages, like
cardboard boxes on paper and sticking basis, as also on base of
fabrics and tissues and Gewirken.
Coating for aquariums/Terrarien
[0064] Other subject-matter of the invention is a coating of the
aforementioned type of aquariums or Terrarien, in particular from
sea water or fresh water aquariums.
Coating of organic materials
[0065] Other subject-matter of the invention is a coating, with
that the support material from the organic materials, in
particular wool, cotton (cellulose), fabrics, paper, paperboard,
nature sponge, art sponge, leather, wood, carton and plastics
exists.
[0066] As substrate surfaces used can become, exist those from
plastic, wood, leather, textile tissues, felts, nonwoven fabrics,
Non wovens and Gewirken. By the ductile properties of the coatings
all geometric shapes can be treated, a very smooth, homogeneous
surface of lowest surface tension always develops.
Coating of inorganic materials
[0067] Other subject-matter of the invention is a coating of the
aforementioned type, with which the support material exists metal,
glass, artificial rock of the inorganic materials, in particular
such as concrete, brick, tiles, fronts, finery.
[0068] Other subject-matter of the invention is a coating of the
aforementioned type, with which the support material contains
composite materials like glass-fiber reinforced plastic and/or
metal plastic fabric.
Coating of plastics
[0069] Other subject-matter of the vorliegenen invention is a
coating of the aforementioned type, with which the support
material artificial fibers, felts and tissue, in particular from
polyester, contains polypropylene, polyethylene of high density,
polyethylene low density, polyacrylonitrile, polyamide, Polyimid,
Polyaramid, aramid, meta aramid, para aramid,
polytetrafluoroethylene, polyvinylidene fluoride, polyphenylene
sulfide
Preparation of the coating
[0070] The present invention is the basis further the object to
make a method available to the preparation of the before-described
coating
[0071] The invention relates to such a method to the preparation
of a coating of the before-described type, how in a first process
step the formation of a Solgels also nano-potash towards particles
in actual known manner by hydrolysis of a Prekcrsors in water
performed becomes and
in a second process step/the dispersed antimicrobial active
ingredients of the before-described type of the sols supplied
solved in an hydrophilic solvent become.
[0072] Here it is prefered that the Prekursor is selected from the
group of the Alkyltriethoxysilane and the
Aminopropyltriethoxysilane, that up to 20 Gew % Al2O3, TiO2, ZrO2,
MgO and/or V2O5, related to the total proportion at SiO2, added
are and that the conversion within 0,5 to 72 h, with temperatures
of 5 deg. C to 60 deg. C made.
[0073] It is more other prefered that the hydrophilic solvent
selected is from water and/or linear or branched alcohols with up
to 6 carbon atoms, in particular water-contained alcohols, in
particular ethanol.
Application of the coating
[0074] The invention is the basis the other object to make
available a method to the application of the coating.
[0075] The invention relates to therefore further a method to the
application of the coating composition, on support materials of
the before-described type by contacting the surface, in particular
spraying, immersion, spinners, capers, Begiessen, Foulardierung,
Filmbegiessen and spraying bars with at least a spray nozzle. The
coating and/or. Surface refinement can take place via conventional
methods such as a spraying (spray coating), immersion (dip
coating), spinners (spin coating) capers, Begiessen. Likewise
possible and established are industrial coating methods such as
Foulardierung, Filmbegiessmaschinen, spraying bar with or several
spray nozzles.
[0076] The present invention concerns finally various types of use
of the application of the coating composition.
antifouling
[0077] First the coating composition according to invention of the
aforementioned type can become as Antifouling means for with
water, in particular with sea and sea water in compound standing
surfaces used.
Cardboard box coating
[0078] More other the coating composition according to invention
of the aforementioned type on/in packages, like cardboard boxes on
paper and sticking basis, can as also on base of fabrics and
tissues and Gewirken used become.
Corrosion protection for
technical apparatuses and containers
[0079] The present invention concerns further the use of the
aforementioned coating composition as corrosion protection of
technical apparatuses or containers, in particular heat
exchangers, evaporation radiators, Kesselrohren, heating surfaces,
spraying adsorbents, spray dryers, refrigerators, chimneys from
metal, catalysts, turbines, fans, reactors, silos for food, cement
silo, lime silo, coal silo.
Corrosion protection for glass
surfaces
[0080] The present invention concerns further the use of the
vorgenanten coating composition as corrosion protection before
glass corrosion of glass surfaces, in particular windows, glass
doors, devices and facade components from glass.
Stömungsverhältnisverbesserer
[0081] The present invention concerns further the use of the
vorgenanten coating composition as surface treatment to the
improvement of flow conditions on surfaces of turbine wheels,
turbine blades, heating snails, extruder screws, screws, injection
nozzles, Windrädern, fans, compressor screws, compressor screws,
turbocharger impellers.
Antimicrobial protective layer
[0082] The present invention concerns further the use of the
coating composition as antimicrobial protective layer of
refrigerators, cooling resting and cooling spaces, in particular
in commercial meat dismantling and processing plants.
[0083] The present invention concerns further the use of the
coating composition as antimicrobial protective layer private
spaces, in particular hospitals, used of surfaces in commercial
or, senior hostels, meat-dismantling-operated, food production
plants, large-scale catering establishments, and in vehicles, in
particular aircrafts, person penalties, ships, trains and
streetcars.
[0084] The present invention concerns further the use of the
coating composition as antimicrobial protective layer of
production machines in the food industry.
[0085] The aforementioned spaces and vehicles are always very
susceptible due to the multiplicity of the users and the type of
the processed stored foods to an increased occurrence of
microorganisms, which establish themselves otherwise on the
surfaces of the spaces. This can by the above mentioned. Coating
(composition) reduced/avoided becomes.
Noise reduction
[0086] The present invention concerns further the use of the
coating composition as slipping layer for reduction/avoidance of
noises, which result one on the other from rubbing surfaces.
Extensibility of the coating
[0087] The composition according to invention is characterised
finally by the fact that it exhibits an extensibility opposite the
origin-large of up to 250%.
[0088] The present invention becomes subsequent first by
embodiments in the form of manufacture examples and application
examples more near explained.
Embodiment 1 “textile substrate”:
1. Preparation aqueous biocides
of a SiO2 - Solgels
[0089] Become 100 ml tetraethoxysilanes, 400 ml waters and 200 ml
0.01 N hydrochloric acid with ambient temperature (20 deg. C)
mixed and continuous agitated (approx. 5 hours). An aqueous SiO2
develops - for Solgel, with a solid content of approx. 4.5% SiO2
with an average particle size of 6 Nm. Mixed in a second step 100
ml this Solgels with 100 ml 2% igen solution of the biocide
combination (mixing ratio 50% chitosan 2s, 25% triclosan and 25%
Cetyltrimethylammoniumbromid) in 5% acetic acid mixed and. The
Solgel developed in such a way can become by means of various
variants on textile substrates applied.
2. Preparation that biocides SiO2
- coating on a textile substrate
[0090] A Polyphenylensulfidfilz in DIN A4-Format became coated by
immersion in that bottom 1 described solution. Subsequent one
became the substrate with ambient temperature 24 hours dried,
after conclusion of the drying phase developed the coating of
approx. 150 Nm layer thickness on the fibers (see fig 2). The sols
became complete reacted into a gel, which the individual fibers of
the felt structure complete coated.
3. Antimicrobial examination of
the felt sample
[0091] The determination biocides of the effect became following
EN 1040 by Institut Fresenius performed. The test organisms
staphylococci became aureus (ATCC 6538) and Pseudomonases
aeruginosa (ATCC 15442) used. With the help of the dilution
Neutralistions and diaphragm filtration method shown could become
that on the coating surface a bacteria reduction around factor
10< 5> after an exposition time of 60 minutes to register
was.
Embodiment 2 “substrate from
plastic”:
1. Preparation aqueous biocides
of a SiO2 - Solgels
[0092] 100 ml tetraethoxysilanes, 400 become ml ethanol and 200 ml
0.01 N hydrochloric acid with ambient temperature (20 deg. C)
mixed and continuous agitated (approx. 5 hours). A liquid SiO2
develops - for Solgel, with a solid content of approx. 4.5% SiO2
with an average particle size of 6 Nm. Mixed in a second step 100
ml this Solgels with 100 ml 2% igen solution triclosan in 5%
acetic acid mixed and. The Solgel developed in such a way can
become by means of various variants on substrates from plastic
applied.
2. Preparation that biocides SiO2
- coating on a plastic substrate
[0093] A plastic plate from PVC in the dimension of 30 cms x 30
cms became coated by spraying with that bottom 1 described
solution. Subsequent one became the substrate with ambient
temperature 24 hours dried, after conclusion of the drying phase
developed the coating of approx. 150 Nm layer thickness on the
plastic plate. The surface of the plate became complete coated.
3. Antimicrobial examination of
the plastic plate
[0094] The determination biocides of the effect became following
EN 1040 by Institut Fresenius performed. The bacteria
“Corynebacterium became minutissiimum (gram positive),
Propionibacterium of acnes (gram positive), staphylococci aureus
(gram positive), staphylococci epidermitis (gram positive),
Strepptococcus courage to (gram positive), Escherichia coli (gram
negative) and Pseudomonases aeruginosa (gram negative) used. With
the help of the dilution Neutralistions and diaphragm filtration
method shown could become that on the coating surface a bacteria
reduction around factor 10< 5> after an exposition time of
60 minutes to register was.
Embodiment 3 “comparative test”
[0095] 8 plastic plates became after embodiment 2 for a
comparative test prepared. In an initial step the plates with a
strong cationic surfactant became purified, subsequent
fine-purified with an isopropanol solution in a second step. The
plates 1 to 8 became as follows coated:
<tb> plate 1< September> uncoated (0-Probe)
<tb> plate 2< September> SiO2-Beschichtung with
Chitosan+Triclosan (2% industrial union)
<tb> plate 3< September> SiO2-Beschichtung with
Chitosan+Triclosan (5% industrial union)
<tb> plate 4< September> SiO2-Beschichtung with
Chitosan+Quats (2% industrial union)
<tb> plate 5< September> SiO2-Beschichtung with
Chitosan+Quats (5% industrial union)
<tb> plate 6< September> SiO2-Beschichtung with
Triclosan+Quats (2% industrial union)
<tb> plate 7< September> SiO2-Beschichtung with
Triclosan+Quats (5% industrial union)
<tb> plate 8< September> SiO2-Beschichtung with
Chitosan+Triclosan+Quats (2% industrial union)
<tb> plate 8< September> SiO2-Beschichtung with
Chitosan+Triclosan+Quats (5% industrial union)
[0096] The examination of the antibacterial activity of the
different coatings against bacteria the shining bacteria test
became after Dr. Prolonged one (DIN 38,412 L 34/341), which as
test on the toxicity of effluents used becomes, applied. As test
bacterium shining bacteria of the type “Vibrio became fischeri”
(NRRL-B-11117, gram negative) used. This test is based on the
ability of certain marine bacteria (v.a.Meeresbakterien) to shine.
This lamps, which due to enzymatic, energy-metabolicdependent
process (Luciferin luciferasesystem) runs off. If these organisms
come however into a toxic medium, then their luminosity becomes
inhibited. The toxicity of single substances, material mixtures or
eluates becomes photometric determined as shining inhibition. From
the degree of the inhibition of shining one can draw conclusions
on the degree of the growth inhibition.
[0097] In an initial step the conserved shining bacteria of the
type NRRL-B-11177 in a broth reactivated and output lights the
photometric measured and thus the zero-sample defined become.
Afterwards the shining bacteria solution becomes applied on the
substrate which can be examined by means of a pipette. After in
each case 20, 40, 60, 80, 100, 120 and 140 minutes luminosity
becomes photometric measured and with the output value of the
zero-sample compared. The decrease of luminosity becomes as
%-value “growth inhibition related to the zero-sample” over the
time applied.
Used one became the Dr. Prolonged LUMIStox measuring position,
existing from the LUMIStox metre, which LUMIStherm Temperiergerät
and the thermal printer see LD 100. e.g.
http://www.rz.fh-ulm.de/labore/chemie/AUSSTATTUNG/BIOLUM/Biolum.htm
[0098] Fig 4 shows the growth inhibition of the various coating in
% measured over the time.
[0099] The long-term effect regarding antimicrobial effect could
become successful detected. Also after more than 12 months
significant restrictions of growth could become from over 90%
shown.
Embodiment 4 “hull”
[0100] 4 plates of 30 x each 30 cms, from an used yacht trunk the
cut became, by the present Antifouling paints by sandblast freed.
The paints became remote up to opening the Gelcoat layer.
Subsequent one became the Gelcoat layer with filler verse lease
ELT and polished. Afterwards the plates with a Vinyl primer
treated and with a commercial bottom structure color (make became:
Jotun Hardtop 2C) dual painted. It concerned a 2-components color
on PU basis. After drying the color different coatings became 2
applied after embodiment. The subsequent biocide combinations
became applied.
<tb> plate 1< September> SiO2-Beschichtung with
Chitosan+Triclosan (2% industrial union)
<tb> plate 2< September> SiO2-Beschichtung with
Chitosan+Quats (2% industrial union)
<tb> plate 3< September> SiO2-Beschichtung with
Triclosan+Quats (2% industrial union)-->
<tb> plate 4< September> SiO2-Beschichtung with
Chitosan+Triclosan+ Quats (2% industrial union)
[0101] The examination of the antimicrobial effect again that
became bottom embodiments 3 described shining bacteria test
performed. Almost identical results, like in fig 4 shown, could
become observed.
Embodiment 5 “cardboard gnawing”
[0102] 8 cardboard plates of 30 x each 30 cms, prepared became
from a commercial cardboard box material with a basis weight of
approx. 400 g/m< 2> , after embodiment 1 with different
biocide coatings equipped.
<tb> plate 1< September> uncoated (0-Probe)
<tb> plate 2< September> SiO2-Beschichtung with
Chitosan+Triclosan (2% industrial union)
<tb> plate 3< September> SiO2-Beschichtung with
Chitosan+Triclosan (5% industrial union)
<tb> plate 4< September> SiO2-Beschichtung with
Chitosan+Quats (2% industrial union)
<tb> plate 5< September> SiO2-Beschichtung with
Chitosan+Quats (5% industrial union)
<tb> plate 6< September> SiO2-Beschichtung with
Triclosan+Quats (2% industrial union)
<tb> plate 7< September> SiO2-Beschichtung with
Triclosan+Quats (5% industrial union)
<tb> plate 8< September> SiO2-Beschichtung with
Chitosan+Triclosan+Quats (2% industrial union)
<tb> plate 8< September> SiO2-Beschichtung with
Chitosan+Triclosan+Quats (5% industrial union)
[0103] Subsequent ones were submitted the cardboard plates to an
antibacterial test. Again the shining bacteria test became also
here after Dr. Prolonged to the application brought. It did not
surprise that also with this test almost identical results were to
be registered, like bottom fig 4 shown. Since the biological
processes on that take place biocides coating, the nature of the
substrate does not have any influence on the antibacterial
activity.
Embodiment 6 “noise reduction
[0104] With various laboratory tests surprising found became that
surfaces, which became according to claim 1 coated with
formulations a significant reduced noise shown. It is known that
if two materials are located in contact and thereby by outside
excitation relative move to each other, thus Knarz and screeching
noises or undesirable friction behavior to develop can. The stick
slip effect, which is major responsible for such phenomena,
becomes minimized by the coating. Bottom stick slip effect
understands one the permanent transition about detention on
sliding friction in a movement motion. Various oscillations
depending upon nature of the surfaces rubbing one on the other,
which become of the resonancable surface radiated as noise,
develop. It is obvious that the coating functions as release layer
between the friction partner and contributes thus to the noise
minimization.
Example 6.1
[0105] A metal plate from stainless steel 1,4571 with the
dimensions 25 x 40 cms was provided to the half along the
longitudinal axis with the coating. Subsequent one became
attempted to produce by means of a cork, piece a rubber, a
polishing cloth, piece a wood and piece a metal on the uncoated
and on the coated surface of the metal plate by friction with
different pressure Knarz and screeching noises. With the fact
found became that noise on the coated half of the metal plate was
more perceptible smaller significant to nearly no longer present.
Example 6.2
[0106] A plastic plate from PMMA with the dimensions 25 x 40 cms
was provided to the half along the longitudinal axis with the
coating. Subsequent one became attempted to produce by means of a
cork, piece a rubber, a polishing cloth, piece a wood and piece a
metal on the uncoated and on the coated surface of the metal plate
by friction with different pressure Knarz and screeching noises.
With the fact found became that noise on the coated half of the
plastic plate was more perceptible smaller significant to nearly
no longer present.
Example 6.3
[0107] A glass plate from window glass with the dimensions 25 x 40
cms was provided to the half along the longitudinal axis with the
coating. Subsequent one became attempted to produce by means of a
cork, piece a rubber, a polishing cloth, piece a wood and piece a
metal on the uncoated and on the coated surface of the metal plate
by friction with different pressure Knarz and screeching noises.
With the fact found became that noise on the coated half of the
glass plate was more perceptible smaller significant to nearly no
longer present.
Embodiment 7 “extensibility
[0108] As in embodiment described, became a polyamide fiber with
approx. 0.80 mm diameters with the coating according to invention
in addition, with a active substance-free coating provide and
subsequent bent. With the fact significant is more recognizable
that in both cases at the outer radius of the fiber no tears arise
and develop at the inner radius of the fiber to only slight
upsettings. The polymer structure of the SiO2-Beschichtung here
exemplary for the fiber shown, leads ductility, elasticity and
extensibility to properties, which are not from crystalline
SiO2-Strukturen known, i.e. Dependent ones of the elasticity of
the substrate are extensibilities of up to 250% more achievable.
[0109] The present invention becomes other more near explained by
figs.
[0110] Show:
Fig. 1: : A rem receptacle
of the coating in accordance with manufacture example 1 on a PPS
fiber (1500x magnification)
Fig. 2: : a rem
receptacle of the aforementioned coating on a PES fiber (1500x
magnification)
Fig. 3: : a rem receptacle
of the aforementioned coating on a metal substrate.
Fig. 4: : the
antibacterial activity shows various coatings over the time.
Fig. 5: : the extension
ability of the aforementioned coating shows on a Pa fiber.
[0111] Fig. 1 shows those much smooth surface of the coating,
which shows at no location porosity. The pores located in the
fiber become covered by the coating.
[0112] Fig. likewise the very smooth surface structure of the
coating shows 2, as well as complete coating of the round fiber.
Only the smooth surface in compound with one much low surface
tension creates the hydrophobic and oleophoben properties, which
contribute to the fact that the Erstbesiedlung is made more
difficult by microorganisms. There is numerous microorganisms
known, which test before the settlement of the substrate by the
delivery of a tacky secretion quasi whether the surface for a
settlement is suitable. Since this secretion on the oleophoben
surface remains hardly clinging, it does not come only at all in
many cases to a settlement and into sequence to a colony
formation.
[0113] Fig. the coating shows 3 on a metal substrate out. It is
clearer more recognizable the fact that the homogeneous layer does
not exhibit any pores but shows a closed, dense surface.
[0114] Fig. the antibacterial activity of the coatings according
to invention shows 4 to hard surfaces, here PVC a plate opposite
an uncoated or a one only with silicon dioxide-coated plate over a
period of up to 140 minutes with ambient temperature, i.e. in the
comparison. approx. 20 deg. C. The uncoated plate shown in the
frame of the measurement inaccuracy no growth inhibition and only
with silicon dioxide-coated plate achieved after 60 min. a growth
inhibition of 20% and after 140 min of 40%
[0115] Fig. a polyamide fiber with approx. shows 5. 0.80 mm
diameters with the coating according to invention provided is and
subsequent bent becomes. With the fact significant is more
recognizable that at the outer radius of the fiber no tears arise
and develop at the inner radius of the fiber to only slight
upsettings.
[0011] An object of the invention is it first to make a novel
antibacterial coating composition available.
[0012] This object becomes by the combination of the Si02 of
producing means as well as particular portions of particular
antimicrobial agents dissolved, those from a selection of two by
three different material classes made.
[0013] The invention relates to so an antibacterial coating
composition, contained 50 Gew % to 99.9 Gew %, preferably 80 Gew %
to 99 Gew %, a SiO2-erzeugenden of means, whereby the coating
composition contains 0.1 Gew % to 50 Gew %, preferably 1 Gew % to
20 Gew %, related to the total composition, at least an
antibacterial active ingredient in the form of cationic, anionic
or nonionic deacetylierten chitosans and Chitosanderivaten and/or
phenols of the group of the halogenated Dihydroxydiphenylmethane,
- sulfides, and - ether and/or substituted quaternary ammonium
salts of the alkylated phosphoric acid, whereby the antibacterial
active ingredient selected from at least 2 compounds of the 3
appended connecting classes in the form of cationic, anionic or
nonionic deacetylierten chitosans and Chitosanderivaten and/or
phenols of the group of the halogenated Dihydroxydiphenylmethane,
- sulfides, and - ether and/or substituted quaternary ammonium
salts of the alkylated phosphoric acid.
[0014] An other prefered embodiment of the present invention
concerns a composition of the before-described type, with that the
SiO2-erzeugenden means selected is out
0 to 100 Gew %, preferably to Gew % tetraethoxysilanes,
0 to 100 Gew %, preferably to Gew % Trimethoxymethylsilan, and
0 to 100 Gew %, preferably to Gew % Dimethoxydimethylsilan.
[0015] An other prefered embodiment of the present invention
concerns a composition of the before-described type, with which
means producing the SiO2 contains Al2O3, TiO2, ZrO2, MgO and/or
V2O5 further up to 20 Gew %, whereby these additives are in
arbitrary mixing ratios present, preferably in mixing ratios
between 0,1 Gew % and 50 Gew % from the group of the Al2O3, TiO2,
ZrO2, MgO and V2O5, particularly prefered in mixing ratios between
1 Gew % and 20 Gew % from the group of the Al2O3, TiO2 and ZrO2.