DE19955153A1 - Aqueous resin emulsion (I) for forming mold-inhibiting protective films on building materials, especially internal walls, containing acrylate or silane-based polymer and 4-hydroxybenzoate ester as non-toxic active agent - Google Patents
Aqueous resin emulsion (I) for forming mold-inhibiting protective films on building materials, especially internal walls, containing acrylate or silane-based polymer and 4-hydroxybenzoate ester as non-toxic active agentInfo
- Publication number
- DE19955153A1 DE19955153A1 DE1999155153 DE19955153A DE19955153A1 DE 19955153 A1 DE19955153 A1 DE 19955153A1 DE 1999155153 DE1999155153 DE 1999155153 DE 19955153 A DE19955153 A DE 19955153A DE 19955153 A1 DE19955153 A1 DE 19955153A1
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- Germany
- Prior art keywords
- hydroxybenzoic acid
- mold
- synthetic resin
- resin emulsions
- hydroxybenzoate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Ceased
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/36—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids
- A01N37/38—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids having at least one oxygen or sulfur atom attached to an aromatic ring system
- A01N37/40—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids having at least one oxygen or sulfur atom attached to an aromatic ring system having at least one carboxylic group or a thio analogue, or a derivative thereof, and one oxygen or sulfur atom attached to the same aromatic ring system
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0058—Biocides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Wood Science & Technology (AREA)
- Engineering & Computer Science (AREA)
- Plant Pathology (AREA)
- Materials Engineering (AREA)
- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Biodiversity & Conservation Biology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
Description
Schimmel ist eine Sammelbezeichnung für Pilze, die sehr schnell auf Substraten ein mit bloßem Auge sichtbares, watteartiges Mycel ausbilden. Wichtige Vertreter der Schimmelpilze sind Aspergillus-, Penicillium-, Monilia-, Köpfchenschimmel- und Candida-Arten oder die Zygomyce ten.Mold is a collective name for fungi that grow very quickly on substrates with a bare one Develop eye-visible, cotton-like mycelium. Important representatives of the mold are Aspergillus, Penicillium, Monilia, Köpfchenschimmel- and Candida species or the Zygomyce ten.
Einige Schimmelpilze sind pathogen; sie können Mykosen und Allergien verursachen.Some molds are pathogenic; they can cause mycoses and allergies.
Größere, dunkelgefärbte Schimmelpilzansiedlungen, insbesondere in Ecken häufiger zu sehen, heißen Stockflecken.Larger, dark-colored mold settlements, especially in corners to see more often, hot mold stains.
Primäre Ursachen für die Ausbildung von Schimmelpilzansiedlungen in Innenräumen, und hier speziell Wohnräumen, sind falsche Heiz- und Lüftungsgewohnheiten, zu geringe Wärmedämmung, Undichtigkeiten an Wänden und Fensteranschlüssen oder aufsteigende Feuchtigkeit im Mauerwerk.Primary causes for the formation of mold settlements indoors, and here especially living rooms, are wrong heating and ventilation habits, insufficient insulation, Leaks on walls and window connections or rising damp in the masonry.
Diese Ursachen führen sekundär zur Feuchtekondensation und Durchfeuchtung von Baumateria lien. In Gegenwart von ausreichender Feuchtigkeit und auf Baumaterialien in Wohnräumen immer vorhandenen organischen Verbindungen können dann Schimmelpilze gedeihen.These causes lead to moisture condensation and moisture in building materials lien. Always in the presence of sufficient moisture and on building materials in living spaces existing organic compounds can then thrive on mold.
Um das Schimmelwachstum zu stoppen oder zumindest zu vermindern, lassen sich physikalische oder chemische Methoden anwenden.In order to stop or at least reduce mold growth, physical or use chemical methods.
Die physikalischen Methoden zielen darauf ab, die Innenraumkondensation zu unterbinden. Das kann durch Lüften, besseres Dämmen oder z. B. stärkeres Heizen erfolgen. Oft lassen sich diese Vorschläge in der Praxis aus technischen Gründen oder Kostenproblemen nicht verwirklichen.The physical methods aim to prevent indoor condensation. The can by ventilation, better insulation or z. B. stronger heating. Often these can be Do not implement suggestions in practice for technical reasons or cost problems.
Dann werden chemische Verfahren angewandt. Zur Abtötung von Schimmelpilzen bzw. zum Entfernen der Stockflecken lassen sich anorganische und organische Wirkstoffe einsetzen. Then chemical processes are applied. For killing molds or for Inorganic and organic substances can be used to remove the mold stains.
Den wohl wichtigsten Vertreter aus der Gruppe der anorganischen Wirkstoffe stellt das Aktivchlor dar. Die Gefahrenmomente, die aber von dieser Verbindung ausgehen, speziell wenn sie im Haushalt von Nichtfachleuten angewandt wird, sind erheblich. Deshalb werden Chlorbleichlaugen, wie die Aktiv-Chlorverbindungen auch genannt werden, im privaten Bereich nur noch selten verwendet. Ein weiterer Nachteil ist der unangenehme und giftige Chlorgeruch, der allen diesen Produkten anhaftet. Außerdem läßt sich ein Depot-Effekt nicht erzielen.The most important representative from the group of inorganic active ingredients is active chlorine The moments of danger, which emanate from this connection, especially if they are in the Household applied by non-professionals are significant. That's why chlorine bleach, as the active chlorine compounds are also called, only rarely in the private sector used. Another disadvantage is the unpleasant and toxic smell of chlorine, all of which Products. In addition, a depot effect cannot be achieved.
Alternativen bilden organische Fungicide. Bei diesen Stoffen handelt es sich z. B. um Chloraroma ten, substituierten Phenolen, organischen Thioverbindungen und einer Vielzahl ähnlich kompliziert aufgebauter Substanzen. Gemeinsam ist allen diesen Stoffen, oder doch den allermeisten, dass sie nach Gefahrstoffverordnung als giftig oder zumindest gesundheitsschädlich einzustufen sind. Für die Anwendung in den Händen von Selbermachern im Haus- und Heimbereich kommen sie daher nicht in Frage.Alternatives are organic fungicides. These substances are e.g. B. chlorine aroma ten, substituted phenols, organic thio compounds and a variety of similarly complicated built up substances. Common to all these substances, or most of them, is that they according to the Ordinance on Hazardous Substances are to be classified as toxic or at least harmful to health. For they are therefore used in the hands of do-it-yourselfers in the home and at home out of the question.
Da die eigentliche Ursache für das Auftreten von Schimmelpilzbefall in Bauwerken in den meisten Fällen die ungenügende Isolation darstellt, liegt es nahe die Abdichtung wiederherzustellen. Wenn eine Außenabdichtung der in Frage stehenden Bauwerken wegen konstruktiver Schwierigkeiten bzw. aus Kostengründen nicht in Frage kommt, so kann eine Innenabdichtung vorgenommen werden.Because the real cause of mold infestation in buildings in most If the insulation is insufficient, it makes sense to restore the seal. If external sealing of the buildings in question due to constructional difficulties or is out of the question for cost reasons, an internal seal can be made become.
Praktisch ausgeführt wird die Innenabdichtung üblicherweise durch Auftragen wässriger Kunst harzdispersionen oder -emulsionen. Nach Abtrocknen der Harze bildet sich ein schützender Fim aus. Daher rührt der in diesem Zusammenhang übliche Ausdruck Filmkonservierung.In practice, the internal sealing is usually carried out by applying watery art resin dispersions or emulsions. After the resins have dried, a protective film forms out. This is where the term film preservation comes from.
Geeignete Kunstharzemulsionen enthalten nach dem Stand der Technik hydrophobierend wirkende Silane oder Siloxane.Suitable synthetic resin emulsions contain, according to the prior art, hydrophobic agents Silanes or siloxanes.
Im Rahmen der vorliegenden Erfindung werden Silan- und Siloxanverbindungen, abweichend von der üblichen chemischen Nomenklatur, als Silikone bezeichnet, also einschließlich der Silane. In the context of the present invention, silane and siloxane compounds, deviating from the usual chemical nomenclature called silicones, including the silanes.
Nachteil dieser Zubereitungen ist, dass sie zwar wasserabweisend und damit abdichtend, aber nicht fungicid wirken.The disadvantage of these preparations is that, although they are water-repellent and therefore sealing, they do do not act fungicidally.
Aufgabe der vorliegenden Erfindung ist es daher, wässrige Kunstharzemulsionen bereitzustellen, die wasserabweisend wirken, gut auf alkalischen Baumaterialien haften und gleichzeitig den Schimmelbefall in Innenräumen wirksam verhindern, ohne nennenswerte toxische Gefahren bei der Anwendung hervorzurufen.The object of the present invention is therefore to provide aqueous synthetic resin emulsions, which are water-repellent, adhere well to alkaline building materials and at the same time Effectively prevent mold infestation indoors without significant toxic hazards of the application.
Diese Aufgabe wird erfindungsgemäß durch die in den Ansprüchen 1 bis 8 aufgeführten Merkmale gelöst.This object is achieved by the features listed in claims 1 to 8 solved.
Unter 4-Hydroxybenzoesäureestern, auch p-Hydroxybenzoesäureester genannt, sollen im Rahmen der vorliegenden Erfindung die Methyl-, Ethyl- und Propyl- (einschließlich i-Propyl-)4-Hydroxy benzoesäureester verstanden werden. Diese Verbindungen lösen sich in verdünnten Laugen unter Bildung der entsprechenden Alkalisalze.Among 4-hydroxybenzoic acid esters, also called p-hydroxybenzoic acid esters, are said to be within the scope In the present invention, the methyl, ethyl and propyl (including i-propyl) 4-hydroxy benzoic acid esters are understood. These compounds dissolve in dilute alkalis Formation of the corresponding alkali salts.
Die 4-Hydroxybenzoesäureester dissoziieren in Wasser nur wenig und sind daher über einen weiten pH-Bereich wirksam. Die Hauptwirkung richtet sich gegen Hefen und Pilze, eingeschränkt aber auch gegen Bakterien. Die Wirkung der Ester ist direkt proportional zur Kettenlänge der Alkylre ste.The 4-hydroxybenzoic acid esters dissociate only slightly in water and are therefore over a wide range effective pH range. The main action is against yeasts and fungi, but limited also against bacteria. The effect of the esters is directly proportional to the chain length of the alkylre ste.
Die angebenen 4-Hydroxybenzoesäureester werden schon seit einiger Zeit zur Konservierung von Lebensmitteln verwendet. Die akute Toxizität ist daher gering. Eine Anreicherung im Körper findet ebenso nicht statt, weil der Abbau rasch vonstatten geht.The specified 4-hydroxybenzoic acid esters have been used for some time to preserve Used food. The acute toxicity is therefore low. An accumulation takes place in the body neither does it take place because the dismantling takes place quickly.
Angewandt in Kunstharzdispersionen oder -emulsionen vermögen diese Verbindungen ebenso wie in Lebensmitteln das Wachstum von Schimmelpilzen und anderen Mikroorganismen über längere Zeiträume zu verhindern, ohne dass unzumutbare toxische Auswirkungen befürchtet werden müssten. Used in synthetic resin dispersions or emulsions, these compounds are just as capable in food the growth of mold and other microorganisms over a longer period Prevent periods of time without fear of unacceptable toxic effects would have to.
Die beanspruchten Ester lösen sich schlecht in Wasser, die Löslichkeit reicht aber aus, um in den erfindungsgemässen Kunstharzemulsionen eine ausreichende fungicide Wirkung zu entfalten. Lediglich dispergierte 4-Hydroxybenzoesäureester vermögen darüber hinaus aber eine Depot wirkung aufzubauen, da die fungizide Wirkung nicht an den Lösezustand gebunden ist.The claimed esters dissolve poorly in water, but the solubility is sufficient to be in the resin emulsions according to the invention to develop a sufficient fungicidal action. However, only dispersed 4-hydroxybenzoic acid esters are able to hold a deposit build up effect, since the fungicidal effect is not tied to the release state.
Will man höher Lösungskonzentrationen der beanspruchten 4-Hydroxybenzoesäureester anwenden, so empfiehlt sich die Verwendung der entsprechenden Alkaliphenolate, speziell und bevorzugt der Natriumalkyl-4-Hydroxybenzoate.If one wants to use higher solution concentrations of the claimed 4-hydroxybenzoic acid esters, the use of the corresponding alkali phenolates is recommended, especially and preferably the Sodium alkyl 4-hydroxybenzoate.
Als Aufwandkonzentrationen in den schimmelpilzhemmend eingesetzten Kunstharzemulsionen haben sich Massenanteile von bis zu 3% und bevorzugt bis zu 1%, gerechnet 4-Hydroxybenzoe säure, bewährt.As an expense concentration in the mold-inhibiting synthetic resin emulsions have mass fractions of up to 3% and preferably up to 1%, calculated 4-hydroxybenzoe acid, proven.
Ein Nachteil bekannter Silikonemulsionen zur Baustoffhydrophobierung ist die oft unzureichende Haftung auf glatten Oberflächen. Zur Überwindung dieses Anwendungsproblems haben sich Zusätze von Acrylsäureestern-Acrylnitril-Mischpolymerisaten in Form wässriger Dispersionen zu den wässrigen Silikonemulsionen bewährt. Angewandt werden Massenanteile von 0,01 bis 5%, gerechnet wasserfreie Mischpolymerisate.A disadvantage of known silicone emulsions for waterproofing building materials is that which is often insufficient Adhesion to smooth surfaces. To overcome this application problem have been Addition of acrylic acid-acrylonitrile copolymers in the form of aqueous dispersions proven in aqueous silicone emulsions. Mass fractions of 0.01 to 5% are used, calculated water-free copolymers.
Die Alkylgruppen in den Acrylaten, formal herrührend von den alkoholischen Veresterungs komponenten, reichen von der Methyl- bis zur Butylgruppe und schließen i-Gruppen, wie z. B. i- Propylgruppen, mit ein.The alkyl groups in the acrylates, formally derived from the alcoholic esterification components range from the methyl to the butyl group and include i groups, such as. B. i- Propyl groups, with a.
Der Massenanteil des Acrylnitrils in den beanspruchten Mischpolymerisaten kann zwischen 1 und 30% variieren. Die Mischpolymerisate aus Acrylnitril und Acrylaten sind seit einiger Zeit tech nisch bekannt und am Markt verfügbar. Eine weitergehende Beschreibung kann daher unterbleiben.The mass fraction of acrylonitrile in the copolymers claimed can be between 1 and 30% vary. The copolymers of acrylonitrile and acrylates have been tech for some time nically known and available on the market. A further description can therefore be omitted.
Die Silikonkomponenten in den erfindungsgemäßen Kunstharzemulsionen bestehen aus Methylal kylsiloxanen bzw. Alkylalkoxysilanen. Unter Alkyl- bzw. Alkoxygruppen sollen aliphatische C- Reste mit bis zu 4 C-Atomen verstanden werden. Auch diese Silan- bzw. Siloxanverbindungen sind schon seit längerer Zeit im Handel frei erhältlich und entsprechen daher dem Stand der Technik. Auf eine genauere Beschreibung wird ebenfalls verzichtet.The silicone components in the synthetic resin emulsions according to the invention consist of methylal kylsiloxanes or alkylalkoxysilanes. Under alkyl or alkoxy groups, aliphatic C- Residues with up to 4 carbon atoms can be understood. These silane or siloxane compounds are also freely available in stores for a long time and therefore correspond to the state of the art. A more detailed description is also omitted.
Die Massenanteile der summarisch als Silikonverbindungen bezeichneten Silane bzw. Siloxane in den erfindungsgemäßen Kunstharzemulsionen liegen bei bis zu 10% Siloxan bzw. bis zu 10% Silan.The mass fractions of the silanes or siloxanes, collectively referred to as silicone compounds in the synthetic resin emulsions according to the invention there is up to 10% siloxane or up to 10% Silane.
Die praktische Anwendung der beschriebenen Kunstharzemulsionen erfolgt ganz überwiegend im Innenbereich von Gebäuden aller Art und hier wieder in den Kellerräumen. Dazu werden die erfindungsgemäßen wässrigen Kunstharzemulsionen satt und gleichmäßig mit Pinsel, Rolle oder Quast aufgetragen bzw. aufgespritzt. Nach 12 Std. Trockenzeit bei 23°C sind die Emulsionen weitgehend abgetrocknet.The practical application of the synthetic resin emulsions described takes place predominantly in Inside of buildings of all kinds and here again in the basement. To do this, the aqueous synthetic resin emulsions according to the invention saturated and even with a brush, roller or Brush applied or sprayed on. After a drying time of 12 hours at 23 ° C the emulsions are largely dried.
Die entstandenen Imprägnierungen mit den erfindungsgemäßen Kunstharzemulsionen sind wasserabweisend, jedoch atmungsaktiv, d. h. wasserdampfdurchlässig. Außerdem sind sie alkali- und UV-beständig. Die Imprägnierungen verhindern Verschmutzungen, Ausblühungen und schützen vor Befall mit Mikroorganismen, wie z. B. Schimmelpilzen, Hefen und Bakterien.The resulting impregnations with the synthetic resin emulsions according to the invention are water-repellent but breathable, d. H. permeable to water vapor. They are also alkaline and UV resistant. The impregnations prevent dirt, efflorescence and protect against infestation with microorganisms, such as. B. molds, yeasts and bacteria.
Claims (8)
Priority Applications (1)
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DE1999155153 DE19955153A1 (en) | 1999-11-17 | 1999-11-17 | Aqueous resin emulsion (I) for forming mold-inhibiting protective films on building materials, especially internal walls, containing acrylate or silane-based polymer and 4-hydroxybenzoate ester as non-toxic active agent |
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DE1999155153 DE19955153A1 (en) | 1999-11-17 | 1999-11-17 | Aqueous resin emulsion (I) for forming mold-inhibiting protective films on building materials, especially internal walls, containing acrylate or silane-based polymer and 4-hydroxybenzoate ester as non-toxic active agent |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2004086867A1 (en) * | 2003-04-03 | 2004-10-14 | Degussa Ag | Method for preventing mold formation by using hydrophobic materials, and mold-controlling agent for building parts |
DE102004047118A1 (en) * | 2004-09-27 | 2006-04-06 | Celanese Emulsions Gmbh | Polymer dispersions with fungicidal activity and their use |
-
1999
- 1999-11-17 DE DE1999155153 patent/DE19955153A1/en not_active Ceased
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2004086867A1 (en) * | 2003-04-03 | 2004-10-14 | Degussa Ag | Method for preventing mold formation by using hydrophobic materials, and mold-controlling agent for building parts |
US8563010B2 (en) | 2003-04-03 | 2013-10-22 | Evonik Degussa Gmbh | Method for preventing mold formation by using hydrophobic materials, and mold-controlling agent for building parts |
DE102004047118A1 (en) * | 2004-09-27 | 2006-04-06 | Celanese Emulsions Gmbh | Polymer dispersions with fungicidal activity and their use |
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