EP2106418A1 - Masses de collage et d'étanchéité présentant un apprêt antimicrobien - Google Patents

Masses de collage et d'étanchéité présentant un apprêt antimicrobien

Info

Publication number
EP2106418A1
EP2106418A1 EP07858198A EP07858198A EP2106418A1 EP 2106418 A1 EP2106418 A1 EP 2106418A1 EP 07858198 A EP07858198 A EP 07858198A EP 07858198 A EP07858198 A EP 07858198A EP 2106418 A1 EP2106418 A1 EP 2106418A1
Authority
EP
European Patent Office
Prior art keywords
adhesive
sealant
octyl
rtv
isothiazolin
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.)
Withdrawn
Application number
EP07858198A
Other languages
German (de)
English (en)
Inventor
Thomas Wunder
Rüdiger Baum
Roman Grabbe
Hans-Jürgen Schmidt
Thomas Schiwek
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Thor GmbH
Original Assignee
Thor GmbH
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Thor GmbH filed Critical Thor GmbH
Publication of EP2106418A1 publication Critical patent/EP2106418A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • 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
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/26—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests in coated particulate form
    • A01N25/28—Microcapsules or nanocapsules
    • 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
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/45—Heterocyclic compounds having sulfur in the ring
    • C08K5/46—Heterocyclic compounds having sulfur in the ring with oxygen or nitrogen in the ring
    • C08K5/47—Thiazoles
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/10—Encapsulated ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/34—Condensation polymers of aldehydes or ketones with monomers covered by at least two of the groups C08L61/04, C08L61/18 and C08L61/20

Definitions

  • the invention relates to a biocidal agent antimicrobially treated adhesive and sealants, especially silicone rubbers and acrylate sealants.
  • the biocidal active ingredient is enclosed in a resin based on, for example, an aminoplast.
  • the encapsulated biocidal active ingredient is useful as an adjunct for finishing adhesives and sealants such as silicone rubbers or acrylate sealants.
  • Under sealing compounds is meant elastic, z. B. applied as flexible profiles or webs substances for sealing buildings or facilities against water, aggressive media or other atmospheric influences.
  • To the sealants u. a. Bitumens, synthetic resin, polysulfides, acrylates and silicones.
  • silicone rubbers and acrylates are preferably used in many branches of industry, but due to their compositions they may, over time, undergo chemical and biological degradation.
  • the silicone rubbers are divided into different types, room temperature vulcanizing rubbers (RTV), liquid silionic rubbers (LSR) and high temperature vulcanizing rubbers (HTV).
  • RTV-I silicone rubbers are one-component systems that are directly applicable and vulcanize at room temperature under the influence of humidity to form an elastic rubber.
  • RTV-2 silicone rubbers vulcanization only occurs after the mixing of at least two components.
  • RTV-I or RTV-2 silicone rubbers are elastic adhesives and sealants.
  • the polymers used for the RTV-I silicone rubbers are usually linear diorganopolysiloxanes with silanol end groups. Chemically they are ⁇ , ⁇ -dihydroxy-organopolysiloxanes following general formula:
  • alkyl radicals in particular methyl groups
  • B trifluoropropyl groups used.
  • the number n can vary widely and is often between 500 and 1500.
  • these polymers have reactive groups (-OH groups) at both ends. Condensation can take place via the silanol group with elimination of water.
  • acrylate polymers Other adhesives and sealants that have proven themselves in practice are elastic compositions based on acrylate polymers. These are z. B. homopolymers or copolymers of alkyl acrylates (having alkyl groups of 1 to 10 carbon atoms) with vinyl monomers (such as styrene, acrylonitrile, vinyl butyl ether, acrylic acid, methacrylic acid, or esters of said acids). Also z. As polyvinyl compounds (such as divinylbenzene) can be used.
  • JP-2002053412 (Daiwa Kagaku Kogyo) it is known to include biocidal agents in a resin matrix.
  • OIT 2-n-octyl-isothiazolin-3-one
  • WO 2006/032019 (Mikrotek) describes an encapsulation of biocidal active substances such as isothiazolinones (eg DCOIT or OIT).
  • a shell material z. B. presented a melamine-formaldehyde resin.
  • EP-A 0 679 333 (Rohm & Haas) are polymers for encapsulation of biocidal agents such.
  • coating compositions for masonry which contain a biocidal active substance such as an isothiazoline in encapsulated form.
  • Plasticizers, water repellents, and / or binders are provided, or during the
  • microbiologically degradable material e.g. organic substances from the environment or soaps (for example in the area of bathrooms).
  • the infestation of the adhesives and sealants by fungi, algae or bacteria can not only affect the appearance, but also the performance characteristics of the adhesives and sealants are adversely affected. In addition, unpleasant odor nuisance and health hazards can be caused by the release of metabolic products.
  • biocides bactericides, fungicides and / or algicides
  • bactericides, fungicides and / or algicides bactericides, fungicides and / or algicides
  • biocides that are subject to only a small degradation and remain largely irrigated in the adhesives and sealants.
  • the biocides that are satisfactory in this respect are often less suitable for the finishing of adhesives and sealants because of their toxic effects.
  • chlorothalonil and carbendazim which, however, have considerable gaps in their effectiveness or ensure good fungicidal protection only in very high concentrations.
  • the active substance remaining on the adhesive and sealing compounds after finishing is washed out in practical use by contact with moisture, for example during irrigation (for example under the shower).
  • moisture for example during irrigation (for example under the shower).
  • a considerable loss of active ingredient is recorded.
  • the influence of light in the area of window seals can also lead to a decomposition of the biocidal active substances remaining after the finishing.
  • unwanted discoloration of the adhesives and sealants can also be observed through the interaction of certain heavy metal ions with biocides, such as zinc pyrithione. Also, an inhibition of vulcanization may occur.
  • the invention is therefore also based on the object of providing antimicrobial adhesive and sealing compounds, in particular silicone rubbers, which largely avoid the disadvantages listed above.
  • antimicrobial adhesive and sealing compounds in particular silicone rubbers
  • the environmental impact and the cost of equipping the adhesives and sealants to combat harmful microorganisms to be reduced and the leaching of the biocidic agent from the finished adhesives and sealants are reduced.
  • the antimicrobial effect The biocide used should be guaranteed for a long time. It is a further object to provide alternatives to toxicologically objectionable compositions.
  • This object is achieved by providing a sealant which is provided with at least one particular biocidal active ingredient.
  • 2-n-octyl-4-isothiazolin-3-one (OIT) which is already known per se as a biocide and has the following formula, is preferably used as the biocidal active substance.
  • OIT 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one (DC-OIT) and / or N-alkyl-l, 2-benzisothiazolin 3-on, whereby a surprisingly durable preservation can be achieved with OIT.
  • DC-OIT 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one
  • N-alkyl-l, 2-benzisothiazolin 3-on whereby a surprisingly durable preservation can be achieved with OIT.
  • one or more further biocides are used in the sealant.
  • the biocidal active substance, in particular OIT may preferably be enclosed in microparticles, in particular in an aminoplast resin, more preferably in a melamine-formaldehyde resin.
  • the active substance (s) are in an aminoplast Resin included.
  • biocidal active ingredient in the context of the present invention refers to the substance or the substance mixture which has the biocidal effect on which the invention is based. "In the biocidally active ingredient component, in each case 2-n-octyl-4-isothiazolin-3-one or contain one of the two alternative agents mentioned above, optionally, other active ingredients may be present.
  • the present invention relates in general to a sealant equipped with a biocidal active substance which contains OIT (or one of the abovementioned alternatives) as biocidic active ingredient and optionally one or more further biocides, the 2-octyl-4-isothiazolin-3-ol preferably used. is encased in microparticles of an encapsulant, in particular an aminoplast resin.
  • sealants RTV-1 or RTV-2 silicone rubber and acrylate sealants are of particular interest, with best results being achieved with sealants of RTV-1 or RTV-2 silicone rubber.
  • the adhesives and sealants in particular the RTV-I or RTV-2 silicone rubbers or the acrylate sealants preferably contain the microparticles used in amounts of from 0.01 to 5% by weight, based on the total weight of the aminoplast resin.
  • the invention also relates to a sealant which is an RTV-I or RTV-2 silicone rubber or an acrylate sealant containing as microparticles 25 to 45% by weight of an aminoplast resin and 55 to 75% by weight of the biocidal active ingredient, based on the total weight of the aminoplast resin and the biocidal active ingredient.
  • a sealant which is an RTV-I or RTV-2 silicone rubber or an acrylate sealant containing as microparticles 25 to 45% by weight of an aminoplast resin and 55 to 75% by weight of the biocidal active ingredient, based on the total weight of the aminoplast resin and the biocidal active ingredient.
  • the sealant is characterized in that the amount of the biocidal active ingredient, based on the total weight of the sealant, is 0.0001% by weight to 0.5% by weight.
  • the sealant is characterized in that the amount of the biocidal active ingredient, based on the total weight of the sealant, is 0.01% by weight to 0.2% by weight.
  • the sealant is characterized in that the aminoplast resin is selected from the group of melamine, urea, cyanogen and dicyandiamide-formaldehyde resins or a mixture of two or more of these resins.
  • An aminoplast resin is preferably a melamine-urea-formaldehyde resin or a melamine-phenol-formaldehyde resin, especially a melamine-formaldehyde resin.
  • the sealant is characterized in that the aminoplast resin is formed from a compound containing NH groups and acetaldehyde or glyoxal.
  • the sealant is characterized in that the microparticles containing the biocidal agent have an average diameter of 0.5 to 100 microns.
  • the D-50 value is preferably 1 to 15 ⁇ m, the D-90 value is preferably less than 60 ⁇ m.
  • the sealant is characterized in that it contains, in addition to the microparticles containing a biocidal active ingredient OIT, another biocidal component which may be encapsulated or unencapsulated. As a further biocidal component in particular OIT is in non-encapsulated form into consideration.
  • the invention also relates to a method for producing a sealant equipped with a biocidal active substance, wherein the microparticles containing 2-n-octyl-4-isothiazolin-3-one (or the alternative active ingredients) are added to a sealant during manufacture. This can e.g. by mixing the components with the manufacturer or only directly during use.
  • the method for producing a sealant equipped with a biocidal active ingredient is characterized in that the sealant is an RTV-I or RTV-2 silicone rubber or an acrylate sealant and used as a biocide OIT containing microparticles in an amount of, based on the total weight of the sealant, 0.01% by weight to 0.2% by weight are mixed in the preparation.
  • the present invention also relates to the use of OIT (or the alternatives) and optionally one or more further biocides containing microparticles based on z.
  • OIT or the alternatives
  • further biocides containing microparticles based on z As an aminoplast resin for the protection of sealants against microorganism infestation, especially fungal infection.
  • the microparticles in an RTV-I and RTV-2 silicone rubber or an acrylate sealant are added during manufacture.
  • the microparticles contain biocidal active ingredient 2-n-octyl-4-isothiazolin-3-one and additionally one or more other biocides.
  • the ratio of 2-n-octyl-4-isothiazolin-3-one to the other biocide (s) can, in principle, vary and be varied within wide limits, for example in the range from 100: 1 to 1: 100, preferably 50: 1 to 1:50, especially 1:25 to 25: 1.
  • the 2-n-octyl-4-isothiazolin-3-one is usually present in amounts of from 10 to 95% by weight, in particular from 20 to 80% by weight, and the other biocide (s) in amounts 5 to 90% by weight, in particular from 20 to 80% by weight, in each case based on the total amount of biocidal active substance contained.
  • the biocidal active ingredient included in the microparticles consists predominantly of 2-n-octyl-4-isothiazolin-3-one.
  • biocidal active ingredient as the main constituent 2-n-octyl-4-isothiazolin-3-one, preferably in an amount equal to or greater than 50% by weight of 2-n-octyl-4-isothiazolin-3-one , preferably in an amount of equal to or greater than 70% by weight, in particular in an amount equal to or greater than 90% by weight, in particular in an amount equal to or greater than 95% by weight of 2-n-octyl-4- isothiazolin-3-one, based on the total mass of biocidal active substance.
  • at least one other biocide eg from the group of isothiazolinones
  • the biocidal active ingredient enclosed in the microparticles consists essentially of 2-n-octyl-4-isothiazolin-3-one, ie, that in addition to 2-n-octyl-4-isothiazolin-3-one still or several other biocides may be present, but these are present in an amount in which no contribution of the respective (of 2-n-octyl-4-isothiazolin-3-one different) biocide to the overall effect of the resulting mixture.
  • biocidal activity of a biocidal active substance which, in addition to 2-n-octyl-4-isothiazolin-3-one as essential constituent, still has one or more further biocides in subordinate or slight concentration, is not changed compared to Use of 2-n-octyl-4-isothiazolin-3-one alone as a single biocide is referred to herein as "consisting essentially of" in the context of the present invention.
  • the biocidal active ingredient may consist of 2-n-octyl-4-isothiazolin-3-one as the sole biocidal active ingredient, ie an active ingredient content of 100% 2-n-octyl-4-isothiazolin-3-one. In such a case, it is possible that one or more other ingredients are present without a biocidal effect.
  • silicone rubber relates in particular to the above-described RTV-1 and RTV-2 silicone rubbers.
  • biocide in LSR and HTV rubbers or other sealants.
  • the polymers used for the RTV-I silicone rubbers are frequently linear diorganopolysiloxanes having silanol end groups of the following formula:
  • n can vary within a wide range and is preferably between 500 and 1500, in particular between 600 and 1500.
  • Suitable crosslinkers for RTV-1 silicone rubber are, in particular, polyfunctional organosilicon compounds which can react at room temperature with OH groups, such as, for example, the silanol groups of the polymers or the OH group of water.
  • Polyfunctional means that at least three reactive groups are present per crosslinker molecule.
  • the crosslinkers have, for example, the general formula Si X 4 or R Si X 3 .
  • the radical R may be, for example, an alkyl or aryl radical, it being possible to influence the solubility, reactivity, boiling point or melting point of the crosslinker and indirectly also the properties of the rubber produced therewith via the radical R.
  • the radicals X can be of very different chemical nature.
  • the radical X in the crosslinker represents in the case of acidic crosslinkers, e.g. an acetoxy group. This is a long-known crosslinking system.
  • the cleavage product here is acetic acid.
  • Another acidic system is called the acetate system.
  • the vulcanization splits off 2-ethylhexanoic acid, which is relatively low in odor due to its low vapor pressure, but remains in the vulcanizate for a long time.
  • amino groups function as radical X in the case of the basic crosslinkers. It is usually primary amino groups of the structure NHRi, used, are used for Ri groups such as n-butyl, sec-butyl or cyclohexyl.
  • X here are alkoxyl groups, e.g. may be methoxy, ethoxy or methylglykoxy groups; - the acid amide system in which X symbolizes an acid amide group.
  • the crosslinker essentially fulfills three chemical tasks and must not be incompatible with the other components (eg the biocide): a) the blocking of the silano end groups of the dimethylpolysiloxane to form a storage-stable product under exclusion of moisture, b) the reaction with the OH groups present in the system, for example in the form of water or silanol groups of the fillers, c) the maintenance of the crosslinking reaction.
  • the other components eg the biocide
  • crosslinker that is not bound by the OH groups serves to render the overall system of adhesive and sealant stocks stable and to play a mediator role as a relatively easily mobile molecule in the polymer matrix upon crosslinking.
  • the crosslinker should be compatible with the biocide.
  • an RTV-1 silicone rubber can only consist of polymer, crosslinker and biocide.
  • the resulting during vulcanization silicone rubber then has only a very low mechanical strength.
  • Fillers can be significantly improved.
  • reinforcing fillers In the case of the fillers, a distinction is made between reinforcing and inactive fillers, although intermediates are also possible.
  • pyrogenic silicas i. amorphous silicic acids produced by flame hydrolysis used, which are particularly suitable for these systems due to their chemical relationship with the silicones. Not only the mechanical, but also the theological properties can be controlled by the addition of fumed silica.
  • inactive fillers true chemical or physical interactions with the polymers or crosslinkers do not occur or occur only to a minor extent.
  • Plasticizers used in the RTV-I according to the invention are silicone rubbers, e.g. used with trimethylsilyl endblocked dialkylpolysiloxanes of the following structure:
  • n and R can have the abovementioned meanings.
  • These silicone oils have the same chemical base as the polymers, so they are fully compatible and interact physically with the polymer and sometimes with filler. Their job is to lower the hardness. Partially, the elongation at break and tear strength of the sealant is increased.
  • catalysts in practice are e.g. Organometallic compounds of tin and titanium. They can have very different chemical structures. As a typical example dibutyltin acetate is mentioned.
  • the catalysts have the task of ensuring a balanced ratio between hydrolysis rate and condensation of the silanol groups, ie the actual crosslinking.
  • RTV-I silicone rubbers can be achieved by adding additives.
  • adhesion of RTV-I silicone rubbers can be significantly improved by the addition of adhesion promoters.
  • adhesion promoters are, for example, alkoxyl-functional silanes of the structure Z-Si (OR) 3 , where Z may be, for example, aminopropyl, glycidoxypropyl or mercaptopropyl groups and the alkoxy groups are usually lower alcohol groups, such as methoxy or ethoxy groups provide chemical bonding to the polysiloxane binder.
  • Additives such as pigments, heat stabilizers, flame retardants and stabilizers make it possible to achieve special properties of the sealants of the invention. All additives used should be compatible with 2-n-octyl-4-isothiazolin-3-one.
  • RTV-2 silicone rubbers likewise according to the invention are divided into two groups:
  • the base polymer in the condensation-crosslinking RTV-2 silicone rubber is analogous to the RTV-1 silicone rubber an ⁇ , ⁇ OH-terminated dialkylpolysiloxane, wherein the molecular weights are usually slightly lower than in RTV-I silicone rubber.
  • crosslinkers used are silicic acid esters which may be monomeric or condensed, for example the general formula Si (OR) 4 , where R represents lower alkyl groups such as ethyl or propyl groups. In general, the larger the remainder R, the slower is the crosslinking.
  • organotin compounds such as dibutyltin dilaurate used.
  • reaction products of silicic acid esters and organotin compounds are used as a hardener.
  • the sealants contain catalytic amounts of water, so that the vulcanization in the entire sample is uniform, regardless of the layer thickness.
  • alcohol is released. It is important that the alcohol from the rubber is volatilized as completely as possible before it is thermally stressed. Contains the vulcanizate still alcohol and it is loaded with temperatures above 90 0 C, the crosslinking reaction is declining and the silicone rubber softens.
  • the condensation-crosslinking RTV-2 rubber necessarily contains a biocide (which may be added at different times and in various ways) and, optionally, fillers, plasticizers, and additives.
  • the addition-crosslinking RTV-2 silicone rubber exploits the fact that Si-bonded hydrogen can be added to unsaturated carbons.
  • the base polymer usually consists of a ⁇ , ⁇ vinylend phenomenon ambiencen dialkylpolysiloxane.
  • crosslinker used is a methylhydrogenpolysiloxane of the general formula
  • the reaction of the Si - H group with the Si - vinyl groups is catalyzed by noble metal catalysts, eg by platinum complexes.
  • the reaction rate can be controlled by the amount of catalyst or by the addition of inhibitors.
  • the addition-crosslinking RTV-2 silicone rubbers according to the invention also contain a biocidal component and optionally fillers, plasticizers and additives. Since the production of addition-crosslinking RTV-2 silicone rubber is a true addition reaction, no cleavage products are released during vulcanization.
  • the addition-crosslinking RTV-2 silicone rubber is characterized by a strong temperature dependence of the Vulkanisations s off. With a temperature increase, a drastic acceleration of the addition reaction occurs, so that masses that require one day to vulcanization at room temperature, are already vulcanized at temperatures of 150 0 C within a few minutes.
  • the RTV-I silicone rubbers according to the invention are ready-to-use one-component compositions of flowable or soft-pasty consistency which may already contain the biocide or else be added to it when used. Under the influence of humidity they react to an elastic rubber. The higher the relative humidity, the higher the vulcanization speed. A skin first forms on the surface of the masses, whereupon the mass vulcanizes in the depths according to the diffusion of the water molecules.
  • the vulcanization rate is e.g. at 50% relative humidity, depending on the system, about 1 to 2 mm per day.
  • RTV-I silicone rubber is therefore less suitable for large-area bonding of air-impermeable substrates, but here the RTV-2 silicone rubbers according to the invention prove their worth.
  • RTV-2 silicone rubbers are two-component systems.
  • a hardener component (and possibly the biocide component) is added and mixed intensively by hand, with stirrer or in fully automatic dosing and mixing devices.
  • the hardeners are mostly liquids, but they can also consist of pastes.
  • the addition of curing agent is generally about 2 to 4% by weight.
  • the processing time is about 20 to 60 minutes and the time to vulcanization 1 to 24 hours.
  • the ratio of the two components is usually 9: 1, with a variation of the mixing ratio of the mechanical
  • the processing time is a few minutes to some
  • RTV silicone rubbers with very flexible systems.
  • the mechanical properties of vulcanized RTV silicone rubbers are highly dependent on their construction.
  • One of the most outstanding features of RTV silicone rubbers is their excellent temperature resistance. Due to their chemical structure of a network and Si-O linkages, most types retain their elasticity at temperatures up to 180 ° C. If a higher temperature exposure is required, and heat-stabilized types can be used, which even withstand temperatures of 250 0 C in the long term (see also HTV silicones). In the range of low temperatures RTV silicone rubbers remain up to about -50 0 C resilient, special types even to -110 0 C. vulcanizates of biocidally vessel equipped RTV silicone rubber have excellent weather and aging resistance, in particular they do not get moldy.
  • the resistance of vulcanizates of RTV silicone rubber according to the invention to weak acids or bases as well as polar solvents and salt solutions is generally very good.
  • solvents such as ketones, ethers, aliphatic, aromatic and chlorinated hydrocarbons
  • a more or less pronounced swelling of the silicone caustic occurs.
  • this is reversible, i. After evaporation of the solvent, the vulcanizate has its original shape and strength again.
  • Whether a use of silicone rubber is possible with permanent or temporary contact with these solvents depends v. a. from the mechanical and chemical stress, the effective area and duration.
  • RTV fluorosilicone rubbers equipped with biocide hardly swell when exposed to these solvents.
  • the electrical properties of the inventive RTV silicone rubbers are well comparable to those of other insulating materials. However, it is important that even at higher temperatures insulation resistance, dielectric strength and dielectric loss factor hardly change. Even when stored in water, the electrical properties hardly change. When burned, the RTV silicone rubbers leave behind a framework of Si O 2 , which increases safety as a nonconductor. The excellent tracking resistance of the silicones according to the invention can thus be explained. While the RTV-I silicone rubbers show very good adhesion on many substrates, the adhesion of RTV-2 silicone rubbers is generally poor without primer. Considering the adhesion of RTV-I silicone rubbers after the crosslinking system, it is generally said that the amine systems have very good adhesion. Vinegar systems follow at a small distance, while the oxime and in particular the alcohol systems have a much lower adhesion. The addition of internal primers can cause significant shifts in this rule.
  • condensation-curing RTV-2 systems which contain special adhesion promoters in the product are known, which have excellent adhesion to a wide variety of substrates.
  • aminoplast resins in the context of the present invention are polycondensation products of carbonyl compounds, in particular of formaldehyde and compounds containing NH groups, such as, for example, urea (urea resins), melamine (melamine resins), urethanes (urethane resins), cyanide and dicyanamide (cyano or dicyanamide), aromatic amines (aniline resins) and sulfonamides (sulfonamide resins), see Rompps Chemie Lexikon, Thieme Verlag Stuttgart, 9, extended edition, 1995, page 159.
  • Preferred materials of Microparticles are melamine, urea and dicyandiamide-formaldehyde resins, particularly preferred materials are melamine-formaldehyde resins.
  • urea resins mentioned above are hardenable condensation products of ureas and aldehydes belonging to the aminoplasts, in particular these include formaldehyde.
  • formaldehyde For their preparation, urea or substituted ureas are reacted with formaldehyde in molar excess under mostly alkaline conditions. The result is hydroxymethyl group-containing oligomers, which are cured with crosslinking.
  • formaldehyde it is also possible to use other aldehydes, for example acetaldehyde or glyoxal. Condensates based on modified ureas are also available In the context of the invention in the preparation of the microparticle material usable starting materials.
  • melamine resins is to be understood as meaning aminoplast resins in which melamine has been polycondensed under suitable conditions with carbonyl compounds such as aldehydes and ketones, for example formaldehyde, acetaldehyde or glyoxal.
  • carbonyl compounds such as aldehydes and ketones, for example formaldehyde, acetaldehyde or glyoxal.
  • melamine is generally reacted with the carbonyl compound in molar excess.
  • microparticles containing the biocidal active ingredient may also be formed from two or more of the aforementioned aminoplast resins.
  • particular care must be taken that there is no destruction or inhibition of the biocidal active substance during production.
  • the biocidal active substance Due to the inclusion of the biocidal active substance in the microparticles, it is not volatilized or released in the preparation of the silicone rubbers and their use, or only to a very limited extent. Furthermore, the silicone rubber remains biocidally effective, since the active ingredient remains in the rubber, so that it can be used in correspondingly low concentrations. In practical use, the biocidal active ingredient is released only slowed down. It has been shown in an advantageous manner that the biocidal active ingredient enclosed in the microparticles is not washed out to a great extent during the irrigation (or washing) of the silicone rubbers equipped therewith.
  • microparticles refers to any type of particle comprising a wall structure and at least one cavity formed by the wall structure.
  • the wall structure in this case contains one or more aminoplast resins, but preferably one.
  • the cavities formed by the wall structure may be closed or open and contain the biocidal active substance and optionally further different auxiliaries. Closed cavities may, for example, be in the form of capsule structures or cell structures, open cavities in the form of pores, channels and the like.
  • microparticles may likewise mean a matrix of an aminoplast resin, wherein the biocidal active ingredient is enclosed in the matrix or enveloped by it.
  • microparticles may refer to so-called microcapsules, in the interior of which the biocidal active ingredient is encapsulated encapsulated.
  • the microparticles have a spherical shape.
  • This shape has the advantage of high volume, low surface area, whereby impinging water has a low wetting area.
  • the average diameter (D-50 value) of the microparticles to be used for finishing sealants is usually in the range of about 0.5 to about 40 microns, the preferred average diameter is in the range of about 1 to about 15 microns.
  • the size of the microparticles can be determined, for example, under a microscope using a micrometer scale.
  • the antimicrobially finished rubber generally contains an amount of biocidal active ingredient, based on the total weight of the rubber, of 0.0001% by weight to 0.5% by weight, preferably of 0.01% by weight. to 0.2% by weight, particularly preferably from 0.05% by weight to 0.15% by weight.
  • the inclusion of the biocidal agent in the microparticles not only has the advantage of sustained release of the biocidal agent, but has the shielding of the biocidal Agent through the particle wall result in that this thereby increased stability to UV radiation, elevated temperatures, heavy metal ions and pH values.
  • the duration of action of the biocidal active ingredient due to a lower rate of decomposition, is considerably prolonged. Also, no discoloration occurs. No disturbances in the vulcanization are observed.
  • the masses equipped with the microparticles are transparent. There is no negative interaction of the resin surrounding the drug with the silicone or acrylate masses. The stability of the formulations is high.
  • Biocidal active substances enclosed in a melamine-formaldehyde resin for application in coating compositions, in particular in facade plasters, are known from EP-A 1 519 995.
  • this document gives no indication that 2-n-octyl-4-isothiazolin-3-one included in an aminoplast resin, preferably in a melamine-formaldehyde resin, is eminently suitable for finishing sealants such as silicone rubbers.
  • the fact that only a slight escape of the biocidal active substance from the microparticles is to be observed is surprising, but after the preparation of the sealant the particles release the biocidal active substance to the desired extent in a retarding manner.
  • biocidal active substance in the microparticles based on the aminoplast resin largely prevents its release.
  • the 2-n-octyl-4-isothiazolin-3-one has antimicrobial properties which are desirable in itself for the finishing of adhesives and sealants.
  • OIT 2-n-octyl-4-isothiazolin-3-one
  • microparticles according to the invention is particularly suitable for the equipment of silicone rubbers which are used in the outdoor area because of the broad spectrum of action of 2-n-octyl-4-isothiazolin-3-one, since 2-n-octyl- 4 isothiazolin-3-one is a biocide with fungicidal, bactericidal and algicidal activity. It contains no halogen or heavy metal compounds, is not persistent or accumulable, is not classified as a CMR substance and has a favorable human and ecotoxicological profile.
  • biocides for inclusion in the microparticles in addition to 2-n-octyl-4-isothiazolin-3-one additionally one or more other biocides are used, which can be selected depending on the field of application. Specific examples of such additional biocides are given below:
  • benzyl alcohol 2,4-dichlorobenzyl; 2-phenoxyethanol; 2-phenoxyethanolhemiformal, phenylethyl alcohol; 5-bromo-5-nitro-l, 3-dioxane; bronopol; Formaldehyde and formaldehyde depot substances; dimethyloldimethylhydantoin; glyoxal; glutaraldehyde; sorbic acid; benzoic acid; salicylic acid; p-hydroxybenzoic acid esters; chloroacetamide; N-methylolchloroacetamide; Phenols such as p-chloro-m-cresol and o-phenylphenol; N-methylol; N, N'-dimethylolurea; benzylformal; 4,4-dimethyl-1,3-oxazolidine; 1,3,5-hexahydro- triazine derivatives; quaternary ammonium compounds such as N-alkyl-N, N-d
  • Examples of a formaldehyde releasing agent are N-formals such as tetramethyloacetylenediurea; N, N'-dimethylourea;N-methylolurea;dimethyloldimethylhydantoin;N-methyl-chloroacetamide; Reaction products of allantoin; Glycol formals, such as ethylene glycol formal; Butyldiglykolformal; Benzylformal.
  • biocidal agents are 2-n-octyl-4-isothiazolin-3-one alone, DC-OIT alone, N-alkyl-1,2-benzisothiazolin-3-one alone or one of these three drugs in combination with one or more biocides from the group BIT, N-butyl-BIT, N-methyl-BIT, IPBC, tebuconazole, DC-OIT, terbutryn, cyfluthrin, isoproturon, triclosan, silver or silver compounds and zinc pyrithione.
  • 2-n-octyl-4-isothiazolin-3-one is used as sole biocidal active substance, the active ingredient either being completely present in microparticles or being present in encapsulated and in unencapsulated form (for example 50% by weight). OIT encapsulated + 50 wt% OIT unencapsulated).
  • this further biocide may be used together with 2-n-octyl-4-isothiazolin-3-one as a mixture contained in the microparticles.
  • microparticles containing only 2-n-octyl-4-isothiazolin-3-one with microparticles containing only the further biocide with each other and to introduce this mixture of microparticles into the silicone rubber.
  • microparticles containing the biocidal active substance may additionally contain other customary additives which are customary for the application and which are known to the person skilled in the art. These are e.g. Thickeners, defoamers, substances for adjusting the pH, fragrances, dispersing aids and coloring or discoloration-preventing substances, complexing agents and stabilizers such as UV stabilizers.
  • the microparticles used to finish silicone rubbers or acrylate sealants preferably do not contain any harmful solvents.
  • the preferred solvent used in the preparation is water, which, however, usually has to be removed before use. If, according to a particular embodiment of the invention, further solvents are used in the preparation of the microparticles, these may be polar or nonpolar or mixtures containing polar and non-polar solvents.
  • Aliphatic alcohols having 1 to 4 carbon atoms for.
  • ethanol and isopropanol for.
  • a glycol for. Ethylene glycol, diethylene glycol, 1,2-propylene glycol, dipropylene glycol and tripropylene glycol, a glycerol ether, e.g. Butyl glycol and butyl diglycol, a glycol ester, eg. B.
  • Butyldiglykolacetat or 2,2,4-Trimethylpentandiolmonoisobutyrat a Po Iy ethylene glycol, a polypropylene glycol, N, N-dimethylformamide or a mixture of two or more such solvents.
  • the polar liquid solvent should preferably be removed prior to use of the microparticles.
  • nonpolar liquid solvents OH-free solvents, e.g. Aromatics, preferably xylene and toluene serve.
  • microparticles can also be used as a powder.
  • a chemical anchoring of the microparticles according to the invention with the surface of the silicone rubber is carried out.
  • the surface of the microparticles has reactive groups, such as amino, hydroxyl and methylol groups (CH 2 -OH), it is possible with the help of a suitable reactive binder, for example an isocyanate, in particular a protected or blocked isocyanate permanently on the To anchor silicone rubber.
  • a suitable reactive binder for example an isocyanate, in particular a protected or blocked isocyanate permanently on the To anchor silicone rubber.
  • the invention further relates to the use of the active ingredient 2-n-octyl-4-isothiazolin-3-one and optionally one or more other biocides containing microparticles based on an aminoplast resin for the protection of adhesives and sealants against microorganism infestation.
  • biocidal active ingredient from 2-n-octyl-4-isothiazolin-3-one is.
  • the advantage of this biocidal active ingredient is also that 2-n-octyl-4-isothiazolin-3-one effectively prevents the infestation of silicone rubber by algae, bacteria and fungi.
  • the biocidal active ingredient is preferably enclosed in finely dispersed, liquid or solid phase, more preferably in the preparation of the microparticles the biocidal active substance is introduced in an aqueous medium.
  • the preparation of the preferably used melamine-formaldehyde microparticles comprises the use of melamine-formaldehyde precondensates which are water-soluble and from which melamine-formaldehyde-resin microparticles are prepared from the aqueous phase.
  • the manufacturing process has several advantages, such as, in addition to inexpensive compared to other possible polymerization process starting materials and the environmentally friendly use of water as a preferred solvent.
  • the entrapped or encapsulated biocidic agents are not readily water soluble, partial substitution of the solvent used in the process with water can be made by water-miscible organic solvents.
  • microparticles according to the invention preference is given to starting from an aqueous suspension of the biocidal active substance or active substance mixture using water as solvent.
  • the microparticles according to the invention are preferably prepared with stirring in an acidic medium.
  • acidic medium serve inorganic and / or organic acids such as hydrochloric acid, phosphoric acid and citric acid.
  • the microparticles can be prepared in conventional apparatus for condensation polymerizations. These include stirred tanks, stirred tank cascades, autoclaves, tube reactors and kneaders.
  • the reaction is carried out, for example, in stirred tanks equipped with an anchor, paddle, impeller, dissolver or multistage pulse counter-flow stirrer are equipped.
  • Particularly suitable are apparatuses that allow the direct isolation of the product following the polymerization, such as. B. paddle dryer.
  • the resulting suspensions can be dried directly in evaporators, such as belt dryers, paddle dryers, spray dryers or fluid bed dryers. But you can also cut off by filtration or centrifugation, the majority of the water.
  • the melamine-formaldehyde resins As starting material for the preferably used melamine-formaldehyde resins, on the one hand available etherified melamine-formaldehyde condensates with preferably low free formaldehyde, such as, for example, Quecodur DM 70 (available from THOR GmbH) are used. Furthermore, the melamine-formaldehyde resin may also be prepared by polycondensation of melamine and formaldehyde in the presence of the biocidal agent by techniques known to those skilled in the art, such as by reaction between melamine and formaldehyde at a molar ratio of 1 to 6 parts of formaldehyde to one part of melamine.
  • the reaction is preferably carried out in aqueous solution.
  • concentration of the prepolymer in the aqueous solution can be varied over a wide range.
  • the prepolymer is supplied or formed such that the prepolymer concentration is from about 1 to about 70 weight percent, preferably from about 5 to about 50 weight percent.
  • the microparticles according to the invention may contain further substances which are generally known and customary depending on the intended use. These include on the one hand corresponding binders and film formers, such as polyacrylates, polystyrene or silicone resins, on the other hand, known auxiliaries, such as pigments; Fillers such as calcium carbonate, talc, kaolins, silicates, fumed silica and / or zeolites; Solvents; Thickeners such as polysaccharides and / or cellulose ethers; defoamers; plasticizers; Dispersants such as phosphates and / or acrylates; Emulsifiers such as fatty alcohol ethoxylates, EO / PO block polymers and / or sulfonates; Stabilizers such as UV stabilizers, dyes or discoloration-preventing substances.
  • binders and film formers such as polyacrylates, polystyrene or silicone resins
  • auxiliaries such as pigments
  • the polycondensation of the aminoplast resin may be conducted anywhere within the range of from about 20 to about 95 ° C., preferably between about 50 and 80 ° C.
  • the reaction will generally be completed within a few hours, although the reaction is at high temperature can be finished within a few minutes.
  • the microparticles Once the microparticles are formed, they can be stored as dispersions and used or filtered as dried particles.
  • the microparticles containing the biocidic agent may also be added to the silicone rubber during its manufacture.
  • the silicone rubbers according to the present invention may e.g. be used in the following areas:
  • microparticles containing the biocidal active ingredient OIT are described below.
  • microparticles based on melamine-formaldehyde were prepared, in which the biocidal active ingredient 2-n-octyl-4-isothiazolin-3-one is included.
  • the water and the melamine-formaldehyde resin were placed in a glass jar. Then, polyacrylate, gum arabic, silicone defoamer and 2-n-octyl-4-isothiazolin-3-one were stirred. The resulting mixture was heated to 90 0 C and added dropwise for 1 hour hydrochloric acid to a pH of 4. Subsequently, the mixture was stirred for 2 hours at the same temperature. The contained mixture contained the desired microparticles in which the biocidal agent is included. The product can be separated (eg filtered) and dried. The use is also possible as a powder.
  • the water and the melamine-formaldehyde resin were placed in a glass jar. Then, with vigorous stirring, polyacrylate, gum arabic, silicone defoamer and the OIT were added. The resulting mixture was heated to 90 ° C. and further stirred for 1 hour with intensive mixing, hydrochloric acid being added dropwise to a pH of 4. Subsequently, the mixture was stirred for 2 hours at the same temperature. The contained mixture contained the desired microparticles in which OIT is included.
  • test specimens were subjected to the ISO 846 test, Part B, both without washing and after 2 days of washing in demineralised water with 24 hour changes of water.
  • the test specimens were placed on carbonated nutrient media ("Complete Agar") to control the fungicidal effect and then sprayed with a mixture of fungal spores, 0.1 ml of suspension per specimen.
  • Complete Agar carbonated nutrient media
  • the spore suspension contained 10 6 CFU / ml and included the following fungi: Aspergillus niger ATCC 6275
  • OIT encapsulated obtained according to the manufacturing example is referred to as OIT encapsulated. This was either introduced by a manufacturer of sealants in the respective sealant or added to the sealant before the test.
  • Sample 1 shows both unsoaked (Od) and 2 days watered (2d) a good fungicidal activity against mold fungus growth.
  • the unequipped control, blank shows strong fungal growth (Od & 2d).
  • the Carbendazim containing reference shows watered (2d) as well as unirrigated (Od) medium fungal growth.
  • Table 1 Results of the tests according to ISO 846 Part B in duplicate (column a or b)
  • Acrylic sealants were tested with increasing OIT encapsulated concentration. As the OIT concentration increased, the fungicidal effect increased. From a quantity of 650 ppm OIT a sufficient fungicidal effect could be achieved even after washing (2d).
  • the encapsulated OIT variants showed no to minimal growth without watering (Od) and even after the loading phase (3 months) the test bodies were encapsulated with 1000 ppm OIT encapsulated free of fungal growth.
  • the free OIT formulations tested in parallel showed good action without washing (Od), but were heavily overgrown after the three month washing cycles.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Biodiversity & Conservation Biology (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Toxicology (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Sealing Material Composition (AREA)

Abstract

L'invention concerne des masses d'étanchéité en silicone, contenant en tant que principe biocide actif de la 2-n-octyl-4-isothiazolin-3-one, ainsi qu'éventuellement un ou plusieurs autres biocides, le principe biocide actif étant intégré dans des microparticules constituées d'une résine aminoplaste.
EP07858198A 2006-12-28 2007-12-28 Masses de collage et d'étanchéité présentant un apprêt antimicrobien Withdrawn EP2106418A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102006061890A DE102006061890A1 (de) 2006-12-28 2006-12-28 Kleb- und Dichtungsmassen mit antimikrobieller Ausrüstung
PCT/EP2007/064602 WO2008080963A1 (fr) 2006-12-28 2007-12-28 Masses de collage et d'étanchéité présentant un apprêt antimicrobien

Publications (1)

Publication Number Publication Date
EP2106418A1 true EP2106418A1 (fr) 2009-10-07

Family

ID=39345285

Family Applications (1)

Application Number Title Priority Date Filing Date
EP07858198A Withdrawn EP2106418A1 (fr) 2006-12-28 2007-12-28 Masses de collage et d'étanchéité présentant un apprêt antimicrobien

Country Status (4)

Country Link
US (1) US20100099793A1 (fr)
EP (1) EP2106418A1 (fr)
DE (1) DE102006061890A1 (fr)
WO (1) WO2008080963A1 (fr)

Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015100198A1 (fr) 2013-12-23 2015-07-02 Dow Corning Corporation Compositions durcissables à l'humidité
WO2017162839A1 (fr) 2016-03-23 2017-09-28 Dow Corning Corporation Compositions durcissant à l'humidité
WO2019027897A1 (fr) 2017-07-31 2019-02-07 Dow Silicones Corporation Compositions durcissant à l'humidité
WO2019190775A1 (fr) 2018-03-30 2019-10-03 Dow Silicones Corporation Compositions durcissables par condensation
WO2019190776A1 (fr) 2018-03-30 2019-10-03 Dow Silicones Corporation Compositions durcissant par condensation
WO2020087316A1 (fr) 2018-10-31 2020-05-07 Dow Silicones Corporation Adhésif
WO2020092483A1 (fr) 2018-10-31 2020-05-07 Dow Silicones Corporation Adhésif
WO2020263762A1 (fr) 2019-06-27 2020-12-30 Dow Silicones Corporation Compositions de silicone vulcanisables
WO2020263763A1 (fr) 2019-06-27 2020-12-30 Dow Silicones Corporation Compositions de silicone vulcanisables à température ambiante
WO2021119971A1 (fr) 2019-12-17 2021-06-24 Dow Silicones Corporation Composition d'agent d'étanchéité
WO2021133622A1 (fr) 2019-12-23 2021-07-01 Dow Silicones Corporation Composition d'agent d'étanchéité
WO2021133621A1 (fr) 2019-12-23 2021-07-01 Dow Silicones Corporation Compositions durcissables à l'humidité
US11168213B2 (en) 2017-07-31 2021-11-09 Dow Silicones Corporation Moisture curable compositions
WO2022046275A1 (fr) 2020-08-31 2022-03-03 Dow Silicones Corporation Préparation de polydiorganosiloxane
WO2022140217A1 (fr) 2020-12-22 2022-06-30 Dow Silicones Corporation Composition d'agent d'étanchéité
WO2023055680A1 (fr) 2021-09-30 2023-04-06 Dow Silicones Corporation Compositions durcissables à l'humidité
WO2023055682A1 (fr) 2021-09-30 2023-04-06 Dow Silicones Corporation Compositions durcissables à l'humidité
WO2023055681A1 (fr) 2021-09-30 2023-04-06 Dow Silicones Corporation Compositions durcissables à l'humidité
WO2023230756A1 (fr) 2022-05-30 2023-12-07 Dow Silicones Corporation Composition d'agent d'étanchéité
WO2024065299A1 (fr) 2022-09-28 2024-04-04 Dow Silicones Corporation Composition de produit d'étanchéité

Families Citing this family (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102010018312A1 (de) 2009-04-24 2010-11-04 Chemische Werke Kluthe Gmbh Verfahren und Erzeugnis für die biozide Behandlung eines Kühlschmierstoffs
US8859707B2 (en) * 2012-03-20 2014-10-14 Empire Technology Development Llc Two-component lignosulfonate adhesives and methods for their preparation
TWI597301B (zh) * 2012-03-23 2017-09-01 湛新智財有限公司 改性胺基樹脂
AR091328A1 (es) * 2012-04-05 2015-01-28 Basf Se Particulas porosas que comprenden aminoplastico
CH706973A1 (de) 2012-09-10 2014-03-14 Greutol Ag Biozidhaltiges Verkleidungssystem.
US20150322318A1 (en) * 2012-12-17 2015-11-12 Lanxess Deutschland Gmbh Fungicide silicon sealing compound
EP2801256A1 (fr) 2013-05-08 2014-11-12 LANXESS Deutschland GmbH Microcapsules contenant un agent algicide et un polymère mélamine-formaldéhyde
CN106028811B (zh) * 2014-02-27 2019-06-18 朗盛德国有限责任公司 杀生物的微胶囊
WO2017095335A1 (fr) * 2015-11-30 2017-06-08 Aquafil S.P.A. Biocides micro-encapsulés, compositions de revêtement comprenant des biocides micro-encapsulés, et utilisation de compositions de revêtement pour filets de pêche
CN109640652B (zh) 2016-08-08 2022-02-22 自主材料有限公司 杀生物保护性制剂
US10624860B2 (en) 2017-03-21 2020-04-21 International Business Machines Corporation Method to generate microcapsules with hexahydrotriazine (HT)-containing shells
PL3669654T3 (pl) 2018-12-18 2022-02-21 Lanxess Deutschland Gmbh Mikrokapsułki zawierające OIT w kombinacji z propikonazolem i/lub IPBC
CN110314672A (zh) * 2019-07-12 2019-10-11 中国海洋大学 一种单分散硅胶微球色谱填料的制备方法
MX2022016438A (es) 2020-07-01 2023-02-01 Laboratorios Miret S A Tcmtb microencapsulado.
KR102600719B1 (ko) * 2020-09-30 2023-11-13 다우 실리콘즈 코포레이션 첨가제 안정화

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1884542A1 (fr) 2006-08-04 2008-02-06 Wacker Chemie AG Compositions reticulables a base d'organosilicium

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0542721A3 (en) 1990-04-27 1993-08-25 Imperial Chemical Industries Plc Biocide composition and its use
EP0679333A3 (fr) * 1994-04-28 1996-01-03 Rohm & Haas Composition biocide non-sensibilisatrice.
US5874476A (en) * 1997-07-14 1999-02-23 Rohm And Haas Company Dihaloformaldoxime carbamates as antimicrobial agents
EP0900525A1 (fr) * 1997-08-20 1999-03-10 Thor Chemie Gmbh Composition biocide synergique
US6294589B1 (en) * 2000-05-12 2001-09-25 Shaw Industries, Inc. Polyurethane composition containing antimicrobial agents and methods for use therefor
JP2002053412A (ja) 2000-08-09 2002-02-19 Daiwa Kagaku Kogyo Kk ２−ｎ−オクチル−４−イソチアゾリン−３−オンを内包したマイクロカプセル化製剤
DE10042894A1 (de) * 2000-08-31 2002-03-14 Thor Chemie Gmbh Synergistische Biozidzusammensetzung mit 2-Methylisothiazolin-3-on
DE10133545A1 (de) * 2001-07-11 2003-02-06 Ge Bayer Silicones Gmbh & Co Benzothiophen-2-cyclohexylcarboxamid-S,S-dioxid enthaltende schimmelresistente Dichtstoff-Formulierungen
CN100344710C (zh) * 2002-06-19 2007-10-24 托尔有限公司 具有生物杀伤剂微胶囊的涂料
CN101137288B (zh) * 2004-09-14 2011-09-28 微技术实验室公司 微胶囊化的杀生物剂和防污剂
WO2007007080A1 (fr) * 2005-07-11 2007-01-18 Thor Specialities (Uk) Limited Composition microbiocide

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1884542A1 (fr) 2006-08-04 2008-02-06 Wacker Chemie AG Compositions reticulables a base d'organosilicium

Cited By (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10308838B2 (en) 2013-12-23 2019-06-04 Dow Silicones Corporation Moisture curable compositions
WO2015100198A1 (fr) 2013-12-23 2015-07-02 Dow Corning Corporation Compositions durcissables à l'humidité
WO2017162839A1 (fr) 2016-03-23 2017-09-28 Dow Corning Corporation Compositions durcissant à l'humidité
WO2019027897A1 (fr) 2017-07-31 2019-02-07 Dow Silicones Corporation Compositions durcissant à l'humidité
US11319446B2 (en) 2017-07-31 2022-05-03 Dow Silicones Corporation Moisture curable compositions
US11168213B2 (en) 2017-07-31 2021-11-09 Dow Silicones Corporation Moisture curable compositions
US10961392B2 (en) 2018-03-30 2021-03-30 Dow Silicones Corporation Condensation curable compositions
WO2019190775A1 (fr) 2018-03-30 2019-10-03 Dow Silicones Corporation Compositions durcissables par condensation
WO2019190776A1 (fr) 2018-03-30 2019-10-03 Dow Silicones Corporation Compositions durcissant par condensation
WO2020087316A1 (fr) 2018-10-31 2020-05-07 Dow Silicones Corporation Adhésif
US11814553B2 (en) 2018-10-31 2023-11-14 Dow Silicones Corporation Adhesive
WO2020092483A1 (fr) 2018-10-31 2020-05-07 Dow Silicones Corporation Adhésif
WO2020263763A1 (fr) 2019-06-27 2020-12-30 Dow Silicones Corporation Compositions de silicone vulcanisables à température ambiante
WO2020263762A1 (fr) 2019-06-27 2020-12-30 Dow Silicones Corporation Compositions de silicone vulcanisables
WO2021119971A1 (fr) 2019-12-17 2021-06-24 Dow Silicones Corporation Composition d'agent d'étanchéité
WO2021133622A1 (fr) 2019-12-23 2021-07-01 Dow Silicones Corporation Composition d'agent d'étanchéité
WO2021133621A1 (fr) 2019-12-23 2021-07-01 Dow Silicones Corporation Compositions durcissables à l'humidité
WO2022046275A1 (fr) 2020-08-31 2022-03-03 Dow Silicones Corporation Préparation de polydiorganosiloxane
WO2022140217A1 (fr) 2020-12-22 2022-06-30 Dow Silicones Corporation Composition d'agent d'étanchéité
WO2023055680A1 (fr) 2021-09-30 2023-04-06 Dow Silicones Corporation Compositions durcissables à l'humidité
WO2023055682A1 (fr) 2021-09-30 2023-04-06 Dow Silicones Corporation Compositions durcissables à l'humidité
WO2023055681A1 (fr) 2021-09-30 2023-04-06 Dow Silicones Corporation Compositions durcissables à l'humidité
WO2023230756A1 (fr) 2022-05-30 2023-12-07 Dow Silicones Corporation Composition d'agent d'étanchéité
WO2024065299A1 (fr) 2022-09-28 2024-04-04 Dow Silicones Corporation Composition de produit d'étanchéité

Also Published As

Publication number Publication date
US20100099793A1 (en) 2010-04-22
DE102006061890A1 (de) 2008-07-03
WO2008080963A1 (fr) 2008-07-10

Similar Documents

Publication Publication Date Title
EP2106418A1 (fr) Masses de collage et d'étanchéité présentant un apprêt antimicrobien
DE4321798C2 (de) Antimikrobische Zusammensetzung
DE2408192C3 (de) Füllstoffhaltige Polymere mit antimikrobieller Wirkung
EP1698672B1 (fr) Microcapsules de biocide
EP1924145A2 (fr) Composition biocide synergique contenant de l'argent
US20070053950A1 (en) Composition of polymer microcapsules of biocide for coating material
DE1932959B2 (de) Biozide elastomere Mischungen
DE60103582T2 (de) Zusammensetzungen mit kontrollierter Freisetzung
EP1814391B1 (fr) Materiaux de construction resistants a la moisissure
EP2038473A2 (fr) Textile à traitement antimicrobien
WO2008000797A2 (fr) Microparticules antimicrobiennes
DE69829798T2 (de) Verfahren zur Herstellung antibakterieller/antifungaler Holzkomposite mit anorgansichem Material
EP0944317A1 (fr) Melanges microbicides
EP0000892B1 (fr) Compositions d'organopolysiloxane à activité microbicide, stables au stockage en l'absence d'humidité
DE10144187A1 (de) Konservierungsmittel für Beschichtungszusammensetzungen
EP0475123B1 (fr) Utilisation de 2-n-alkyle-1,2-benzisothiazolin-3-ones comme microbiocides techniques
DE69535600T2 (de) Bakterizide zusammensetzungen und diese enthaltende artikel
EP3739008A1 (fr) Matière de revêtement aqueuse, en particulier matière de revêtement aqueuse pâteuse, revêtement obtenu à partir de la matière de revêtement et son utilisation
EP1412426B1 (fr) Compositions pour joints d'etancheite resistant a la moisissure contenant du s,s-dioxyde de benzothiophene-2-cyclohexylcarboxamide
DE202013002158U1 (de) Zementäre Beschichtungszusammensetzung
WO2000059305A1 (fr) Composition microbiocide
DE2845408B2 (de) N-(2-Methyl-l-naphthyl)-maleinimid, Verfahren zu dessen Herstellung und seine Verwendung
DE19641890A1 (de) Mikrobiozide und mikrobizide Gemische
WO2022096176A1 (fr) Revêtement anti-algues et antifongique
DE2237961B2 (de) Verwendung von Chlorphenoxysilanen als biozide Schutzstoffe für Kunststoffe

Legal Events

Date Code Title Description
TPAC Observations filed by third parties

Free format text: ORIGINAL CODE: EPIDOSNTIPA

PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20090703

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC MT NL PL PT RO SE SI SK TR

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION HAS BEEN WITHDRAWN

18W Application withdrawn

Effective date: 20091112