DE102012216190A1 - Composite e.g. fiber composite materials or composite coatings e.g. paint coatings, useful in a component, comprises a matrix material, and microcapsules comprising a shell material consisting of a cell wall and/or a cell membrane - Google Patents

Abstract

Composites, preferably fiber composite materials or composite coatings, preferably paint coatings comprise (A) a matrix material, and (B) microcapsules comprising a shell material consisting of a cell wall and/or a cell membrane, where the shell material of the microcapsules consists of a yeast cell, and one or more active substances included in the shell material, where the active substances consist of e.g. dyes, messengers, corrosion inhibitors, catalysts, solvents, thickeners, adhesion-reducing substances, de-icing reagents, and antimicrobial substances. Composites, preferably fiber composite materials or composite coatings, preferably paint coatings comprise (A) a matrix material, and microcapsules comprising a shell material consisting of a cell wall and/or a cell membrane, where the shell material of the microcapsules consists of a yeast cell, and one or more active substances included in the shell material, where the active substances consist of dyes, messengers, corrosion inhibitors, catalysts, solvents, thickeners, adhesion-reducing substances, de-icing reagents, antimicrobial substances, slip additive, lubricants and components for self-healing systems, the microcapsules have an average diameter of 10, preferably 20-150 mu m, the shell material further consists of a sporoderm of a pollen grain, preferably at least one exine sporoderm, and the shell material is partially covalently bonded to the matrix material. Independent claims are included for: (1) a coating material, preferably paint or adhesive for producing a coating, comprising (A) and (B); (2) producing a coating material, comprising (i) providing one or more binding agents, preferably consisting of epoxy resins, polyurethanes, acrylates, alkyd resins, formaldehyde condensation resins, polyesters, polyethers, polyethylene and PVC, (ii) providing the microcapsules, and mixing the microcapsules from step (ii) with the binder agents from the step (i) and optionally with other ingredients; (3) a component comprising the composite material, preferably the fiber composite material; (4) a product comprising a substrate and the coating applied on a surface portion of the substrate, where the substrate consists of metals and alloys, preferably light metal, silicate glasses such as slices or ceramics, organic surfaces, bones, teeth, wood, laminates, polymers and fiber-reinforced polymers, casting resins, fibers such as glass, carbon, aramid and natural fibers, leather, fabrics, paper and cardboard; and (5) improving the corrosion resistance of a metal, comprising applying the coating material according onto the surface of the metal, where the active substances in the shell material are corrosion inhibitors.

Description

The present invention relates to composites, in particular (fiber) composite materials and (composite) coatings, in addition to a matrix material, a plurality of microcapsules having a, in particular in the undried state, average diameter in the range of 10 to 200 .mu.m, in particular from 20 to 200 μm, which in turn each comprise or consist of a shell material and selected active ingredients included therein, the shell material of the microcapsules being (at least) one (ie one or more, preferably a few, more preferably one) cell wall and / or (at least) a (ie one or more, preferably a few, more preferably one) cell membrane comprises or consists thereof, in particular wherein the shell material of the microcapsules comprises or consists of a sporoderm or at least the exorns of a sporoderm, and wherein the shell material of the microcapsules at least partially covalently attached to the Matrix material is bound.

The present invention additionally relates to coating materials, in particular paints, preferably coating materials for producing coatings according to the invention, wherein the coating materials comprise, in addition to one or more binders, a multiplicity of microcapsules to be used according to the invention.

Furthermore, the present application relates to components made of a (composite) fiber according to the invention, products coated with a coating according to the invention and selected processes, in particular processes for the preparation of novel coating materials, in particular coating materials according to the invention.

Further aspects of the present invention will become apparent from the following description, in particular the examples described and the appended claims.

In a variety of industries, particularly in the automotive, aerospace and wind energy industries, as well as in maritime and coastal areas (eg shipbuilding, port facilities or offshore installations), innovative and increasingly diversified tailor-made composites, in particular fiber composites and ( Composite) coatings, and coating materials, especially paints, steadily in importance.

In the context of the present text, a "composite" is to be understood in particular as a composite material (composite material) in the broader sense, i. a material of two or more bonded materials, wherein the composite material has different material properties than its individual components and / or in the (cured) composite more physico-chemical phases, e.g. a polymeric matrix and fillers, or a polymeric matrix and fibers. As composites of the invention (as described in the context of the present text), for example, fiber composites are to be understood. However, in the context of the present text, the term "composite" also includes, in particular, coatings (composite coatings), i. optionally cured coatings made from appropriate coating materials (as described herein) (also as described herein). In the context of the present text, according to a preferred embodiment, adhesives (as described herein) can also be assigned to the coating materials according to the invention.

Both when using classic, as well as the use of new materials is trying to make this or the surface thereof against stress, especially against caused by certain media, mechanical and / or corrosive stress, as resistant as possible. On the other hand, from a user's point of view - especially in the case of modern materials and coating systems - custom-made functional integration is often desired, preferably in conjunction with multifunctionality. For example, there is often interest in providing materials and / or surfaces thereof with an active corrosion protection, with a scratch protection effect, with a self-healing system or other functionalities (eg anti-graffiti effect, easy-to-clean effect, anti-soiling -, anti-freeze effect, anti-biotic / microbial and / or disinfecting effect, stimulus-responsive effects or tear-stopping effects). In summary, there is a continuing need for improved materials and coatings that can result in increased resistance (of the material or any material in contact therewith or, optionally, the coating itself) and / or can be used to achieve desired functionality.

In the production of new materials or coating materials, the skilled person often faces the problem that he due to possible compatibility problems and / or incompatibilities in the selection of the ingredients, especially when using chemically reactive or reactive or physically setting systems is severely limited in terms of the selection of the components to be used and desired proportions. Further limitations arise from the availability of the ingredients to be used and the cost of these ingredients. Regularly, in terms of the environment, certain quantities and limits must be adhered to. It should also be noted that new, previously unusual components often adversely affect the properties of known, common materials, eg in terms of their capacity. Further restrictions in connection with coating materials or coatings produced therefrom arise from the typical, desired dimensions of the coatings to be produced on the basis of such coating materials, in particular with regard to a maximum layer thickness. Furthermore, for example, in the modification of fiber composites, the geometrical dimensions with respect to the fiber layer distances are taken into account. In addition, it must be taken into account that the constituents used can have a disadvantageous effect on the properties of a coating produced from the coating material, for example with regard to the wetting behavior and / or the load-bearing capacity of the surface. If a composite has to contain several different phases to achieve desired properties, for example in the case of fluid self-healing active ingredients and systems distributed in matrices, a robust production process suitable for such purposes must also be provided (often favored by spatial separation of the phases).

Materials are often multicomponent materials containing different substances in the extent required by the desired application. Coating materials, in particular adhesives and paints, are generally multicomponent mixtures which, in addition to customary organic-chemical polymer-forming systems, also contain hardening-accelerating substances, solid, frequently inorganic fillers, pigments and / or additives in the extent required by the desired application. A modification or functionalization of such materials or coatings can basically be achieved by the individual components used, by a specific combination of several components, by interactions with adherends or (to be coated) substrates or other interactions with the environment. The methods previously described in the prior art are often suitable only for very specific applications.

For example, solutions known in the prior art are concerned with sparingly soluble, dispersible particulate fillers in the binder system of coating materials, such as (a) pigments (eg alkaline earth dichromates) for the corrosion protection of aluminum alloys (eg AA2024), (b) metal particles (eg silver for antibacterial functionalization) or (c) to use molecular active substances (eg water-repellent oligosiloxanes as leveling agents or as anti-graffiti active substances, further example: fluid chemically reactive components of self-healing systems). In particular, the use of dispersed microparticles or nanoparticles which fulfill specific functions in some applications is known in the art. The use of such particles is, however, usually on a one-to-one basis, i. certain functionalizations, limited. A comprehensive multi-functionality is usually not given. In particular, the person skilled in the art is severely limited in the selection of the active substances or pigments or particles to be used, i.a. due to possibly resulting compatibility problems with the other constituents of coating materials or due to any stability problems of the active ingredients, pigments or particles to be used, which may result in the production or processing of the coating materials.

Another (known) approach is to modify existing coatings by often multilayer, thick, usually layered, successively cured structures in terms of surface durability and / or for the purposes of a particular functionalization, especially when components used in such structures have compatibility problems with others Expect components. However, such an approach involves additional work. In addition, such a system is usually also limited to certain purposes.

An innovative (known) approach consists in the encapsulation of active ingredients and the subsequent admixture of the capsules to the other constituents of the coating material or composite to be produced. Here, the function-bearing active ingredients are spatially separated from the other constituents of the coating materials, wherein the materials used for the encapsulation are chosen so that they are compatible both with the active ingredients to be included, as well as with the other constituents of the coating materials or composites. As a result, often occurring compatibility problems (between the different components) can be avoided or at least reduced. This approach requires that the capsules to be used have a sufficiently high mechanical resistance, in particular with regard to the (shear) forces prevailing in the production or processing of coating materials or composites. In addition - especially at hot-curing paints or adhesives - make sure that the capsules have a sufficiently high temperature stability. Accordingly, solid, inorganic capsule materials which have cavities of a few nanometers in size (eg phyllosilicates, halloysites, zeolites or carbon nanotubes) have hitherto been investigated. For example, by spray-drying processes, layer-by-layer, microemulsion-based processes or by chemical synthesis, polymeric capsules (physically) can be prepared, usually based on petrochemical starting materials (eg urea-formaldehyde capsules) or biological macromolecules (eg coacervation capsules). The capsules or the shell material thereof are formed in the presence of the active ingredients to be encapsulated. However, such a method has the disadvantage that the active ingredients to be used are limited to those which do not negatively or undesirably affect the capsule formation. In addition, for example, the above-mentioned coacervation capsules are not sufficiently mechanically stable for many applications.

As a result, there remains a need for improved or at least alternative materials and coating materials which make it possible to improve the materials or coatings resulting from corresponding coating materials with respect to their durability and / or to provide them with desired functionalizations. In particular, there is a need for a multifunctional system, i. a system that is not limited or at best to a limited extent to certain agents or functionalizations.

It was therefore a primary object of the present invention to provide a multifunctional material which makes it possible to provide particularly stable and / or functionalized materials, in particular composites.

Another object of the present invention is to provide coating materials for producing improved or functionalized coatings.

Other objects of the present invention are to provide correspondingly improved or modified components and products.

Other objects of the present invention will become apparent from the following description and in particular the appended claims.

• (A) einem Matrixmaterial und
• (B) einer Vielzahl von (zumindest teilweise in dem Matrixmaterial eingebetteten) Mikrokapseln mit einem mittleren Durchmesser, insbesondere im nicht getrockneten Zustand, im Bereich von 10, bevorzugt von 20, bis 200 µm, vorzugsweise im Bereich von 20 bis 150 µm, jeweils umfassend oder bestehend aus
• – einem Hüllmaterial umfassend oder bestehend aus (wenigstens) einer (d.h. einer oder mehreren, vorzugsweise wenigen, besonders bevorzugt einer) Zellwand und/oder (wenigstens) einer (d.h. einer oder mehreren, vorzugsweise wenigen, besonders bevorzugt einer) Zellmembran, insbesondere einem Sporoderm, d.h. der Umhüllung bzw. Außenschicht eines Pollenkorns, oder wenigstens der Exine eines Sporoderms, d.h. der äußeren Wand eines Sporoderms, und
• – einem oder mehreren in dem Hüllmaterial inkludierten Wirkstoffen, wobei der bzw. ein, mehrere oder sämtliche der inkludierten Wirkstoffe ausgewählt ist bzw. sind aus der Gruppe bestehend aus (festen, flüssigen oder zumindest fließenden) Farbstoffen, z.B. Fluoreszenzfarbstoffe (z.B. zur Detektion von (Oberflächen-)Defekten), Botenstoffen, z.B. Pheromone, (festen, flüssigen oder zumindest fließenden) Korrosionsinhibitoren, insbesondere organische Korrosionsinhibitoren (z.B. Triazole, Chinoline, Phosphonsäuren, Tenside/Amphiphile, polymere Inhibitoren) oder anorganische Korrosionsinhibitoren (z.B. Salze oder Lösungen von Salzen, z.B. Oxiden, Hydroxiden, Carbonaten, Phosphaten), Katalysatoren, Lösungsmitteln, zum Beispiel Wasser, Alkoholen, Ethern, Estern, Ketonen, fetten oder etherischen Ölen, Verdickungsmitteln, haftmindernden Substanzen, z.B. hydrophobierende Substanzen (z.B. fluorierte Kohlenwasserstoff- oder Organosiloxan-Gruppierungen enthaltende Verbindungen), Enteisungsreagenzien, z.B. wasserlösliche anorganische Salze (z.B. Alkaliformiate) oder (niedermolekulare) organische, wasserlösliche Moleküle (z.B. Einfach-/Mehrfachalkohole oder Lösungen von Antifreeze-Proteinen), antimikrobiellen Substanzen, zum Beispiel quartären Ammoniumsalzen, Metallen und deren Salzen, etherischen Ölen, Peptiden, Proteinen, Antibiotika, Phytoalexine, Antimykotika, Antiparasitika, insbesondere Mikrobiziden und Antimikrobiotika, Gleitmitteln, Schmiermitteln und Bestandteilen für Selbstheilungssysteme, insbesondere Katalysatoren und Initiatoren (z.B. Sikkative bzw. Trockenstoffe) für Selbstheilungssysteme, z.B. Metallkomplexe (z.B. Grubbs' Katalysator, Metallcarboxylate und deren Lösungen, Radikalbildner (z.B. Peroxide), oder Beschleuniger (z.B. tertiäre Amine und Imidazole), sowie Bestandteile reaktiver Harz- oder Härtersysteme für Selbstheilungssysteme, z.B. mehrfach ungesättigte Kohlenwasserstoffe (z.B. Dicyclopentadien, Leinsamenöl, Lackleinöl, Alkydharze oder Acrylate), reaktive Monomere und Mischungen davon (z.B. Epoxidharze, Amine, Isocyanate oder latente Härter (z.B. Thiole)),

wobei das Hüllmaterial (zumindest im teilweise oder im vollständig gehärteten Zustand des Komposit) zumindest teilweise kovalent an das Matrixmaterial gebunden ist. The primary object is achieved by a composite comprising or consisting of

• (A) a matrix material and
• (B) a plurality of (at least partially embedded in the matrix material) microcapsules having an average diameter, in particular in the undried state, in the range of 10, preferably from 20 to 200 microns, preferably in the range of 20 to 150 microns, each comprising or consisting of
• A shell material comprising or consisting of (at least) one (ie one or more, preferably a few, more preferably one) cell wall and / or (at least) one (ie one or more, preferably a few, more preferably one) cell membrane, in particular a sporoderm , ie the envelope or outer layer of a pollen grain, or at least the exine of a sporoderm, ie the outer wall of a sporoderm, and
• One or more active ingredients included in the shell material, the one or more, or all of the included active ingredients being selected from the group consisting of (solid, liquid or at least flowing) dyes, eg fluorescent dyes (eg for the detection of ( Surface defects), messenger substances, eg pheromones, (solid, liquid or at least flowing) corrosion inhibitors, in particular organic corrosion inhibitors (eg triazoles, quinolines, phosphonic acids, surfactants / amphiphiles, polymeric inhibitors) or inorganic corrosion inhibitors (eg salts or solutions of salts, for example, oxides, hydroxides, carbonates, phosphates), catalysts, solvents, for example water, alcohols, ethers, esters, ketones, fatty or ethereal oils, thickeners, adhesion-reducing substances, eg hydrophobic substances (eg fluorinated hydrocarbon or organosiloxane group-containing compounds ), Deicing reagents, For example, water-soluble inorganic salts (eg alkali formates) or (low molecular weight) organic, water-soluble molecules (eg single / multiple alcohols or solutions of antifreeze proteins), antimicrobial substances, for example quaternary ammonium salts, metals and their salts, essential oils, peptides, proteins, antibiotics, phytoalexins, antimycotics, antiparasitics, in particular microbicides and antimicrobials, lubricants, lubricants and constituents for self-healing systems, in particular catalysts and initiators (eg siccatives or Dry substances) for self-healing systems, eg metal complexes (eg Grubbs' catalyst, metal carboxylates and their solutions, radical formers (eg peroxides), or accelerators (eg tertiary amines and imidazoles), as well as components of reactive resin or hardener systems for self-healing systems, eg polyunsaturated hydrocarbons (eg Dicyclopentadiene, linseed oil, lake oil, alkyd resins or acrylates), reactive monomers and mixtures thereof (eg epoxy resins, amines, isocyanates or latent hardeners (eg thiols)),

wherein the shell material (at least partially or in the fully cured state of the composite) is at least partially covalently bonded to the matrix material.

Particularly preferred components to be used for self-healing systems are described below.

In addition to the abovementioned active ingredients, depending on the desired functionalization of the coating material, additional or other active substances can be used (in addition). For example, one or more markers (in the sense of a "certificate of authenticity") can be introduced to protect against or control product piracy.

Active substances which are suitable as markers for the durability of a coating material can also be used in the context of the present invention.

In addition to the abovementioned active ingredients, it is also possible to use one or more flavorings or fragrances, in particular in the form of or as part of essential oils.

In principle, both hydrophobic and hydrophilic active ingredients or mixtures of active substances can be used in the context of the present invention. The microcapsules contained in a composite according to the invention may also contain different active substances among one another. The included active ingredients may advantageously have molecular weights of up to several 100 g / mol. The active compounds to be used according to the invention preferably have a molecular weight in the range from 15 to 150,000 g / mol, preferably in the range from 50 to 10,000 g / mol, particularly preferably in the range from 50 to 1000 g / mol.

The proportion of the active ingredients included in the shell material (as described above), based on the total weight of the substances present in the interior of the shell material (ie in the space defined by the shell material and thus limited), is particularly preferably 0.01 to 100% by weight. %, preferably 1 to 100 wt .-%, particularly preferably 5 to 50 wt .-%.

From the above explanations it follows that the microcapsules to be used according to the invention may contain, in addition to the included active ingredients, one or more further constituents which, for example, depending on the optionally carried out (pre) treatment of the (biological) shell material used, are naturally present in the cells or pollen grains , which are the basis of the shell material used, are included.

The cell walls and / or cell membranes to be used as or for the shell material are those which are at least intact to the extent that they are sufficiently stable for the purposes of a barrier (with regard to the active ingredients to be included). The terms "cell wall" and "cell membrane" are therefore not to be understood in the context of the present invention as being completely biologically intact membranes or cell walls. Rather, it is sufficient if the cell wall and / or the cell membrane is suitable for encapsulating the active ingredients to be included, so that the active ingredients can not readily escape, in particular not without medial, mechanical or other stimuli.

The sheath material to be used according to the invention preferably consists of or is based on a naturally produced sheath or capsule with a carbohydrate, glycoprotein and / or chitin (containing) cell wall and / or a lipid bilayer membrane.

According to a preferred embodiment of the present invention, the shell material to be used according to the invention is a (biological) shell material of pollen grains, the shell material of the microcapsules preferably consisting of the sporoderm of a pollen grain, preferably at least of the exine of the sporoderm, or e) includes such. The shell material of the microcapsules particularly preferably consists of the sporoderm of a pollen grain or of the exine of the sporoderm of a pollen grain.

It is not necessary - and according to one embodiment of the present invention also not preferred - that it is the shell material biologically intact cells or pollen grains.

If the sporoderm of a pollen grain or the exine of the sporoderm of a pollen grain is used as the shell material or as a component for the shell material, it is particularly preferred if the pollen grain is selected from the group of medium-sized (preferably> 25 μm), large (preferably> 50μm) and very large (preferably> 100μm) pollen of terrestrial plants, preferably from pollen from trees, pollen from food and food plants, floral pollen and bee pollen, preferably from the group of medium sized and large pollen from the group consisting of conifer pollen and fodder plant pollen.

The shell material, preferably the purified (homogeneous) shell material, may be in the moist and / or dried state as well as in the non-germinated and / or germinated state, serving for the purpose of a barrier. Preferably, the shell material is obtainable by harvesting pollen, preferably intact pollen grains (preferably those as described above), preferably non-germinated pollen. With regard to the recovery of the shell material based on pollen grains as well as the loading and other aspects associated with it, for example Barrier et al., "Viability of plant spore exine capsules for microencapsulation", J. Mater. Chem., 2011, 21, 975-981 , and M. Lorch, "MRI contrast agent delivery using spore capsules: controlled release in blood plasma", Chem. Commun., 2009, 6442-6444 directed. The pollen grains to be used to obtain the shell material preferably to be used can be partially or completely emptied before the active ingredients are incorporated, so that the proportion of the active ingredients included in the shell material, based on the total weight of the substances present in the interior of the shell material, is up to 100% by weight. %. With regard to the emptying of pollen grains, for example, on S. Becket and G. Mackenzie, "Using Nature to Preserve Fish Oil", Chemistry Review, Vol. 2, November 2010 , referenced (see section "Preparing pollen shells").

The loading of the capsules / inclusion of the active ingredients in the shell material takes place, for example, by incubation of the (biological) shell material with the substance (s) to be included in preferably dissolved, liquid form. Depending on the selected shell material and the substances to be included, the person skilled in the art sets the appropriate conditions with regard to the volume, the mixing ratio, the temperature, the stirring speed and the incubation time. Advantageously, such an inclusion process usually requires no special additives, but can already be carried out alone in the presence of water, shell material and substances to be included. Also multi-phase systems can be used according to the invention. Upon inclusion or incubation (as described above), the substances to be included (agents) pass through the shell material through active (in living pollen) and / or passive transport, e.g. passively "stored" and thereby form capsules with included active ingredients - the active ingredients are enclosed by the wrapping material. Harvesting of the loaded capsules is preferably accomplished by physical separation (e.g., centrifugation and / or filtration) of the liquid phases from the capsules, optionally followed by washes and final drying (e.g., freeze-drying and / or spray-drying). Storage of the product is preferably dry and preferably at room or lower temperature.

In the context of the present text, "included active ingredients" are foreign substances, i. Substances that are not naturally or at least not included in the amount included in the invention in the space defined and limited by the shell material (e.g., in a corresponding naturally occurring, biologically intact pollen grain).

For the term "composite" the definition described above applies. This is particularly preferably a (fiber) composite material or a coating, in particular a lacquer layer. Preferred embodiments of such (fiber) composite materials as well as such coatings are described below.

As described above, the microcapsules or the shell material thereof to be used according to the invention are at least partially covalently bonded to the matrix material. Basically, that can Covering material both directly and indirectly, ie indirectly (for example, by a layer or shell surrounding the shell material), be bound to the matrix. According to a preferred embodiment of the present invention, the microcapsules or the shell material are modified before introduction into the matrix. Details are described below.

Covalent bonds between functional groups of the shell material, in particular functional groups of the sporoderm or the exine of a sporoderm, with reactive components of the matrix material occur in particular before or during the curing process of the coating or of the material. Furthermore, ionic, dipole and / or van der Waals interactions play a role in the adhesion between the capsule material and the curable and / or cured matrix.

Depending on the active ingredients included (see above), a material according to the invention or a coating according to the invention can be modified for different purposes or functionalizations. By way of example, it should be mentioned at this point that a composite according to the invention in the form of a coating containing one or more corrosion inhibitors as included active ingredients (as described above) has or offers improved corrosion protection properties. Because in case of violation of the coating (eg mechanical: crack, scratches) the included active ingredients can be selectively released when the at least partially covalently bound to the matrix material shell material (rips) or otherwise damaged by appropriate mechanical stimuli such that its barrier effect the included active ingredients lost or reduced. Targeted release zones form. As a result, a coated substrate can advantageously be purposefully protected against corrosion.

The microcapsules to be used according to the invention advantageously have an average diameter in the range from 20 to 200 .mu.m, preferably in the range from 20 to 150 .mu.m, more preferably in the range from 30 to 100 .mu.m, more preferably from 30 to 70 .mu.m. Such capsules offer the advantage that a loading of active substances which is increased in comparison to smaller capsules is possible in order to obtain sufficient or particularly advantageous active substance reservoirs for the respective purposes of use.

According to a preferred embodiment of the present invention, a composite according to the invention is a fiber composite containing one or more included dyes (as described above). Such a material offers the advantage that (surface) defects of the material can be detected quickly. For in case of injury or damage to the material (eg mechanical: crack, scratch), the included active ingredients can be selectively released when the at least partially covalently bound to the matrix material shell material (rips) or otherwise damaged by appropriate mechanical stimuli such that its barrier effect against the included active ingredients is lost or reduced. Selective release zones are formed, the damaged areas being colored in accordance with the dyes included in the microcapsules (originally) for the detection of the defect.

Further possible applications arise in particular from the abovementioned active ingredients preferably contained according to the invention. Accordingly, active substances contained in the microcapsules according to the invention can protect or "cure" not only a substrate to be coated, but also the material itself, in particular a fiber composite material according to the invention or a coating according to the invention (for example when using components of known self-healing systems).

Accordingly, particularly preferred according to the invention are composites which contain one or more constituents for self-healing systems as active ingredients, if appropriate spatially separated from one another, ie. in different microcapsules.

Preferably, the microcapsules to be used according to the invention contain one or more of such constituents for self-healing systems, as described in the following publications: US 2007/0166542 A1 ; US 2006/0111469 A1 ; Murphy et Wudl, 2010 ("The world of smart healable materials", Progress in Polymer Science 35 (2010) 223-251); Nesterova et al., 2010 ( "Synthesis of durable microcapsules for self-healing anticorrosive coatings: A comparison of selected methods", Progress in Organic Coatings (2010)) and Syrett et al., 2010 ( "Self-healing and self-mature polymers", Polym. Chem., 2010, 1, 978-987 ).

According to a preferred embodiment of the present invention contains at least a portion of the microcapsules according to the invention (as described above) an active ingredient (as part of a self-healing system), which is suitable when in contact with another substance (as another component of a self-healing system), preferably is also contained as active ingredient in another part of the microcapsules according to the invention (as described above), (by chemical reaction, eg Polymerization by polyaddition, polymerization or polycondensation) to generate a new, higher molecular weight compound. According to a particularly preferred embodiment of the present invention, at least a portion of the microcapsules according to the invention (as described above) contains a polymerizable monomer, wherein at least one further portion of the microcapsules according to the invention preferably contains a corresponding activator / initiator for the polymerization of the monomer. In the case of injury or damage to the material (eg mechanical: crack, scratches), the (different) included active substances can be released in a targeted manner if the shell material bound at least partially covalently to the matrix material ruptures or is otherwise damaged by corresponding mechanical stimuli in that its barrier action against the included active ingredients is lost or reduced so that the monomer contained can polymerize and thereby at least partially fill (re) fill the damaged area and / or protect or "cure" in the manner of a seal.

According to a preferred embodiment of the present invention, at least a portion of the microcapsules according to the invention (as described above) contains a "polymerizer" as in US 2007/0166542 A1 or US 2006/0111469 A1 described, in particular as described in the claims thereof, wherein at least one further part of the microcapsules according to the invention contains a corresponding activator / initiator for the (siloxane) polymerizer, preferably one as in US 2007/0166542 A1 or US 2006/0111469 A1 described, in particular as described in the claims thereof.

According to a preferred embodiment of the present invention contains at least a portion of the microcapsules according to the invention - to achieve a self-healing effect - components or additives (eg accelerators, catalysts, inhibitors, initiators) of adhesive systems that are chemically reactive by polyaddition, polymerization or polycondensation or by physical Abbindevorgänge (For example, the evaporation of solvents, eg water) are cured.

As explained above by way of example, the microcapsules according to the invention are suitable for selectively releasing the active substances contained, in particular in the case of mechanical stimuli (for example pressure, tension, crack, scratches). However, the materials of the invention may also be designed so that further / other stimuli lead to a targeted release of the active ingredients contained.

The person skilled in the art can e.g. Depending on the desired barrier effect of the shell material, depending on the desired (release) stimulus or depending on the desired release amount to select or assemble a suitable for the particular purpose envelope material. By means of appropriate tests, it can be quickly determined whether the examined or which wrapping material is particularly suitable for the desired purpose.

According to a further, preferred embodiment of the present invention, the microcapsules contain two or more different active ingredients, the inclusion of a first active ingredient facilitating or promoting the (subsequent) inclusion of a further active ingredient (eg in the case of inclusion of a chelating ligand and subsequent inclusion of a suitable central ion, in particular a transition metal ion or a doubly positively charged metal ion, or a complexed central ion, for example when an oil is included and subsequently encapsulated in a lipophilic active substance, in particular a lipophilic molecule or metal complex).

It was particularly surprising from the prior art that the coating materials described herein are suitable for the purpose of improving or modifying conventional materials. As described in the introduction, effective (and permanent) encapsulation of active ingredients for use in conventional materials, especially in coatings prepared from corresponding coating materials, requires that the capsules have sufficiently high mechanical stability and, optionally, thermal resistance, especially when used in thermoset systems , Surprisingly, the shell material to be used according to the invention, in particular the shell material referred to above as preferred, is particularly suitable for encapsulating different active ingredients and incorporating them (in encapsulated form) into compositions for the production of materials described herein.

Surprisingly, the shell materials to be used according to the invention can also be used for the encapsulation of substances which are gaseous, for example at a temperature of 60 ° C., these being characterized by mere thermal stimuli (eg at a temperature of 180 ° C.), for example in hot-curing coating systems (HT -Lacke), at least predominantly included. Furthermore, the According to the invention to be used shell materials a sufficiently high mechanical stability in order to be used in a variety of materials can.

The use of yeast cells as encapsulating material for use with different substances is already known in the art (see, for example Bishop et al (1998, Microencapsulation in yeast cells, J. Microencapsulation, Vol.15, No. 6: 761-773) in which the encapsulation of various (aromatic) oils in bakers' yeast is described, wherein the survival of the microorganisms used is not a prerequisite for a successful encapsulation, Shi et al (2007, Yeast-cell-based microencapsulation of chlorogenic acid as a water-soluble antioxidant, J. of Food Engineering, Vol. 80: 1060-1067) which describes the inclusion of chloric acid in yeast cells, EP 0 242 135 A2 . EP 1 693 445 . EP 1 693 445 A1 . EP 1 693 445 B1 . US 4,001,480 . US 5,288,632 and Nelson (2002, Application of microencapsulation in textiles, Int. J. of Pharmaceutics, Vol. 242: 55-62) , which describes in particular the use of yeast capsules in textiles.) Furthermore, the encapsulation of active ingredients in pollen or pollen grains is known (US Pat. S. Barrier et al., "Viability of plant spore exine capsules for microencapsulation", J. Mater. Chem., 2011, 21, 975-981 ; EP 04743123.4 . EP 06765121.6 . EP 08861899.6 . EP 06765123.2 ).

In the publications US 2004/0109853 A1 . US 2004/0175407 A1 . GB 02410249 B and US 2009/0238811 A1 the incorporation of biological materials such as enzymes in coatings is described as well as the company Reactive Surfaces Ltd. in the publication "Bioengineered Enzymes and Peptides - Bringing Coatings to Life". The incorporation of pollen as a filler into physically setting matrix systems is also known and has been described, for example, by J.-H. Lee et al. "Pollen: A novel, biorenewable filler for polymer composites", Macromol. Mater. Closely. 2011, 296, 1055-1062 ).

However, the usability of a biological shell material as described in the context of the present invention for the encapsulation of certain active substances for the specific modification of materials or coating materials is not described in the prior art.

The use of microcapsules described herein, particularly microcapsules referred to herein as preferred, has numerous advantages.

On the one hand, the microcapsules to be used according to the invention are readily dispersible in chemically reactive and physically setting systems. Furthermore, the introduction of different active ingredients in (conventional) materials is made possible, so that - depending on the included active ingredients - composites with high stability and / or desired functionalization can be produced.

The microcapsules to be used in accordance with the present invention also allow the incorporation of active ingredients which, when used alone (i.e., unencapsulated), may have compatibility problems with one or more other constituents of the material or coating material. In addition, the risk is reduced that the active substances to be incorporated (for example in the production of materials) negatively or undesirably influence, for example, the curing reaction of reactive resin systems.

Another advantage of the microcapsules to be used according to the invention is that the material used for the encapsulation consists of or comprises biodegradable and renewable raw materials.

The microcapsules to be used according to the invention also offer the advantage that a shell material is used which does not have to be constructed or produced by targeted measures. The shell materials to be used according to the invention described in the context of the present text are usually already present as inclusion bodies suitable for the purposes of the present invention.

Preferably, for the vast majority of microcapsules (as described herein), preferably for all microcapsules, the total weight of the amount of active ingredients included in a microcapsule based on the total weight of the microcapsule is in the range of 1 to 80 weight percent, preferably in the range from 5 to 80 wt .-%, particularly preferably in the range of 5 to 40 wt .-%, is.

According to the present invention, a composite according to the invention (as described above) is in particular a composite material, preferably a fiber composite material, wherein the matrix material preferably comprises one or more plastics, in particular one or more crosslinked polymers, preferably one or more plastics from the group from thermosets, in particular epoxides, acrylates, polyurethanes, polyimides, phenol-formaldehyde condensation resins, unsaturated Polyester, vinyl ester resins, and thermoplastics, in particular polyaryletherketones, polyarylethersulfones, polypropylene, polyamides and polyesters, comprises or consists of.

In addition, a fiber composite material according to the invention may contain (in addition to the microcapsules to be used according to the invention) further components customary in the prior art.

• (a) ein oder mehrere Bindemittel und
• (b) eine Vielzahl von Mikrokapseln mit einem mittleren Durchmesser im Bereich von 20 bis 200 µm, vorzugsweise im Bereich von 20 bis 150 µm, jeweils umfassend oder bestehend aus
• – einem Hüllmaterial wie oben beschrieben, d.h. einem Hüllmaterial umfassend oder bestehend aus einer Zellwand und/oder einer Zellmembran (wie oben beschrieben), vorzugsweise aus einem Sporoderm eines Pollenkorns, bevorzugt wenigstens aus der Exine eines Sporoderms (wie jeweils oben beschrieben), und
• – einem oder mehreren in dem Hüllmaterial inkludierten Wirkstoffen, wobei der bzw. ein, mehrere oder sämtliche der inkludierten Wirkstoffe ausgewählt ist bzw. sind aus der Gruppe bestehend aus (festen, flüssigen oder zumindest fließenden) Farbstoffen, z.B. Fluoreszenzfarbstoffe (z.B. zur Detektion von (Oberflächen-)Defekten), Botenstoffen, z.B. Pheromone, (festen, flüssigen oder zumindest fließenden) Korrosionsinhibitoren, insbesondere organische Korrosionsinhibitoren (z.B. Triazole, Chinoline, Phosphonsäuren, Tenside/Amphiphile, polymere Inhibitoren) oder anorganische Korrosionsinhibitoren (z.B. Salze oder Lösungen von Salzen, z.B. Oxiden, Hydroxiden, Carbonaten, Phosphaten), Katalysatoren, Lösungsmitteln (vgl. oben) Verdickungsmitteln, haftmindernden Substanzen, z.B. hydrophobierende Substanzen (z.B. fluorierte Kohlenwasserstoff- oder Organosiloxan-Gruppierungen enthaltende Verbindungen), Enteisungsreagenzien, z.B. wasserlösliche anorganische Salze (z.B. Alkaliformiate) oder (niedermolekulare) organische, wasserlösliche Moleküle (z.B. Einfach-/Mehrfachalkohole oder Lösungen von Antifreeze-Proteinen), antimikrobiellen Substanzen (wie oben beschrieben), Gleitmitteln, Schmiermitteln und Bestandteilen für Selbstheilungssysteme (wie oben beschrieben), insbesondere Katalysatoren und Initiatoren für Selbstheilungssysteme, z.B. Metallkomplexe (z.B. Grubbs' Katalysator), Radikalbildner (z.B. Peroxide), oder Beschleuniger (z.B. tertiäre Amine und Imidazole), und Bestandteile reaktiver Harzsysteme für Selbstheilungssysteme, z.B. mehrfach ungesättigte Kohlenwasserstoffe (z.B. Dicyclopentadien, Leinsamenöl oder Acrylate), reaktive Monomere und Mischungen davon (z.B. Epoxidharze, Isocyanate).

A further aspect of the present invention relates to a coating material, in particular a coating material for producing a coating according to the invention (as described herein), the coating material comprising or consisting of the following constituents:

• (a) one or more binders and
• (B) a plurality of microcapsules having an average diameter in the range of 20 to 200 .mu.m, preferably in the range of 20 to 150 .mu.m, each comprising or consisting of
• A shell material as described above, ie a shell material comprising or consisting of a cell wall and / or a cell membrane (as described above), preferably a sporoderm of a pollen grain, preferably at least the exine of a sporoderm (as described above), and
• One or more active ingredients included in the shell material, the one or more, or all of the included active ingredients being selected from the group consisting of (solid, liquid or at least flowing) dyes, eg fluorescent dyes (eg for the detection of ( Surface defects), messenger substances, eg pheromones, (solid, liquid or at least flowing) corrosion inhibitors, in particular organic corrosion inhibitors (eg triazoles, quinolines, phosphonic acids, surfactants / amphiphiles, polymeric inhibitors) or inorganic corrosion inhibitors (eg salts or solutions of salts, eg oxides, hydroxides, carbonates, phosphates), catalysts, solvents (see above) thickening agents, adhesion-reducing substances, eg hydrophobizing substances (eg fluorinated hydrocarbon or organosiloxane groupings containing compounds), deicing reagents, eg water-soluble inorganic salts (eg alkali formates) or (niedermolekul are) organic, water-soluble molecules (eg, single / multiple alcohols or solutions of antifreeze proteins), antimicrobial substances (as described above), lubricants, lubricants and self-healing system components (as described above), especially catalysts and initiators for self-healing systems, eg metal complexes (eg, Grubbs' catalyst), free radical generators (eg, peroxides), or accelerators (eg, tertiary amines and imidazoles), and reactive resin system components for self-healing systems, eg, polyunsaturated hydrocarbons (eg, dicyclopentadiene, linseed oil, or acrylates), reactive monomers, and mixtures thereof (eg Epoxy resins, isocyanates).

For the constituents of the coating material according to the invention, in particular for the microcapsules, in particular the shell material to be used and the active ingredients included, the statements made above apply mutatis mutandis.

The coating materials according to the invention are in particular paints, ie coating materials which, in addition to the microcapsules to be used according to the invention and one or more binders for (conventional) lacquers, contain conventional constituents. With particular preference the coating materials of the invention are paints. To DIN EN 971-1 For example, a varnish is a liquid, pasty or powdered, pigmented coating that provides a covering coating with protective, decorative or specific technical properties. These include clear lacquers that form a transparent coating with protective, decorative or specific technical properties.

A coating material according to the invention is preferably a paint or an adhesive, preferably a paint, preferably a powder paint, in particular a hot-curing paint (HT paint) or stoving enamel.

The or one, several or all binders of a coating material according to the invention is or are preferably selected from conventional constituents of known chemically reactive or reactive systems or physically setting systems. Particularly preferred is an inventive Coating material, wherein the or one, several or all of the binders is or are selected from the group consisting of epoxy resins, polyurethanes, acrylates, alkyd resins, formaldehyde condensation resins, polyesters, polyethers, PVC and polyethylene. Particularly preferred are epoxy resins, polyurethanes, acrylates, polyesters and epoxy resin-polyester hybrid systems.

According to an (alternative) preferred embodiment, the or one, several or all binders are selected from biodegradable binders, e.g. PLA.

According to our own investigations, the coating materials according to the invention, in particular the coating materials preferred according to the invention (as described above), can also be stored (stably) over a relatively long period of time in accordance with customary requirements. The storage stability of conventional coating materials is advantageously not or not affected by the addition according to the invention to be used microcapsules to disturbing extent.

A coating according to the invention (as described above) preferably results from an applied and optionally cured coating material according to the invention (as described above). Accordingly, a preferred embodiment of a coating according to the invention is a lacquer layer, i. a layer of paint applied to an article (and possibly cured).

• – ein oder mehrere organische Lösungsmittel, wobei das bzw. ein, mehrere oder sämtliche der Lösungsmittel vorzugsweise ausgewählt ist bzw. sind aus der Gruppe bestehend aus Alkohole, Glykole, Ketone, Ester und Ether, und/oder
• – Wasser und/oder
• – ein oder mehrere weitere Bestandteile bzw. Additive ausgewählt aus der Gruppe bestehend aus Pigmente, Füllstoffe, Entschäumer, Entlüfter, Korrosionsinhibitoren, Verdicker, Dispergieradditive, Benetzungsadditive, Hydrophobierungsadditive, Reaktivverdünner, Entwässerungsmittel und Netzmittel

enthalten. In addition to the constituents described above, a coating material according to the invention can also

• - One or more organic solvents, wherein the or one, more or all of the solvents is preferably selected from the group consisting of alcohols, glycols, ketones, esters and ethers, and / or
• - water and / or
• - One or more other ingredients or additives selected from the group consisting of pigments, fillers, defoamers, deaerators, corrosion inhibitors, thickeners, dispersing additives, wetting additives, hydrophobing additives, reactive diluents, dehydrating agents and wetting agents

contain.

The constituents mentioned above are not primarily substances included in the microcapsules, but constituents which, in addition to the microcapsules to be used according to the invention, are preferably used as further constituents in coating materials according to the invention.

According to a preferred embodiment of the present invention, the proportion of microcapsules to be used according to the invention in a composite according to the invention and / or in a coating material according to the invention (as described above), based on the total weight of the composite or the coating material, 0.1 to 80 wt .-%, preferably 0.5 to 50 wt .-%, particularly preferably 2 to 10 wt .-%. Based on the state of the art, it was not to be expected that such a content of microcapsules could be incorporated into (customary) works or coating materials, in particular not without undesirable effects on their processability or other properties.

According to the invention, preference is given to a coating material as described above, wherein for the majority of the microcapsules, preferably for all microcapsules, it holds true that
the proportion of the active ingredients included in the shell material, based on the total weight of the substances present in the interior of the shell material, is in the range from 0.01 to 100% by weight, preferably in the range from 1 to 100% by weight, more preferably in Range from 5 to 50 wt%,
and or
the total weight of the amount of active ingredients included in a microcapsule, based on the total weight of the microcapsule, in the range from 1 to 80% by weight, preferably in the range from 5 to 80% by weight, more preferably in the range from 5 to 40% by weight .-%, lies.

• (I) Aufbringen (beispielsweise durch Tauchen, Streichen, Rollen, Walen, Fluten, Gießen, Vakumat, Hochdruck-Zerstäuben, Hochrotations-Zerstäuben, Elektrostatisches-Zerstäuben, Airless-Zerstäuben, HVLP-Pistole, Airmix-Zerstäuben, oder mittels Becherpistole) eines erfindungsgemäßen Beschichtungsstoffs (wie hierin beschrieben), vorzugsweise eines erfindungsgemäßen Beschichtungsstoffs wie oben als bevorzugt beschrieben, auf eine zu beschichtende Oberfläche;
• (II) optional: Aushärten des aufgebrachten Beschichtungsstoffs.

A composite according to the invention in the form of a coating (as described above), preferably a lacquer layer (as described above), can preferably be produced by a process comprising the following steps:

• (I) Application (for example, by dipping, brushing, rolling, whale, flood, pouring, vacuum, high pressure sputtering, high rotation sputtering, electrostatic sputtering, airless sputtering, HVLP gun, Airmix sputtering, or by cup gun) coating material according to the invention (as described herein), preferably a coating material according to the invention as described above as preferably on a surface to be coated;
• (II) optional: curing of the applied coating material.

Both for the coatings according to the invention (as described above), in particular a lacquer layer according to the invention, and for the products according to the invention (as described herein), in the event that the coating material is cured, the curing preferably takes place at a temperature in the range of 60, preferably from 80, to 300 ° C, preferably in the range of 100 to 250 ° C, more preferably in the range of 150 to 200 ° C.

• (i) Bereitstellen eines oder mehrerer Bindemittel (wie oben beschrieben), vorzugsweise eines oder mehrerer Bindemittel ausgewählt aus der Gruppe bestehend aus Epoxidharze, Polyurethane, Acrylate, Alkydharze, Formaldehydkondensationsharze, Polyester, Polyether, Polyethylen und PVC sowie gegebenenfalls bioabbaubaren Bindemitteln (vgl. oben),
• (ii) Bereitstellen von Mikrokapseln (vorzugsweise wie oben beschrieben) mit einem mittleren Durchmesser, insbesondere im nicht getrockneten Zustand, im Bereich von 10, bevorzugt von 20, bis 200 µm, vorzugsweise im Bereich von 20 bis 150 µm, jeweils umfassend oder bestehend aus
• – einem Hüllmaterial umfassend oder bestehend aus einer Zellwand und/oder einer Zellmembran (wie oben beschrieben), vorzugsweise aus einem Sporoderm eines Pollenkorns, bevorzugt wenigstens aus der Exine eines Sporoderms (wie jeweils oben beschrieben), und
• – einem oder mehreren in dem Hüllmaterial inkludierten Wirkstoffen (wie oben beschrieben), wobei der bzw. ein, mehrere oder sämtliche der inkludierten Wirkstoffe ausgewählt ist bzw. sind aus der Gruppe bestehend aus Farbstoffen, Botenstoffen, Korrosionsinhibitoren, Katalysatoren, Lösungsmitteln, Verdickungsmitteln, haftmindernden Substanzen, Enteisungsreagenzien, antimikrobiellen Substanzen, Gleitmitteln, Schmiermitteln und Bestandteilen für Selbstheilungssysteme (vgl. oben), und
• (iii) Mischen der Mikrokapseln aus Schritt (ii) mit dem bzw. den Bindemitteln aus Schritt (i) sowie optional weiteren Bestandteilen.

A further aspect in connection with the present invention relates to a process for the preparation of a coating material, preferably a coating material according to the invention (as described above), the process comprising the following steps:

• (i) providing one or more binders (as described above), preferably one or more binders selected from the group consisting of epoxy resins, polyurethanes, acrylates, alkyd resins, formaldehyde condensation resins, polyesters, polyethers, polyethylene and PVC and optionally biodegradable binders (see above )
• (Ii) providing microcapsules (preferably as described above) having an average diameter, in particular in the undried state, in the range of 10, preferably from 20 to 200 microns, preferably in the range of 20 to 150 microns, each comprising or consisting of
• A shell material comprising or consisting of a cell wall and / or a cell membrane (as described above), preferably a sporoderm of a pollen grain, preferably at least the exine of a sporoderm (as described above), and
• - One or more included in the shell material ingredients (as described above), wherein the or one, several or all of the included active ingredients is or are selected from the group consisting of dyes, messengers, corrosion inhibitors, catalysts, solvents, thickeners, adhesion-reducing Substances, de-icing reagents, antimicrobials, lubricants, lubricants and self-healing components (see above), and
• (iii) mixing the microcapsules of step (ii) with the binder (s) of step (i) and optionally other ingredients.

Again, this again applies to the respective constituents, i. in particular the active ingredients to be included, the binders and microcapsules to be used according to what has been said above. For the optionally used further constituents, what has been said above with respect to the constituents contained in a (inventive) coating material also applies accordingly.

Another aspect of the present invention relates to a component consisting of a composite according to the invention, in particular of a fiber composite material according to the invention (as described above), wherein the component is preferably selected from the group consisting of components of the primary structure and secondary structure of aircraft and vehicles of the agricultural and Sea transport, eg Roofing components, bumpers and spoilers, pressure vessels and fuel tanks or components thereof, e.g. Tank linings, interior components and decorative elements, as well as articles of household decoration and ornaments, shipbuilding components, components of off-shore (wind power) installations, components of port constructions and in general components for installations used in maritime and / or or coastal area, office supplies, telecommunications articles, bicycle frames and attachments, sports equipment, hard hats, rotor blades, suitcases and play equipment.

• (I) Aufbringen (beispielsweise wie oben beschrieben) eines erfindungsgemäßen Beschichtungsstoffs (wie hierin beschrieben), vorzugsweise eines als bevorzugt bezeichneten Beschichtungsstoffs, an zumindest einem Oberflächenabschnitt des Substrats und
• (II) optional Aushärten des aufgebrachten Beschichtungsstoffs.

A further aspect of the present invention relates to a product comprising a substrate and a coating according to the invention adhering to at least a surface portion of the substrate (as described above). The coating is preferably produced by

• (I) applying (for example as described above) a coating material according to the invention (as described herein), preferably a coating material designated as preferred, to at least one surface portion of the substrate and
• (II) optionally curing the applied coating material.

Again, the above for the coating according to the invention and the coating material according to the invention applies in turn accordingly.

Accordingly, for example, the adhering coating is preferably a lacquer layer.

The substrate is an article which, for the desired purposes, can be partially or completely coated, in particular coated, with a coating according to the invention.

For products preferred according to the invention, the substrate to be coated on at least one surface section is selected from the group consisting of: metals and alloys, in particular light metals, silicate glasses, e.g. Slices or ceramics, organic surfaces, bones, teeth, woods, laminates, polymers and fiber-reinforced polymers, cast resins, fibers, e.g. Glass, charcoal, aramid and natural fibers, leather, cloth, paper and cardboard.

Further aspects related to the present invention relate to advantageous uses of coating materials or coatings according to the invention, e.g. the use of a coating material according to the invention (as described above) or a coating according to the invention (as described above) for improving the corrosion resistance of a substrate (to be coated). Further uses or possible uses result from the above statements, in particular in connection with the active ingredients preferably contained according to the invention.

• – Aufbringen eines erfindungsgemäßen Beschichtungsstoffs (wie oben beschrieben) auf die Oberfläche des Metalls, wobei der bzw. einer, mehrere oder sämtliche der in dem Hüllmaterial inkludierten Wirkstoffe Korrosionsinhibitoren sind.

A preferred aspect of the present invention relates to a method for improving the corrosion resistance of a metal, comprising the following step:

• - Applying a coating material according to the invention (as described above) on the surface of the metal, wherein the or one, more or all of the active ingredients included in the shell material are corrosion inhibitors.

As mentioned above, the microcapsules or shell material are modified prior to introduction into the matrix or mixing with the binder (s) according to a preferred embodiment of the present invention.

Accordingly, a preferred aspect of the present invention relates to a composite or coating material (as described above) and to methods and uses described above wherein the microcapsules are modified, in particular wherein the microcapsules are modified by a gas phase process. In the context of such a modification, for example, a cleaning, an activation or functionalization and / or a coating of the microcapsules or the shell material (as described above) take place. Such a treatment or modification preferably takes place before the introduction of the microcapsules into the matrix material or the mixing with the binder (s) and can take place before and / or after inclusion of the active compounds.

Preferably, the microcapsules are modified or treated by means of a plasma process, preferably by means of an atmospheric pressure plasma process.

Particularly preferred is a composite or a coating material (as described above), wherein the microcapsules are surface-modified by means of a gas phase process, in particular to change the release properties with respect to the included active ingredients and / or the incorporability of the microcapsules in the composite or the coating material.

By gas phase modification, in particular an atmospheric pressure plasma treatment, the surface of the biological shell material can be advantageously functionalized in such a way that the wettability is increased by the formation of hydrophilic, oxygen and / or nitrogen-containing groups, as a result of which the loading of the shell material or microcapsules to improve. Furthermore, the surface functionalization thus achieved can advantageously enable improved dispersion in aqueous solvents, paints or adhesives or corresponding matrix materials.

Further, by the treatment with an atmospheric pressure plasma, the surface of the shell material or the microcapsules can advantageously be changed so that the water absorption of the shell material is increased and thus the swelling increases (if desired).

For the purposes of the present invention, atmospheric pressure plasmas operating at moderate gas temperatures (preferably below or at room temperature) are particularly suitable for surface modification. As process gases are preferably nitrogen, oxygen, hydrogen or mixtures containing or consisting of these gases to use (eg simple compressed air). Reactive nitrogen radicals, oxygen radicals, hydrogen radicals and / or reaction products thereof are then formed in the plasma, which can advantageously undergo plasma-chemical and / or chemical interactions on the surface of the shell material, in particular in order to form functional groups.

By means of gas phase processes, in particular by means of atmospheric pressure (AD) plasma, it is also advantageously possible to deposit functional (nano) layers, in particular by PE-CVD processes, in order to give the shell material or microcapsules new, particularly advantageous surface functions. It is thus possible, after the filling material has been filled in, to provide it with a hydrophobic barrier layer which can be used to reduce the swelling behavior of the microcapsules. In addition, the (re-) release of the included active ingredients can be influenced, in particular delayed or reduced, in order to achieve a demand-oriented "release control". Furthermore, a hydrophobic coating can advantageously improve the dispersibility in organic solvents.

For the deposition of functional nano-layers by means of AD plasma, organic or organosilicon compounds are preferably fed into the AD plasma. There they are fragmented and ionized and can enter into plasma-chemical interactions with the selected process gas (preferably N ₂ , O ₂ , H ₂ and / or noble gases or mixtures thereof). The reactive radicals formed in this way can undergo a plasma polymerization reaction on the surface of the shell material or of the microcapsules and thus deposit or form functional nanosheets.

In the following, the present invention is explained in more detail with reference to figures and selected examples.

shows an active ingredient-filled pine pollen grain introduced into a cured lacquer layer; above: the surface-near pine pollen grain causes a local bulge of the undamaged paint layer according to the invention; bottom: using Focussed Ion Beam (FIB) technique, a local cut shows that a pollen grain actually hides under the surface structure shown above. In the FIB preparation, the surface is cut and imaged by a material-removing ion-cutting technique in an electron microscope. It can be seen that the outermost shell of the pollen capsules (Exine) contacts the paint matrix.

shows an electron micrograph of a scored by scoring a composite / paint layer according to the invention by means of a Hartmaterialspitze introduced at room temperature fracture edge. It becomes clear that approximately 40 μm wide, roundish structures are embedded in the matrix. The outermost shell (exine) adheres so strongly to the matrix in the area of the fracture edge that the pollen capsule was torn open as a result of the mechanical stress and the interior of the pollen capsules was exposed. In places, the active ingredient material is thus released during bursting (mechanical release stimulus) and the interior of the pollen capsules becomes physically-chemically accessible (medial release stimulus) in the region of the tear edge to a liquid medium which dissolves the active substance.

Examples:

1. Preparation of a composite according to the invention:

Example of use: 5 parts Microcapsules to be used according to the Invention (Containing Corrosion Protection Inhibitors (as Described Above)) 77.5 parts Resin: Araldite GY 250 17,5 parts Hardener: isophoronediamine

production:

The matrix used is, for example, a cold-curing or heat-curing 2-component epoxy resin adhesive (for example as mentioned above), which can be processed as follows:
First, the resin portion is introduced, and the desired amount according to the invention to be used microcapsules is added with stirring by hand. A fine distribution of isolated microcapsules is achieved by using shearing forces of introducing machines and succeeds especially with surface-modified microcapsules (as described above). Subsequently, the mixture is optionally mixed under vacuum (eg 10 mbar) in a mixer, preferably in a Thinky mixer, for a certain period of time (eg 1000 rpm for 2 min) and degassed to allow a later bubble-free application.

The hardener is stirred by hand before being applied in the resin-microcapsule mixture.

The curing of the resulting composite can be carried out at 60 to 140 ° C, preferably at 140 ° C, for e.g. 1 hour to be performed.

2. Production of a Fiber Composite Material According to the Invention

Application Example 1 5 parts Microcapsules to be used according to the Invention (Containing Corrosion Protection Inhibitors (as Described Above)) 77.5 parts Resin: Araldite GY 250 17,5 parts Hardener: isophoronediamine n parts: fiber material Application Example 2 25 parts Microcapsules to be used according to the invention (containing "Self-healing" agents (as described above)) 61 parts Resin: Araldite GY 250 14 parts Hardener: Isophorone diamine n parts: fiber material

production:

In this case, the fibers can be present as follows: as prefabricated and / or hand-laid tissue, scrims and / or fiber mats (prepreg technology). The fibers can be used according to the invention in amounts customary for fiber composites.

The matrix used is, for example, a heat-curing 2-component epoxy resin adhesive (for example as described above), which can be processed as follows:
First, the resin portion is introduced, and the desired amount according to the invention to be used microcapsules is added with stirring by hand. Subsequently, this mixture is optionally mixed under vacuum (eg 10 mbar) in a mixer, preferably in a Thinky mixer, for a certain period of time (eg 1000 rpm for 2 min) and optionally degassed.

The hardener is added to the resin-microcapsule mixture prior to combining fiber and matrix (2K-EP).

The connection of the fibers to the matrix microcapsule system can be carried out in a variety of ways, e.g. by vacuum infusion method or by hand lamination.

Curing of the resulting fiber composite may be carried out at 60 to 140 ° C, preferably at 140 ° C, for e.g. 1 hour to be performed.

3. Preparation of a coating material according to the invention:

3.1 Preparation of an Epoxy (EP) Lacquer System

The desired (parent) components are dispersed to desired parts (see table, Ex. 4.1 and 4.2) by means of dissolver for up to 60 min at up to 700 rpm.

The initially introduced binder is gradually "filled in" with microcapsules to be used according to the invention and the (aqueous) solvent with constant dispersion. Subsequently, the stirred and (i.d.R) foamed EP system with the microcapsules is preferably stored overnight at room temperature to guarantee subsequent bubble-free application of the lacquer to a surface.

Before application, the hardener is stirred in by hand.

As a variant, a desired amount of microcapsules to be used in accordance with the invention can also be incorporated into an initially introduced hardening system with shearing action and then the resin portion can be stirred in. This variant is particularly preferable if the microcapsules required for incorporation of the desired amount according to the invention in finely divided form would exceed the shear stability of the resin portion.

Optimal curing of the system can take up to a week at room temperature.

3.2 Preparation of a solvent-based 2-component polyurethane coating system:

The desired (parent) components are dispersed to desired parts (see table, Ex. 4.3) by dissolver for up to 60 min at up to 700 rpm in a PE beaker.

The initially introduced binder is gradually "filled in" with microcapsules to be used according to the invention and the solvent components with constant dispersion. After the above components are homogeneously dispersed, the hardener is added.

Subsequently, the stirred system containing the microcapsules to be used according to the invention can be applied to a desired surface.

The (paint) system is preferably dried forcibly at 60 ° C, for up to 60 minutes.

3.3 Preparation of a hot-curing powder coating system:

The microcapsules to be used according to the invention are incorporated in an epoxy-polyester (EP / PES) powder coating system, e.g. in a concentration of 3 wt .-%, incorporated (see table according to Example 4, Ex. 4.4).

The curing temperature is 180 ° C. The curing time is 20 min.

4. Examples of coating materials according to the invention:

The coating materials are basically prepared according to Example 3.

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Cited patent literature

• US 2007/0166542 A1 [0042, 0044, 0044]
• US 2006/0111469 A1 [0042, 0044, 0044]
• EP 0242135 A2 [0051]
• EP 1693445 [0051]
• EP 1693445 A1 [0051]
• EP 1693445 B1 [0051]
• US Pat. No. 4001480 [0051]
• US 5288632 [0051]
• EP 04743123 [0051]
• EP 06765121 [0051]
• EP 08861899 [0051]
• EP 06765123 [0051]
• US 2004/0109853 A1 [0052]
• US 2004/0175407 A1 [0052]
• GB 02410249 B [0052]
• US 2009/0238811 A1 [0052]

Cited non-patent literature

• Barrier et al., "Viability of plant spore exine capsules for microencapsulation", J. Mater. Chem., 2011, 21, 975-981 [0031]
• M. Lorch, "MRI contrast agent delivery using spore capsules: controlled release in blood plasma", Chem. Commun., 2009, 6442-6444 [0031]
• G. Mackenzie, "Using Nature to Preserve Fish Oil", Chemistry Review, Vol. 2, November 2010 [0031]
• Murphy et Wudl, 2010 ("The world of smart healable materials", Progress in Polymer Science 35 (2010) 223-251); Nesterova et al., 2010 [0042]
• "Synthesis of durable microcapsules for self-healing anticorrosive coatings: A comparison of selected methods", Progress in Organic Coatings (2010)) and Syrett et al., 2010 [0042]
• "Self-healing and self-mature polymers", Polym. Chem., 2010, 1, 978-987 [0042]
• Bishop et al (1998, Microencapsulation in yeast cells, J. Microencapsulation, Vol.15, No. 6: 761-773) [0051]
• Shi et al (2007, yeast-cell-based microencapsulation of chlorogenic acid as a water-soluble antioxidant, J. of Food Engineering, Vol. 80: 1060-1067) [0051]
• Nelson (2002, Application of microencapsulation in textiles, Int. J. of Pharmaceutics, Vol. 242: 55-62) [0051]
• S. Barrier et al., "Viability of plant spore exine capsules for microencapsulation", J. Mater. Chem., 2011, 21, 975-981 [0051]
• "Pollen: A novel, biorenewable filler for polymer composites", Macromol. Mater. Closely. 2011, 296, 1055-1062 [0052]
• DIN-EN-971-1 [0064]

Claims (17)

 Composite, comprising or consisting of (A) a matrix material and (B) a plurality of microcapsules having an average diameter in the range of 10, preferably from 20, to 200 microns, preferably in the range of 20 to 150 microns, each comprising or consisting of A shell material comprising or consisting of a cell wall and / or a cell membrane, in particular a sporoderm or at least the exine of a sporoderm, and - One or more included in the shell material agents, wherein the or one, several or all of the included active ingredients is selected from the group consisting of dyes, messengers, corrosion inhibitors, catalysts, solvents, thickeners, adhesion-reducing substances, deicing reagents, antimicrobial Substances, lubricants, lubricants and components for self-healing systems, wherein the shell material is at least partially covalently bonded to the matrix material. Composite according to claim 1, wherein the composite is a composite material, in particular a fiber composite material, or a coating, in particular a lacquer layer. Composite according to claim 1 or 2, wherein the shell material of the microcapsules in each case from the Sporoderm a pollen grain, preferably at least from the exine of the Sporoderms, consists of or comprises (s) such (s). Composite according to one of the preceding claims, wherein for the majority of microcapsules, preferably for all microcapsules, it holds that the proportion of the active ingredients included in the shell material, based on the total weight of the substances present in the interior of the shell material, is in the range from 0.01 to 100% by weight, preferably in the range from 1 to 100% by weight, more preferably in Range from 5 to 50 wt%, and or the total weight of the amount of active ingredients included in a microcapsule, based on the total weight of the microcapsule, in the range from 1 to 80% by weight, preferably in the range from 5 to 80% by weight, more preferably in the range from 5 to 40% by weight .-%, lies. Composite material, in particular fiber composite material, according to one of claims 2 to 4, wherein the matrix material one or more plastics, in particular one or more crosslinked polymers, preferably one or more plastics from the group consisting of thermosets, especially epoxies, acrylates, polyurethanes, polyimides, phenol Formaldehyde condensation resins, unsaturated polyesters, vinyl ester resins, and thermoplastics, especially polyaryletherketones, polyarylethersulfones, polypropylene, polyamides and polyesters, or consists thereof. Coating material, in particular coating material for producing a coating according to one of claims 2 to 4, comprising or consisting of (a) one or more binders and (B) a plurality of microcapsules having a mean diameter in the range of 10, preferably from 20 to 200 microns, preferably in the range of 20 to 150 microns, each comprising or consisting of A shell material comprising or consisting of a cell wall and / or a cell membrane, preferably a sporoderm of a pollen grain, preferably at least the exine of a sporoderm, and - One or more included in the shell material agents, wherein the or one, several or all of the included active ingredients is selected from the group consisting of dyes, messengers, corrosion inhibitors, catalysts, solvents, thickeners, adhesion-reducing substances, deicing reagents, antimicrobial Substances, lubricants, lubricants and components for self-healing systems. A coating material according to claim 6, wherein the one or more or all of the binders is or are selected from the group consisting of epoxy resins, polyurethanes, acrylates, alkyd resins, formaldehyde condensation resins, polyesters, polyethers, PVC and polyethylene. A coating material according to claim 6 or 7, further comprising - one or more organic solvents, wherein one or more or all of the solvents are preferably selected from the group consisting of alcohols, glycols, ketones, esters and ethers, and / or - water and / or - one or more further constituents or additives selected from the group consisting of pigments, fillers, defoamers, deaerators, corrosion inhibitors, thickeners, dispersing additives, wetting additives, hydrophobing additives, reactive diluents, dehydrating agents and wetting agents. Coating material according to one of claims 6 to 8, wherein for the majority of microcapsules, preferably for all microcapsules, it holds that the proportion of the active ingredients included in the shell material, based on the total weight of the substances present in the interior of the shell material, is in the range from 0.01 to 100% by weight, preferably in the range from 1 to 100% by weight, more preferably in Range from 5 to 50 wt%, and or the total weight of the amount of active ingredients included in a microcapsule, based on the total weight of the microcapsule, in the range from 1 to 80% by weight, preferably in the range from 5 to 80% by weight, more preferably in the range from 5 to 40% by weight .-%, lies. Coating material according to one of claims 6 to 9, wherein the coating material is a lacquer or adhesive, preferably a lacquer, preferably a powder lacquer, in particular a hot-hardening lacquer. Composite according to one of claims 2 to 4, wherein the composite is a coating, preferably a lacquer layer, which can be produced by a method comprising the following steps: (I) applying a coating material according to any one of claims 6 to 10 on a surface to be coated; (II) optionally curing the applied coating material. Composite according to claim 11, wherein the (II) curing of the coating material at a temperature in the range of 80 to 300 ° C, preferably in the range of 100 to 250 ° C, particularly preferably in the range of 150 to 200 ° C. Process for the preparation of a coating material, preferably a coating material according to one of claims 6 to 10, comprising the following steps: (i) providing one or more binders, preferably selected from the group consisting of epoxy resins, polyurethanes, acrylates, alkyd resins, formaldehyde condensation resins, polyesters, polyethers, polyethylene and PVC, (ii) providing microcapsules having an average diameter in the range of 10, preferably from 20 to 200 μm, preferably in the range from 20 to 150 μm, each comprising or consisting of A shell material comprising or consisting of a cell wall and / or a cell membrane, preferably a sporoderm of a pollen grain, preferably at least the exine of a sporoderm, and - One or more included in the shell material agents, wherein the or one, several or all of the included active ingredients is selected from the group consisting of dyes, messengers, corrosion inhibitors, catalysts, solvents, thickeners, adhesion-reducing substances, deicing reagents, antimicrobial Substances, lubricants, lubricants and components for self-healing systems, and (iii) mixing the microcapsules of step (ii) with the binder (s) of step (i) and optionally other ingredients. Component consisting of a composite material according to one of claims 2 to 5, in particular a fiber composite material, wherein the component is preferably selected from the group consisting of components of the primary structure and secondary structure of aircraft and vehicles of land and sea transport, e.g. Roofing components, bumpers and spoilers, pressure vessels and fuel tanks or components thereof, e.g. Tank linings, interior components and decorative elements, and articles of household equipment / decoration and ornaments, shipbuilding components, components of off-shore wind turbines, components of port constructions, office supplies, telecommunication articles, bicycle frames and attachments, sports equipment, protective helmets, Rotor blades, cases and play equipment. Product comprising a substrate and a coating adhering to at least a surface portion of the substrate according to any one of claims 2 to 4, 11 or 12. Composite or coating material according to one of claims 1 to 12, wherein the microcapsules are modified by means of a gas phase process, in particular by means of a plasma process, preferably by means of an atmospheric pressure plasma process.  A composite or coating material according to claim 16, wherein the microcapsules are surface-modified by means of a gas-phase process to alter the release properties of the included active ingredients and / or the incorporability of the microcapsules in the composite or coating material.

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