DE102017125179A1 - Modified hardener component for a polymer and especially for 2K formulations with self-healing properties - Google Patents

Abstract

The invention relates to a modified hardener component for a polymer, in particular a modified isocyanate component as a hardener for 2K formulations (two-component formulations), with self-healing properties. The invention further relates to a two-component system for a self-healing polymer, comprising a hardener component according to the invention and a binder component reactive with the hardener component according to the invention (resin, polymer, reactive binding component). The invention also relates to the use of a hardener component according to the invention for improving the self-healing power of a polymer, and to a method for producing a hardener component according to the invention.

Description

The invention relates to a modified hardener component for a polymer, in particular a modified isocyanate component as a hardener for 2K formulations (two-component formulations), with self-healing properties. The invention further relates to a two-component system for a self-healing polymer, comprising a hardener component according to the invention and a binder component reactive with the hardener component according to the invention (resin, polymer, reactive binding component). The invention also relates to the use of a hardener component according to the invention for improving the self-healing power of a polymer, and to a method for producing a hardener component according to the invention.

So-called two-component formulations (two-component formulations) are known in the art, for example as two-component adhesives, also called two-component adhesives or two-component adhesives. A 2K formulation is thus a formulation consisting of various components, in particular the resin (polymer; reactive binder component) and the hardener. By mixing the two components immediately before use, the curing reaction is usually started already at room temperature. Two-component systems cure by chemical reactions such as polyaddition, polycondensation and polymerization. Examples of two-component systems are unsaturated polyester resins (UP resins), epoxy resins (EP resins), methyl methacrylate adhesive.

Coating materials play an important role in a wide variety of applications. Thus, coating materials, e.g. be an effective barrier against various environmental influences, such as UV light and tree resin, while being resistant to internal stresses, abrasion and microcracks. The highest priority is the protection of the underlying material against damage, corrosion and failure in order to preserve the value and visual impression of the component and to counteract the decay.

Here, mainly, e.g. The following problems existing in the prior art are to be named: mechanical damage of coatings; Destruction of the protective properties and reduction of the visual appearance; Damage due to tensions and vibrations due to the formation of cracks; Loss of protective properties and possible loss of liability; Damage by other environmental influences such. UV radiation, chemicals and aggressive agents; Occurrence of premature aging due to cracking and embrittlement; Damage to the visual appearance.

The consequences of these problems include, for example, the premature failure of equipment and machinery, the increased need for repair and increased maintenance and associated costs, and increased human hazard in relation to possible component failure and also increased incidents Danger to the environment through accidental leakage or emission of environmentally hazardous substances from failing containers or equipment.

In order to meet high demands on coating systems, in recent years more and more innovative and novel polymer systems have come into the focus of modern research and industry - the self-healing paints. The conception of self-healing coatings or lacquers can be roughly divided into three areas, the reflow effect, the intrinsic self-healing and extrinsic self-healing.

The reflow effect aims to compensate for very fine scratches and microcracks on, for example, automotive topcoats caused, for example, by sand grains between the brush fibers of a carwash. This effect can be achieved by adjusting the glass transition temperature T _g to 50-60 ° C. When this glass transition temperature range is exceeded by thermal energy, such as solar radiation, the mobility of the polymer network is increased, so that the polymer can go into a viscoelastic state. Due to the softening of the material small deformations and fine scratches can flow away. The disadvantage of the reflow effect is that it depends on the viscoelastic properties of the polymer and thus there are limitations to the selection of suitable self-healing polymers. Also, although a certain self-healing can be effected by viscoelastic flow of small plastic deformations, large scratches with material removal can not be closed by the reflow effect. A disadvantage of this concept is thus that only very fine superficial deformations of the paint can be restored. Damage that goes into the depth and / or lead to material removal, can not be compensated by the reflow effect.

"Extrinsic self-healing" refers to self-healing processes in which a self-healing reagent embedded in capsules or hollow fibers is used. After damage occurs Self-healing reagent from the capsules or hollow fibers to effect self-healing. A serious disadvantage of extrinsic self-healing is that self-healing is possible only once, thus achieving sustainable self-healing effects is not possible or at least only partially possible. This conceptual extension of a self-healing strategy was achieved for the first time by the White working group at the University of Illinois with the extrinsic self-healing of polymers. In the process, microcapsules are embedded in the polymer matrix in which liquid monomer and a catalyst have been immobilized. If the surface is damaged, the capsules break up along the crack and release the contents. The monomer polymerizes and seals the crack. The incorporation of the capsules in a topcoat system is only conditionally possible because the capsules cause a glossy haze (resins) in the clearcoat. Another limitation of extrinsic self-healing is that if the material is repeatedly damaged at the same site, the scratches can not be cured because the capsules were irreversibly destroyed.

This problem could be circumvented with the intrinsic self-healing, the third self-repair concept. The intrinsic self-healing is based on a special polymer architecture in which the polymer is capable of forming a variety of reversible bonds. Here, a distinction is made between i) covalent and ii) physical, supramolecular network bonds. Possible reversible covalent systems are retro-Diels-Alder and disulfide bridge bonds. The covalent systems imperatively require an external stimulus such as temperature, UV light, pH change, or a catalyst for the bond opening and binding reaction.

Systems based on weak physical and supramolecular interactions, such as hydrogen bonding, π-π stacking, and metal-coordinated systems can self-heal both by stimulus and autonomously. The polymer network is equipped with a variety of physical binding sites, allowing the construction of a supramolecular network. Upon molecular, microscopic or macroscopic damage, the reversible bonds are opened and can then aggregate autonomously or via a stimulus into a new network.

The working group of Sijbesma ( Sijbesma RP, Beijer FH, Brunsveld L, Folmer BJB, Hirschberg JHKK, Long RFM, Lowe JKL, Meijer EW (1997) Science 278: 1601-1604 ) developed a polymer system based on polyethylene glycol (PEG), which was functionalized with ureidopyrimidone units (UPy) with fourfold hydrogen-bonding sites. The polymers thus build up a strong self-dimerized supramolecular network and exhibit self-healing under light pressure. The self-healing of the material is autonomous, only by a moderate force. For the first time, it was possible to commercialize an elastomer as SupraPolix BV.

The group of Leibler from Paris developed a thermo-reversible polymer with low glass transition temperature. The elastomer consists of polyamide units composed of dimeric and trimeric fatty acids and ethylenediamine units (UDETA, DETA, etc.). Subsequently, the end groups of the fatty acids are covalently linked to each other in an epoxy network consisting of DGEBA, so that a covalently linked network is formed (see, for example, US Pat Cordier P, Tournilhac F, Soulie-Ziakovic C, Leibler L (2008) Nature 451: 977-980 ). To build up the thermo-reversible polymer, the primary amine is attached to trimeric or dimeric fatty acids, and then the fatty acids are cross-linked with epoxides. The system is additionally softened by the addition of dodecane so that the glass transition temperature T _{g is} lowered to 8 ° C. Complete self-healing of two intersected and reassembled sections of the elastomer could be observed after three hours at room temperature.

However, the systems known in the prior art can only be conditionally transferred to a potential application. In addition, the described systems of the prior art are a very special polymer construction which in practice is not transferable in combination with common polymer binders or hardeners.

Due to the prior art described above, there is thus a great need for the development of 2K hardener components based on modified isocyanate components or polyepoxide components, which can be crosslinked with conventional binders containing hydroxyl and / or amine groups and to a self-healing effect to lead.

worin A Sauerstoff, Schwefel oder NH bedeutet, wobei die Kohlenstoffatome der Formel (F) substituiert sein können. A bedeutet vorzugsweise Sauerstoff. Vorteilhafterweise umfasst das Material (i) Moleküle mit mindestens 3 assoziativen Gruppen und (ii) Moleküle mit einer einzigen assoziativen Gruppe. Vorzugsweise werden die Moleküle der WO 2006/087475 A1 aus Fettsäurederivaten erhalten.A self-healing property, which preferably takes place in a polymeric network, is already known for certain classes of molecules based on dimeric and trimeric fatty acids WO 2006/087475 A1 described. So revealed the WO 2006/087475 A1 Rubbery elastic materials comprising molecules of mass between 9 and 9000 g / mol, all or part of the molecules being at least three also have groups known as associative groups which can associate by means of non-covalent interactions. The described material comprising non-polymerized and non-chemically crosslinked small molecules has rubbery elasticity properties. In one embodiment, the described material has a rubber-like elasticity at ambient temperature. Above a certain temperature, the material flows like a simple liquid. The material is thermo reversible, that is, a material having rubbery elasticity can be repeatedly obtained by cooling. In addition, the described material includes a self-healing material that is potentially recyclable, which is not the case with a chemically crosslinked elastomer. In one embodiment of the described material, the molecules forming the material carry associative groups of the formula (F),

wherein A is oxygen, sulfur or NH, wherein the carbon atoms of the formula (F) may be substituted. A is preferably oxygen. Advantageously, the material comprises (i) molecules having at least 3 associative groups and (ii) molecules having a single associative group. Preferably, the molecules of the WO 2006/087475 A1 obtained from fatty acid derivatives.

Against the background of the prior art described, it was the object of the present invention to crosslink a hardener component for a polymer (2K hardener component) based on modified isocyanate components or polyepoxide components, which preferably binds with conventional binders containing hydroxyl and / or amine groups can lead to a self-healing effect, which overcomes a variety of the above-described disadvantages of the prior art. In particular, it was desired that the hardener component for a polymer (2K hardener component) based on modified isocyanate components or polyepoxide components be versatile and relatively inexpensive, a good self-healing ability, in particular for self-healing of a coating even of small in a coating to larger, eg mechanical, damage, such as from microcracks to macrocracks and scratches, can ensure good protection especially against mechanical, chemical and / or physical stress. Furthermore, the hardener component for a polymer (2K hardener component) based on modified isocyanate components or polyepoxide components should preferably be versatile in relation to the type of 2K formulations (two-component formulations) and two-component systems.

This object is achieved in general by a hardener component according to the invention as defined in the claims for a polymer (2K hardener component), in particular based on modified isocyanate components or polyepoxide components, preferably containing conventional hydroxyl and / or amine groups Binders can be crosslinked and lead to a self-healing effect, wherein the hardener component of the invention is prepared or prepared by reaction of (a) a compound containing substituents independently comprise at least one functionalizing element or modified therewith, selected from the group consisting of Double bond, triple bond, OH, NH ₂ , NH, CONH, COOH, NCO, thioisocyanate, aldehyde, urethane, urea, imine, sulfo, sulfino, sulfeno, mercapto, Oxime, imino, hydrazino, halogen and nitrosyl group; and (b) a polyisocyanate or a polyepoxide.

The invention relates in this case to a chemically modified hardener component, preferably based on isocyanate and / or epoxy, which can cure molecular, microscopic (microcracks) and macroscopic damage as a 2K formulation.

1. (a) einer Verbindung oder mehrerer Verbindungen der Formel (I),
   
   wobei X unabhängig von den gegebenenfalls anderen X jeweils eine S, O oder NH-Gruppe bedeutet, und
   • (i) R1 und R2 unabhängig voneinander jeweils eine lineare gesättigte oder ungesättigte Kohlenwasserstoffkette mit 1 bis 12 C-Atomen bedeuten oder R1 und R2 gemeinsam einen cycloheteroaliphatischen oder heterocyclischen Ring mit 5 bis 6 Atomen bilden, wobei R2 unabhängig auch H bedeuten kann, und R3 wie nachfolgend unter (ii) definiert ist, oder
   • (ii) R2 wie vorstehend unter (ii) definiert ist, und R1 und R3 unabhängig voneinander jeweils eine lineare gesättigte oder ungesättigte Kohlenwasserstoffkette mit 1 bis 12 C-Atomen oder eine lineare gesättigte oder ungesättigte Kohlenwasserstoffkette mit 1 bis 12 C-Atomen, die einen cycloheteroaliphatischen oder heterocyclischen Ring mit 5 bis 6 Atomen umfasst, darstellt, und wobei R1 und/oder R3 unabhängig voneinander jeweils wenigstens ein funktionalisierendes Element umfassen oder damit modifiziertsind, ausgewählt aus der Gruppe bestehend aus Doppelbindung, Dreifachbindung, OH-, NH₂-, NH-, CONH-, COOH-, NCO-, Thioisocyanat-, Aldehyd-, Urethan-, Urea-, Imin-, Sulfo-, Sulfino-, Sulfeno-, Mercapto-, Oxim-, Imino-, Hydrazino-, Halogen- und Nitrosylgruppe; und n = 1, 2 oder 3 ist; und
2. (b) einem Polyisocyanat oder einem Polyepoxyd.

This object is achieved in particular by a hardener component for a polymer, prepared or preparable by reaction

1. (a) one or more compounds of the formula (I),
   
   wherein X is independently of the optionally other X each represents an S, O or NH group, and
   • (i) R 1 and R 2 independently of one another each denote a linear saturated or unsaturated hydrocarbon chain having 1 to 12 C atoms or R 1 and R 2 together form a cycloheteroaliphatic or heterocyclic ring having 5 to 6 atoms, where R 2 can also be independently H, and R 3 as defined below under (ii), or
   • (ii) R2 is as defined above under (ii), and R1 and R3 independently of one another in each case a linear saturated or unsaturated hydrocarbon chain having 1 to 12 carbon atoms or a linear saturated or unsaturated hydrocarbon chain having 1 to 12 carbon atoms, a includes cycloheteroaliphatic or heterocyclic ring having 5 to 6 atoms group, and wherein R1 and / or R3 independently of one another each comprise a functionalizing element at least or so modified are selected from the group consisting of double bond, triple bond, OH, NH ₂ -, NH , CONH, COOH, NCO, thioisocyanate, aldehyde, urethane, urea, imine, sulfo, sulfino, sulfeno, mercapto, oxime, imino, hydrazino, halogen and nitrosyl; and n = 1, 2 or 3; and
2. (b) a polyisocyanate or a polyepoxide.

In a preferred variant, the invention relates to a hardener component according to the invention as defined above comprising 1, 2 or 3 isocyanate and / or epoxy groups.

wobei R1 und R5 unabhängig voneinander H oder ein gesättigter Kohlenwasserstoffrest mit 1 bis 8 C-Atomen sind oder gemeinsam eine zu einem heterocycloaliphatischen Ring verbrückende Carbonylgruppe darstellen,
R2, R3 und R4 jeweils unabhängig voneinander einen gesättigten, linearen oder verzweigten Kohlenwasserstoffrest mit 1 bis 8 C-Atomen, einen gegebenenfalls mit 1 bis 6 Kohlenwasserstoffresten mit 1 bis 2 C-Atomen substituierten Cycloalkylrest oder einen mit 1 bis 2 Kohlenwasserstoffresten mit 1 bis 2 C-Atomen substituierten Benzylrest darstellen, wobei der Cycloalkylrest oder der Benzylrest jeweils mit einer linearen gesättigten Kohlenwasserstoffkette mit 1 bis 8 C-Atomen mit dem jeweiligen N verbunden sein kann und jeder Rest R2, R3 und R4 über eine bevorzugt endständige Epoxyd- oder Isocyanatgruppe verfügt.In a further preferred variant, the invention relates to an above-mentioned hardener component according to the invention, where the polyisocyanate or the polyepoxide is a compound of the formula (II)

wherein R1 and R5 independently of one another are H or a saturated hydrocarbon radical having 1 to 8 C atoms or together represent a heterocycloaliphatic ring-bridging carbonyl group,
R 2, R 3 and R 4 each independently represent a saturated, linear or branched hydrocarbon radical having 1 to 8 C atoms, a cycloalkyl radical optionally substituted by 1 to 6 hydrocarbon radicals having 1 to 2 C atoms or one having 1 to 2 hydrocarbon radicals having 1 to 2 C atoms represent substituted benzyl radical, wherein the cycloalkyl radical or the benzyl radical may each be connected to a linear saturated hydrocarbon chain having 1 to 8 carbon atoms with the respective N and each radical R2, R3 and R4 has a terminal epoxide or isocyanate preferably terminal ,

In another preferred variant, the invention relates to an above-mentioned hardener component according to the invention, wherein in formula (I) n = 1.

Furthermore, the invention relates in a preferred variant to an above-mentioned hardener component according to the invention, wherein in formula (I) R1 and R2 together form a ring having five atoms, wherein R1 and R2 are linked to one another via an etylene group.

Furthermore, in another preferred variant, the invention relates to a plurality of above-mentioned hardener components according to the invention selected from the group consisting of polyepoxides and polyisocyanates, wherein the hardener components are reacted with compounds of the formula (I) as defined above such that on average at least 1, preferably at least 1.5, more preferably at least 2 epoxy or isocyanate groups remain per hardener component.

In a preferred variant, the invention relates to an abovementioned plurality of hardener components according to the invention, wherein the hardener components before the reaction with the compound of the formula (I) were a compound of the formula (II).

Surprisingly, it has been found that with the aid of one or more compounds of the formula (I) it has become possible to use the above-described hardener components for a polymer according to the invention based on a reaction of one or more compounds of the formula (I) with a polyisocyanate or a polyepoxide, which prove to be clearly superior to the conventional self-healing coating variants of the prior art, including electrically insulating self-healing coating variants (insulating lacquers) in terms of ability, quality and sustainability for self-healing.

The term "self-healing" in the context of the invention means in one aspect the ability of a coating, in particular a lacquer coating or an adhesive mixture, including e.g. in an insulating varnish, understood, stand alone, so in particular without complex external intervention such. a repainting of damage, in particular z. Mechanical damage, such as microcracks, macrocracks and scratches, and eliminate the corresponding functions and properties of a coating, especially a paint coating, including e.g. in an insulation varnish, to restore. In particular, "without costly external intervention" in the context of the present invention means that the self-healing occurs by heat, in particular by such heat that generates the electrical component or surrounding component during operation itself. Alternatively or additionally, "without costly external intervention" also means that the self-healing occurs due to the humidity in the ambient air.

In a further aspect, the term "self-healing" in the context of the invention refers to the ability of polymers, preferably in paints or in a coating, in particular in a paint coating, including e.g. in an insulating varnish, understood, stand alone, so in particular without complex external intervention such. a repainting of molecular, microscopic and / or macroscopic damage, autonomously and / or by means of an external stimulus of damage, in particular e.g. after electrical breakdown and / or after mechanical damage such as microcracks, macrocracks and scratches, and the corresponding functions and properties of the polymer, preferably in a coating, especially in a lacquer coating, including e.g. in an insulating varnish, restoring the mechanical and physical properties of the polymer. In principle, the definition "without costly external intervention" from the preceding paragraph applies. However, the definition also includes that as external stimulus the air humidity is increased (specifically) or (specifically) heat is supplied in order to trigger and / or support the self-healing process.

In order to meet high demands on coating systems, as already stated, in recent years more and more innovative and novel polymer systems have become the focus of modern research and industry, such as self-healing coatings or lacquers and adhesives, in particular 2-component adhesives roughly divided into three areas, the reflow effect, the intrinsic self-healing and extrinsic self-healing. The reflow effect and extrinsic self-healing were already explained in the introduction to the state of the art.

The present invention now relates, in a preferred variant, to intrinsic self-healing. By "intrinsic self-healing" is thus understood according to the invention a self-healing process, in the self-healing in the polymer matrix is effected via reversible bonds. These reversible bonds may be covalent bonding systems (eg Diels-Alder) or non-covalent bonding systems (eg via hydrogen bonds). An advantage of intrinsic self-healing is that self-healing is repeatable, and thus sustainable self-healing effects can be achieved. In addition to the reversibility, the intrinsic self-healing in a lacquer coating is coined according to the invention by effects of the molecular dynamics, amorphicity and / or functionality of the compound of the formula (I) proposed according to the invention for modifying the coating.

Further advantages of the invention are that the self-healing or the production of durable products is made possible. This is due to the fact that unlike the self-healing concept with capsules (extrinsic self-healing), healing at the same place in this system (theoretically infinite) is often repeatable. It is also possible, unlike the self-healing concept with capsules (extrinsic self-healing) to produce materials without haze. In addition, there is an advantageous system variation with a large selection of usable coatings and polymer-based materials for 2K systems with a modified according to the invention hardener component for polymers, as defined above.

The invention thus relates to a chemically modified, preferably isocyanate- and / or epoxy-based, modified hardener component which can cure molecular, microscopic (microcracks) and macroscopic damage as a 2K formulation. The curing agent component of the invention for a polymer is prepared or preparable by reacting a compound or compounds of formula (I) with a polyisocyanate or a polyepoxide.

The polyisocyanate may in this case be any polyisocyanate known to the person skilled in the art. Polyisocyanates are organic compounds containing two or more isocyanate groups (-N = C = O). They can be divided into aliphatic and aromatic isocyanates. Polyisocyanates are highly reactive compounds. The polyaddition reactions of polyisocyanates with diols (dihydric alcohols) or polyols (polyhydric alcohols) are the basis of polyurethane chemistry. Alcohols with more than two hydroxy groups as crosslinkers have a significant influence on the processing and curing as well as the resulting properties of polyurethane coatings [and adhesives].

Examples of lisocyanates known to those skilled in the art are aliphatic di- and tri-diisocyanates, aromatic di- and tri-diisocyanates and aromatic polyisocyanates. Aliphatic and cycloaliphatic isocyanates are mainly used in paints because of their light resistance. They have a high hardness, but in many systems tend to be brittle to respond to mechanical loads. By using other aminoalcohols one can adjust the flexibility of the substances. Examples known to the person skilled in the art that can be used in a preferred variant of the invention are: hexamethylene diisocyanate (HDI); Isophorone diisocyanate (IPDI); and 1,4-cyclohexyl diisocyanate (CHDI). The aromatic polyisocyanates have a higher reactivity to hydroxy groups due to the aromatic radical and are therefore preferably used in PU applications. They are more flexible than aliphatic polymers. Examples which are known to the person skilled in the art and which can be used in a preferred variant of the invention are: tolylene diisocyanate (TDI) and diphenylmethane diisocyanate (MDI). Due to homologous secondary products of MDA, MDI homologues are also produced in the MDI production process. These "polymeric diphenylmethane isocyanates" (PMDI) are manufacturer-typical minor constituent of MDI. Unlike MDI, PDMI has a cross-linking effect. A well-known to the expert example, which can be used in a preferred variant of the invention, is polymeric diphenylmethane diisocyanate (PMDI).

The polyepoxide (synonymously also polyepoxide) can in this case be any polyepoxide known to the person skilled in the art. A polyepoxide, also called epoxy resin, is a polymer of several epoxide segments. These are used as adhesives or in composite materials. Epoxides or epoxides, also called oxiranes or oxacyclopropanes, according to the exchange nomenclature, are a chemical substance group of highly reactive cyclic organic compounds. They contain a three-membered ring in which a carbon atom is replaced by an oxygen atom compared to cyclopropane. The oxygen bridge is called the epoxy bridge. The simplest and most technically interesting epoxy is ethylene oxide (ethene oxide). Due to the ring strain prevailing in a triple ring, the ring can be opened relatively easily by nucleophilic attack on a carbon atom. Although the oxygen atom of the epoxide ring is the leaving group, it remains attached to a carbon atom of the epoxide and thus remains a constituent of the molecule. If one or more hydrogen atoms of the ethylene oxide are replaced by organyl radicals (alkyl radicals, aryl radicals, alkylaryl radicals, etc.), these compounds are likewise oxiranes.

In a preferred variant, the present invention relates to a hardener component according to the invention for a polymer which, as a hardener component, for example in a paint coating, enables a self-healing effect in a variety of 2K systems.

The term "lacquer" or "lacquer coating" is understood by the person skilled in the art to mean a liquid or powdery coating material applied to a substrate, e.g. on an object, and is built up by chemical or physical processes (for example, evaporation of a solvent) to a continuous, solid film. Paints generally consist of binders, fillers, pigments, solvents, resins and / or acrylates and additives, which are known in the art each. The main tasks of paints are in particular: protection (protective effect, eg protective coating, protective lacquers); Decoration (optical effect, eg a certain color effect); and function (special surface properties, eg altered electrical conductivity). An "insulating varnish" is in this case a "varnish" or "varnish coating", which shields against electrical conductivity, ie an electrically insulating covering or coating, in order to achieve and / or support electrical insulation.

As materials for a 2K formulation or a 2K system, comprising at least one chemically modified, preferably isocyanate- and / or epoxy-based, hardener component for a polymer, as defined above, which is a 2K formulation of molecular, microscopic ( Microcracks) and can heal macroscopic damage, in general, the components known to those skilled in the art - such as in particular binders and (known per se) hardener; Pigments and fillers; Additives and solvents - included. The following are examples of such ingredients as binders and (known per se) hardener; Pigments and fillers; Additives and solvents, which in a preferred variant of the invention, in particular also for 2K formulations or 2K systems based on polymers, such. Coatings, which produce self-healing properties through the use of UDETA (1- (2-aminoethyl) imidazolidin-2-one). 2K formulations or 2K systems composed according to the invention are in particular composed of the following constituents:

Binders and hardeners:

Isocyanates ester polyols, ether polyols, epoxides, acrylates, polyamines, polyamides, imides, silanes, silanols, silicones, silazanes, polyureas, melamines, alkyds, formaldehyde condensation resins, acidic polyesters, polyethylene, polypropylene, polyvinyl butyral, polyvinyl acetate, polyvinyl alcohols, polytetrafluoroethylene, polyvinyl chloride, polyethylene glycols, Polypropylene glycols and other binders known to those skilled in the art and / or hardeners.

Pigments and fillers:

Titanium dioxide, iron oxides, phthalocyanides, azo compounds, perylenes, carbon black, talc, calcium carbonates, barium sulfate, indanthrones, chromium oxides, chromium phosphates, zinc oxides, zinc phosphates, magnesium, zinc, lead oxides and other pigments and fillers known to the person skilled in the art.

additives:

Defoamers, deaerators, rheology additives, thickeners, UV stabilizers, UV absorbers, free-radical scavengers, quenchers, catalysts, plasticizers, heat stabilizers, flow control additives, drying agents, protective colloids, dispersing additives, wetting agents, coalescing agents and other additives known to the person skilled in the art.

Solvent:

N-methylpyrolidone, ethylpyrolidones, alcohols, esters, ethers, kentones, aromatics, aldehydes, glycols, solvent naphtha, methyl ethyl ketone, acetone, butyl acetate, water, butanol, isopropanol, ethanol, methanol, dimethyl sulfoxide, xylene, dimethylformamide, methyl 5- (dimethylamino ) -2-methyl-5-oxopentanoate (Rhodiasolv Polarclean) and other solvents known to those skilled in the art.

The present invention relates, in a preferred variant, to a hardener component modified according to the invention based on one or more compounds of the formula (I) for a polymer which is, for example, a hardener component for a lacquer coating, including an insulating lacquer having a self-healing action based on weakly covalently crosslinked systems with a high number of weak physical interactions that are dynamic above the glass transition temperature of the material.

In this material, a network is built up of chemical (covalent) and physical bonds that can change its topology through thermally and / or moisture-activated hydrogen bond exchange reactions. In the context of the present invention, this behavior opens up new possibilities in the self-healing of lacquer coatings which have been modified according to the invention with a compound of the formula (I) for lacquer coatings or insulating lacquers for an electrical component, in particular for passive and active electronic and electrotechnical assemblies or components. Preferred such systems are polyurethane-urea elastomers having a high number of hydrogen-bond donors and acceptors.

According to the invention with a compound of formula (I) modified lacquer coatings or insulating coatings for an electrical component, in particular for passive and active electronic and electrical assemblies or components, with self-healing effect based on covalent systems with weak interactions, characterized in that the lacquer coatings or insulating lacquers in a preferred variant imidazolidine groups (H-bridges), amide functionalities (H-bridges), carboxylic acid groups (transesterification), and / or diene structures (Diels-Alder) include, and in one Another preferred variant in that the lacquer coating or the insulating lacquer over an external trigger such as in particular temperature, humidity, pressure and / or (eg UV radiation) partially softened and heals.

Without being bound to any theory, the compound of formula (I) in thus modified hardener components in paint coatings or insulating coatings (eg for an electrical component) seems to be damaged, especially after electrical breakdown and / or after mechanical damage, such as microcracks, macrocracks and scratches, effectively heal or at least significantly limited, so that to a considerable extent a restoration of performance and possibly performance increase in the case of encumbrances of the protective effects of the modified lacquer coatings or insulation coatings is achieved on an electrical component.

For a hardener component modified according to the invention and based on one or more compounds of the formula (I) as defined above, for a polymer, for a polymer modified with a hardener component according to the invention or for a lacquer coating modified with a hardener component according to the invention including an insulating lacquer (eg for an electrical component) with a self-healing effect, the self-healing modified polymers and lacquer coatings according to the invention, including insulating lacquers, can be characterized and detected with limited equipment complexity, for example starting from the self-healing materials. Proof of the self-healing properties can be carried out at different humidities by a practical hand test as a simple test. Alternatively and / or subsequently, more precise investigations by means of instrumental analysis are also possible, such as, for example: IR spectroscopy (water absorption); DSC analysis (T _g change after aging experiments in water); NMR (structure analysis); TGA (water loss after swapping); Mass spectrometry (eg Maldi-ToF); XPS (structure analysis); AFM (change in viscoelastic properties on the surface after and before water removal).

Moreover, in order to prove the self-healing inventively modified polymers and lacquer coatings including insulating lacquers, the polymer or the lacquer can be damaged by an electrical breakdown analogously to the described procedure in the experimental procedure of the examples and then by measuring the regeneration of the chip breakdown strength of the material, for example after thermal treatment , or else otherwise suitable treatment according to the invention. Measurements of the breakdown strengths of self-healing lacquer coatings or lacquers in the context of this invention were given in the manual DIN EN 60243-1 and DIN EN 60243-2 carried out. The term "dielectric strength" is therefore familiar to the person skilled in the art and is used in this context in the context of the invention.

The invention thus also relates, in a preferred variant, to a hardener component modified for a polymer according to the invention, based on one or more compounds of the formula (I) as defined above, for use in a protective lacquer, and such a protective lacquer itself, which is one according to the invention based on one or more compounds of formula (I) as defined above, modified hardener component for a polymer. A protective varnish, as defined above, is a protective varnish, with electrical insulation effect for electronic and electrical components with self-repairing properties of molecular, microscopic (microcracks) and macroscopic damages and / or after voltage breakdowns by voltage-induced overloading.

For this purpose according to the invention, in a polymeric network, for example based on polyurethane or epoxide, a hardener component modified according to the invention and based on one or more compounds of the formula (I) as defined above, for a polymer having at least one reactive functional group of the type defined above, for example an amine or isocyanate group, in a particularly preferred variant, for example an isophorone diisocyanate group, comprises covalently integrated. The synthesis of these inventively covalently integrated compounds of formula (I) (self-healing molecules) is already in the patents US 8536281 B2 and US 20130023667 Al described.

The invented, e.g. preferably covalent, integrated compounds of the formula (I) (self-healing molecules) - without being bound to a particular theory - function in the polymeric network as hydrogen-bond donors and acceptors and create a hydrogen-bonded physics interacting supramolecular network in the polymer network.

After a damage event such as a scratch, micro cracks or a voltage breakdown, the damage can be cured via a trigger (eg temperature, UV light, pressure, humidity), which leads to an increase in molecular dynamics (see 1 ). The increased molecular dynamics favors the opening of the physical interactions and the reformation of the hydrogen bond elsewhere, which leads to a healing of the damage. 1a Star-shaped damage of the self-healing lacquer with a dry film thickness of 40 μm over an Erichsen recess on an aluminum sheet. 1b : Self-healing of damage at 120 ° C after 60 seconds.

An important criterion - without wishing to be bound by any particular theory - for the self-healing process in a preferred variant of the invention is the presence of atmospheric moisture. Water molecules are able to disperse in the polymeric network structure and disrupt the hydrogen bonds of the self-healing molecules of the present invention so sustainably that the network density is lowered and the stiffness of the material decreases. This circumstance can also be described as a reversible plasticizer effect and also leads to an increase in the molecular dynamics and thus to a favoring of the self-healing by network remodeling processes. If the water is removed from the system (thermally or by negative pressure) the system immediately regenerates the hydrogen bonds and the rigidity of the material returns to its original value. For this reason - without wishing to be bound by any particular theory - of reversible plasticizer effect in the presence of a compound of formula (I) in modified therewith hardener components for polymers, as well as in these modified hardener component-containing polymers and lacquer coatings including insulating lacquers (eg for a electrical component), are spoken. It must be emphasized that this reversible softening effect of air humidity on the self-healing properties of a polymeric material modified with a compound of the formula (I) and especially of a hardener component for polymers modified with a compound of the formula (I) has not hitherto been known in the prior art were mentioned.

It should also be emphasized that the affinity of self-healing lacquers could be suppressed by the addition of microparticles (e.g., microcapsules) and / or natural fibers as additives to lacquers. The invention thus has the great advantage that - unlike self-healing by reflow effect or extrinsic self-healing - can be dispensed with such addition of additives of microparticles and / or natural fibers.

Preferred fields of application according to the invention for a novel hardener component for a polymer having self-healing properties and based on one or more compounds of the formula (I) as defined above, and for self-healing protective coatings of the invention, such as those modified above in combination with the invention modified Hardener component are defined for a polymer are passive and active electronic and electrical components such as sensors, IC's, chips, printed circuit boards, resistors, windings of electrical machines and capacitors. In particular, owing to the temperature stability of the coating ≦ 210 ° C., the paints according to the invention, as defined above, are also suitable for areas subject to high thermal stress, e.g. Power electronics.

Of course, the coatings which can be prepared by means of the hardener according to the invention are particularly suitable in the paint application for areas in which paints are exposed to mechanical stresses. Of course, these mechanical loads can be, for example, those in which the paint has a protective effect for the painted component (eg in auto parts) or even in areas where the paint due to mechanical stress during operation of a device (quasi load of "inside") its protective function exercises. In addition, self-healing can also eliminate negative visual impressions, which is of course very welcome in many cases.

The situation with adhesives is similar: if the bond joint is subjected to a mechanical load and thereby, e.g. Cracks in the polymer arise, it is highly desirable for the function of the adhesive that these damages are closed again.

The abovementioned fields of application according to the invention are of importance, inter alia, for this invention, for processes, semi-finished products and products, in particular in the fields comprising: consumer electronics such as e.g. Televisions, computers, cameras, mobile phones; White goods; Electrical machines; and control electronics; Electric drives (e.g., coils and laminations) and power electronics (e.g., in railway and automotive); and generators (e.g., wind energy).

In a variant, the invention therefore also relates to the use of a hardener component for a polymer modified according to the invention based on one or more compounds of the formula (I) as defined above, having self-healing properties, as defined above, as hardening component in one Lackbeschichtung including in an insulating varnish (eg for an electrical component), which eg serve in a electrical component as a self-healing coating for self-healing after electrical breakdown.

Hereinafter, further preferred variants of the present invention are shown.

The invention also relates to a two-component system for a self-healing polymer, comprising a hardener component according to the invention, as defined above, or a plurality of hardener components according to the invention, as defined above, and one reactive with the hardener component according to the invention or the plurality of hardener components according to the invention binding component.

In a preferred variant, the invention relates to an abovementioned two-component system according to the invention for a self-healing polymer, where the binder component is selected from the group consisting of respectively aromatic or aliphatic polyols, polyamides, polyimides, polythiols, polyepoxides, polyaspartates and polyacrylates.

The terms "aromatic" or "aliphatic", "polyol", "polyamide", "polyimide", "polythiol", "polyepoxide", "polyaspartate" (polyaspartic acid ester, polyaspartics, in short often also called asparagine esters) and "polyacrylate", and also "isocyanate" and "epoxide" are used in the context of the present invention in each case in the well-known to the skilled person.

In a further preferred variant, the invention relates to one of the abovementioned two-component systems according to the invention for a polymer, where the binder component is a polyether or a polyester, preferably having 2 to 16 hydroxyl groups.

In a variant, therefore, the invention also relates to the use of a hardener component according to the invention, as defined above, or the use of a variety of hardener components according to the invention, as defined above, for improving the self-healing power of a polymer.

In principle, the variants according to the invention can be more preferably combined with one another in the sense of the invention, and the technical effects of the invention can be achieved to a particular extent.

Areas of application according to the invention for a hardener component according to the invention, as defined above, a plurality of hardener components according to the invention as defined above or a two-component system according to the invention for a self-healing polymer, as defined above, therefore also comprise self-healing protective coatings comprising at least one this hardener component according to the invention, one of the plurality of hardener components according to the invention and / or one of the two-component systems according to the invention for a self-healing polymer.

The fields of application of the invention are, inter alia, of importance for processes, semi-finished products and products in particular in the fields comprising: self-healing protective coatings, in particular such coatings and materials in the automotive, wind power, aerospace and furniture industries as well as with regard to corrosion protection Machine and system parts, pipes and lines. In addition, self-healing coatings or protective coatings of the invention are useful for consumer electronics, white goods, floor coatings, and ophthalmic lenses.

1. a) Bereitstellen einer Verbindung der Formel (I),
2. b) Bereitstellen eines Polyisocyanates oder eines Polyepoxydes, bevorzugt gemäß der Formel (II) und
3. c) Reagierenlassen der in Schritt a) und b) bereitgestellten Verbindungen miteinander.

Finally, the invention also relates to a method for producing a hardener component as defined above, comprising the steps:

1. a) providing a compound of the formula (I)
2. b) providing a polyisocyanate or a Polyepoxydes, preferably according to the formula (II) and
3. c) reacting the compounds provided in step a) and b) with each other.

1. a) Bereitstellen eines Polymers, hergestellt unter Verwendung einer Härterkomponente, wie in einem der Ansprüche 1 bis 5 definiert, oder einer Vielzahl von Härterkomponenten wie in einem der Ansprüche 6 oder 7 definiert oder eines Zwei-Komponentensystems nach einem der Ansprüche 8 bis 10, das eine Oberflächenverletzung erlitten hat und
2. b) Aussetzten des Polymeres wenigstens im Bereich der Oberflächenverletzung mit einem Stimulus ausgewählt aus der Gruppe bestehend aus Wärme, Feuchtigkeit, Druck und Strahlung, so dass die Selbstheilungskraft Polymers aktiviert wird.

In a preferred variant, the invention additionally relates to a method for self-healing of a polymer after surface injury, comprising the steps:

1. a) providing a polymer prepared using a hardener component as defined in any one of claims 1 to 5 or a plurality of hardener components as defined in any one of claims 6 or 7 or a two-component system according to any one of claims 8 to 10 has suffered a surface injury and
2. b) exposing the polymer at least in the area of surface injury with a stimulus selected from the group consisting of heat, moisture, pressure and radiation so that the self-healing polymer is activated.

Below, the invention and its advantages over the prior art using the example of the determination of breakdown strengths and the specified figures will be further explained.

Examples

The invention describes a chemically modified hardener component, preferably based on isocyanate and / or epoxy, which as a 2K formulation can cure molecular, microscopic (microcracks) and macroscopic damage.

example 1

Starting from the polyurethane approach:

For this purpose, a trimeric isocyanate, preferably biuret-based, has been covalently linked to a molecule having one of the following general formula (I) and / or formula (III) (UDETA = 1- (2-aminoethyl) imidazolidin-2-one) :

The molecule has a variable X which may contain oxygen, NH or sulfur (preferably oxygen) and R1 and R2 variable moieties which may be cycloaliphatically or aromatically linked together or may be linear hydrocarbon chains (unbound) (preferably cycloaliphatic-incorporated ethylene chain). The radical R3 contains at least one reactive group with intervening hydrocarbon chain of n = 0-8, preferably n = 2 (eg OH, NH ₂ , NH, CONH, COOH, NCO, thioisocyanate, aldehyde, urethane, urea, double bond, triple bond, imine , Sulfo-sulfino-sulfeno group, mercapto, oxime, imino, hydrazino, halogeno-CW, nitrosyl group, (preferably primary ethyleneamine)).

The repeating units can be n = 1-3, wherein in the case of n = 3 a six-membered ring is preferred.

The synthesis of the self-healing molecule UDETA (formula (III)) is already in the patents: US8536281 B2 and US20130023667 A1 described. Also, the self-healing property of this class of molecules in preferably a supramolecular network based on di- and trimeric fatty acids has already been described: WO 2006/087475 ,

This molecule and its variants function as hydrogen-bond donors and acceptors in the polymeric network, creating a physically-interacting supramolecular network in the polymer network through hydrogen bonds.

As materials for the 2K formulation, comprising the inventively modified hardener component for a polymer, as defined in the description and which can cure molecular, microscopic (microcracks) and macroscopic damage as a 2K formulation, those described in the description, the Professional per se known components - such as in particular binders and (known per se) hardener; Pigments and fillers; Additives and solvents - are used.

Example 2

coating formulations

In the first step of the synthesis, the UDETA ₁ BIURET of the formula (IV) was first prepared (see ). The biuret (Desmodur N3200) was dissolved in acetone and cooled to 0 ° C in an ice bath. Subsequently, the UDETA (formula (III)) dissolved in acetone was carefully dropped thereto. The reaction mixture was then stirred for a further 20 minutes over a magnetic stirrer and warmed to room temperature.

The next reaction step was followed by the addition of the TMP-based polyol (solvent-free). The formulation was finally homogenized by hand for at least 30 sec. Formulations of the self-healing polymers based on the above-prepared hardener component according to the invention and comparative polymers are shown in Table 1. Table 1: Formulations of self-healing polymers. NH / NCO ratio /% Trimethylolpropane ethoxylate / g (Sigma Aldrich) UDETA / g (re-link UDETA1IPDI, ARKEMA) Desmodur N3200 / g (Covestro) Acetone / g (Sigma Aldrich) 0 5.70 0 19.30 25 9 5.06 1.2 18.75 25 20 4.30 2.61 19.09 25 33 3.44 4.20 17,36 25

The following samples were prepared with and without UDETA1Biuret (UDETA): (1) STD (without UDETA1 biuret); (STD = standard, control) (2) NH / NCO ratio 9%; (3) NH / NCO ratio 20% (4) NH / NCO ratio 33%

The formulations have a non-volatile content (nfA) of 50%.

The reaction mixtures of samples (1) to (4) were knife-coated onto aluminum Q panels with a wet layer thickness of 200 μm, then flashed off for 5 minutes and then cured in the oven at 80 ° C. for 24 hours.

Example 3

Validation of self-healing properties

Example 3a

Self-healing after a damage event

After a damage event such as a scratch, micro cracks or a voltage breakdown, the damage can be cured via a trigger (eg temperature, UV light, pressure, humidity), which leads to an increase in molecular dynamics (see 1 ). The increased molecular dynamics favors the opening of the physical interactions and the reformation of the hydrogen bond elsewhere, which leads to a healing of the damage. 1a Star-shaped damage of the self-healing lacquer with a dry film thickness of 40 μm over an Erichsen recess on an aluminum sheet. 1b : Self-healing of damage at 120 ° C after 60 seconds.

Example 3b

Testing with abrasion tester for self-healing properties

Prepared polymer formulations with a polyether-based polyol are in 2 A comparison of the hardened paint films (200 μm wet on Alu-Q panels) is shown. Various degrees of modification measured by the ratio of amine to isocyanic conversion were tested (STD (0%), 9%, 20%, 33%). After two days of aging in the standard climate laboratory (23 ° C, 60% RH), the samples were tested for their self-healing properties using an abrasion tester.

Example 4

Gloss measurements for comparison of samples

Gloss measurements were carried out with paints before damage, after damage and after removal from storage in the standard climate laboratory. The gloss measurements were after DIN EN ISO 2813 performed in 20 ° and 60 ° reflection.

Using an Abrasion Tester, samples were damaged with 30 scraps of Scotch Brite weighing 1 kg at a rate of 60 cycles / min. The unmodified hardener STD was more scratch sensitive compared to the other samples. This optical impression is also confirmed by the gloss measurements of the samples in 3 , The gloss levels of the undamaged samples (blue) show no significant difference between each other. For the freshly damaged samples (red) an increasing degree of gloss with a higher NH / NCO ratio can be measured. After three days of storage in the standard climate laboratory, the samples returned to their original gloss value with an NH / NCO ratio of 20 and 33%.

These measurement results can be phenomenologically, as in 4 shown, confirming the comparisons of the damaged samples after removal from storage in the standard climate laboratory. Damage can still be seen in the STD (1) and in the 9% sample (2). The other two samples (3) and (4) (20% and 33%) no longer show any scratches.

Example 5

Oven test on samples and gloss measurements

Following the gloss measurements of Example 3, the samples were placed in the oven for 24 hours. It was found that after heat input, all samples can reach their initial gloss level, as in 3 (24h, 120 ° C) shown.

Example 6

Self-healing properties of 2-component PU coatings

In this experiment, the isocyanate Desmodur N3200 from Covestro, 2-aminoethyl-imidazolidones (UDETA) from Arkema SA (trade name: Reverlink U) and trimethylolpropane-ethoxylate (Sigma Aldrich) Mn = 170 g / mol (three OH groups) were used to formulate 2K- PUR paints used. As a solvent, acetone of omnilab (purity: 99.5% / water: 0.3%) was used.

Subsequent tests followed to test the self-healing properties of the coating over an Abrasion Tester.

The components of the paint (binder, hardener) can be varied as follows:

Formula (I) and UDETA (Formula (III)):

In the synthesis of the paint, the curing agent, preferably a biuret-based trimeric isocyanate, was covalently bonded to a molecule of formula (I) and / or formula (III) as set forth in Example 1. The molecule has a variable X which may contain oxygen, NH or sulfur (preferably oxygen) and R1 and R2 variable radicals which may be linear hydrocarbon chains (unbound) or may be cycloaliphatically or aromatically linked together (preferably cycloaliphatic-incorporated ethylene chain). The radical R 3 contains at least one reactive group with intervening hydrocarbon chain of n = 0-8, preferably n = 2 (eg OH, NH 2, NH, CONH, COOH, NCO, thioisocyanate, aldehyde, urethane, urea, double bond, triple bond, imine, Sulfo-sulfino-sulfeno, mercapto, oxime, imino, hydrazino, halo-HC, nitrosyl, (preferably primary ethyleneamine)).

The repeating units can be n = 1-3, wherein in the case of n = 3 a six-membered ring is preferred.

For the synthesis of the self-healing molecule UDETA (formula (III)) see above Example 1.

Harder:

The self-healing hardener is covalently linked to the self-healing molecule via one or two functional groups. The functional groups may be NCO or epoxy groups, preferably NCO groups. The self-healing hardener then contains 1-3 NCO or epoxy groups, preferably two.

General formula (II)

R1 and R5 can be bonded either unbound or cycloaliphatically via a carbonyl group (C =O), preferably unbound especially R1 and R5 = H.

R 2, R 3 and R 4 may be aliphatic (CH 2) n chains with n = 1-5 or 6 or repeat units of linear hydrocarbon chains of 5 or 6 carbon atoms (bridged by, for example, urethane or urea groups). And each contain one terminal NCO group , R 2, R 3 and R 4 can also each be 1- (isocyanatomethyl) -1,3,3,5-tetramethylcyclohexane radicals (trimer of IPDI or biuret + 3 × IPDI), isocyanatobenzyl radicals, isocyanatomethylbenzyl radicals or aliphatic oxiranes (see, for example, formula ( V)).

However, isocyanatobenzyl radicals can also be linked via a hydrocarbon chain with n = 0-6 (for example polymeric diphenylmethane diisocyanate (PMDI), see the following formula (VI)). polymer Diphenylmethane diisocyanate (PMDI), see the following formula (VI), also called technical MDI, is a mixture of methylene diphenyl isocyanates and homologous aromatic polyisocyanates, with a general structure of PMDI with n = 0, 1, 2, ... 6, wherein different constitution isomers with respect to the isocyanate groups. The term "polymeric diphenylmethane diisocyanate" thus does not designate a polymer, but a mixture of compounds with several (typically up to 6) phenylene groups, each carrying an isocyanate group. A common trade name is also polymethylene polyphenyl isocyanate.

The preparation of a hyperbranched polyisocyanate can the EP 1631609 B1 be removed.

Binder:

The binder may consist of aromatic or aliphatic diols and polyols, e.g. Polyether or polyester, preferably polyether having 3-100 OH groups, preferably 3, and an average molecular mass of 134-5000 g / mol, preferably 170 g / mol. Further, polyamides and polyimides as well as polythiols, polyepoxides or polyacrylates can be used.

Solvent:

As solvents, solvents having a polarity in the range of 0.56 ± 0.20 can generally be used in the invention. Preferred variants of the invention generally focus on the following solvents: esters, ketones, aromatics, gasolines, aliphatic mixtures. Examples of solvents and their polarities are given in Table 2. The solvent used in this experiment was acetone.

After the elutropene series alternative or substitute solvents can be found (see also Table 2). Table 2: Solvents and their polarities substance polarity substance polarity fluoroalkane -, 25 nitropropane 12:53 n-hexane 0.00 acetone 0.56 Petrol ether 0.01 dioxane 0.56 cyclohexane 0.04 ethyl acetate 0.58 xylene 0.26 methyl acetate 0.60 isopropyl 0.28 amyl alcohol 0.61 isopropyl 0.29 aniline 0.62 toluene 0.29 DMSO 0.62 chlorobenzene 0.30 diethylamine 0.63 benzene 0.32 nitromethane 0.64 ethyl bromide 0.37 acetonitrile 0.65 diethyl ether 0.38 pyridine 0.71 ethyl sulfide 0.38 Isopropanol / n-propanol 0.82 chloroform 0.40 ethanol 0.88 dichloromethane 0.42 methanol 0.95 Methyllsobutylketon 0.43 ethylene glycol 1.11 tetrahydrofuran 0.45 ethylene dichloride 0.49 butanone 0.51

Experimental procedure:

For the experiment, the UDETA ₁ BIURET was first produced. The hardener Desmodur N3200 was dissolved in acetone and cooled to 0 ° C in an ice bath. Subsequently, the dissolved in acetone UDETA was slowly added dropwise via a dropping funnel. The temperature should not rise above 5 ° C. The reaction mixture was then stirred for a further 20 minutes over a magnetic stirrer and warmed to room temperature.

The next step was the addition of the polyol (solvent-free). The varnish was homogenized by hand for at least 30 sec. Table 3: Formulations of self-healing polymers of the present experiment. NH / NCO ratio /% Trimethylolpropane ethoxylate / g (Sigma Aldrich) UDETA / g (re-link UDETA1IPDI, ARKEMA) Desmodur N3200 / g (Covestro) Acetone / g (Sigma Aldrich) 0 5.70 0 19.30 25 9 5.06 1.2 18.75 25 20 4.30 2.61 19.09 25 33 3.44 4.20 17,36 25

• (5) NCO/NH-Verhältnis 0 (STD), nfA 50 %
• (6) NCO/NH-Verhältnis 9, nfA 50 %
• (7) NCO/NH-Verhältnis 20, nfA 50 %
• (8) NCO/NH-Verhältnis 33, nfA 35 %

The following samples (5) to (8) were prepared:

• (5) NCO / NH ratio 0 (STD), nfA 50%
• (6) NCO / NH ratio 9, nfA 50%
• (7) NCO / NH ratio 20, nfA 50%
• (8) NCO / NH ratio 33, nfA 35%

The sample (5) with an NCO / NH ratio of 0 contains no UDETA and is henceforth referred to as standard.

The varnishes were knife-coated on Q-panels with wet layer thicknesses of 200 μm, flashed off for 5 min and then cured in the oven for 24 h at 80 ° C.

The gloss measurements were after DIN EN ISO 2813 performed in 20 ° and 60 ° reflection.

Results of the experiments and discussion:

The wet coatings produced are in 4 to see a comparison of the wet paint formulations (NCO / NH = 0-33) reproduces. The paints with NCO / NH ratios of 9 and 33 have a slight haze, which in the cured sample in 5 , which shows a comparison of the cured paint films (200 microns wet on Alu-Q panels), is no longer visible. At the highest NCO / NH ratio of 33, LM had to be added in order not to exceed the solubility product (nfA 35 instead of 50%).

After two days of storage in the standard climate laboratory, the paint was tested. With an Abrasion Tester, the coatings were damaged with 1 kg weight, a speed of 60 cycles / min and 30 DHH. In the visual comparison of sample damage, the scratches were most pronounced in the STD.

The results of the 20 ° and 60 ° gloss measurements of the samples are in 7 , which shows gloss measurements of paints before damage, after damage and after removal from storage in the standard climatic laboratory, as "damaged" applied. The gloss levels of the undamaged samples (blue) show a slight increase in gloss levels from 109 to 117 at 20 ° and 135 to 146 at 60 °, respectively, with increasing NCO / NH ratio. After previously described damage by means of an abrasion tester, the gloss values drop to 51-96 or 96-133. The gloss decrease tends to be lower with higher NCO / NH ratio. This means that the STD is more scratch sensitive compared to the SH samples. After three days of outsourcing in the standard climate lab, the samples with NCO / NH ratios of 20 and 33 returned to their initial gloss levels of 115 (20 °) and 149 and 146 (60 °) (green). The samples with NCO / NH ratios of 0 and 9 were able to achieve regeneration from 51 to 66 and 83 to 98 (20 °) and 95 to 111 and 120 to 135 (60 °), respectively.

The measurement results can be phenomenologically in 8th confirming comparisons of the damaged samples after removal from storage in the standard climate laboratory. Damage can still be seen in the STD and in the 9% sample. The other two samples (20 and 33) show no scratches.

These measurements were repeated periodically for a total of two cycles of damage and annealing at 23 ° C and 60% RH; please refer 9 , which reproduces the multiple damage and healing cycles of self-healing paints. It was found that in particular the samples with a high NCO / NH ratio of 20 and 33 can withstand two damage cycles well. However, there is a trend that the gloss decreases with increasing damage frequency. The undamaged sample with an NCO / NH ratio of 9 shows the same initial gloss value as 20 and 33 of 110 and can no longer reach this after damage. The STD is unable to regenerate the initial gloss value of 100.

Conclusion on the results of the experiments:

After storage in the standard climate laboratory, the samples with self-healing reagent show an increased resistance to scratches compared to STD. When stored in a standard climate laboratory, the self-healing paints were completely cured by the gloss value and visually with NCO / NH ratios of 20 and 33.

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

• WO 2006/087475 A1 [0015]
• US 8536281 B2 [0050, 0076]
• US 20130023667 A1 [0050, 0076]
• WO 2006/087475 [0076]
• EP 1631609 B1 [0100]

Cited non-patent literature

• Sijbesma RP, Beijer FH, Brunsveld L, Folmer BJB, Hirschberg JHKK, Long RFM, Lowe JKL, Meijer EW (1997) Science 278: 1601-1604 [0011]
• Cordier P, Tournilhac F, Soulie-Ziakovic C, Leibler L (2008) Nature 451: 977-980 [0012]
• DIN EN 60243-1 [0048]
• DIN EN 60243-2 [0048]
• DIN EN ISO 2813 [0086, 0109]

Claims (13)

Hardening component for a polymer, prepared or preparable by reaction of (a) one or more compounds of the formula (I),

wherein X independently of the optionally other X each represents an S, O or NH group, and (i) R1 and R2 independently of one another denote a linear saturated or unsaturated hydrocarbon chain having 1 to 12 carbon atoms or R1 and R2 together form a cycloheteroaliphatic or heterocyclic ring having 5 to 6 atoms, wherein R2 may independently also be H, and R3 is as defined below under (ii), or (ii) R2 is as defined under (ii) above, and R1 and R3 are each independently a linear saturated or unsaturated hydrocarbon chain having 1 to 12 C atoms or a linear saturated or unsaturated hydrocarbon chain having 1 to 12 C atoms, which comprises a cycloheteroaliphatic or heterocyclic ring having 5 to 6 atoms, and wherein R1 and / or R3 each independently comprise or are modified with at least one functionalizing element selected from the group consisting of consisting of double bond, triple bond, OH, NH ₂ , NH, CONH, COOH, NCO, thioisocyanate, aldehyde, urethane, urea, imine, sulfo, sulfino, sulfeno, mercapto , Oxime, imino, hydrazino, halogen and nitrosyl group; and n = 1, 2 or 3; and (b) a polyisocyanate or a polyepoxide. Hardener component after Claim 1 comprising 1, 2 or 3 isocyanate and / or epoxy groups. Hardener component after Claim 1 or 2 in which the polyisocyanate or the polyepoxide is a compound of the formula (II)

wherein R1 and R5 independently of one another are H or a saturated hydrocarbon radical having 1 to 8 C atoms or together represent a heterocycloaliphatic ring-bridging carbonyl group, R 2, R 3 and R 4 each independently represent a saturated, linear or branched hydrocarbon radical having 1 to 8 C atoms, a cycloalkyl radical optionally substituted by 1 to 6 hydrocarbon radicals having 1 to 2 C atoms or one having 1 to 2 hydrocarbon radicals having 1 to 2 C atoms represent substituted benzyl radical, wherein the cycloalkyl radical or the benzyl radical may each be connected to a linear saturated hydrocarbon chain having 1 to 8 carbon atoms with the respective N and each radical R2, R3 and R4 has a terminal epoxide or isocyanate preferably terminal , Hardener component according to one of the preceding claims, wherein in formula (I) n = 1. Hardener component according to one of the preceding claims, wherein in formula (I) R1 and R2 together form a ring having five atoms, wherein R1 and R2 are linked together via an etylene group. A variety of hardener components selected from the group consisting of polyepoxides and polyisocyanates, wherein the hardener components with compounds of formula (I) as in one of Claims 1 . 4 or 5 have been reacted so that on average at least 1, preferably at least 1.5, more preferably at least 2 epoxy or isocyanate groups remain per hardener component. Variety of hardener components after Claim 6 wherein the hardener components prior to reaction with the compound of formula (I) were a compound of formula (II). A two-component system for a self-healing polymer comprising a hardener component as in one of Claims 1 to 5 defined, or a variety of hardener components as in one of Claims 6 or 7 defined and a reactive with the hardener component or the plurality of hardener components binding component. Two-component system for a self-healing polymer after Claim 8 wherein the binding component is selected from the group consisting of in each case aromatic or aliphatic polyols, polyamides, polyimides, polythiols, polyepoxides, polyaspartates and polyacrylates. Two-component system for a polymer after Claim 8 or 9 wherein the binding component is a polyether or a polyester, preferably having 2 to 16 hydroxy groups. Use of a hardener component, as in one of Claims 1 to 5 defined, or a variety of hardener components as in one of Claims 6 or 7 defined for improving the self-healing power of a polymer. Process for the preparation of a hardener component as in one of Claims 1 to 5 a) comprising the steps of: a) providing a compound of the formula (I), b) providing a polyisocyanate or a polyepoxide, preferably according to the formula (II) and c) reacting the compounds provided in step a) and b) with one another. A method of self healing a polymer after surface damage comprising the steps of: a) providing a polymer prepared using a hardener component as in any of Claims 1 to 5 defined, or a variety of hardener components as in one of Claims 6 or 7 defined or a two-component system according to one of Claims 8 to 10 b) exposing the polymer at least in the area of surface injury with a stimulus selected from the group consisting of heat, moisture, pressure and radiation so that the self-healing polymer is activated.

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