EP2000221A1 - Method for manufacturing a coating - Google Patents

Abstract

Coating production involves applying a synthetic resin. A temporary coating component is applied to the sections of the surface of the synthetic resin before hardening the synthetic resin. The temporary coating component is unreactive and immiscible with the synthetic resin, and has a lower specific weight than the synthetic resin at the time of application. The temporary coating component is partially removed after hardening the synthetic resin to maintains surface structure.

Description

Technical area

The invention is based on a method for producing a coating according to the preamble of the first claim.

State of the art

Coatings are well known. Usually, such coatings consist of synthetic resin compositions and are used to protect surfaces but also as a floor covering.

From the GB 1 237 252 are coatings with colored deposits known. Such inserts have a decorative effect and improve the stability of the coating. However, such deposits are sometimes problematic in the coating, as they tend to dissolve from the coating material and thus do not adhere properly. In addition, in the decorative field, the possibilities are limited to produce a variety of decorations in such coatings.

Presentation of the invention

The invention has for its object to avoid the disadvantages of the prior art in a method for producing a coating of the type mentioned.

According to the invention this is achieved by the features of the first claim.

• Aufbringen eines ersten Kunstharzes,
• Aufbringen einer temporären Beschichtungskomponente auf zumindest Teilbereiche der Oberfläche des ersten Kunstharzes vor dem Aushärten des ersten Kunstharzes, wobei die temporäre Beschichtungskomponente nicht reaktiv ist, mit dem ersten Kunstharz nicht mischbar ist und zumindest zum Zeitpunkt des Auftrages ein geringeres spezifisches Gewicht als das erste Kunstharz aufweist,
• Zumindest teilweises Entfernen der temporären Beschichtungskomponente nach dem Zeitpunkt, bei dem das erste Kunstharz zumindest soweit ausgehärtet ist, dass es seine Oberflächenstruktur beibehält.

The core of the invention thus comprises the following steps:

• Applying a first synthetic resin,
• Applying a temporary coating component to at least portions of the surface of the first resin prior to curing of the first resin, wherein the temporary coating component is unreactive, immiscible with the first resin and has a lower specific gravity than the first resin at least at the time of application;
• At least partially removing the temporary coating component after the time at which the first synthetic resin has cured at least to the extent that it retains its surface structure.

Among other things, the advantages of the invention can be seen in the fact that a better adhesion with cover layers is achieved by changing the surface of the synthetic resin and, moreover, anti-slip properties can be set. In the decorative field, the design options are much greater than was previously possible because the three-dimensional structure of the surface of the resin can be influenced.

It is particularly useful when the resin is provided with additives such as pigments. By introducing pigments, the adhesion of cover layers can be further improved and it results countless possibilities for decorative design, which are also enhanced by the possibility of three-dimensional design of the surface.

Further advantageous embodiments of the invention will become apparent from the dependent claims.

Ways to carry out the invention

The present invention relates to a method for producing a coating of any desired substrates. In particular, the present invention relates to the coating of concrete or cement screeds for the manufacture of floors. For this purpose, the substrate is provided in a first step with a synthetic resin layer. A synthetic resin is understood below to mean a composition which comprises at least one organic molecule which is polymerized in any desired manner, in particular an epoxide, a polyurethane, a polyester, an acrylate resin composition, etc.
Before the resin layer cures, a temporary coating component is now applied to the surface of the resin, the temporary coating component being non-reactive, immiscible with the first resin and having a lower specific gravity than the first resin at least at the time of application. Such a temporary coating component is preferably liquid at room temperature. Such a temporary coating component is preferably a polydimethylsiloxane PDMS, a silicone oil. One such silicone oil is, for example, Rossil Fluid sold by Integrated Chemicals Specialties, Lisse, Holland. Preference is given to temporary coating components, silicone oils, having a relatively high viscosity, ie a viscosity higher than 100,000 cSt, ie 100,000 mm ² / s. Particularly preferred is as a temporary Coating component Rossil Fluid 5 1'000'000, with a viscosity in the range of 1'000'000 cSt, ie 1'000'000 mm ² / s.
The temporary coating component can be applied by a variety of methods, wherein the chosen method affects the appearance of the surface, such as the temporary coating component can be dropped, poured, sprayed, etc. become. After the temporary coating component has been applied, the surface of the synthetic resin is changed by the temporary coating component and can additionally be changed by treatment of the temporary coating component such as air blowing, brush, rotating heads, etc. Through all these methods, the appearance of the surface can be changed largely arbitrarily.
Additives such as pigments which can improve the properties of the coating and / or produce optical effects can additionally be incorporated into the synthetic resin and / or the temporary coating component. In addition to well-known color pigments it is also possible to use pigments with pearlescent or mother-of-pearl effect, phosphorescent pigments, for example "Glow in the Dark" from Glow Inc., etc. In addition, any other additives may be used to create effects and / or to improve the properties of the coating.
After the time at which the synthetic resin has cured at least to the extent that it retains its surface structure, the temporary coating component is removed again. This is done, for example, from the time that is referred to in the technical data sheets as walkable or synthetic resin layer is reworkable, eg after 18 hours at 20 ° C curing temperature for Sikafloor® 162. The removal of the temporary component can be done in different ways, but preferably with an alkaline detergent.
Optionally, then the synthetic resin layer can be coated with other layers of synthetic resin, in particular by means of the use of adhesives (primer). When decorative effects of the resin layer visible should be made of course, such cover layers are transparent or at least to choose semitransparent.
The substrate to which the synthetic resin layer is applied can be processed before application of the synthetic resin layer, for example, by grinding, sandblasting, etc. Especially in concrete substrates, first a mortar layer can be applied, especially a self-leveling mortar on concrete floors. Then an adhesive layer and synthetic resin layers can then be applied.

epoxy resin

The epoxy resin composition consists of two components K1 and K2. The component K1 comprises at least one epoxy resin A and the component K2 at least one curing agent H, which is reactive with the epoxy groups of the epoxy resin A.

The epoxy resin A having an average of more than one epoxy group per molecule is preferably an epoxy liquid resin or a solid epoxy resin. The term "solid epoxy resin" is well known to the person skilled in the art and is used in contrast to "liquid epoxy resins". The glass transition temperature of solid resins is above room temperature, ie they can be comminuted at room temperature to form pourable powders.

Preferred solid epoxy resins have the formula (X)

Here, the substituents R 'and R "are independently of one another either H or CH ₃ - Furthermore, the index s is a value of> 1.5, in particular from 2 to 12.
Such solid epoxy resins are commercially available, for example, from Dow or Huntsman or Hexion.
Compounds of formula (X) with an index s between 1 and 1.5 are referred to by the skilled person as semisolid epoxy resins. For the present invention, they are also considered as solid resins.
However, preference is given to epoxy resins in the narrower sense, ie where the index s has a value of> 1.5.

Preferred liquid epoxy resins have the formula (XI)

Here, the substituents R '"and R""independently of one another are either H or CH _3. Furthermore, the index r stands for a value from 0 to 1. Preferably, r stands for a value of less than 0.2.
These are thus preferably diglycidyl ethers of bisphenol A (DGEBA), bisphenol F and bisphenol A / F (The term 'A / F' refers to a mixture of acetone with formaldehyde, which is used as starting material in its preparation is used). Such liquid resins are available, for example, as Araldite® GY 250, Araldite® PY 304, Araldite® GY 282 (Huntsman) or DER ™ 331 or DER ™ 330 (Dow) or Epikote 828 (Hexion).

Preferably, the epoxy resin A is an epoxy liquid resin of the formula (XI). In a more preferred embodiment, the epoxy resin composition contains both at least one epoxy liquid resin of the formula (XI) and at least one solid epoxy resin of the formula (X).

The proportion of epoxy resin A is preferably 10 to 85% by weight, in particular 15 to 70% by weight, preferably 15 to 60% by weight, of the weight of the composition.

• Glycidylether von monofunktionellen gesättigten oder ungesättigten, verzweigten oder unverzweigten, zyklischen oder offenkettigen C₄ - C₃₀ Alkoholen, z.B. Butanolglycidylether, Hexanolglycidylether, 2-Ethylhexanolglycidylether, Allylglycidylether, Tetrahydrofurfuryl- und Furfurylglycidylether, Trimethoxysilylglycidylether etc.
• Glycidylether von difunktionellen gesättigten oder ungesättigten, verzweigten oder unverzweigten, zyklischen oder offenkettigen C₂ - C₃₀ Alkolen, z.B Ethylenglykol-, Butandiol-, Hexandiol-, Oktandiolgylcidylether, Cyclohexandimethanoldigylcidylether, Neopentylglycoldiglycidylether etc.
• Glycidylether von tri- oder polyfunktionellen, gesättigten oder ungesättigten, verzweigten oder unverzweigten, zyklischen oder offenkettigen Akoholen wie epoxidiertes Rhizinusöl, epoxidiertes Trimethylolpropan, epoxidiertes Pentaerythrol oder Polyglycidylether von aliphatischen Polyolen wie Sorbitol, Glycerin, Trimethylolpropan etc.
• Glycidylether von Phenol- und Anilinverbindungen wie Phenylglycidylether, Kresylglycidylether, p-tert.-Butylphenylglycidylether, Nonylphenolglycidylether, 3-n-Pentadecenyl-glycidylether (aus Cashewnuss-Schalen-Öl), N,N-Diglycidylanilin etc.
• Epoxidierte Amine wie N, N-Diglycidylcyclohexylamin etc.
• Epoxidierte Mono- oder Dicarbonsäuren wie Neodecansäureglycidylester, Methacrylsäureglycidylester, Benzoesäureglycidylester, Phthalsäure-, Tetra- und Hexahydrophthalsäurediglycidylester, Diglycidylester von dimeren Fettsäuren etc.
• Epoxidierte di- oder trifunktionelle, nieder- bis hochmolekulare Polyetherpolyole wie Polyethylenglycol-diglycidylether, Polypropyleneglycol-diglycidylether etc.

Preferably, the component K1 contains additionally at least one epoxide group-containing reactive diluent G. These reactive diluents G are in particular:

• Glycidyl ethers of monofunctional saturated or unsaturated, branched or unbranched, cyclic or open-chain C ₄ -C ₃₀ alcohols, for example butanol glycidyl ether, hexanol glycidyl ether, 2-ethylhexanol glycidyl ether, allyl glycidyl ether, tetrahydrofurfuryl and furfuryl glycidyl ether, trimethoxysilyl glycidyl ether etc.
• Glycidyl ethers of difunctional saturated or unsaturated, branched or unbranched, cyclic or open-chain C ₂ -C ₃₀ -alcohols, for example ethylene glycol, butanediol, hexanediol, octanediol glycidyl ethers, cyclohexanedimethanol diglycidyl ethers, neopentylglycol diglycidyl ethers, etc.
• Glycidyl ethers of trifunctional or polyfunctional, saturated or unsaturated, branched or unbranched, cyclic or open-chain alcohols such as epoxidized castor oil, epoxidized trimethylolpropane, epoxidized pentaerythrol or polyglycidyl ethers of aliphatic polyols such as sorbitol, glycerol, trimethylolpropane etc.
• Glycidyl ethers of phenolic and aniline compounds such as phenyl glycidyl ether, cresyl glycidyl ether, p-tert-butylphenyl glycidyl ether, nonyl phenol glycidyl ether, 3-n-pentadecenyl glycidyl ether (from cashew nut shell oil), N, N-diglycidyl aniline, etc.
• Epoxidized amines such as N, N-diglycidylcyclohexylamine etc.
• Epoxidized mono- or dicarboxylic acids such as glycidyl neodecanoate, glycidyl methacrylate, glycidyl benzoate, Phthalic acid, tetra- and hexahydrophthalic acid diglycidyl esters, diglycidyl esters of dimer fatty acids, etc.
• Epoxidized di- or trifunctional, low to high molecular weight polyether polyols such as polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether etc.

Particularly preferred are hexanediol diglycidyl ethers, cresyl glycidyl ethers, p- tert- butylphenyl glycidyl ethers , polypropylene glycol diglycidyl ethers and polyethylene glycol diglycidyl ethers.
Advantageously, the total proportion of epoxide group-carrying reactive diluent G is 0.5-20% by weight, preferably 1-8% by weight, based on the weight of the entire composition.

Component K2 contains at least one hardener H which has reactive groups with the epoxide groups of epoxy resin A.
Such hardeners are in particular polyamines and polymercaptans. Such polyamines are in particular diamines or triamines, preferably aliphatic or cycloaliphatic diamines or triamines.

Examples of polyamines are

• Aliphatische Diamine wie Ethylendiamin, 1,2- und 1,3-Propandiamin, 2-Methyl-1,2-propandiamin, 2,2-Dimethyl-1,3-propandiamin, 1,3- und 1,4-Butandiamin, 1,3- und 1,5-Pentandiamin, 1,6-Hexandiamin, 2,2,4- und 2,4,4-Trimethylhexamethylendiamin und Mischungen davon, 1,7-Heptandiamin, 1,8-Octandiamin, 1,9-Nonandiamin, 1,10-Decandiamin, 1,11-Undecandiamin, 1,12-Dodecandiamin, Methyl-bis-(3-aminopropyl)amin, 1,5-Diamino-2-methylpentan (MPMD), 1,3-Diaminopentan (DAMP), 2,5-Dimethyl-1,6-hexamethylendiamin, cycloaliphatische Polyamine wie 1,3- und 1,4-Diaminocyclohexan, Bis-(4-aminocyclohexyl)-methan, Bis-(4-amino-3-methylcyclohexyl)-methan, Bis-(4-amino-3-ethylcyclohexyl)-methan, 2-Methylpentamethylendiamin, Bis-(4-amino-3,5-dimethylcyclohexyl)-methan, 1-Amino-3-aminomethyl-3,5,5-trimethylcyclohexan (= Isophorondiamin oder IPDA), 2- und 4-Methyl-1,3-diaminocyclohexan und Mischungen davon, 1,3- und 1,4-Bis-(aminomethyl)cyclohexan, 1-Cyclohexylamino-3-aminopropan, 2,5(2,6)-Bis-(aminomethyl)-bicyclo[2.2.1]heptan (NBDA, hergestellt von Mitsui Chemicals), 3(4),8(9)-Bis-(aminomethyl)-tricyclo[5.2.1.0^2.6]decan, 1,4-Diamino-2,2,6-trimethylcyclohexan (TMCDA), 3,9-Bis-(3-aminopropyl)-2,4,8,10-tetra-oxaspiro[5.5]undecan, Piperazin, 1-(2-Aminoethyl)piperazin, 1,3- und 1,4-Xylylendiamin;
• zwei- oder mehrwertige aliphatische Amine, welche neben einer oder mehreren primären Aminogruppen mehr als eine sekundäre Aminogruppe tragen, wie Diethylentriamin (DETA), Triethylentetramin (TETA), Tetraethylenpentamin (TEPA), Pentaethylenhexamin und höhere Homologe linearer Polyethylenamine, N,N'-Bis-(3-aminopropyl)-ethylendiamin, Polyvinylamine, sowie Polyethylenimine unterschiedlichen Polymerisationsgrades (Molmassen-Bereich 500 bis 1'000'000 g/mol), wie sie beispielsweise unter dem Handelsnamen Lupasol^® von BASF in reiner Form oder als wässrige Lösungen erhältlich sind, wobei diese Polyethylenimine neben primären und sekundären auch tertiäre Aminogruppen enthalten;
• Polyamidoamine
• Ethergruppen-haltige aliphatische Polyamine wie Bis-(2-aminoethyl)-ether, 4,7-Dioxadecan-1,10-diamin, 4,9-Dioxadodecan-1,12-diamin und höhere Oligomere davon, Polyoxyalkylen-Polyamine mit zwei oder drei Aminogruppen, beispielsweise erhältlich unter dem Namen Jeffamine® (von Huntsman Chemicals), unter dem Namen Polyetheramin (von BASF) oder unter dem Namen PC Amine^® (von Nitroil), sowie Mischungen der vorgenannten Polyamine.

Derartige Triamine werden beispielsweise unter der Jeffamine® T-Line von Huntsman Chemicals vertrieben, wie beispielsweise Jeffamine® T-3000, Jeffamine® T-5000 oder Jeffamine® T-403.
Bevorzugte Diamine sind Polyoxyalkylen-Polyamin mit zwei Aminogruppen solche der Formel der Formel (V').

• Aliphatic diamines such as ethylenediamine, 1,2- and 1,3-propanediamine, 2-methyl-1,2-propanediamine, 2,2-dimethyl-1,3-propanediamine, 1,3- and 1,4-butanediamine, 1 , 3- and 1,5-pentanediamine, 1,6-hexanediamine, 2,2,4- and 2,4,4-trimethylhexamethylenediamine and mixtures thereof, 1,7-heptanediamine, 1,8-octanediamine, 1,9- Nonanediamine, 1,10-decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine, methyl bis (3-aminopropyl) amine, 1,5-diamino-2-methylpentane (MPMD), 1,3-diaminopentane ( DAMP), 2,5-dimethyl-1,6-hexamethylenediamine, cycloaliphatic polyamines such as 1,3- and 1,4-diaminocyclohexane, bis (4-aminocyclohexyl) -methane, bis (4-amino-3-methylcyclohexyl) methane, bis (4-amino-3-ethylcyclohexyl) methane, 2-methylpentamethylenediamine, bis (4-amino-3,5-dimethylcyclohexyl) methane, 1-amino-3-aminomethyl-3,5,5 -trimethylcyclohexane (= isophorone diamine or IPDA), 2- and 4-methyl-1,3-diaminocyclohexane and mixtures thereof, 1,3- and 1,4-bis (aminomethyl) cyclohexane, 1-cyclohexylamino-3-aminopropane, 2,5 (2,6) bis (aminomethyl) bicyclo [2.2.1] heptane (NBDA, manufactured by Mitsui Chemicals), 3 (4), 8 (9) -bis (aminomethyl) -tricyclo [5.2.1.0 ^2.6 ] decane, 1,4-diamino-2,2,6-trimethylcyclohexane (TMCDA) , 3,9-bis- (3-aminopropyl) -2,4,8,10-tetra-oxaspiro [5.5] undecane, piperazine, 1- (2-aminoethyl) piperazine, 1,3- and 1,4-xylylenediamine ;
• di- or polyhydric aliphatic amines which carry more than one secondary amino group in addition to one or more primary amino groups, such as diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), pentaethylenehexamine and higher homologs of linear polyethyleneamines, N, N'-bis - (3-aminopropyl) ethylenediamine, polyvinylamines, as well as polyethylenimines of different degrees of polymerization (molar mass range 500 to 1,000,000 g / mol), such as those available under the trade name Lupasol ^® from BASF in pure form or as aqueous solutions , wherein these polyethyleneimines contain not only primary and secondary but also tertiary amino groups;
• polyamidoamines
• Ether group-containing aliphatic polyamines such as bis (2-aminoethyl) ether, 4,7-dioxadecane-1,10-diamine, 4,9-dioxadodecane-1,12-diamine and higher oligomers thereof, polyoxyalkylene polyamines having two or three amino groups, obtainable for example under the name Jeffamine® (from Huntsman Chemicals), under the name polyetheramine (from BASF) or under the name PC amines ^® (of Nitroil), and mixtures of the aforementioned polyamines.

Such triamines are marketed, for example, under the Jeffamine® T-Line by Huntsman Chemicals, for example Jeffamine® T-3000, Jeffamine® T-5000 or Jeffamine® T-403.
Preferred diamines are polyoxyalkylene-polyamine having two amino groups, those of the formula of the formula (V ').

Here, g 'represent the structural element derived from propylene oxide and h' the structural element derived from ethylene oxide. In addition, g, h and i each represent and stand for values from 0 to 40, with the proviso that the sum of g, h and i ≥ 1.
In particular, molecular weights between 200 and 5000 g / mol are preferred. Especially preferred are Jeffamine®, as available under the D-line and ED line from Huntsman Chemicals, such as Jeffamine® D-230, Jeffamine® D-400, Jeffamine® D-2000, Jeffamine® D-4000, Jeffamine® ED-600, Jeffamine® ED-900, Jeffamine® ED-2003 or Jeffamine® EDR-148.

• Polyoxyalkylenpolyole, auch Polyetherpolyole genannt, welche das Polymerisationsprodukt von Ethylenoxid, 1,2-Propylenoxid, 1,2- oder 2,3-Butylenoxid, Tetrahydrofuran oder Mischungen davon sind, gegebenenfalls polymerisiert mit Hilfe eines Startermoleküls mit zwei oder drei aktiven H-Atomen wie beispielsweise Wasser oder Verbindungen mit zwei oder drei OH-Gruppen. Eingesetzt werden können sowohl Polyoxyalkylenpolyole, die einen niedrigen Ungesättigtheitsgrad aufweisen (gemessen nach ASTM D-2849-69 und angegeben in Milliequivalent Ungesättigtheit pro Gramm Polyol (mEq/g)), hergestellt beispielsweise mit Hilfe von sogenannten Double Metal Cyanide Complex Katalysatoren (kurz DMC-Katalysatoren), als auch Polyoxyalkylenpolyole mit einem höheren Ungesättigtheitsgrad, hergestellt beispielsweise mit Hilfe von anionischen Katalysatoren wie NaOH, KOH oder Alkalialkoholaten. Besonders geeignet sind Polyoxypropylendiole und -triole mit einem Ungesättigtheitsgrad tiefer als 0.02 mEq/g und mit einem Molekulargewicht im Bereich von 300 - 20'000 Dalton, Polyoxybutylendiole und -triole, Polyoxypropylendiole und - triole mit einem Molekulargewicht von 400 - 8'000 Dalton, sowie sogenannte "EO-endcapped" (ethylene oxide-endcapped) Polyoxypropylendiole oder -triole. Letztere sind spezielle Polyoxypropylenpolyoxyethylenpolyole, die beispielsweise dadurch erhalten werden, dass reine Polyoxypropylenpolyole nach Abschluss der Polypropoxylierung mit Ethylenoxid alkoxyliert werden und dadurch primäre Hydroxylgruppen aufweisen.
• Hydroxyterminierte Polybutadienpolyole, wie beispielsweise solche, die durch Polymerisation von 1,3-Butadien und Allylalkohol oder durch Oxidation von Polybutadien hergestellt werden, sowie deren Hydrierungsprodukte;
• Styrol-Acrylnitril gepfropfte Polyetherpolyole, wie sie beispielsweise von Elastogran unter dem Namen Lupranol® geliefert werden;
• Polyesterpolyole, hergestellt beispielsweise aus zwei- bis dreiwertigen Alkoholen wie beispielsweise 1,2-Ethandiol, Diethylenglykol, 1,2-Propandiol, Dipropylenglykol, 1,4-Butandiol, 1,5-Pentandiol, 1,6-Hexandiol, Neopentylglykol, Glycerin, 1,1,1-Trimethylolpropan oder Mischungen der vorgenannten Alkohole mit organischen Dicarbonsäuren oder deren Anhydriden oder Estern wie beispielsweise Bernsteinsäure, Glutarsäure, Adipinsäure, Korksäure, Sebacinsäure, Dodecandicarbonsäure, Maleinsäure, Fumarsäure, Phthalsäure, Isophthalsäure, Terephthalsäure und Hexahydrophthalsäure oder Mischungen der vorgenannten Säuren, sowie Polyesterpolyole aus Lactonen wie beispielsweise ε-Caprolacton;
• Polycarbonatpolyole, wie sie durch Umsetzung beispielsweise der oben genannten - zum Aufbau der Polyesterpolyole eingesetzten - Alkohole mit Dialkylcarbonaten, Diarylcarbonaten oder Phosgen zugänglich sind;
• 1,2-Ethandiol, Diethylenglykol, 1,2-Propandiol, Dipropylenglykol, 1,4-Butandiol, 1,5-Pentandiol, 1,6-Hexandiol, 1,7-Hepandiol, Octandiol, Nonandiol, Decandiol, Neopentylglykol, Pentaerythrit (= 2,2-Bis-hydroxymethyl-1,3-propandiol), Dipentaerythrit (= 3-(3-Hydroxy-2,2-bis-hydroxymethyl-propoxy)-2,2-bis-hydroxymethyl-propan-1-ol), Glycerin (= 1,2,3-Propantriol), Trimethylolpropan (= 2-Ethyl-2-(hydroxymethyl)-1,3-propandiol), Trimethylolethan (= 2-(hydroxymethyl)-2-Methyl-1,3-propandiol, Di(trimethylolpropan) (= 3-(2,2-Bis-hydroxymethyl-butoxy)-2-ethyl-2-hydroxymethyl-propan-1-ol), Di(trimethylolethan) (= 3-(3-Hydroxy-2-hydroxymethyl-2-methyl-propoxy)-2-hydroxymethyl-2-methyl-propan-1-ol), Diglycerin (= Bis-(2,3-dihydroxypropyl)-ether);
• Polyole, wie sie durch Reduktion von dimerisierten Fettsäuren enthalten werden.

Dimercaptans are particularly preferred as polymercaptan.
Suitable polymercaptans are, for example, polymercaptocetates of polyols. These are, in particular, polymercaptocetates of the following polyols:

• Polyoxyalkylenpolyole, also called polyether polyols, which are the polymerization of ethylene oxide, 1,2-propylene oxide, 1,2- or 2,3-butylene oxide, tetrahydrofuran or mixtures thereof, optionally polymerized by means of a starter molecule having two or three active H atoms such For example, water or compounds having two or three OH groups. Both polyoxyalkylene polyols having a low level of unsaturation (measured according to ASTM D-2849-69 and expressed in milliequivalents of unsaturation per gram of polyol (mEq / g)) prepared, for example, with the aid of so-called double metal cyanide complex catalysts (in short DMC) can be used. catalysts) as well as polyoxyalkylene polyols having a higher degree of unsaturation, prepared for example with the aid of anionic catalysts such as NaOH, KOH or alkali metal alkoxides. Particularly suitable are polyoxypropylene diols and triols having a degree of unsaturation lower than 0.02 meq / g and having a molecular weight in the range of 300-20,000 daltons, polyoxybutylene diols and triols, polyoxypropylene diols and triols having a molecular weight of 400-8,000 daltons. and so-called "EO-endcapped" (ethylene oxide-endcapped) polyoxypropylene diols or triols. The latter are special polyoxypropylene-polyoxyethylene polyols obtained, for example, by alkoxylating pure polyoxypropylene polyols with ethylene oxide after completion of the polypropoxylation and thereby having primary hydroxyl groups.
• Hydroxy-terminated polybutadiene polyols, such as those prepared by polymerization of 1,3-butadiene and allyl alcohol or by oxidation of polybutadiene, and their hydrogenation products;
• Styrene-acrylonitrile grafted polyether polyols, such as those supplied by Elastogran under the name Lupranol®;
• Polyester polyols prepared, for example, from dihydric to trihydric alcohols, for example 1,2-ethanediol, diethylene glycol, 1,2-propanediol, dipropylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, glycerol, 1,1,1-trimethylolpropane or mixtures of the abovementioned alcohols with organic dicarboxylic acids or their anhydrides or esters such as succinic, glutaric, adipic, suberic, sebacic, dodecanedicarboxylic, maleic, fumaric, phthalic, isophthalic, terephthalic and hexahydrophthalic or mixtures of the aforementioned acids , and polyester polyols from lactones such as ε-caprolactone;
• Polycarbonatepolyols, as they are accessible by reaction, for example, of the abovementioned alcohols used to form the polyesterpolyols with dialkyl carbonates, diaryl carbonates or phosgene;
• 1,2-ethanediol, diethylene glycol, 1,2-propanediol, dipropylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-hepanediol, octanediol, nonanediol, decanediol, neopentyl glycol, pentaerythritol ( = 2,2-bis-hydroxymethyl-1,3-propanediol), dipentaerythritol (= 3- (3-hydroxy-2,2-bis-hydroxymethyl-propoxy) -2,2-bis-hydroxymethyl-propan-1-ol ), Glycerol (= 1,2,3-propanetriol), trimethylolpropane (= 2-ethyl-2- (hydroxymethyl) -1,3-propanediol), trimethylolethane (= 2- (hydroxymethyl) -2-methyl-1,3 -propanediol, di (trimethylolpropane) (= 3- (2,2-bis-hydroxymethylbutoxy) -2-ethyl-2-hydroxymethyl-propan-1-ol), di (trimethylolethane) (= 3- (3-hydroxy 2-hydroxymethyl-2-methylpropoxy) -2-hydroxymethyl-2-methylpropan-1-ol), diglycerol (= bis (2,3-dihydroxypropyl) ether);
• Polyols as they are contained by reduction of dimerized fatty acids.

Particularly preferred are glycol dimercaptoacetate, trimethylolpropane trimercaptoacetate and butanediol dimercaptoacetate.

Hierbei steht y für einen Wert von 1 bis 45, insbesondere von 5 bis 23. Die bevorzugten Molekulargewichte sind zwischen 800 und 7500 g/mol, insbesondere zwischen 1000 und 4000 g/mol,.
Derartige Polymercaptane sind kommerziell erhältlich unter der Thiokol® LP-Reihe von Toray Fine Chemicals Co.The most preferred polymercaptans are dimercaptans of the formula (V ").

Here, y stands for a value from 1 to 45, in particular from 5 to 23. The preferred molecular weights are between 800 and 7500 g / mol, in particular between 1000 and 4000 g / mol.
Such polymercaptans are commercially available under the Thiokol® LP series from Toray Fine Chemicals Co.

As a hardener, adducts of polyamines and / or polymercaptans, in particular of the abovementioned polyamines and / or polymercaptans, with epoxides, in particular with the previously mentioned epoxy resins A and / or reactive diluents G, can also be used.

The amounts of hardener are preferably such that the epoxide-reactive groups of the hardener in component K2 stoichiometrically react with the epoxide groups present in component K1 .

The components K1 and / or K2 may contain further constituents. In particular, these are solvents, plasticizers, thixotropic agents, catalysts, biocides, such as algicides, fungicides or fungal growth inhibiting substances, heat and / or light stabilizers, mineral or organic fillers, dyes and pigments, additives, in particular leveling agents, defoamers, surfactants or adhesion promoters ,

polyurethane compositions

Polyurethane compositions may be one-component or two-component.
The two-part polyurethane compositions contain a component K1 ' which contains a polyisocyanate and / or an isocyanate group-containing polyurethane polymer P polyurethane polymer, as described below. In another component K2 ' are compounds which contain two or more NCO-reactive groups, in particular polyols, polyamines and / or (poly) amino alcohols, in particular such polyols and / or polyamines, as described below.

The polyurethane composition is preferably a one-component, moisture-curing composition which contains at least one polyurethane polymer P containing isocyanate groups.
The polyurethane polymer P is obtainable, for example, from the reaction of at least one polyol with at least one polyisocyanate. This reaction can be carried out by reacting the polyol and the polyisocyanate with customary processes, for example at from 50 ° C. to 100 ° C., if appropriate with concomitant use of suitable catalysts, the polyisocyanate being metered in such a way that its Isocyanate groups in proportion to the hydroxyl groups of the polyol in stoichiometric excess are present. Advantageously, the polyisocyanate is metered so that an NCO / OH ratio of 1.5 to 5, in particular one of 1.8 to 3, is maintained. The NCO / OH ratio here means the ratio of the number of isocyanate groups used to the number of hydroxyl groups used. In the polyurethane polymer P, after the reaction of all hydroxyl groups of the polyol, a content of free isocyanate groups of from 0.5 to 15% by weight, particularly preferably from 3.5 to 10% by weight, preferably remains.

• Polyoxyalkylenpolyole, auch Polyetherpolyole oder Oligoetherole genannt, welche Polymerisationsprodukte von Ethylenoxid, 1,2-Propylenoxid, 1,2- oder 2,3-Butylenoxid, Tetrahydrofuran oder Mischungen davon sind, eventuell polymerisiert mit Hilfe eines Startermoleküls mit zwei oder mehreren aktiven Wasserstoffatomen wie beispielsweise Wasser, Ammoniak oder Verbindungen mit mehreren OH- oder NH-Gruppen wie beispielsweise 1,2-Ethandiol, 1,2- und 1,3-Propandiol, Neopentylglykol, Diethylenglykol, Triethylenglykol, die isomeren Dipropylenglykole und Tripropylenglykole, die isomeren Butandiole, Pentandiole, Hexandiole, Heptandiole, Octandiole, Nonandiole, Decandiole, Undecandiole, 1,3- und 1,4-Cyclohexandimethanol, Bisphenol A, hydriertes Bisphenol A, 1,1,1-Trimethylolethan, 1,1,1-Trimethylolpropan, Glycerin, Anilin, sowie Mischungen der vorgenannten Verbindungen. Eingesetzt werden können sowohl Polyoxyalkylenpolyole, die einen niedrigen Ungesättigtheitsgrad aufweisen (gemessen nach ASTM D-2849-69 und angegeben in Milliequivalent Ungesättigtheit pro Gramm Polyol (mEq/g)), hergestellt beispielsweise mit Hilfe von sogenannten Double Metal Cyanide Complex-Katalysatoren (DMC-Katalysatoren), als auch Polyoxyalkylenpolyole mit einem höheren Ungesättigtheitsgrad, hergestellt beispielsweise mit Hilfe von anionischen Katalysatoren wie NaOH, KOH, CsOH oder Alkalialkoholaten. Besonders geeignet sind Polyoxyalkylendiole oder Polyoxyalkylentriole, insbesondere Polyoxypropylendiole oder Polyoxypropylentriole. Speziell geeignet sind Polyoxyalkylendiole oder Polyoxyalkylentriole mit einer tiefen Viskosität und mit einem Molekulargewicht im Bereich von 400 - 8'000 g/mol.

Ebenfalls besonders geeignet sind Polytetrahydrofurane aufgrund ihrer guten Lichstabilität.
Ebenfalls besonders geeignet sind sogenannte Ethylenoxid-terminierte ("EO-endcapped", ethylene oxide-endcapped) Polyoxypropylenpolyole. Letztere sind spezielle Polyoxypropylenpolyoxyethylenpolyole, die beispielsweise dadurch erhalten werden, dass reine Polyoxypropylenpolyole, insbesondere Polyoxypropylendiole und -triole, nach Abschluss der Polypropoxylierungsreaktion mit Ethylenoxid weiter alkoxyliert werden und dadurch primäre Hydroxylgruppen aufweisen.

• Styrol-Acrylnitril- oder Acrylnitril-Methylmethacrylat-gepfropfte Polyetherpolyole.
• Polyesterpolyole, auch Oligoesterole genannt, hergestellt beispielsweise aus zwei- bis dreiwertigen Alkoholen wie beispielsweise 1,2-Ethandiol, Diethylenglykol, 1,2-Propandiol, Dipropylenglykol, 1,4-Butandiol, 1,5-Pentandiol, 1,6-Hexandiol, Neopentylglykol, Glycerin, 1,1,1-Trimethylolpropan oder Mischungen der vorgenannten Alkohole mit organischen Dicarbonsäuren oder deren Anhydride oder Ester wie beispielsweise Bernsteinsäure, Glutarsäure, Adipinsäure, Korksäure, Sebacinsäure, Dodecandicarbonsäure, Maleinsäure, Fumarsäure, Phthalsäure, Isophthalsäure, Terephthalsäure und Hexahydrophthalsäure oder Mischungen der vorgenannten Säuren, sowie Polyesterpolyole aus Lactonen wie beispielsweise ε-Caprolacton.
• Polycarbonatpolyole, wie sie durch Umsetzung beispielsweise der oben genannten - zum Aufbau der Polyesterpolyole eingesetzten - Alkohole mit Dialkylcarbonaten, Diarylcarbonaten oder Phosgen zugänglich sind.
• Polyacrylat- und Polymethacrylatpolyole.
• Polykohlenwasserstoffpolyole, auch Oligohydrocarbonole genannt, wie beispielsweise polyhydroxyfunktionelle Ethylen-Propylen-, Ethylen-Butylen-oder Ethylen-Propylen-Dien-Copolymere, wie sie beispielsweise von der Firma Kraton Polymers hergestellt werden, oder polyhydroxyfunktionelle Copolymere aus Dienen wie 1,3-Butandien oder Diengemischen und Vinylmonomeren wie Styrol, Acrylnitril oder Isobutylen, oder polyhydroxyfunktionelle Polybutadienpolyole, wie beispielsweise solche, die durch Copolymerisation von 1,3-Butadien und Allylalkohol hergestellt werden und auch hydriert sein können.
• Polyhydroxyfunktionelle Acrylonitril/Polybutadien-Copolymere, wie sie beispielsweise aus Epoxiden oder Aminoalkoholen und carboxylterminierten Acrylonitril/Polybutadien-Copolymeren (kommerziell erhältlich unter dem Namen Hycar^® CTBN von Noveon) hergestellt werden können.

As polyols for the preparation of a polyurethane polymer P , for example, the following commercial polyols or mixtures thereof can be used:

• Polyoxyalkylenpolyole, also called polyether polyols or oligoetherols, which are polymerization of ethylene oxide, 1,2-propylene oxide, 1,2- or 2,3-butylene oxide, tetrahydrofuran or mixtures thereof, possibly polymerized with the aid of a starter molecule having two or more active hydrogen atoms such as Water, ammonia or compounds with several OH or NH groups such as 1,2-ethanediol, 1,2- and 1,3-propanediol, neopentyl glycol, diethylene glycol, triethylene glycol, the isomeric dipropylene glycols and tripropylene glycols, the isomeric butanediols, pentanediols, Hexanediols, heptanediols, octanediols, nonanediols, decanediols, undecanediols, 1,3- and 1,4-cyclohexanedimethanol, bisphenol A, hydrogenated bisphenol A, 1,1,1-trimethylolethane, 1,1,1-trimethylolpropane, glycerine, aniline, and mixtures of the aforementioned compounds. Both polyoxyalkylene polyols having a low degree of unsaturation (measured according to ASTM D-2849-69 and expressed in milliequivalents of unsaturation per gram of polyol (mEq / g)) prepared, for example, by means of so-called double metal cyanide complex catalysts (DMC) can be used. Catalysts), as well as polyoxyalkylene polyols having a higher degree of unsaturation, prepared for example with the aid of anionic catalysts such as NaOH, KOH, CsOH or alkali metal alkoxides. Particularly suitable are polyoxyalkylenediols or polyoxyalkylenetriols, in particular polyoxypropylenediols or polyoxypropylenetriols. Especially suitable are polyoxyalkylenediols or polyoxyalkylenetriols having a low viscosity and having a molecular weight in the range from 400 to 8000 g / mol.

Polytetrahydrofurans are also particularly suitable because of their good light stability.
Also particularly suitable are so-called ethylene oxide-terminated ("EO-endcapped", ethylene oxide-endcapped) polyoxypropylene polyols. The latter are specific polyoxypropylene polyoxyethylene polyols obtained, for example, by further alkoxylating pure polyoxypropylene polyols, especially polyoxypropylene diols and triols, upon completion of the polypropoxylation reaction with ethylene oxide, thereby having primary hydroxyl groups.

• Styrene-acrylonitrile or acrylonitrile-methyl methacrylate grafted polyether polyols.
• Polyesterpolyols, also called oligoesterols, prepared for example from dihydric to trihydric alcohols such as 1,2-ethanediol, diethylene glycol, 1,2-propanediol, dipropylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, Neopentyl glycol, glycerol, 1,1,1-trimethylolpropane or mixtures of the aforementioned alcohols with organic dicarboxylic acids or their anhydrides or esters such as succinic, glutaric, adipic, suberic, sebacic, dodecanedicarboxylic, maleic, fumaric, phthalic, isophthalic, terephthalic and hexahydrophthalic or Mixtures of the aforementioned acids, and polyester polyols from lactones such as ε-caprolactone.
• Polycarbonate polyols, as they are accessible by reacting, for example, the abovementioned alcohols used to form the polyesterpolyols with dialkyl carbonates, diaryl carbonates or phosgene.
• Polyacrylate and polymethacrylate polyols.
• Polyhydrocarbons, also called Oligohydrocarbonole, such as polyhydroxy-functional ethylene-propylene, ethylene-butylene or Ethylene-propylene-diene copolymers, such as those produced by the company Kraton Polymers, or polyhydroxy-functional copolymers of dienes such as 1,3-butadiene or diene mixtures and vinyl monomers such as styrene, acrylonitrile or isobutylene, or polyhydroxy-functional polybutadiene, such as those can be prepared by copolymerization of 1,3-butadiene and allyl alcohol and can also be hydrogenated.
• Polyhydroxy-functional acrylonitrile / polybutadiene copolymers, as they can be prepared, for example, from epoxides or aminoalcohols and carboxyl-terminated acrylonitrile / polybutadiene copolymers (Hycar ^® CTBN under the name of Noveon commercially available).

These stated polyols preferably have an average molecular weight of 250-12,000 g / mol, in particular of 400-8,000 g / mol, and an average OH functionality in the range of 1.7-3.

In addition to these mentioned polyols, small amounts of low molecular weight di- or polyhydric alcohols such as 1,2-ethanediol, 1,3- and 1,4-butanediol, 1,2- and 1,3-propanediol, neopentyl glycol, diethylene glycol, triethylene glycol , the isomeric dipropylene glycols and tripropylene glycols, the isomeric pentanediols, hexanediols, heptanediols, octanediols, nonanediols, decanediols, undecanediols, 1,3- and 1,4-cyclohexanedimethanol, hydrogenated bisphenol A, dimeric fatty alcohols, 1,1,1-trimethylolethane, 1 , 1,1-trimethylolpropane, glycerol, pentaerythritol, sugar alcohols such as xylitol, sorbitol or mannitol, sugars such as sucrose, other higher alcohols, low molecular weight alkoxylation of the aforementioned dihydric and polyhydric alcohols, as well as mixtures of the aforementioned alcohols in the preparation of a polyurethane polymer P are used , Similarly, small amounts of polyols having an average OH functionality of more than 3 may be included, for example, sugar polyols.

As polyisocyanates for the preparation of a polyurethane polymer P it is possible to use commercially available aliphatic, cycloaliphatic or aromatic polyisocyanates, in particular diisocyanates, for example the following:
Diisocyanates with isocyanate groups bonded to an aliphatic, cycloaliphatic or araliphatic C atom, also called "aliphatic diisocyanates", such as 1,6-hexamethylene diisocyanate (HDI), 2-methylpentamethylene-1,5-diisocyanate, 2,2,4 and 2,4,4-trimethyl-1,6-hexamethylene diisocyanate (TMDI), 1,12-dodecamethylene diisocyanate, lysine and lysine ester diisocyanate, cyclohexane-1,3- and 1,4-diisocyanate and any mixtures of these isomers, 1 Isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (= isophorone diisocyanate or IPDI), perhydro-2,4'- and -4,4'-diphenylmethane diisocyanate (HMDI), 1,4-diisocyanato-2, 2,6-trimethylcyclohexane (TMCDI), 1,3- and 1,4-bis- (isocyanatomethyl) -cyclohexane, m- and p-xylylene diisocyanate (mund p-XDI), m- and p-tetramethyl-1,3- and -1,4-xylylene diisocyanate (m- and p-TMXDI), bis (1-isocyanato-1-methylethyl) naphthalene; and diisocyanates having isocyanate groups bonded to one aromatic carbon atom in each case, also called "aromatic diisocyanates", such as 2,4- and 2,6-toluene diisocyanate and any desired mixtures of these isomers (TDI), 4,4'-, 2,4 ' and 2,2'-diphenylmethane diisocyanate and any mixtures of these isomers (MDI), 1,3- and 1,4-phenylene diisocyanate, 2,3,5,6-tetramethyl-1,4-diisocyanatobenzene, naphthalene-1,5- diisocyanate (NDI), 3,3'-dimethyl-4,4'-diisocyanatodiphenyl (TODI); Oligomers and polymers of the aforementioned isocyanates, as well as any mixtures of the aforementioned isocyanates. For the formulation of light-stable coatings, aliphatic diisocyanates are preferred, in particular HDI and IPDI.
Of the aromatic diisocyanates, preferred are MDI and TDI.

The polyols and polyisocyanates are chosen so that a polyurethane polymer P formed therefrom has a low viscosity. A low-viscosity polyurethane polymer P is particularly well suited to obtain coatings with high flowability. As "low viscosity" is here a Viscosity of not more than 25 Pa.s, in particular of very high 20 Pa.s, preferably not more than 15 Pa.s, denoted at 20 ° C.
Usually, the polyurethane polymer P is present in an amount of 10-80% by weight, preferably in an amount of 15-70% by weight, based on the total composition.

The moisture-curing composition may contain, in addition to the polyurethane polymer P, an oligomeric polyisocyanate OP .
Suitable oligomeric polyisocyanate OP are both aliphatic oligomeric polyisocyanates and aromatic oligomeric polyisocyanates and aliphatic-aromatic mixed forms, wherein the aliphatic oligomeric polyisocyanates are preferred. Suitable aliphatic oligomeric polyisocyanates OP are derived, for example, from the following diisocyanates: 1,6-hexamethylene diisocyanate (HDI), 2-methylpentamethylene-1,5-diisocyanate, 2,2,4- and 2,4,4-trimethyl-1,6 hexamethylene diisocyanate (TMDI), 1,12-dodecamethylene diisocyanate, cyclohexane-1,3- and 1,4-diisocyanate and any mixtures of these isomers, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (= isophorone diisocyanate or IPDI), perhydro-2,4'- and -4,4'-diphenylmethane diisocyanate (HMDI), 1,4-diisocyanato-2,2,6-trimethylcyclohexane (TMCDI), m- and p-xylylene diisocyanate (XDI), 1 , 3- and 1,4-tetramethylxylylene diisocyanate (TMXDI), 1,3- and 1,4-bis (isocyanatomethyl) cyclohexane, preferably HDI and IPDI. Suitable aromatic oligomeric polyisocyanates OP are derived from the same aromatic diisocyanates as have already been mentioned for the preparation of a polyurethane polymer P.
Technical forms of these oligomers are usually mixtures of substances with different degrees of oligomerization and chemical structures. Suitable are technical oligomer mixtures which have an average NCO functionality of preferably 2.4 to 4.0 and in particular contain isocyanurate, iminooxadiazinedione, uretdione or biuret groups. In addition, allophanate, carbodiimide, uretonimine or oxadiazinetrione groups may also be included.

Suitable commercially available technical oligomer mixtures of aliphatic diisocyanates HDI biurets, for example, as Desmodur® N 100 and N 3200 (Bayer), Tolonate ^® HDB and HDB-LV (Rhodia) and Duranate 24A-100 ^® (Asahi Kasei); HDI-Isocyanurates, for example, as Desmodur® N 3300, N 3600 and N 3790 BA (all from Bayer), Tolonate ^® HDT, HDT-LV and HDT-LV2 (Rhodia), Duranate ^® TPA-100 and THA-100 (Asahi Kasei ) and Coronate® HX (Nippon Polyurethane); HDI uretdiones, for example, as Desmodur ^® N 3400 (Bayer); HDI Iminooxadiazindiones, for example, as Desmodur ^® XP 2410 (Bayer); HDI-allophanates, for example as Desmodur ^® VP LS 2102 (Bayer); and also IPDI isocyanurate, for example in solution as Desmodur® Z 4470 (Bayer) or in solid form as Vestanat ^® T1890 / 100 (Degussa).
Preference is given to the trimers of HDI and / or IPDI, in particular the isocyanurates. A technical oligomer mixture of aromatic diisocyanates is TDI isocyanurate, available for example as Desmodur® IL (Bayer). Also commercially available are mixed aromatic-aliphatic isocyanurates based on TDI / HDI, for example as Desmodur® HL (Bayer). The oligomeric polyisocyanate OP is usually present in an amount of 0-20% by weight, preferably in an amount of 0.5-20% by weight, more preferably in an amount of 1.0-15% by weight, based on the total composition.
The addition of the oligomeric polyisocyanate OP is advantageous because on the one hand this further reduces the viscosity of the composition and on the other hand increases the hardness of the cured composition due to its high content of isocyanate groups and its relatively high average NCO functionality.

Advantageously, the moisture-curing composition contains no or at most 5% by weight of a solvent L based on the total composition.
Suitable solvents L are, for example, ketones such as acetone, methyl ethyl ketone, diisobutyl ketone, acetylacetone, mesityl oxide, cyclohexanone and methylcyclohexanone; Esters, for example acetates such as ethyl acetate, propyl acetate and butyl acetate, formates, propionates and malonates such as diethyl malonate; Ethers, such as dialkyl ethers, ketone ethers and ester ethers, for example diisopropyl ether, diethyl ether, dibutyl ether, diethylene glycol diethyl ether and ethylene glycol diethyl ether; aliphatic and aromatic hydrocarbons such as toluene, xylene, heptane, octane and petroleum fractions such as naphtha, white spirit, petroleum ether and gasoline; halogenated hydrocarbons such as methylene chloride; and N-alkylated lactams such as N-methylpyrrolidone. Preferred are xylene, toluene, white spirit and petroleum fractions in the boiling range of 100 ° C to 200 ° C.
Because of the low viscosity of the polyurethane polymer P, even without solvent L , the composition is generally readily processable as a self-leveling floor coating. In order to improve the processability, however, it may be advantageous to add small amounts of up to 5% by weight of the solvent L mentioned.

Advantageously, the composition contains at least one filler F. The filler F influences both the rheological properties of the uncured composition and the mechanical properties and surface finish of the cured composition. Suitable fillers F are inorganic and organic fillers, for example natural, ground or precipitated calcium carbonates, which are optionally coated with fatty acids, in particular stearates, barite (BaSO ₄ , also called barite), calcined kaolins, aluminum oxides, aluminum hydroxides, silicic acids, in particular highly dispersed Silicas from pyrolysis processes, Russian, in particular industrially produced Russian (hereinafter referred to as "soot"), PVC powder or hollow spheres. Preferred fillers are barytes and calcium carbonates, as well as flame retardant fillers such as hydrates or hydroxides, in particular of aluminum, preferably aluminum hydroxide.
A suitable amount of filler F is, for example, in the range of 10 to 70% by weight, preferably 20 to 60% by weight, based on the total composition.

It is quite possible and may even be advantageous to use a mixture of different fillers F.

Advantageously, the composition contains at least one catalyst K , which accelerates the hydrolysis of the aldimine groups and / or the reaction of the isocyanate groups. Catalysts K , which accelerate the reaction of the isocyanate groups with water, are, for example, organotin compounds such as dibutyltin dilaurate, dibutyltin dichloride, dibutyltin diacetylacetonate, bismuth organic compounds or bismuth complexes, or compounds containing tertiary amino groups such as 2,2'-dimorpholinodiethyl ether or 1,4-diazabicyclo [2.2.2] octane, or other catalysts customary in polyurethane chemistry for the reaction of the isocyanate groups. It may be advantageous if a mixture of a plurality of catalysts K is present in the composition, in particular a mixture of an acidic compound and an organometallic compound or a metal complex, of an acidic compound and a tertiary amino group-containing compound, or a mixture of an acidic one A compound, an organometallic compound or a metal complex, and a tertiary amino group-containing compound. A typical content of catalyst K is usually 0.005 to 2% by weight, based on the total composition, it being clear to the person skilled in the art which quantities are useful for which catalysts.

• Weichmacher, beispielsweise Ester organischer Carbonsäuren oder deren Anhydride, zum Beispiel Phthalate wie Dioctylphthalat und Diisodecylphthalat, Adipate wie Dioctyladipat, Azelate und Sebacate; organische Phosphor- und Sulfonsäureester und Polybutene;
• Fasern, beispielsweise aus Polyethylen;
• Pigmente, beispielsweise Titandioxid, Eisenoxide oder Chromverbindungen;
• weitere in der Polyurethanchemie übliche Katalysatoren;
• Reaktivverdünner und Vernetzer, beispielsweise Polyisocyanate wie MDI, PMDI, TDI, HDI, 1,12-Dodecamethylendiisocyanat, Cyclohexan-1,3-oder 1,4-diisocyanat, IPDI, Perhydro-2,4'- und -4,4'-diphenylmethandiisocyanat, 1,3- und 1,4-Tetramethylxylylendiisocyanat, Oligo- und Polymere dieser Polyisocyanate, Addukte von Polyisocyanaten mit kurzkettigen Polyolen, sowie Adipinsäure-dihydrazid und andere Dihydrazide;
• weitere latente Härter wie beispielsweise andere Aldimine oder Oxazolidine;
• Trocknungsmittel, wie beispielsweise p-Tosylisocyanat, Orthoameisensäureester, Calciumoxid, Vinyltrimethoxysilan und andere schnell hydrolysierende Silane, wie beispielsweise Organoalkoxysilane, welche in α-Stellung zur Silangruppe eine funktionelle Gruppe aufweisen, und Molekularsiebe;
• Haftvermittler, insbesondere Organoalkoxysilane, im Folgenden "Silane" genannt, wie beispielsweise Epoxysilane, Vinylsilane, (Meth)acrylsilane, Isocyanatosilane, Carbamatosilane, S-(Alkylcarbonyl)-mercaptosilane und Aldiminosilane, sowie oligomere Formen dieser Silane;
• Stabilisatoren gegen Wärme, Licht- und UV-Strahlung;
• flammhemmende Substanzen;
• oberflächenaktive Substanzen wie beispielsweise Netzmittel, Verlaufsmittel, Entlüftungsmittel oder Entschäumer;
• Biozide, wie beispielsweise Algizide, Fungizide oder das Pilzwachstum hemmende Substanzen;

sowie weitere, üblicherweise in einkomponentigen Polyurethanzusammensetzungen eingesetzte Substanzen.In the moisture-curing composition may be present as further components, inter alia, the following auxiliaries and additives:

• Plasticizers, for example esters of organic carboxylic acids or their anhydrides, for example phthalates such as dioctyl phthalate and diisodecyl phthalate, adipates such as dioctyl adipate, azelates and sebacates; organic phosphoric and sulfonic acid esters and polybutenes;
• Fibers, such as polyethylene;
• Pigments, for example titanium dioxide, iron oxides or chromium compounds;
• other catalysts customary in polyurethane chemistry;
• Reactive diluents and crosslinkers, for example polyisocyanates such as MDI, PMDI, TDI, HDI, 1,12-dodecamethylene diisocyanate, cyclohexane-1,3- or 1,4-diisocyanate, IPDI, perhydro-2,4'- and -4,4'- diphenylmethane diisocyanate, 1,3- and 1,4-tetramethylxylylene diisocyanate, oligo- and polymers of these polyisocyanates, adducts of polyisocyanates with short-chain polyols, and adipic acid dihydrazide and other dihydrazides;
• other latent hardeners such as other aldimines or oxazolidines;
• Drying agents such as p-tosyl isocyanate, orthoformic acid esters, calcium oxide, vinyltrimethoxysilane, and other fast-hydrolyzing silanes such as organoalkoxysilanes which have a functional group α to the silane group, and molecular sieves;
• Adhesion promoters, in particular organoalkoxysilanes, hereinafter referred to as "silanes", for example epoxysilanes, vinylsilanes, (meth) acrylsilanes, isocyanatosilanes, carbamatosilanes, S- (alkylcarbonyl) -mercaptosilanes and aldiminosilanes, and oligomeric forms of these silanes;
• Stabilizers against heat, light and UV radiation;
• flame-retardant substances;
• surfactants such as wetting agents, leveling agents, deaerators or defoamers;
• Biocides, such as algicides, fungicides or fungal growth inhibiting substances;

and further, usually used in one-component polyurethane compositions substances.

It is advantageous to ensure that the additional ingredients do not affect storage stability. This means that during storage the reactions leading to crosslinking such as crosslinking of the Isocyanate groups must not trigger to a significant extent. In particular, this means that all these components should contain no or at most traces of water. It may be useful to dry certain components chemically or physically before mixing into the composition.

The moisture-curing composition is prepared and stored in the absence of moisture. It is storage stable, i. it may be stored in the absence of moisture in a suitable packaging or arrangement, such as a keg, bucket or bag, for a period of several months to one year and more, without being affected by its performance or properties changed after curing in a relevant for their use extent. Usually, the storage stability is determined by measuring the viscosity.

Compositions which can be used by way of example for the invention are, for example, the products Sikafloor® from Sika Schweiz AG, Zurich, Switzerland. As a small selection, mention may be made of Sikafloor® 162 and 156 as epoxy resin compositions, Sikafloor® 400 and 410 as one-component polyurethane compositions, and Sikafloor® 300 and 302 as two-component polyurethane compositions

example 1 Production of a synthetic resin floor:

A concrete substrate is prepared by grinding. Thereafter, a self-leveling mortar is applied to level out the substrate. Then a coat of Sikafloor® 156 is applied as primer and primer. After curing, a synthetic resin layer of Sikafloor® 162 applied. After a certain waiting time, but before the resin layer has hardened, Rossil Fluid 5'000'000 silicone oil is dropped. It forms a crater-like surface. After curing the synthetic resin layer Sikafloor® 162, the silicone oil is removed with a strong Alaklian cleaner. Then the surface is sealed with Sikafloor® 302. Optionally, a layer of Sikafloor® 162 can be applied again before the surface is sealed in order to level out the surface.

Example 2 Production of a synthetic resin floor:

A concrete substrate is prepared by grinding. Thereafter, if necessary, a self-leveling mortar is applied to level out the substrate. Then a coat of Sikafloor® 156 is applied as primer and primer. After curing, a synthetic resin layer of Sikafloor® 300 is applied. After a certain waiting time, but before the resin layer has hardened, Rossil Fluid 5'000'000 silicone oil is dropped. It forms a crater-like surface. After curing the synthetic resin layer Sikafloor® 300, the silicone oil is removed with a strong Alaklian cleaner. Then the surface is sealed with Sikafloor® 302.

Example 3

A synthetic resin floor is produced analogously to Examples 1 and 2, but pigments with a mother-of-pearl effect are mixed into the synthetic resin layer of Sikafloor® 162 or Sikafloor® 300 before they are processed. In addition to the crater-like surface, the pigments create a multicolored surface with optical effects.

Example 4

Analogously to Example 1 and 2 and at best Example 3, a synthetic resin soil is produced, however, that silicone oil is blown after application with pressurized air in different directions on the surface, depending on the selected blowing direction different patterns with different effects.

Example 5

Analogously to Example 1 and 2 and at best Example 3, a synthetic resin soil is prepared that silicone oil is distributed after the application with a rotating head analogous to a polishing machine, depending on the direction of rotation and exposure time different patterns with different effects, in particular circular patterns.

Example 6

Analogously to the preceding examples, a synthetic resin floor is produced, but silicone oil is also provided with pigments which partly remain in the synthetic resin floor and produce further optical effects.

Of course, the invention is not limited to the embodiments shown and described. Any synthetic resin compositions and layers can be joined together. In the resin compositions, various additives such as pigments, dyes, inserts, etc. may be added. Also in the silicone oil pigments can be added, which then at least partially remain in the synthetic resin layer. The individual layers can also be connected to each other via adhesive.

Claims (15)

Process for the preparation of a coating of a substrate, comprising: Application of a first synthetic resin, - Applying a temporary coating component on at least portions of the surface of the first resin prior to curing of the first resin, wherein the temporary coating component is not reactive, is immiscible with the first resin and at least at the time of the order has a lower specific gravity than the first resin . At least partially removing the temporary coating component after the time at which the first synthetic resin has cured at least to the extent that it retains its surface structure. Method according to claim 1,
characterized,
that the temporary coating component is liquid at room temperature. Method according to claim 1 or 2,
characterized,
that the temporary coating component is a polydimethylsiloxane (PDMS), in particular a silicone oil. Method according to one of claims 1 to 3,
characterized,
that the temporary coating component, in particular the silicone oil has a viscosity of at least 100,000 mm ² / s, preferably a viscosity in the range of or greater than 1,000,000 mm ² / s, comprising. Method according to one of the preceding claims,
characterized,
that the temporary coating component is dropped and / or poured and / or sprayed on. Method according to one of the preceding claims,
characterized,
that the applied temporary coating component by means of tools, in particular with compressed air, is distributed on the surface of the resin. Method according to one of the preceding claims,
characterized,
that the temporary coating component is removed with an alkaline detergent. Method according to one of the preceding claims,
characterized,
in that at least one further layer of a synthetic resin is applied to the first synthetic resin layer. Method according to one of the preceding claims,
characterized,
that at least one further layer of a synthetic resin, prior to the application of the first synthetic resin layer applied to the substrate and / or an adhesive layer is applied and / or the substrate pre-treated, in particular machined, is. Method according to one of the preceding claims,
characterized,
that an adhesive layer is applied between at least two synthetic resin layers. Method according to one of the preceding claims,
characterized,
that in the synthetic resin layer or the temporary coating component additives, in particular pigments or dyes are incorporated. Method according to one of the preceding claims,
characterized,
in that the synthetic resin layer or layers consist of an epoxy resin composition and / or a polyurethane resin composition and / or a polyester resin composition and / or an acrylic resin composition or a combination of these resins. Coating produced by the method according to one of claims 1 to 12 Coating according to claim 13,
characterized,
that the coating is a floor covering. Use of the coating produced by the process according to any one of claims 1 to 12 in the arts and crafts.