WO2008148870A2

WO2008148870A2 - Method for producing a coating

Info

Publication number: WO2008148870A2
Application number: PCT/EP2008/057070
Authority: WO
Inventors: Jacob Nicolaas Blokhuis
Original assignee: Sika Technology Ag
Priority date: 2007-06-06
Filing date: 2008-06-06
Publication date: 2008-12-11
Also published as: EP2000221A1; WO2008148870A3

Abstract

The invention relates to a method for producing a coating on a base. The method according to the invention comprises the following steps: applying a first synthetic resin; applying a temporary coating component to at least sections of the surface of the first synthetic resin prior to the curing of the first synthetic resin, the temporary coating component not being reactive, being immiscible with the first synthetic resin and having a lower specific weight at least at the time of application than the first synthetic resin; at least partially removing the temporary coating component after the time at which the first synthetic resin is at least cured to such an extent that it maintains its surface structure.

Description

Process for the preparation of a coating

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 GB 1 237 252 coatings with colored inserts are 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 Beschichtungsmatehal and thus 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.

The core of the invention thus comprises the following steps:

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.

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 in the following 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 temporary coating components, silicone oils, having a relatively high viscosity, ie a viscosity higher than 100'0OO cSt, ie 100O00 mm ² / s. Particularly preferred is as a temporary Coating component Rossil Fluid 5 10OOOOO, with a viscosity in the range of 10OOOOO cSt, ie 10OOOOO 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

Be dropped coating component, poured, sprayed, etc. are. 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 pearlescent effect, phosphorescent pigments, for example "Glow in the Dark" from Glow Inc., etc. In addition, any further additives can be used to produce effects and / or the 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, for example, from the time that is referred to in the technical data sheets or the Synthetic resin layer is reworkable, for example, after 18 hours at 20 ⁰ C curing temperature for Sikafloor® 162. The removal of the temporary component can be done in different ways, but preferably with an alkaline cleaning agent Optionally, then the resin layer with further layers

Synthetic resin are coated, in particular by 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, i. they can be ground at room temperature to give pourable powders.

Preferred solid epoxy resins have the formula (X)

(X)

Here, the substituents R 'and R "are independently of one another either H or CH _3. Furthermore, the subscript s stands for 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, preferred are epoxy resins in the narrower sense, i. where the index s one

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.

It is 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 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 D.E.R. ™ 331 or D.E.R. ™ 330 (Dow) or Epikote 828 (Hexion).

Preferably, the epoxy resin A is an epoxy liquid resin of the formula (XI). In a still more preferred embodiment, the

Epoxy resin composition both at least one epoxy liquid resin of the formula (Xl) 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.

Component K1 additionally preferably contains at least one reactive diluent G carrying epoxide groups. 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, octanediolglycidyl ether, cyclohexanedimethanol diglycidyl ether, neopentylglycol diglycidyl ether, 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, nonylphenol 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 ethers, polypropyleneglycol diglycidyl ethers, 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 total 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 - 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-diamino-cyclohexane, bis (4-aminocyclohexyl) -methane, bis (4-amino-3-methylcyclohexyl) -methane, bis (4-amino-3-methylcyclohexyl) -methane amino-3-ethylcyclohexyl) -methane, 2-

Methylpentamethylenediamine, bis (4-amino-3,5-dimethylcyclohexyl) methane, 1-amino-3-aminomethyl-3,5,5-thmethylcyclohexane (= isophoronediamine or IPDA), 2- and 4-methyl-1,3 -diaminocyclohexane and mixtures thereof, 1, 3 and 1, 4-bis (aminomethyl) cyclohexane, 1-cyclohexylamino-3-anninopropane, 2,5 (2,6) -bis (aminonnethyl) bicyclo [2.2.1] heptane (NBDA, manufactured by Mitsui Chemicals), 3 (4), 8 (9) -bis (aminomethyl) -thcyclo [5.2.1.0 ^{2 6} ] decane, 1, 4-diamino-2,2,6-trimethylcyclohexane (TMCDA ), 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro [5.5] undecane, piperazine, 1- (2-aminoethyl) piperazine, 1, 3- and 1, 4- xylylenediamine;

divalent or polyvalent aliphatic amines which contain 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 1000000 g / mol), as described, for example, in US Pat Trade name Lupasol ^® from BASF in pure

Form or as aqueous solutions are available, 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 with 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 thamins are sold, for example, under the Jeffamine® T-Line by Huntsman Chemicals, such as Jeffamine® T-3000, Jeffamine® T-5000 or Jeffamine® T-403. Preferred diamines are polyoxyalkylene polyamine having two amino groups and those 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 offered by the D-line and ED line of Huntsman Chemicals, for example 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.

Dimercaptans are particularly preferred as polymercaptan.

Suitable polymercaptans are, for example, polymercaptocetates of polyols. These are, in particular, polymercaptocetates of the following polyols:

Polyoxyalkylene polyols, also called polyether polyols, which are the polymerization product of ethylene oxide, 1, 2-propylene oxide, 1, 2 or 2,3-

Butylene oxide, tetrahydrofuran or mixtures thereof, optionally polymehsiert using a starter molecule having two or three active H atoms such as water or compounds having two or three OH groups. Both polyoxyalkylene polyols can be used which have a low degree of unsaturation (measured after

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 for short). 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 Dalton, polyoxybutylenediols and -triols, polyoxypropylene diols and triols having a molecular weight of 400-8'00 O daltons, and so-called "ethylene oxide-endcapped" polyoxypropylene diols or triols, the latter being special polyoxypropylene polyoxyethylene polyols, obtained, for example, by being pure

Polyoxypropylenpolyole be alkoxylated after completion of the polypropoxylation with ethylene oxide and thereby having primary hydroxyl groups.

Hydroxy-terminated polybutadiene polyols, such as those obtained by polymerization of 1,3-butadiene and allyl alcohol or by

Oxidation of polybutadiene are prepared, and their hydrogenation products;

Styrene-acrylonitrile grafted polyether polyols, such as those supplied by Elastogran under the name Lupranol®; - Polyesterpolyols, prepared for example from di- to trivalent

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 -Tπmethylolpropan or mixtures of the aforementioned alcohols with organic dicarboxylic acids or their anhydrides or esters such as succinic acid, glutaric acid,

Adipic acid, suberic acid, sebacic acid, dodecanedicarboxylic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid and hexahydrophthalic acid or mixtures of the abovementioned acids, as well as polyester polyols of lactones such as ε-caprolactone; Polycarbonate polyols as obtainable by reacting, for example, 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-hepandiol, 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-hydroxynethyl-propane-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-hydroxymethyl-butoxy) -2-ethyl-2-hydroxymethyl-propan-1-ol), di (trimethylolethane) (= 3- (3-hydroxy-2-hydroxymethyl- 2-methylpropoxy) -2-hydroxyethyl-2-methylpropane-1-ol),

Diglycerin (= bis (2,3-dihydroxypropyl) ether);

- Polyols, as they are contained by reduction of dimehsierten fatty acids.

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

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 KV 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. These

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.

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

Polyoxyalkylene polyols, also called polyether polyols or oligoetherols, which are polymerization products of ethylene oxide, 1, 2

Propylene oxide, 1, 2- or 2,3-butylene oxide, tetrahydrofuran or mixtures thereof are, possibly polymerized using a starter molecule having two or more active hydrogen atoms such as water, ammonia or compounds having multiple OH or NH groups such as 1, 2-ethanediol, 1, 2- and 1, 3-propanediol, neopentyl glycol, diethylene glycol, ethylene 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, glycerol, 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 of 400-8000 g / mol.

Also particularly suitable are polytetrahydrofurans due to their good

Light stability.

Also particularly suitable are so-called ethylene oxide-terminated

(EO-endcapped) polyoxypropylene polyols, the latter being 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, glycehn, 1,1,1-methylolpropane or mixtures of the abovementioned alcohols with organic dicarboxylic acids or their anhydrides or esters such as succinic acid, glutaric acid, adipic acid, suberic acid, sebacic acid, dodecanedicarboxylic acid, maleic acid, fumaric acid, phthalic acid , Isophthalic acid, terephthalic acid and hexahydrophthalic acid or mixtures of the abovementioned acids, as well as polyester polyols from lactones such as ε-caprolactone.

Polycarbonate polyols as obtainable by reacting, for example, the abovementioned alcohols used to form the polyesterpolyols with dialkyl carbonates, diaryl carbonates or phosgene.

Polyacrylate and polymethacrylate polyols.

Polyhydrocarbyl polyols, also called oligohydrocarbonols, such as, for example, polyhydroxy-functional ethylene-propylene, ethylene-butylene or ethylene-propylene-diene copolymers, for example as produced by 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 polyols, such as, for example, which are prepared by copolymerization of 1, 3-butadiene and allyl alcohol and may 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 250-1200 g / mol, in particular of 400-800 mol / g, and an average OH functionality in the range of 1.7-3.

In addition to these mentioned polyols may be 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-Thmethylolpropan, glycerol, pentaerythritol, sugar alcohols such as XyNt, sorbitol or mannitol, sugars such as sucrose, other higher alcohols, low molecular weight alkoxylation of the aforementioned di- and polyhydric alcohols, and mixtures of the aforementioned alcohols in the preparation of a polyurethane polymer P be used. Similarly, small amounts of polyols having an average OH functionality of more than 3 may be included, for example, sugar polyols. Commercially available aliphatic, cycloaliphatic or aromatic polyisocyanates, in particular diisocyanates, can be used as polyisocyanates for the preparation of a polyurethane polymer P, 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 diisocyanate, cyclohexane-1, 3- and -1, 4-diisocyanate and any mixtures of these isomers, 1 -lsocyanato-3,3,5-thmethyl-5-isocyanatomethyl-cyclohexane (= isophorone diisocyanate or IPDI), perhydro-2,4'- and -4,4'-diphenylmethanediisocyanate (HMDI), 1, 4-diisocyanato-2,2,6-thmethylcyclohexane (TMCDI), 1, 3 and 1, 4 Bis- (isocyanatomethyl) -cyclohexane, m- and p-xylylene diisocyanate (m- and p-XDI), m- u 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 desired mixtures of the aforementioned isocyanates For formulating light-stable coatings, aliphatic diisocyanates are preferred, in particular HDI and IPDI Preferred aromatic diisocyanates 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 sen 20 Pa-s, preferably at most 15 Pa-s, denoted at 20 ⁰ 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, i-isocyanato-SSδ-trimethyl-δ-isocyanatomethyl cyclohexane (= isophorone diisocyanate or IPDI), perhydro-2,4'- and -4,4'-di-phenylmethane diisocyanate (HMDI), 1, 4-diisocyanato-2,2,6-thmethylcyclohexane (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 ^® T1890 / 100 as Vestanat ^® (Bayer) or in solid form (Degussa).

Preference is given to the trimers of HDI and / or IPDI, in particular the isocyanurates. A technical oligomer mixture of aromatic diisocyanates TDI isocyanurate is, for example, available 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. Xylene, toluene, white spirit and mineral oil fractions boiling in the range of 100 ⁰ C to 200 ⁰ C., are preferred

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 Silica 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, and flame retardant fillers such as hydrates or hydroxides, especially 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, common in polyurethane chemistry, catalysts 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.

In the moisture-curing composition can be as more

Components including the following auxiliaries and additives may be present:

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 customary in polyurethane chemistry catalysts;

Reactive diluents and crosslinkers, for example polyisocyanates such as MDI, PMDI, TDI, HDI, 1,1-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, for example, p-tosyl isocyanate, ortho-formic acid esters, calcium oxide, vinyltrimethoxysilane and other rapidly hydrolyzing silanes, for example organoalkoxysilanes which have a functional group in the α-position 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;

- Surface-active substances 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 means of 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 curing of the resin layer, silicone oil Rossil Fluid 5 10OOOOO 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 curing of the resin layer, silicone oil Rossil Fluid 5 10OOOOO 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 e

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

claims

A method of making a coating of a substrate comprising:

Application of a first synthetic resin; application of a temporary coating component to at least portions of the surface of the first synthetic resin prior to curing of the first synthetic resin, wherein the temporary coating component is unreactive, immiscible with the first synthetic resin and has a lower specificity at least at the time of application Having weight as the first synthetic resin,

2. The method according to claim 1, characterized in that the temporary coating component is liquid at room temperature.

3. The method according to claim 1 or 2, characterized in that the temporary coating component is a polydimethylsiloxane (PDMS), in particular a silicone oil.

4. The method according to any one of claims 1 to 3, characterized the temporary coating component, in particular the silicone oil, has a viscosity of at least 100 000 mm ² / s, preferably viscosity in the range of or greater than 10 000 000 mm ² / s.

5. The method according to any one of the preceding claims, characterized in that the temporary coating component is dropped and / or poured and / or sprayed.

6. The method according to any one of the preceding claims, characterized in that the applied temporary coating component by means of

Aids, in particular with compressed air, on the surface of the

Resin is distributed.

7. The method according to any one of the preceding claims, characterized in that the temporary coating component is removed with an alkaline cleaning agent.

8. The method according to any 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.

9. The method according to any one of the preceding claims, characterized in that prior to the application of the first synthetic resin layer at least one further layer of a synthetic resin is applied to the substrate and / or an adhesive layer is applied and / or the substrate pretreated, in particular mechanically processed, is.

10. The method according to any one of the preceding claims, characterized in that an adhesive layer is applied between at least two synthetic resin layers.

11. The method according to any one of the preceding claims, characterized in that in the synthetic resin layer or the temporary coating component additives, in particular pigments or dyes are incorporated.

12. The method according to any one of the preceding claims, characterized in that the synthetic resin layer or the synthetic resin layers 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.

13. Coating produced by the method according to one of claims 1 to 12

14. Coating according to claim 13, characterized in that the coating is a floor covering.

15. Use of the coating produced by the method according to any one of claims 1 to 12 in the arts and crafts.