Aqueous composition for coatings

FIELD: chemistry.

SUBSTANCE: aqueous composition for coatings has a rapid curing mechanism and allows cross-linking of poorly illuminated areas, the composition comprising (I) at least one polyisocyanate (A), (II) at least one polyurethane (B) containing from 0 to 0.53 mmole/g of active, according to Tserevitinov, hydrogen atoms and being a product of reaction of: (a) one or several polyisocyanates, (b1) one or more compounds with hydrophilising action having ion groups and/or groups transferable to ion groups, and/or non-ionic groups, (b2) one or more compounds capable of radical polymerisation and including unsaturated acrylate or methacrylate groups, (b3) if necessary, one or more polyols with an average molecular weight of 50-500 and a hydroxyl functionality more than or equal to 2 and less than or equal to 3, (b4) if necessary, one or more polyols with an average molecular weight of 500 to 13,000 g/mole and an average hydroxyl functionality of 1.5 to 2.5, and (b5) if necessary, one or more di- or polyamines, and (III) an initiator (C).

EFFECT: capable to cross-link poorly illuminated areas and to cause radical polymerisation.

8 cl, 15 ex, 8 tbl

 

The invention relates to compositions for coatings, and more particularly to aqueous composition for coating.

Known aqueous one-component formulations for coatings containing binder with active hydrogen atoms, and a curing agent, structuring and hardening which occurs due to thermal activation. However, the disadvantage of such systems is that the cure is slow and requires high temperatures.

Also known aqueous formulations for coatings, which otverzhdajutsja physical way, i.e. the curing of the layer is due to the film formation. Usually in such systems are not used cross-linking agents. Natural cures can promote chemical structuring with the help of oxygen.

Much faster otverzhdajutsja coatings based on polyurethane dispersions capable of curing under the action of radiation, i.e. capable of containing polymerization group. Such dispersions are described, for example, in EP-A 0942022. Here the disadvantage is that capable of curing under the action of radiation coverage only fully otverzhdajutsja when they are exposed to, for example, UV radiation with a certain dose and intensity. If you want to apply coating on objects with complex geometry, for example, in the shadow zone to obtain coatings with high pairs is investment destinations chemical and physical stability is problematic.

In WO-A 00/59978 described curable thermally and/or with actinic radiation aqueous composition for coating in which the binder contains a polyurethane with the active hydrogen atoms on the basis of bis-(4-isocyanato-cyclohexyl)methane content of TRANS/TRANS-patterns to 30 wt.% based on the diisocyanate and at least one crosslinking agent. Unsaturated groups introduced by this lateral or terminal in polyurethane with low molecular weight, reactive to isocyanate compounds, such as trimethylolpropane. The disadvantage to this is the use of Monomeric unsaturated structural units, which, being monofunctional structural units, limit the molecular weight of the polyurethane, but as pure difunctional substances, for example, trimethylolpropane, very expensive.

In EP-A 0952170 describes an aqueous composition for coating, which contains a urethane(meth)acrylate with the free NCO-groups, photoinitiator binder and water with one or more active hydrogen atoms. Curing this system includes the stitching due to the reaction of isocyanate groups with active hydrogen atoms and ultraviolette curing through the urethane(meth)acrylate. Here the disadvantage is the low reactivity to UV radiation due to the low density is Voynich links, and the worst physical drying before UV-curing due to the low molecular weight urethane(meth)acrylate.

The objective of the invention is the development of UV curable by radiation polyurethane aqueous composition for coating, which has a mechanism for fast curing and allows you to properly sew areas that are poorly lit.

The problem is solved by the proposed water composition for coatings containing

(I) at least one polyisocyanate (A),

(II) at least one polyurethane (B), with the contents of the groups having active Servicenow hydrogen atoms, from 0 to 0.53 mmol/g and which is the reaction product of:

(a) one or more polyisocyanates,

(B1) one or more compounds with gidrofiliziruyuschim, with ionic groups and/or groups capable of translation into ionic groups and/or nonionic groups,

(B2) one or more compounds capable of radical polymerization containing unsaturated acrylate or methacrylate group,

(B3) optionally, one or more polyols with an average molecular weight of 50-500 and a hydroxyl functionality greater than or equal to 2 and less than or equal to 3,

(B4) optionally, one or more polyols with an average molecular weight from 500 up to 13,000 g/mol and with Edna hydroxyl functionality of from 1.5 to 2.5 and

(B5) optionally, one or more di - or polyamines, and (III) the initiator (In)capable of causing radical polymerization.

In the sense of the present invention groups with active Servicenow hydrogen atoms are hydroxyl groups, primary and secondary amino groups and tirinya group.

The polyisocyanate (A) composition for coatings according to this invention can be used in the form of non-blocked MDI (A') or blocked MDI (A").

According to this invention the polyurethanes can be in the form of aqueous dispersions, emulsions or solutions which are obtained by the polyaddition reaction of polyisocyanates [component (a)] and the above-mentioned compounds reactive to isocyanates [components (B1)to(B5)].

Suitable polyisocyanates (a) are aromatic, analiticheskie, aliphatic or cycloaliphatic polyisocyanates. Can also be used mixtures of such polyisocyanates. Examples of suitable polyisocyanates are butylanisole, hexamethylenediisocyanate (HDI), isophoronediisocyanate (IPDI), 2,2,4 and/or 2,4,4-trimethylhexamethylenediamine, the isomeric bis(4,4'-isocyanatophenyl) methanes or mixtures thereof with any content of isomers, isocyanatomethyl-1,8-octadienal, 1,4-cyclohexa-levitational, 1,4-phenylene-diisocyanate, 2,4 - and/or the 2,6-toluylenediisocyanate, 1,5-naphthylenediisocyanate, 2,4'- or 4,4'-diphenylmethanediisocyanate, triphenylmethane-4,4',4"-triisocyanate or their derivatives with urethane, which, allophanate, biuret, uretdione, iminoimidazolidine structure, or a mixture thereof. Preferred are hexamethylenediisocyanate, isophoronediisocyanate and the isomeric bis(4,4'-isocyanatophenyl)methane, and mixtures thereof.

Component (B1) contains ionic groups, which can be either cationic or anionic nature, and/or nonionic hydrophilic groups. Cationic, anionic or a nonionic dispersing agents are such compounds that contain, for example, sulfonate, ammonium, postname, carboxylate, sulphonate, phosphonate groups or groups capable through the scale to move in the above group (potentially ionic groups), or the group of ethers, and due to the available reactive to isocyanate groups can be introduced into the molecule.

Preferred groups reactive toward isocyanates, are a hydroxyl group and an amino group.

Suitable ionic or potentially ionic compounds (B1) are mono - and dihydroxycinnamate acid, mono - and diaminocarbenes acid, mono - and dihydroxyanthraquinone, mono - and diaminoalkylene, and mono - and dihydroxyacetone to the slots or mono - and diaminooctane acids and their salts, such as dimethylolpropionic acid, dimethylaniline acid, hydroxypivalic acid, N-(2-amino-ethyl)-β-alanine, 2-(2-amino-ethylamino)-econsultation, ethylendiamine or butylsulfonyl, 1,2 - or 1,3-Propylenediamine-β-ethylsulfonyl, malic, citric, glycolic, lactic acid, glycine, alanine, taurine, lysine, 3,5-diamino-benzoic acid, the product of the interaction of isophorondiisocyanate (IPDI) and acrylic acid (EP-A 0916647, example 1) and its alkali and/or ammonium salt of the adduct of sodium bisulfite and butene-2-diol-1,4, simple polyethersulfone, propoxycarbonyl adduct 2-butandiol and NaHSO3for example, described in DE-A 2446440 (p.5-9, formula I-III), and can pass into cationic groups of the structural units, such as N-methyldiethanolamine as hydrophilic structural components. Preferred ionic or potentially ionic compounds are those which have a carboxyl or carboxylate and/or sulphonate groups and/or ammonium groups. Particularly preferred ionic compounds are those which contain as ionic or potentially ionic groups, carboxyl and/or sulphonate groups, such as the salts of N-(2-amino-ethyl)-β-alanine, 2-(2-amino-ethylamino)econsultancy or product of the interaction of isophorone-socyanate and acrylic acid (EP-A 0916647, example 1), and dimethylolpropionic acid.

Suitable non-ionic compounds with gidrofiliziruyuschim action are simple polyoxyalkylene esters, which contain at least one hydroxyl group, or amino group. These polyesters contain from 30 to 100 wt.% ethylenoxide structural links. Suitable polyethers of linear structure with the functionality of from 1 to 3, but also compounds of General formula (I),

in which

R1and R2independently from each other represent a divalent aliphatic, cycloaliphatic or aromatic residue with the number of carbon atoms from 1 to 18, which may be interrupted by oxygen atoms and/or nitrogen and

R3represents polietilenoksidnoy balance ending CNS group.

Non-ionic compounds with gidrofiliziruyuschim action are, for example, also monohydroxy polyalkyleneglycol with average 5-70, preferably 7-55 ethyleneoxide units in the molecule, which is obtained from the appropriate starting compounds in a known manner alkoxysilane (for example, described in Ullmanns Encyclopaedic der technischen Chemie, 4th edition, publisher Chemie, Weinheim, t, p.31-38).

Suitable source substances, for example, are saturated monosperma, such kaklamanos, ethanol, n-propanol, ISO-propanol, n-, ISO - and sec.-butanol, isomeric pentanol, hexanol, octanol and nonanol, n-decanol, n-dodecanol, n-tetradecanol, n-hexadecanol, n-octadecanol, cyclohexanol, the isomeric methylcyclohexanols or hydroxymethylcellulose, 3-ethyl-3-hydroxyethyloxy or tetrahydrofurfuryl alcohol, monoalkyl ethers of diethylene glycol such as, for example, monobutyl ether of diethylene glycol, unsaturated alcohols such as allyl alcohol, 1,1-dimethylallyl alcohol or oleic alcohol, aromatic alcohols such as phenol, the isomeric Cresols and methoxyphenol, analiticheskie alcohols such as benzyl alcohol, anise alcohol or cinnamic alcohol, secondary monoamines such as dimethylamine, diethylamine, dipropylamine, Diisopropylamine, dibutylamine, bis(2-ethylhexyl)-amine, N-methyl and N-ethyl-cyclohexylamine or dicyclohexylamine, and also heterocyclic secondary amines such as morpholine, pyrrolidine, piperidine or 1H-pyrazole. Preferred parent compounds are saturated monosperma. It is most preferable as a source of compounds used monobutyl ether of ethylene glycol.

Suitable for reaction alkoxysilane acceleratedly are, in particular, ethylene oxide and propylene oxide, which can be used in the reaction alkoxysilane the I in any sequence or in a mixture.

In the case of polyalkyleneglycol we are talking either about the individual polyethylenepolyamine, or mixtures polyalkyloxy-polyesters, polyalkylbenzene links which not less than 30 mol.%, preferably not less than 40 mol.%, consist of ethylenoxide links. Preferred nonionic compounds are monofunctional mixed simple polyalkyleneglycols that have at least 40 mol.% ethyleneoxide units and not more than 60 mol.% propylenoxide links.

Component (B1) is preferably a combination of nonionic and ionic compounds with gidrofiliziruyuschim action. Particularly preferred combinations of nonionic and anionic compounds with gidrofiliziruyuschim action.

Component (B2) is a compound capable of radical polymerization containing unsaturated acrylate or methylacrylate group. Examples are 2-hydroxyethyl(meth)acrylate, polyethylene oxide mono(meth)acrylates, polypropyleneoxide-mono(meth)acrylates, polyalkylene-mono(meth)acrylates, poly(ε-caprolactone)mono(meth)acrylates, such as, for example, Tone® M100 (Union Carbide, USA), 2-hydroxypropyl(meth)acrylate, 4-hydroxybutyl(meth)acrylate, 3-hydroxy-2,2-dimethylpropyl(meth)acrylate, mono-, di or tetraacrylate polyhydric alcohols, such as trimethylolpropane, gli is Erin, the pentaerythritol, dipentaerythritol, ethoxylated, propoxycarbonyl or alkoxycarbonyl trimethylolpropane, glycerin, pentaerythritol, dipentaerythritol or their technical mixtures. Preferred acrylates of monospitovo. Suitable alcohols which can be obtained by the interaction containing the double bond of the acid monomer, epoksidnymi compounds, containing, if necessary, double bonds, such as, for example, the products of the interaction of (meth)acrylic acid with glycidyl(meth)acrylate or glycidyloxy ether versatool acid.

Then we can use reactive to isocyanates oligomeric or polymeric compounds containing unsaturated acrylate or methacrylate groups, one at a time or in combination with the above-mentioned Monomeric compounds. Preferably as component (B2) used complex preferability having a hydroxyl group, with a hydroxyl number of from 30 to 300 mg KOH/g, preferably from 60 to 200, most preferably from 70 to 120. Upon receipt complex poliefirakrilaty with hydroxyl groups in total can be used with 7 groups of Monomeric components:

1. (Cyclo)arcangioli, such as (cyclo)aliphatic diatomic alcohols with a molecular weight in the range from 62 to 286, for example, ethanediol, 1,2 - and 1,3-propandiol, 1,2-, 1,3 - and 1,4-buta is diols, 1,5-pentanediol, 1,6-hexanediol, neopentylglycol, cyclohexane-1,4-dimethanol, 1,2 - and 1,4-cyclohexanediol, 2-ethyl-2-buypropecia, diols containing oxygen simple ether, such as diethylene glycol, triethylene glycol, tetraethylene glycol, dipropyleneglycol, tripropyleneglycol, polyethylene-, polypropylene - or polietilenglikoli with a molecular weight of from 200 to 4000, preferably from 300 to 2000, most preferably from 450 to 1200. The reaction products of the above mentioned diols with ε-caprolactone or other lactones may also be used as diols.

2. Triatomic and polyatomic alcohols with a molecular weight in the range from 92 to 254, such as, for example, glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol and sorbitol or derived from these alcohols, polyethers, such as, for example, the reaction product of 1 mole of trimethylolpropane with 4 moles of ethylene oxide.

3. Monosperma, such as, for example, ethanol, 1-and 2-propanol, 1-and 2-butanol, 1-hexanol, 2-ethylhexanol, cyclohexanol and benzyl alcohol.

4. Dicarboxylic acid with a molecular weight in the range from 104 to 600, and/or their anhydrides, such as phthalic acid, phthalic anhydride, isophthalic acid, tetrahydrophtalic acid, anhydride tetrahydrophthalic acid, hexahydrophthalic acid, anhydride hexahydrophthalic acid, College santarpana acid, the anhydride of maleic acid, fumaric acid, malonic acid, succinic acid, succinic acid anhydride, glutaric, adipic, Emelyanova, cortical, sabotinova, decanedicarbonitrile acid, hydrogenated dimer fatty acid.

5. Multifunctional carboxylic acids and their anhydrides, such as, for example, trimellitate acid and its anhydride.

6. Monocarboxylic acids, such as, for example, benzoic, cyclohexanecarbonyl, 2-ethylhexanoate, Caproic, Caprylic, capric, lauric acid, natural and synthetic fatty acids.

7. Acrylic, methacrylic acid or dimeric acrylic acid.

Suitable complex preferability having hydroxyl groups, contain the product of the interaction of at least one component from group 1 or 2 with at least one component from a group of 4 or 5 and at least one component from group 7.

If necessary, in these difficult preferability can be integrated also known dispersing groups. So, as an alcohol component together can be applied as a percentage of the glycols and/or methoxypolyethyleneglycol. As compounds would, for example, to name derived from alcohols, glycols, polypropylenglycol and their block copolymers, as well as monomethylamine rostie esters of these polyglycols. Particularly suitable onomatology simple ether of polyethylene glycol-1500 and onomatology simple ether of polyethylene glycol-500.

Further, the esterification is possible to substitute a part of the carboxyl groups, in particular carboxyl group of (meth)acrylic acid mono-, di - or polyepoxide. Preferred are, for example, epoxides (simple glycidyloxy esters) of Monomeric, oligomeric or polymeric bisphenol-A, bisphenol-F, hexanediol and/or butanediol or their ethoxylated and/or propoxycarbonyl derivatives. This reaction can be used, in particular, to increase the hydroxyl number of complex, polyester(meth)acrylate, since the reaction of the epoxide with an acid is formed, respectively, one Oh-group. Acid number of the resulting product is in the range from 0 to 20 mg KOH/g, preferably from 0 to 10 mg KOH/g and most preferably from 0 to 5 mg KOH/g, the Reaction is preferably catalyzed by such catalysts as triphenylphosphine, thiodiglycol, halides of ammonium and/or phosphonium and/or compounds of zirconium or tin, for example, ethylhexanoates tin (II).

Obtaining complex poliefirakrilaty described in DE-A 4040290 (page 3, line 25 to page 6, line 24), DE-A 3316592 (page 5, line 14 to page 11, line 30) and the monograph RCT Oldring (Ed.), Chemistry &Technology of UV &EB Formulations For Coatings, Inks &Paints, 1991, Vol.2, SITA Technology, London, p.123-135.

Also the quality is as component (B2) is preferred containing hydroxyl group of the epoxy(meth)acrylate with a hydroxyl number of from 20 to 300 mg KOH/g, preferably from 100 to 280 mg KOH/g, most preferably from 150 to 250 mg KOH/g or containing hydroxyl groups of the polyurethane(meth)acrylate with a hydroxyl number of from 20 to 300 mg KOH/g, preferably from 40 to 150 mg KOH/g, most preferably from 50 to 100 mg KOH/g, and mixtures thereof with each other and the mixture containing the hydroxyl group of the unsaturated complex polyesters, and mixtures with complex polyester(meth)acrylates or mixtures containing hydroxyl groups, unsaturated polyesters with complex polyester(meth)acrylates. Such compounds are also described in the monograph RCT Oldring (Ed.), Chemistry &Technology of UV &EB Formulations For Coatings, Inks &Paints, 1991, Vol.2, SITA Technology, London, pp.37-56. Epoxy(meth)acrylate with hydroxyl groups are, in particular, on the interaction products of acrylic and/or methacrylic acid with epoxides (glycidyloxy compounds) of Monomeric, oligomeric or polymeric bisphenol-A, bisphenol-F, hexanediol and/or butanediol or their ethoxylated and/or propoxycarbonyl derivatives.

Suitable low molecular weight polyhydric alcohols (B3) are short-chained, i.e. containing 2 to 20 carbon atoms, aliphatic, analiticheskie or cycloaliphatic diols and triodes. Examples of diols are ethylene glycol, diethylene glycol, triethylene glycol, tetraethyleneglycol is, dipropyleneglycol, tripropyleneglycol, 1,2-propandiol, 1,3-propandiol, 1,4-butanediol, neopentylglycol, 2-ethyl-2-buypropecia, trimethylpentanediol, isomers position diethylacetanilide, 1,3-butyleneglycol, cyclohexanediol, 1,4-cyclohexanedimethanol, 1,6-hexanediol, 1,2 - or 1,4-cyclohexanediol, hydrogenated bisphenol a (2,2-bis(4-hydroxycyclohexyl)propane), 2,2-dimethyl-Z-hydroxy-propyl ether of 2,2-dimethyl-3-hydroxypropionic acid. Predpochtitelnye are 1,4-butanediol, 1,4-cyclohexanedimethanol and 1,6-hexanediol. Examples of suitable triolo are trimethylated, trimethylolpropane or glycerol, preferred trimethylolpropane.

Suitable high molecular weight polyhydric alcohols (B4) are diols and polyols with molecular weights in the range from 500 to 13,000 g/mol, preferably from 700 to 4000 g/mol. Preferred are polymers with an average hydroxyl functionality of from 1.5 to 2.5, preferably from 1.8 to 2.2, most preferably from 1.9 to 2.1. These include, for example, a complex politicalparty based on aliphatic, cycloaliphatic and/or aromatic di-, tri - and/or polycarboxylic acids and di-, tri - and polyols, as well as complex politicalparty on the basis of lactones. Preferred complex politicalparty are the products of interaction of adipic acid with hexandiol, b is landiolol or neopentylglycol or with mixtures of these diols with a molecular weight of from 500 to 4000, particularly preferred diols with a molecular weight of from 800 to 2500. Also suitable simple politicalparty, which is obtained by polymerization of cyclic ethers or by the interaction of alkalisation the parent compound. For example, should be called polyethylene or polypropyleneglycol with an average molecular weight from 500 to 13.000, then, polytetrahydrofuran with an average molecular weight of from 500 to 8000, preferably from 800 to 3000. Also suitable polycarbonates having terminal hydroxyl that obtained by the interaction of the diols or lactone-modified diols or bisphenols, such as, for example, bisphenol a, with phosgene or a complex diesters of carbonic acid, such as diphenylcarbonate or dimethylcarbonate. As an example, should be called polymeric carbonates 1,6-hexandiol with an average molecular weight of from 500 to 8000, and carbonates of products of interaction of 1,6-hexandiol with ε-caprolactone in a molar ratio of 1 to 0.1. Preferred to the above-mentioned polycarbonatediol with an average molecular weight of from 800 to 3000 based on 1,6-hexanediol and/or carbonates of products of interaction of 1,6-hexandiol with ε-caprolactone in a molar ratio from 1 to 0.33. Can also be used polyamidimide with terminal hydroxyl and polyacrilamide with terminal hydroxyl, e.g. the, Tegomer® BD 1000 (firm Tego GmbH, Essen, Germany).

Components (B5) selected from the group of di - and/or polyamines, which are used to increase the molar mass and added preferably at the end of the polyaddition reaction. This reaction preferably occurs in the aquatic environment. Then di - and/or polyamine should be more reactive to isocyanate groups of the component (a)than water. As an example include Ethylenediamine, 1,3-Propylenediamine, 1,6-hexamethylene-diamine, ISOPHORONEDIAMINE, 1,3 - and 1,4-phenylenediamine, 4,4'-diphenylmethylene, oxides or polypropyleneoxide with amino groups, which are commercially available under the name Jeffamin®, D-series (firm Hustmann Corp. Europe, Belgium), Diethylenetriamine and hydrazine. The preferred ISOPHORONEDIAMINE, Ethylenediamine, 1,6-hexamethylenediamine were. Particularly preferred Ethylenediamine.

As a percentage can also be added monoamines such as butylamine, ethylamine and amines Jeffamin®M-series (firm Hustmann Corp. Europe, Belgium), oxides and polypropyleneoxide with amino groups.

Obtaining an aqueous polyurethane (B) may be carried out in one or in several stages in a homogeneous phase or multi-phase reaction partly dispersed phase. After a full polyaddition or partially held polyaddition stage is dispersed through the project, emulsification or dissolution. In conclusion, if needed, is additional polyprionidae or modification in the dispersed phase.

To obtain the polyurethane (B) may apply all known methods such as a method of obtaining polyurethanes in emulsion using a high shear forces, the acetone method, a way of getting through the prepolymers way to melt emulsification, kamiminami way and the way of spontaneous dispersion of solids or derived from these methods. An overview of these methods is available in the book "Methods der organischen Chemie" (Houben-Weyl, supplementary volumes to the 4th edition, the, 1987, str-1682, H.Bartl and J.Falbe, Stuttgart, new York, published by Tieme). The preferred method of emulsification of the melt and the acetone method. Especially preferred acetone method.

Usually the components (B1)to(B5), which do not contain primary or secondary amino groups, and the polyisocyanate (a) is wholly or partly placed in the reactor for the production of polyurethane prepolymer and, if necessary, dilute miscible with water, but inertnet towards isocyanate groups, solvent, but preferably without solvent, is heated to temperatures preferably in the range from 50 to 120°C.

Suitable solvents are acetone, butanone, tetrahydrofuran, dioxane, acetone is home to the thrill, dimethyl ether of dipropyleneglycol and 1-methyl-2-pyrrolidone, which can be added not only at the beginning of the reception, but if you need parts or later. Preferred acetone and butanone. It is possible to conduct the reaction at normal or elevated pressure, for example, above the boiling temperature at normal pressure used, if necessary, a solvent such as acetone.

Further, to accelerate the reactions of addition of the isocyanate immediately or can be added later known catalysts, such as, for example, triethylamine, 1,4-diazabicyclo-[2,2,2]-octane, diktat tin or dibutyltindilaurate. The preferred dibutyltindilaurate.

Then add not added to the beginning of the reaction components (a) and/or (B1)-(B4), which do not have a primary or secondary amino groups. Upon receipt of the polyurethane prepolymers, the ratio of isocyanate groups to groups reactive toward isocyanates is from 0.90-3, preferably from 0.95 to 2, most preferably of 1.05 to 1.5. The interaction of components (a) and (b) is partially or completely based on the total number of reactive toward isocyanate groups used of the component (b)having no primary or secondary amino groups, but preferably completely. For the degree of interaction usually follow along maintained the Yu in the reaction medium NCO-groups. This can be done as IR-spectroscopic measurements and the determination of the refractive index, and perform chemical tests, such as the titration of samples. Polyurethane prepolymers which contain free isocyanate groups are obtained in the form of a substance or in solution.

After receipt or at the time of receipt of the polyurethane prepolymers (a) and (b) occurs, if it has not yet been implemented in the original substances, partial or complete salt formation of anionic and/or cationic hydrophilic groups, contributing to the dispersion. In the case of anionic groups are used bases, such as ammonia, carbonate or bicarbonate of ammonium, trimethylamine, triethylamine, tributylamine, diisopropylethylamine, dimethylethanolamine, diethylethanolamine, triethanolamine, potassium hydroxide or sodium carbonate, the preferred triethylamine, triethanolamine, dimethylethanolamine or diisopropylethylamine. The amount used shall be from 50 to 100%, preferably from 60 to 90%, the number of anionic groups. In the case of cationic groups are dimethyl ether sulfuric acid or succinic acid. If you use only non-ionic Hydrophilidae compounds (B1) with groups of ethers, stage neutralization no. Neutralization may also occur simultaneously with di is piergiovanni, when water dispersion already contains a substance for neutralization.

Still remaining isocyanate groups interact with di - or polyamines (B5) and/or, if available, with listeriosis component (B1). Such elongation of the chain can occur either in the solvent prior to dispersion or water dispersion. If the component (B1) has listeriosis component, the elongation of the chain is preferably before dispersing.

Di - or polyamine (B5) and/or, if available, listeriosis components (B1) can be added to the reaction mixture, razbavlennye organic solvents or water. Preferably used 70-95 wt.% solvent and/or water. If you have multiple aminobenzoic components (B1) and/or (B5), the interaction may occur sequentially in any order or simultaneously by adding the mixture.

With the aim of obtaining polyurethane dispersion (B) polyurethane prepolymers, optionally, with a strong shift, for example, with vigorous stirring, contribute or dispersing water or, conversely, the dispersing water is mixed with the prepolymers. Then, if it is not in the homogeneous phase, there could be an increase in molar mass due to the reaction are available, if necessary, ISOC analnyj groups of component (B5). The quantity added of the component (B5) depends on the remaining unreacted isocyanate groups. Preferably, polyamines (B5) interact 50-100%, most preferably 75-95% of the total number of isocyanate groups.

The resulting polyurethane-polycarbonate polymers contain 0-2 wt.%, preferably 0-0,5 wt.% isocyanate groups.

If necessary, an organic solvent, it is possible to drive away. The dispersions have a solids content 20-70 wt.%, preferably 35-65 wt.%. Non-volatile constituents of these dispersions contain chemical groups that have active Servicenow hydrogen atoms in an amount of 0-0,53 mmol/g, preferably 0-0,4 mmol/g, most preferably 0-0,25 mmol/g

As MDI (A) can be used unlocked the polyisocyanates (A')obtained by modifying simple aliphatic, cycloaliphatic, alifaticheskih and/or aromatic diisocyanates and constructed from at least two diisocyanates with uretdione, which, allophanate, biuret, aminoacid-Akindinova and/or oxidization structure, which is described, for example, in the journal J. Prakt. Chem. 1994, t, str-200.

Suitable diisocyanates for more polyisocyanates (A') are available by vosganian or bezposrednimi methods, nab is emer, thermal decomposition of urethanes, aliphatic, cycloaliphatic, analiticheskie and/or aromatic diisocyanates with molekulyarnym weight in the range from 140 to 400 g/mol, such as, for example, 1,4-diisocyanatobutane, 1,6-diisocyanatohexane (HDI), 2-methyl-1,5-diiso-centofante, 1,5-diisocyanato-2,2-dimethylpentane, 2,2,4 - or 2,4,4-trimethyl-1,6-diisocyanatohexane, 1,10-diisocyanatohexane, 1,3 - and 1,4-diisocyanato-cyclohexane, 1,3 - and 1,4-bis-(isocyanatomethyl)-cyclohexane, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl (isophorondiisocyanate, IPDI), 4,4'-diisocyanatohexane, 1-isocyanato-1-methyl-4(3)-isocyanato-methylcyclohexane, bis-(isocyanatomethyl)-norbornane, 1,3 - and 1,4-bis-(2-isocyanato-prop-2-yl)-benzene (TMXDI), 2,4 - and 2,6-diisocyanates (TDI), 2,4'- and 4,4'-diisocyanato-difenilmetana, 1,5-diisocyanatomethyl or any mixtures of these diisocyanates.

Next, fit triisocyanate, such as triphenylmethane-4,4',4"-triisocyanate and/or 4-isocyanato-methyl-1,8-octadienal.

If the source component (A') preferably it is about the only aliphatic and/or cycloaliphatic the polyisocyanate or mixture of polyisocyanates of the named type.

Particularly preferred source components (A') are polyisocyanates or mixtures of polyisocyanates with which the structure and/or biuret structure by 1,diisocyanatohexane (HDI), isophorondiisocyanate (IPDI) and/or 4,4'-diisocyanato-dicyclohexylmethane.

To achieve the best ability of the above mentioned polyisocyanates (A') be incorporated in the aqueous binder, the polyisocyanates are preferably modified to increase their hydrophilicity. For this purpose the above-mentioned polyisocyanates, hydrophilisation known methods. Gidrogenizirovanii can occur, for example, anion, cation or deionno through internal or external emulsifiers.

Suitable internal emulsifiers are such that the above-described additional components (B1). The polyisocyanates that hydrophiliclipophilic due to carboxyl groups after neutralization of the carboxyl groups can be very vysokodispersnoi transfer of the water system without the use of high shear forces. Applicable also modified due to the polyether polyisocyanates. The receipt of such polyisocyanates capable of dispergirujutsja in water, is described in detail, for example, in EP-A 0959087 (page 2, lines 25-46) and EP-A 1065228 (page 4, line 43 to page 10, line 35).

Suitable internal emulsifiers are described in EP-A 0703255 emulsifiable in water, polyisocyanates, which as emulsifiers contain the reaction products of MDI and any compounds with hydroxyl, mercapto and amino groups and which is out, at least one sulfate group or its anion. The preferred acid components to obtain emulsifiers are called when this hydroxysulfonic acid with HE-groups in the aliphatic part of the molecule, or a salt of these hydroxysulfonic acids, for example, some polyethersulfone, which are commercially available under the name Tegomer® (Th. Goldschmidt AG, Essen, Germany), bisulfite adducts of unsaturated alcohols, hydroxyethanesulfonic and hydroxypropanesulfonic and aminosulfonates, which can be obtained by quaternization of the tertiary aminoalcohols with 1,3-propanesultone. Predpochtitelnye as hydrophilicity components are also 2-(pilosellae)-econsultation and 3-(cyclohexylamino)-propane-acid or their salts.

Suitable external emulsifiers are, for example, anionic emulsifiers, such as emulsifiers based on alkylsulfate, alkylarylsulfonate, alkylphenolethoxylate which, for example, stated in the book Houben-Weyl "Methods der organischen Chemie", supplementary volumes to the 4th edition, the, 1987 (part 1, str-262), or alkylpolyglycoside or nonionic emulsifiers, such as, for example, food alkoxysilane, preferably products amoxilonline, alcohols, phenols or fatty acids.

Further, it is possible that poleis cyanate additionally contain unsaturated groups, preferably acrylate or methacrylate groups. Such polyisocyanates are known and described for example in US-A 6,335,381 (page 1, line 43 to page 8, line 48). They are obtained, for example, by partial interaction of the above-mentioned polyisocyanates with acrylate or methacrylate compounds containing a hydroxyl group such as, for example, hydroxyethylacrylate or pentaerythrityl. It is used predominantly acrylate compounds with an average hydroxyl functionality of from 0.2 to 2, preferably from 0.4 to 1.2.

The NCO content of the polyisocyanates (A') is 1-50%, preferably 8-25%. If necessary, they can be diluted with a solvent which is inert to isocyanates, but can be mixed with water.

Preferred polyisocyanates are used, hydrophilisation inert emulsifiers, particularly preferably allianceofdelray, hydrophilisation simple polyester polyisocyanates, for example those described in EP-A 1065228 (page 4, line 43 to page 10, line 35). Preferably from 60 to 90 mol.% simple ester is connected through allophanate group with a polyisocyanate.

Suitable blocked polyisocyanates (A)used in the coating materials according to this invention are dispersible in water or water-soluble blocked p is diisocyanate,

Suitable dispersible in water or soluble in water polyisocyanates (A) are obtained by interaction

(A"1) at least one MDI with isocyanate groups in the aliphatic, cycloaliphatic, analiticheskoi, and/or the aromatic part of the molecule,

(2) at least one ionic or potentially ionic and/or nonionic compounds

(A"3) at least one blocking means,

(A"4) optionally, one or more (cyclo)aliphatic mono - or polyamines with the number of amino groups from 1 to 4 and a molecular weight in the range from 32 to 300,

(A"5) if necessary, one or more polyhydric alcohols with the number of hydroxyl groups of from 1 to 4 and a molecular weight of from 50 to 250 and

(A"6) optionally, one or more compounds containing reactive to isocyanate groups and unsaturated groups.

The polyisocyanates (A) may contain, if necessary, a stabilizer (a-7) and other excipients, and, optionally, a solvent (A"8).

Dispersible in water or water-soluble blocked polyisocyanates (A) are constructed from 20-80 wt.%, preferably 25-75 wt.% and most preferably 30-70 weight. % component (A"1); 1-40 wt.%, preferably 1-35 wt.%, most preferably 5-30 wt.% the components is the same (2); 15-60 wt.%, preferably 20-50 wt.%, most preferably 25-45 wt.% component (A"3); 0-15 wt.%, preferably 0-10 wt.%, most preferably 0-5 wt.% component (A"4); 0-15 wt.%, preferably 0-10 wt.%, most preferably 0-5 wt.% component (A"5); 0-40 wt.%, preferably 0 wt.%, component (A"6); and 0-15 wt.%, preferably 0-10 wt.%, most preferably 0-5 wt.% component (a-7) and, if needed, 0-20 wt.%, preferably 0-15 wt.%, most preferably 0-10 wt.% component (A"8), and the sum of the components is 100 wt.%.

Dispersible in water or water-soluble blocked polyisocyanates (A) can be used in the coating materials according to this invention in the form of aqueous solutions or dispersions. The content of solids in the solution or dispersion of the polyisocyanates is from 10 to 70 wt.%, preferably from 20 to 60 wt.% and most preferably from 25 to 50 wt.% and share (A"8) in the total composition is less than 15 wt.%, preferably less than 10 wt.% and most preferably less than 5 wt.%.

Used to obtain the blocked polyisocyanates (a) polyisocyanates (A"1) have an (average) NCO functionality of 2.0 to 5.0, preferably from 2.3 to 4.5; the content of isocyanate groups of from 5.0 to 27 wt.%, preferably of 14.0 to 24.0 wt.% and a content of Monomeric diisocyanates of less than 1 in the C.%, preferably less than 0.5 wt.%. Isocyanate groups in the polyisocyanate (A"1) not less than 50%, preferably not less than 60% and most preferably not less than 70% are blocked.

Suitable polyisocyanates (A"1) to obtain the blocked polyisocyanates (A) are named under (A')obtained by modifying simple aliphatic, cycloaliphatic, alifaticheskih and/or aromatic diisocyanates, synthesized, of at least two diisocyanates of the polyisocyanates with uretdione, which, allophanate, biuret, iminoimidazolidine and/or oxidization structure, which is described, for example, in the journal J. Prakt. Chem. 1994, t, str-200.

Suitable compounds for component (2) are ionic or potentially ionic and/or nonionic compounds, which are described among the components (B1).

Component (2) is preferably a combination of nonionic and ionic hydrophilizing funds. Particularly preferred combinations of nonionic and anionic hydrophilizing funds.

As examples of the blocking means (A"3) include: alcohols, lactams, oximes, complex malonic esters, allylacetate, triazoles, phenols, imidazoles, pyrazoles, and also amines, such as, for example, butanonoxime, Diisopropylamine, 1,2,4-triazole,dimethyl-1,2,4-triazole, the imidazole, diethyl ester of malonic acid, acetoacetic ester, acetonates, 3,5-dimethylpyrazole, ε-caprolactam, N-tert.-butyl-benzylamine or any mixtures of these blocking means. Preferably as a blocking means (A"3) apply butanonoxime, 3,5-dimethylpyrazole, ε-caprolactam, N-tert.-butylbenzylamine. The preferred locking means (And 3) are butanonoxime and ε-caprolactam.

As component (A"4) are mono-, di-, tri - and/or tetraaminodiphenyl with molecular weight up to 300, such as Ethylenediamine, 1,2 - and 1,3-diaminopropane, 1,3-, 1,4 - and 1,6-diaminohexane, 1,3-diamino-2,2-DIMETHYLPROPANE, 1-amino-3,3,5-trimethyl-5-amino-ethyl-cyclohexane (ACCESSORIES>), 4,4'-diaminodecane-hekselman, 2,4 - and 2,6-diamino-1-methylcyclohexane, 4,4'-diamino-3,3'-dimethylcyclohexylamine, 1,4-bis-(2-amino-prop-2-yl)-cyclohexane or mixtures of these compounds.

In the case of components (A"5) we are talking about connections with one, two, three or four hydroxyl groups with a molecular weight of up to 250, such as, for example, ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, glycerin, trimethylacetyl, trimethylolpropane, isomer of hexanetriol, pentaerythritol or mixtures of these compounds.

As component (A"6) interact with isocyanates compounds with hydroxyl and (meth)acrylic groups. So the e compounds described above, for example, as constituents of component (B2), the Preferred compounds with an average hydroxyl functionality of from 0.2 to 2, most preferably from 0.7 to 1.3, Most preferred are 2-hydroxyethyl(meth)acrylate, poly(ε-caprolacton)monoacrylate, such as, for example, Tone M100® (Union Carbide, USA), 2-hydroxypropylmethacrylate, 4-hydroxyethylacrylate, trimethylolpropane, glycerinated, pentaerythrityl or dipentaerythritol.

The blocked polyisocyanates (A), if necessary, may contain a stabilizer or mixture of stabilizers (a-7). Suitable compounds (a-7) are, for example, antioxidants, such as 2,6-decret.-butyl-4-METHYLPHENOL, UV absorbers type 2-hydroxyphenylacetate or light stabilizers of the type of sterically obstructed amines and other trade quality stabilizers, which, for example, described in "Lichtschutzmittel für Lacke" ("light stabilizers for paints") (A.Valet, publisher Vicentz, Hannover, 1996) and "Stabilisation of Polymeric Materials" ("Stabilization of polymeric materials") (H.Zweifel, Springer, Berlin, 1997, Appendix 3, str-213).

Preferred are mixtures of stabilizers, compounds that have 2,2,6,6-tetramethylpiperidinyloxy balance. Piperidinyl nitrogen in this cycle is not replaced and never has hydrazide structure. Especially n ecocriticism is a compound of formula (II)

which, for example, sold under the name Tinuvin® 770 DF firm Ciba Spezialitaeten (Lampertheim, Germany).

In the ideal case, the above-described compounds are combined with substances that have a structure hydrazide, such as hydrazides or dihydrazide acids, such as, for example, hydrazides acetic, adipic acid, dihydrazide adipic acid or adducts of hydrazine and cyclic carbonates, such as are mentioned, for example, in EP-A 654490 (page 3, line 48 to page 4, line 3). Preferably used dehydrated adipic acid and the adduct of 2 moles of propylene carbonate and 1 mole of hydrazine of General formula (III)

Especially preferred adduct of 2 moles of propylene carbonate and 1 mole of hydrazine of General formula (IV)

As the organic solvent (A"8) suitable conventional solvents for varnishes, such as, for example, ethyl acetate, butyl acetate,

1-methoxypropyl-2-acetate, 3-methoxy-n-butyl acetate, acetone, 2-butanone, 4-methyl-2-pentanone, cyclohexanone, toluene, xylene, chlorobenzene or white spirit. Also suitable mixtures that contain primarily highly-substituted PCB aromatic compounds, such as, for example, commercially available under the names Solvent Naphtha, Solvesso® (Exxon Chemicals, Houston, USA), Cypar® (Shel Chemicals, Eschborn, Germany), Cycio Sol® (Shell Chemicals, Eschborn, Germany), Tolu Sol® (Shell Chemicals, Eschborn, Germany), Shellsol® (Shell Chemicals, Eschborn, Germany). Other solvents, for example, esters of carbonic acid, such as dimethylcarbonate, diethylcarbamyl, 1,2-ethylene carbonate resulting and 1,2-propylene carbonate, lactones, such as, β-propiolactone, γ-butyrolactone, ε-caprolacton, ε-methylcaprolactam, propilenglikolstearat, dimethyl ether of diethylene glycol, dimethyl ether of dipropyleneglycol, diethylenglycol - and-butylaminoethyl, N-organic N-methyl-caprolactam, or any mixture of these solvents. Preferred solvents are acetone, 2-butanone, 1-methoxypropyl-2-acetate, xylene, toluene, mixtures which contain, above all, highly-substituted PCB aromatic compounds, such as, for example, commercially available under the names Solvent Naphtha, Solvesso® (Exxon Chemicals, Houston, USA), Cypar® (Shell Chemicals, Eschborn, Germany), Cycle Sol® (Shell Chemicals, Eschborn, Germany), Tolu Sol® (Shell Chemicals, Eschborn, Germany), Shellsol® (Shell Chemicals, Eschborn, Germany)and N-organic. The most preferred acetone, 2-butanone and N-organic.

Getting blocked polyisocyanates (A) may be izvestnimi methods (for example, described in DE-A 2456469, columns 7-8, examples 1-5 and DE-A 2853937, columns 21-26, examples 1-9).

Dispersible in the ode and the water-soluble blocked polyisocyanates (A) can be obtained, for example, by reacting components (A"1), (2), (A"3) and, if necessary, (And 4)-(a-7) in any order, optionally using an organic solvent (A"8).

Preferably, first (A"1) interacts, if necessary, with a part, predominantly non-ionic part, component (2)and, if necessary, (A"4) and (A"5). Then there is a blocking component (A"3) and then the reaction occurs with part of component (2)containing an ionic group. If necessary, the reaction mixture may be added to the organic solvent (A"8). At the next stage, if necessary, are added to the components (a-7).

Then there is the obtaining of an aqueous solution or dispersion of the blocked polyisocyanates (A), which dispersible in water, the blocked polyisocyanates are transferred to the aqueous dispersion or solution, or by putting them in water or by the addition thereto of water. Used, if necessary, an organic solvent (A"8) may, at the completion of the dispersion is removed by distillation. Preferably without application (A"8).

Mentioned previously dispersible in water or water-soluble blocked polyisocyanates can also contain unsaturated group capable of radical polymerization. For this polyisocyanates before dispersing, emulge is a Finance or dissolved in water can first be partially blocked and then interact with the compounds (A"6), containing reactive to isocyanates and unsaturated groups, or polyisocyanates first communicate with the compounds (A"6)containing reactive to isocyanates and unsaturated groups, and then with blocking means (A"3).

To obtain aqueous solutions or dispersions of blocked polyisocyanates (A) use such amount of water that the resulting dispersion contains from 10 to 70 wt.% solids, preferably from 20 to 60 wt.% and most preferably from 25 to 50 wt.%.

As an initiator (radical polymerization can be used that is activated by radiation and/or thermal initiators. Photoinitiator, which are activated by UV radiation or visible light, are preferred. Photoinitiators are known, commercially available compounds and initiators differ on monomolecular (type I) and bimolecular (type II). Appropriate systems of type I are aromatic ketones, such as benzophenone in combination with tertiary amines, alkylbenzene, 4,4'-bis(dimethylamino)benzophenone (michler ketone), Andron and halogenated benzophenone or a mixture of these types. Also suitable type II initiators, such as benzoin and its derivatives, benzylacetone, acylphosphatase, for example, 2,4,6-trimethyl-benzoyl-diphenylprop noxid, besatisfied, esters phenylglycolic acid, kamarainen, α-aminoacetophenone, α,α-dialkoxybenzene and α-hydroxyacetophenone. Preferred photoinitiator, which are easily incorporated into aqueous material to cover. Such products are, for example, Irgacure® 500, Irgacure® 819 DF (company Ciba, Lampertheim, Germany), Esacure® KIP (the company Lamberti, Aldizzate, Italy). Can also be used mixtures of these compounds.

If the curing is initiated thermally suitable such peroxide compounds, as diazepamonline, for example, benzoyl peroxide, alkylhydroperoxides, such as diisopropylbenzene monohydroperoxide, alkylperoxide, such as tert.-butylperbenzoate, dialkylamide, such as tert.-butylperoxide, peroxycarbonates, such as dicetylperoxydicarbonate, inorganic peroxides, such as peroxodisulfate ammonium, peroxodisulfate potassium or azo compounds such as 2,2'-azobis[N-(2-propenyl)-2-methylpropionamide], 1-[cyano-1-methylethyl)azo]-formamide, 2,2'-azobis(N-butyl-2-methylpropionamide), 2,2'-azobis(N-cyclohexyl-2-methylpropionamide), 2,2'-azobis{2-methyl-N-[2-(1-hydroxybutyl)]propionamide}, 2,2'-azobis{2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl] propionamide and benzopinacol. Preferred are compounds that are soluble in water or exist in the form of a water emulsion is rd. These sources of radicals can be combined in a known manner accelerators.

The subject of this invention is also a method of obtaining an aqueous coating materials according to this invention, wherein components (I), (II) and (III) are mixed with each other sequentially in any order or simultaneously. If the coatings contain a polyisocyanate (A'), which is still available, non-blocked isocyanate groups, they have viability (sustainability during storage) from 1 to 96, preferably from 2 to 24 hours, during which they should be used. Therefore, preferably component (II) should be added to the components (I) as close as possible before coating. If the coating materials do not contain free isocyanate groups by using the component (A), they do not have such properties as viability, and are stable when stored for one month or more.

You can apply a material for coatings used for the method according to this invention, one or mix it together with the known technology of coatings, binders, auxiliary substances and additives, in particular with light shielding means, such as UV absorbers or sterically difficult amines, next, antioxidants, fillers, and that the same auxiliary means for varnishes, for example, means preventing the assertion of, or non-wetting, means facilitating filling the reagent-diluent, a softening agent, catalysts, auxiliary solvents and/or thickener, and additives such as dispersion, pigments, dyes or compounds for katirovki. In particular, without problems possible combinations of binder, such as polyurethane dispersions or polyacrylate dispersion, which, if necessary, may also be a hydroxyl group.

The coating materials according to this invention after removal of water without the addition of auxiliary funds provide coverage from not susceptible to dust until solid, able to withstand the mechanical load. The removal of water may occur by evaporation or forced drying, for example, by heat, warm and/or dry air and/or heat radiation. Due to the subsequent structuring of induced radiation-chemically and, if necessary, additional heat, film otverzhdajutsja with getting high, scratch resistant and resistant to chemicals lacquer coatings. Preferably after removal of water first utverjdayut UV radiation or Dnevnik light, then there is dauvergne at temperatures from 0 to 200°With, however, the site is preferably in the range from 20 to 100° C. by dauvergne also poorly lit or not lit areas is achieved by curing of the coating. This is particularly advantageous when the substrate should not be heated, for example, wood. Through the use of coating materials according to this invention improves the adhesion to the substrate.

The subject of this invention is also a method of producing coatings, characterized in that the aqueous coating media according to this invention is applied to the substrate, remove the water and then utverjdayut.

The coating materials according to this invention can be applied to various substrates using a conventional technology, for example, by spraying, roller coating, applied using a squeegee, drenching, spraying, brushing or dipping. Substrates selected from the group comprising wood, metal, plastic, paper, leather, textiles, fur, glass or mineral substrate. Preferred substrates are wood, fiberglass, or carbon fiber.

The thickness of the applied layer (before curing) usually lies in the range from 0.5 to 5000 μm, preferably from 5 to 1500 μm, most preferably from 15 to 1000 μm.

Radiation curing preferably takes place due to exposure to hard radiation, i.e. radiation of UV or visible light is, for example, light with a wavelength of from 200 to 700 nm, or by irradiation by an electron beam with high energy (cathode electron radiation, 150-300 Kev). As a light source or UV radiation are, for example, mercury lamps high or medium pressure, and mercury vapors can be modified by adding other elements such as gallium or iron. It is also possible lasers in pulsed mode lamp (known as the ultraviolet lamps flash), halogen lamps or excimer emitters. The emitters can be equipped with filters that prevent the release of the emitted radiation. For example, on the basis of sanitary-hygienic requirements, filtered radiation related to UV-C or UV-C and UV-b radiation. The emitter may be mounted stationary, so that the irradiated material using a mechanical device moves past the radiation source or emitter can be movable and the irradiated material during curing does not change its location. Usually sufficient for structuring the radiation dose during curing by UV radiation is in the range from 80 to 5000 MJ/cm2.

Exposure may occur, if necessary, also with the exclusion of oxygen, for example, in an atmosphere of inert gas or in an atmosphere having a reduced content of acid is kind. As the inert gases are suitable, preferably nitrogen, carbon dioxide, noble gases or combustion gases. Exposure can occur in such a way that the floor is covered with a transparent to the radiation environment. Examples for this are films made of polymers, glass or liquids such as water.

Depending on the radiation dose and curing conditions can be varied according to the type and concentration used, if necessary, the initiator of the well-known specialist way.

Particularly preferably used for curing mercury lamps high pressure in stationary installations. Then photoinitiator used in a concentration of from 0.1 to 10 wt.%, particularly preferably from 0.2 to 3.0 wt.% in the calculation of the solid matter of the coating. For curing these coatings are mainly applied dose from 200 to 3000 MJ/cm2measured in the wavelength range from 200 to 600 nm.

The subject of the invention is also the use of aqueous coatings according to this invention in adhesive substances, sealing masses and varnishes, it is preferable to use in varnishes for coating wood, for example, in coatings for furniture and flooring, as well as use in dressing, preferably in dressing for fiberglass.

Examples:

UV curable by radiation poliuretano the s dispersion (B):

Example 1:

Obtaining complex preferability (1A) similarly, DE-C 19715382 (page 5, line 21-27), hydroxyl number: 160 mg KOH/g, acid value: 11 mg KOH/g, viscosity: 0.5 PA·s at 23°C.

Obtaining complex preferability (1B):

In a heated reaction vessel with a stirrer, inlet gas temperature measurement, water separator and reflux condenser to 98.1 g of maleic anhydride, 739,2 g four times propoxyethanol of trimethylolpropane, 259,2 g of acrylic acid and 10.5 g of the monohydrate of 4-toluenesulfonic acid, 3.2 g of 4-methoxyphenol, 0.2 g of 2,5-decret.-butylhydroquinone and 448,3 g of isooctane was heated with obratnim refrigerator with stirring and supply airflow at a rate of 1 l/h At a temperature of 100-105°With separated water up until the acid number reached a value of 5 or below. Then the solvent was removed by distillation in vacuum. Received complex preferablyat with an acid number of 4 mg KOH/g, a hydroxyl number of 110 mg KOH/g and a viscosity of 1.6 PA·s at 23°C.

Obtaining polyurethane dispersion:

In a reaction vessel with stirrer, internal thermometer and inlet gas (air flow 1 l/h) were placed 278,9 g preferability (1B), 63,0 g preferability (1A), 8.5 g of neopentyl glycol, 21,9 dimethylolpropionic acid, 0.5 g of dibutyltindilaurate, 167,6 g of acetone, mixed with 101,8 g Desmodur® W (aliphatic the cue diisocyanate; Bayer AG, Leverkusen, Germany) and was heated so that was a constant return flow of acetone. Was stirred at this temperature until, until the NCO content in the reaction mixture did not reach 1,8±0.1 wt.%.

Then the mixture was cooled to 40°and was quickly added to 14.7 g of triethylamine. After 10 min the reaction mixture with rapid stirring, poured in 883,2 g of water with a temperature of 20°C. After formation of the dispersion, was added 27.7 g of ISOPHORONEDIAMINE in of 77.0 g of water.

After 30 min stirring without heating or cooling, the product was distilled in a vacuum (50 mbar, Max. temperature 50° (C) has not yet been achieved, the solids content of 39±1 wt.%. The pH of the dispersion is equal to 8.0 and the average particle size of 159 nm (measurement method of laser correlation spectroscopy: Zetasizer1000, Malvern Instruments, Malvern, UK). The product contained 0.52 mmol/g groups with active hydrogen.

Example 2;

Getting poliuretanovoy dispersion:

In a reaction vessel with stirrer, internal thermometer and inlet gas (air flow 1 l/h) were placed 169,0 g epoxyacrylate with hydroxyl groups Ebecryl® 600 (firm UCB GmbH, Kerpen, Germany), 34,5 g polyacrylamdie Tegomer® BD 1000 (the company Goldschmidt, Essen, Germany), and 9.8 g of neopentyl glycol, 17,1 dimethylolpropionic acid, 0.4 g of dibutyltindilaurate, 133,8 g of acetone, mixed with 113,7G Desmodur® I (aliphatic diisocyanate; Bayer AG, Leverkusen, Germany) and 56,6 g Desmodur® H (aliphatic diisocyanate; Bayer AG, Leverkusen, Germany) and was heated so that was a constant return flow of acetone. Was stirred at this temperature until, until the NCO content in the reaction mixture did not reach 4,0±0.1 wt.%.

Then the mixture was cooled to 40°and quickly added 495,1 g of acetone. After 5 min stirring at 40°With added 15,84 g of Ethylenediamine in of 63.7 g of water. After reaching an NCO content of<0.1 wt.% the reaction mixture with vigorous stirring, poured in 580 g of water at 20°C.

After 30 min stirring without heating or cooling, the product was distilled in a vacuum (50 mbar, Max. temperature 50° (C) has not yet been achieved, the solids content of 39±1 wt.%. The pH of the dispersion is equal to 8.9 and the average particle size of 262 nm (measurement method of laser correlation spectroscopy: Zetasizer1000, Malvem Instruments, Malvern, UK). The product contained 0.2 mmol/g groups with active hydrogen.

Example 3:

Obtaining polyurethane dispersion:

In a reaction vessel with stirrer, internal thermometer and inlet gas (air flow 1 l/h) were placed 169,0 g epoxyacrylate with hydroxyl groups Ebecryl® 600 (firm UCB GmbH, Kerpen, Germany), 144,8 g complex polyetherdiol of adipic acid, hexanediol, Neopan is alpicola with molecular weight of 1700, of 3.9 g of neopentyl glycol, 13,1 g dimethylolpropionic acid, 0.3 g of dibutyltindilaurate, of 127.5 g of acetone, mixed with 47,2 g Desmodur® I (aliphatic diisocyanate, Bayer AG, Leverkusen, Germany) and 77.9 g Desmodur® H (aliphatic diisocyanate, Bayer AG, Leverkusen, Germany) and was heated so that was a constant return flow of acetone. Was stirred at this temperature until, until the NCO content in the reaction mixture did not reach 3,3±0.1 wt.%.

Then the mixture was cooled to 40°and quickly added 481,7 g of acetone. After 5 min stirring at 40°With added was 12.75 g of Ethylenediamine in 38.3 g of water. After reaching an NCO content of<0.1 wt.% the reaction mixture with vigorous stirring, poured in 625,6 g of water at 20°C.

After 30 min stirring without heating or cooling, the product was distilled in a vacuum (50 mbar, Max. temperature 50° (C) has not yet been achieved, the solids content of 39±1 wt.%. The pH of the dispersion is equal to 8.9 and the average particle size of 110 nm (measurement method of laser correlation spectroscopy: Zetasizer1000, Malvem Instruments, Malvern, UK). The product contained 0.03 mmol/g groups with aktivnim hydrogen.

Example 4:

Obtaining polyurethane dispersion:

In a reaction vessel with stirrer, internal thermometer and inlet gas (air flow 1 l/h) was placed 298,0 g complex preferablyat the (1A) and of 27.0 g of polyether LB 25 (Bayer AG, Germany, monofunctional simple polyester on ethylene oxide/propylenoxide basis with an average molecular weight of 2250 (hydroxyl number = 25) and melted. After adding 168,6 g isophorondiisocyanate (Desmodur® I, Bayer AG, Germany) and is 170.0 g of acetone, the reaction mixture was heated up to the temperature of the return stream. At this temperature, stirred up until the NCO content in the reaction mixture did not become a 3.6-3.8 wt.%. When this was achieved the NCO content, prepolymer was dissolved in 350,0 g of acetone and set the temperature up to 40°C.

Then was added a solution of 9.9 g of Ethylenediamine, and 47.5 g of 45%aqueous solution of 2-(2-aminoethylamino)econsultancy in water (AAS-solution) (Bayer AG, Leverkusen, Germany) and of 67.6 g of water for 2 min and stirred 5 minutes

Then added 692,8 g of water for 10 minutes the Resulting dispersion was stirred for another at 40°up until the IR by a spectroscope in the dispersion no longer showed the presence of NCO.

The product was distilled in a vacuum at a temperature below 50°yet achieved a solids content of 39 wt.%. The pH of the dispersion is equal to 7.0 and an average particle size of 86 nm (measurement method of laser correlation spectroscopy: Zetasizer1000, Malvem Instruments, Malvern, UK).

Example 5:

Obtaining polyurethane dispersion:

In a reaction vessel with stirrer, internal thermome the rum and supply of gas (air flow 1 l/h) were placed 298,0 g complex preferability (1A) and of 27.0 g of polyether LB 25 (Bayer AG, Germany, monofunctional simple polyester on ethylene oxide/propylenoxide basis with an average molecular weight of 2250 (hydroxyl number = 25) and melted. After adding 168,6 g isophorondiisocyanate (Desmodur® I, Bayer AG, Germany) and is 170.0 g of acetone, the reaction mixture was heated up to the temperature of the return stream. At this temperature, stirred up until the NCO content in the reaction mixture did not reach 4.2 to 4.4 wt.%. When this was achieved the NCO content, prepolymer was dissolved in 350,0 g of acetone and set the temperature up to 40°C.

Then was added a solution of 11.4 g of Ethylenediamine, 36,9 g of 45%aqueous solution of 2-(2-aminoethylamino)econsultancy in water (AAS-solution) (Bayer AG, Leverkusen, Germany) and 63.7 g of water for 2 min and stirred 5 minutes and Then added 698,5 g of water for 10 minutes the Resulting dispersion was stirred for another at 40°up until the IR by a spectroscope in the dispersion no longer showed the presence of NCO.

The product was distilled in a vacuum at a temperature below 50°yet achieved a solids content of 39 wt.%. The pH of the dispersion is equal to 6.6 and the average particle size of 113 nm (measurement method of laser correlation spectroscopy: Zetasizer1000, Malvern Instruments, Malvern, UK).

Example 6:

Obtaining polyurethane dispersion:

In a reaction vessel with stirrer, internal therm is a meter and a supply of gas (air flow 1 l/h) were placed 298,0 g complex preferability (1A) and of 27.0 g of polyether LB 25 (Bayer AG, Germany, monofunctional simple polyester on ethylene oxide/propylenoxide basis with an average molecular weight of 2250 (hydroxyl number = 25) and melted. After adding 168,6 g isophorondiisocyanate (Desmodur® I, Bayer AG, Germany) and is 170.0 g of acetone, the reaction mixture was heated up to the temperature of the return stream. At this temperature, stirred up until the NCO content in the reaction mixture did not reach 4.2 to 4.4 wt.%. When this was achieved the NCO content, prepolymer was dissolved in 350,0 g of acetone and set the temperature up to 40°C.

Then was added a solution of 12.1 g of Ethylenediamine, and 31.7 g of 45%aqueous solution of 2-(2-aminoethylamino)econsultancy in water (AAS-solution) (Bayer AG, Leverkusen, Germany) and of 61.7 g of water for 2 min and stirred 5 minutes and Then added 700,9 g of water for 10 minutes the Resulting dispersion was stirred for another at 40°up until the IR by a spectroscope in the dispersion no longer showed the presence of NCO.

The product was distilled in a vacuum at a temperature below 50°yet achieved a solids content of 39 wt.%. The pH of the dispersion is equal to 6.8 and the average particle size of 83 nm (measurement method of laser correlation spectroscopy: Zetasizer1000, Malvern Instruments, Malvern, UK).

Example 7:

Obtaining polyurethane dispersion:

In a reaction vessel with stirrer, internal therm is a meter and a supply of gas (air flow 1 l/h) were placed 139,0 g complex polyester PE 170 HN (ester-based adipic acid, 1,6-hexandiol, neopentyl glycol with a molecular weight of 1700 (Bayer AG, Leverkusen, Germany), 238,5 g complex preferability (1A)of 27.0 g of polyether LB 25 (Bayer AG, Germany, monofunctional simple polyester on ethylene oxide/propylenoxide basis with an average molecular weight of 2250 (gidroksilnye number =25) and melted. After adding 168,6 g isophorondiisocyanate (Desmodur® I, Bayer AG, Germany) and is 170.0 g of acetone, the reaction mixture was heated up to the temperature of the return stream. At this temperature, stirred up until the NCO content in the reaction mixture did not reach the 3.6-3.8 wt.%. When this was achieved the NCO content, prepolymer was dissolved in 350,0 g of acetone and set the temperature up to 40°C.

Then was added a solution of 11.4 g of Ethylenediamine, 36,9 g of 45%aqueous solution of 2-(2-aminoethylamino)econsultancy (AAC) (Bayer AG, Leverkusen, Germany) in water and 63.7 g of water for 2 min and stirred 5 minutes and Then added 817,7 g of water for 10 minutes the Resulting dispersion was stirred for another at 40°up until the IR by a spectroscope in the dispersion no longer showed the presence of NCO.

The product was distilled in a vacuum at a temperature below 50°yet achieved a solids content of 40 wt.%. The pH of the dispersion is equal to 6.8 and the average particle size of 83 nm (measurement method of laser correlation spectroscopy: Zetasizer1000, Malven Instruments, Malvern, UK).

Example 8:

Obtaining polyurethane dispersion:

In a reaction vessel with stirrer, internal thermometer and inlet gas (air flow 1 l/h) were placed 278,0 g complex polyester PE 170 HN (ester based on adipic acid, 1,6-hexandiol, neopentyl glycol with a molecular weight of 1700 (Bayer AG, Leverkusen, Germany), 179,0 g complex preferability (1A)of 27.0 g of polyether LB 25 (Bayer AG, Germany, monofunctional simple polyester on ethylene oxide/propylenoxide basis with an average molecular weight of 2250 (hydroxyl number = 25) and melted. After adding 168,6 g isophorondiisocyanate (Desmodur® I, Bayer AG, Germany) and is 170.0 g of acetone, the reaction mixture was heated up to the temperature of the return stream. At this temperature, stirred up until the NCO content in the reaction mixture did not reach the 3.3-3.5 wt.%. When this was achieved the NCO content, prepolymer was dissolved in 350,0 g of acetone and set the temperature up to 40°C.

Then was added a solution of 11.4 g of Ethylenediamine, 36,9 g of 45%aqueous solution of 2-(2-aminoethylamino)econsultancy in water (AAS-solution) (Bayer AG, Leverkusen, Germany) and 63.7 g of water for 2 min and stirred 5 minutes and Then added 936,9 g of water for 10 minutes the Resulting dispersion was stirred for another at 40°up until the IR by a spectroscope in the dispersion is no longer OBN who was rugulose the presence of NCO.

The product was distilled in a vacuum at a temperature below 50°yet achieved a solids content of 40 wt.%. The pH value of the dispersion 6.7 and the average particle size of 176 nm (measurement method of laser correlation spectroscopy: Zetasizer1000, Malvern Instruments, Malvern, UK).

Example 9:

Obtaining polyurethane dispersion:

In a reaction vessel with stirrer, internal thermometer and inlet gas (air flow 1 l/h) were placed 418,0 g complex polyester PE 170 HN (ester based on adipic acid, 1,6-hexandiol, neopentyl glycol with molekulyarnym weighing 1700 (Bayer AG, Leverkusen, Germany), 119,0 g complex preferability (1A)of 27.0 g of polyether LB 25 (Bayer AG, Leverkusen, Germany, monofunctional simple polyester on ethylene oxide/propylenoxide basis with an average molekulyarnym weight of 2250 (hydroxyl number=25)) and melted. After adding 168,6 g isophorondiisocyanate (Desmodur® I, Bayer AG, Germany) and is 170.0 g of acetone, the reaction mixture was heated up to the temperature of the return stream. At this temperature, stirred up until the NCO content in the reaction mixture did not reach to 3.0-3.2 wt.%. When this was achieved the NCO content, prepolymer was dissolved in 350,0 g of acetone and set the temperature up to 40°C.

Then was added a solution of 11.4 g of Ethylenediamine, 36,9 g of 45%aqueous solution of 2-(2-aminoethylamino)Athens is locality in water (AAS-solution) (Bayer AG, Leverkusen, Germany) in water and 63.7 g of water for 2 min and stirred 5 minutes and Then added 1057,2 g of water for 10 minutes the Resulting dispersion was stirred for another at 40°up until the IR by a spectroscope in the dispersion no longer showed the presence of NCO.

The product was distilled in a vacuum at a temperature below 50°yet achieved a solids content of 40 wt.%. The pH-value of the dispersion 6.7 and the average particle size of 192 nm (measurement method of laser correlation spectroscopy: Zetasizer1000, Malvern Instruments, Malvern, UK).

Dispersible in water, the blocked polyisocyanate (component a")

Example 10:

154,1 g containing biuret groups MDI based on 1,6-diisocyanatohexane (HDI) with an NCO content of 23.0 per cent were mixed with 6.3 g of polyether LB 25 (Bayer AG, Germany, monofunctional simple polyester on ethylene oxide/propylenoxide basis with an average molecular weight of 2250 (hydroxyl number = 25)) for 30 min at 100°C. Then at 90°C for 20 min was added to 60.6 g butanonoxime so that the temperature of the reaction mixture did not exceed 110°C. the Reaction mixture was stirred at 100°until then, until he reached theoretical NCO value and then cooled to 90°C. After additional mixing time of 5 min was added within 2 min the mixture of 22,0g hydrophiloidea funds KV 1386 (N-(2-amino-ethyl)-β -alanine, BASF AG, Ludwigshafen, Germany) and 37.5 g of water and stirred without temperature change. After this was carried out by dispersion by adding 485,5 g of water. After additional stirring for 4 h had been stable during storage of the aqueous dispersion with a solids content 29,8%.

Materials for coatings cured by UV radiation polyurethane dispersions and polyisocyanates (A')

Example 11:

Obtaining pigmented lacquers:

Table 1:
Manufacturer of pigment paste by dispersing the following components in dissolver at 2000 rpm
SubstanceFunctionWeight. partManufacturer
Water24.3
Disperbyk®Auxiliary disperser. Wed-in7,5BYK-Chemie GmbH (Wesel, Germany)
Dehydran® 1293The non0,7Cognis GmbH & Co. KG (düsseldorf, Germany)
R-KB-2Pigment titanium oxidea 50.5Kerr McGee GmbH & Co. KG (Leverkusen, Germany)
Blanc Fix®Pigment titanium oxide of 17.0Sachtleben Chemie GmbH (Duisburg, Germany)

Table 2:
5 fabrication of varnishes by dispersing the following components in dissolvere at 500 rpm
SubstanceWeight. partManufacturer
UV-curable polyurethane dispersion58,8
UV-PU 1Example 1
UV-PU 2Example 2
UV-PU 3Example 3
UV-PU 4= Bayhydrol® UF VP LS 2317 (UV curable by radiation polyurethane dispersion, ˜37%in water, the content of the groups having active hydrogen, 0,0 mmol/g)Bayer AG, Leverkusen, Germany
UV-PU 5= Bayhydrol® UF VP LS 2280 (UV curable by radiation polyurethane dispersion, ˜39%in the water content of the groups having active hydrogen, 0.2 mmol/g)Bayer AG, Leverkusen, Germany
Butylglycol/water 1:18,6
Acemat® TS100 (matting agent)0,5Degussa AG, marl, Germany
Lanco Wax® TF 1778 (supporting the dispersant) 0,5Langro-Chemie, Stuttgart, Germany
Dehydran® 1293 (non)0,45Cognis GmbH & CoKG, Dusseldorf, Germany
Irgacure® 1700 (photoinitiator)0,95Ciba-Spezialitaeten GmbH Lampertheim, Germany
BYK® 348 (additive that promotes bottling)0,5BYK-Chemie GmbH, Wesel, Germany
Tafigel® PUR 50 (thickener)0,3Muenzing-Chemie GmbH, Heilbronn, Germany
Pigment paste29,4Table 1

Hardener:Bayhydur® VP LS 2336, solvent free, hydrophilizing the polyisocyanate-based hexamethylenediisocyanate, the NCO content of 16.2 wt.%, the viscosity of 6800 MPa·s at 23°With (Bayer AG, Leverkusen, Germany).

Deposited two series of varnishes. 1. A series of comparative only with UV curable by radiation polyurethane dispersions as binders. 2. Series according to this invention additionally with 10 weight parts of curing agent. Using a handheld squeegee applied film thickness wet 150 μm on white fibreboard (MDF) with a film coating of average thickness. Was dried for 15 minutes at 20°C and 45 min at 50° C. Then utverjdali at the facility for UV curing of the 1ST company (nürtingen, Germany) with UV emitter with the addition of gallium (type IC I) capacity of 80 W/cm lamp when the feeding speed of 2.5 m/min through UV-light. Lacquer surface after curing for seven days was treated with various chemicals/colored liquids and then visually controlled for damage. The results are presented in tables 3 and 4.

Table 3:
Series 1 (not according to invention)
UV-PU 1UV-PU 2UV-PU 3UV-PU 4UV-PU 5
Ethanol (6 h) 50%OP/2OP/OP5/55/5OP/OP
Water (16 h)OP/0OP/OPOP/0OP/OPOP/OP
Red wine (6 h)OP/4OP/3OP/4OP/OPOP/OP
Coffee (16 h)OP/4OP/34/4OP/4OP/4

Table 4:
Series 2 (in accordance with this invention, an additional 10 weight. - parts hardener)
UV control Desk 1 incorporates thermalUV-2UV-PU 3UV-PU 4UV-PU 5
Ethanol (6 h) 50%1/03/22/02/12/0
Water (16 h)0/01/00/0OP/00/0
Red wine (6 h)4/43/24/44/23/2
Coffee (16 h)4/41/14/44/43/3

Evaluation:

Evaluation 0: not found

Assessment 6: test the surface completely destroyed

OP: bubbles

First evaluation: immediately after processing

Second assessment: 3 days after processing

Example 12:

Improved adhesion to aluminum foil:

Preparation of transparent varnish:

of 86.00 weight. - partsBayhydrol® UF VP LS 2282 (UV curable by radiation polyurethane dispersion, ˜39%in water, Bayer AG, Leverkusen, Germany), the product contains 0.0 mmol/g groups having active hydrogen
4.30 weight. - partBayhydrol�AE; PR 340 (dispersion of aliphatic, anionic complex politicalarena no functional groups, ˜40%in water, Bayer AG, Leverkusen, Germany)
0,40 weight. - partsBYK® 348
0,80 weight. - partsIrgacure® 500
8,40 weight. - partsBayhydur® VP LS 2336, (not containing solvent, hydrophilizing the polyisocyanate-based hexamethylenediisocyanate, the NCO content of 16.2 wt.%, the viscosity of 6800 MPa·s at 23°Bayer AG, Leverkusen, Germany).

According to the invention:

Using a manual doctor blade on the aluminum foil was applied film thickness in the wet state 25 μm. Was dried for 1 min at 50°C. Then utverjdali on the installation of UV curing firm IST (nürtingen, Germany) with a mercury UV emitter (type IC) with a capacity of 80 W/cm lamp when the feeding speed of 5 m/min through UV-light. Painted surfaces were subjected to load after curing for 7 days and then were monitored visually for damage.

Tests and results:

The resistance 1 at 300°With: in order

Stability during sterilization (40 min, 125°C water bath with pH 8.0): in order

Strength in dry and wet conditions: in order

A comparison (not according to the invention):

The test was repeated without addition of hardener Bayhydur® VPLS 2336. Not detected stability during sterilization and strength in wet condition because the varnish film was separated from the aluminum foil.

The material for the coating of UV curable by radiation polyurethane dispersions and dispersible in water blocked polyisocyanates (A')

Examples 13-15:

The compositions of the coating materials described in tables 5-8. Determination of mechanical properties of material of coating was performed on free films as described below:

In a device for obtaining films consisting of two polished rolls that can be installed at a precise distance from each other, in front of the lower roller inserted separating paper. With a plate thickness set the distance between the paper and the front roller. This distance corresponds to the film thickness (wet) of the resulting coating and can be installed on the desired thickness of each layer of varnish. The coating can be made of several layers. For deposition of the individual layers products (viscosity of aqueous compositions is set in advance on the value of 4500 MPa·-1by adding a mixture of ammonia/polyacrylic acid) was poured in the gap between the paper and the front roller, the separator paper was pulled down at the paper formed the corresponding film. If you want to apply a few layers of lacquer, each of the first separate layer dried and the paper insert again.

The definition of 100% of the module is carried out according to DIN 53504 on the films, the thickness of 100-200 μm.

Storage of the films in the conditions of hydrolysis was carried out according to DIN EN 12280-3. Determination of mechanical properties of these samples of the films was carried out after 24 h storage in standard climatic conditions (20°C and humidity 65%) according to DIN 53504.

The results of testing the mechanical properties of free films prove that the above coating materials depending on the drying conditions selectively, separately from each other can have different mechanisms structuring.

1. Conditions (comparison)

- dried at 20°45 min

- dried at 80°10 min

Table 5:
The film thickness of 500 μm in a wet condition, marked on the separating paper
CompositionExample 13Example 14Example 15
UV-curable PU dispersion
Example 4 [g]360,0
Example 5 [g]360,0
Example 6 [g]360,0
The polyisocyanate And"/td>
Example 10 [g]40,040,040,0
Irgacure® 500 [y]2,83,03,0
The ratio of components in the mixture90:1090:1090:10
The non-volatile portion of the mixture [%]34,43837,7
Irgacure® 500 per fixed part2%2%2%
Cooking pastes
A mixture of [g]200,0200,0200,0
Ammonia 25%3 ml2 ml2 ml
Mirox®AM, 1:1 in N2O3 ml3.5 ml2 ml
Tensile testing of free films
Module 100% [MPa]0,40,50,4
Ultimate tensile strength [MPa]0,50,60,6
Elongation at break [%]450590610
14 days hydrolysisspreads spreadsspreads
Ultimate tensile strength [MPa]
Elongation at break [%]
Mirox® AM = g (Stockhausen, Krefeld, Germany)

2. Conditions (comparison)

- dried at 20°45 min

- dried at 80°10 min

- dried at 150°30 min

Table 6:
The film thickness of 500 μm in a wet condition, marked on the separating paper
CompositionExample 13Example 14Example 15
UV-curable PU dispersion
Example 4 [g]360,0
Example 5 [g]360,0
Example 6 [g]360,0
The polyisocyanate And"
Example 10 [g]40,040,040,0
Irgacure® 500 [y]2,83,03,0
The ratio of components in the mixture90:1090:1090:10
The non-volatile portion of the mixture [%]34,43837,7
Irgacure® 500 per fixed part2%2%2%
Cooking pastes
A mixture of [g]200,0200,0200,0
Ammonia 25%3 ml2 ml2 ml
Mirox®AM, 1:1 in N2O3 ml3.5 ml2 ml
Tensile testing of free films
Module 100% [MPa]33,11,8
Ultimate tensile strength [MPa]4.34,3the 3.8
Elongation at break [%]290270380
14 days hydrolysisspreadsspreadsspreads
Ultimate tensile strength [MPa]
Elongation at break [%]
Mirox® AM = g (Stockhausen, Krefeld, Germany)

3. Conditions (comparison)

- dried at 20°45 min

- dried at 80°10 min

UV-drying: 2.5 m/min 80 W/cm

Table 7:
The film thickness of 500 μm in a wet condition, marked on the separating paper
CompositionExample 13Example 14Example 15
UV-curable PU dispersion
Example 4 [g]360,0
Example 5 [g]360,0
Example 6 [g]360,0
The polyisocyanate And"
Example 10 [g]40,040,040,0
Irgacure® 500 [y]2,83,03,0
The ratio of the components of the mixture 90:1090:1090:10
The non-volatile portion of the mixture [%]34,43837,7
Irgacure® 500 per fixed part2%2%2%
Cooking pastes
A mixture of [g]200,0200,0200,0
Ammonia 25%3 ml2 ml2 ml
Mirox®AM, 1:1 VN3 ml3.5 ml2 ml
Tensile testing of free films
Module 100% [MPa]5,63,63,4
Ultimate tensile strength [MPa]6,84,44,6
Elongation at break [%]120120130
14 days hydrolysis
Ultimate tensile strength [MPa]11,79,29,2
Elongation at break [%]120130140
4 weeks hydrolysis
Tensile strength p and tensile [MPa] 11,59,39,6
Elongation at break [%]100120130
6 weeks hydrolysis
Ultimate tensile strength [MPa]11,911,511
Elongation at break [%]140160160
8 weeks hydrolysis
Ultimate tensile strength [MPa]8,77,79,9
Elongation at break [%]140180160
10 weeks hydrolysis
Ultimate tensile strength [MPa]5,9a 3.98,1
Elongation at break [%]170210170
Mirox® AM = g (Stockhausen, Krefeld, Germany)

4. Conditions (according to the invention)

- dried at 20°45 min

- dried at 80°10 min

UV-drying: 2.5 m/min 80 W/cm

- dried at 150°30 min

200,0
Table 8:
The film thickness of 500 μm in a wet condition, marked on the separating paper
CompositionExample 13Example 14Example 15
UV-curable PU dispersion
Example 4 [g]360,0
Example 5 [g]360,0
Example 6 [g]360,0
The polyisocyanate And"
Example 10 [g]40,040,040,0
Irgacure® 500 [y]2,83,03,0
The ratio of components in the mixture90:1090:1090:10
The non-volatile portion of the mixture [%]34,43837,7
Irgacure® 500 per fixed part2%2%2%
Cooking pastes
A mixture of [g]200,0200,0
Ammonia 25%3 ml2 ml2 ml
Mirox®AM, 1:1 in N2O3 ml3.5 ml2 ml
Tensile testing of free films
Module 100% [MPa]not measurednot measurednot measured
Ultimate tensile strength [MPa]2119,118,4
Elongation at break [%]505050
14 days hydrolysis
Ultimate tensile strength [MPa]16,814,715,4
Elongation at break [%]606060
4 weeks hydrolysis
Ultimate tensile strength [MPa]1817,617
Elongation at break [%]507050
6 weeks hydrolysis
Ultimate tensile strength [MPa]16,51,7 18,1
Elongation at break [%]707050
8 weeks hydrolysis
Ultimate tensile strength [MPa]14,611,715,4
Elongation at break [%]908070
10 weeks hydrolysis
Ultimate tensile strength [MPa]11,410,712,8
Elongation at break [%]11011070
Mirox® AM = g (Stockhausen, Krefeld, Germany)

1. Aqueous composition for coatings containing

(I) at least one polyisocyanate (A),

(II) at least one polyurethane (B), with the contents of the groups having active Servicenow hydrogen atoms, from 0 to 0.53 mmol/g and which is the reaction product

(a) one or more polyisocyanates,

(B1) one or more compounds with gidrofiliziruyuschim, with ionic groups and/or groups capable of translation into ionic groups and/or nonionic groups,

(B2) one or more compounds with osobnych to radical polymerization, containing unsaturated acrylate or methacrylate group,

(B3) optionally, one or more polyols with an average molecular weight of 50-500 and a hydroxyl functionality greater than or equal to 2 and less than or equal to 3,

(B4) optionally, one or more polyols with an average molecular weight from 500 to 13,000 g/mol and an average hydroxyl functionality of from 1.5 to 2.5, and

(B5) optionally, one or more di - or polyamines, and

(III) the initiator (In)capable of causing radical polymerization.

2. Water) for coating according to claim 1, characterized in that the polyisocyanate (A) is used in the form of non-blocked MDI (A') or blocked MDI (A").

3. An aqueous composition for coating according to claim 1, characterized in that the polyisocyanate (A') is a polyisocyanate or mixture of polyisocyanates with which the structure and/or biuret structure based on 1,6-diisocyanatohexane (HDI), isophoronediisocyanate (IPDI) and/or 4,4'-diisocyanato-dicyclohexylmethane.

4. An aqueous composition for coating according to claim 1, characterized in that the polyisocyanate (A') hydrophilic modified.

5. An aqueous composition for coating according to claim 1, characterized in that the polyisocyanate (A') is hydrophilizing due to internal emulsifier a polyisocyanate.

6. Water status is in the coating according to claim 1, characterized in that the polyisocyanate (A') is allianceofdelray, hydrophilizing simple polyester polyisocyanate.

7. An aqueous composition for coating according to claim 1, characterized in that the polyisocyanate (A) is dispersible in water or water-soluble blocked polyisocyanate.

8. An aqueous composition for coating according to one of claims 1 to 7, characterized in that the initiator (C) is activated by radiation and/or thermal initiator.



 

Same patents:

FIELD: powder covers.

SUBSTANCE: invention relates to a powder cover composition and to a method for its preparing that forms cover with reduced luster after hardening. Composition comprises one or some cross-linked basic polymers: cross-linked polyester, cross-linked polyurethane, cross-linked acrylated polyether and their combinations, about from 5 to 60 wt.-%; cross-linked acrylic polymer with solidification point about from 40°C to 100°C, and about 0.1 to 10 wt.-% of one or some free-radical initiating agents. Additional reducing luster and improved smoothness can be obtained by addition spheroidal particles to the powder cover composition. Proposed compositions can be used for making covers on metallic backings, such as vehicle bodies and on nonmetallic backings, such as backings made of pressed wood materials with impregnation used for making table tops of different species.

EFFECT: improved and valuable properties of covers.

21 cl, 4 tbl

FIELD: polymers, covering compositions.

SUBSTANCE: invention relates to photoactivating aqueous-base covering composition. The proposed composition comprises the following components: a)(meth)acryloyl-functional polyurethane dispersion wherein this (meth)acryloyl-functional polyurethane comprises from 5 to 18 weight % of alkylene-oxide groups and (meth)acryloyl functionality represents a value in the range from 2 to 40, and b) UV-initiating agent. The presence of reactive diluting agent in the covering composition is preferable. (Meth)acryloyl-functional polyurethane can be prepared by carrying out the following interactions: a) at least one organic polyisocyanate; b) optionally, at least one organic compound comprising at least two isocyanate-reactive groups and having an average molecular mass in the range from 400 to 6000 Da; c) at least one isocyanate-reactive and/or isocyanate-functional compound comprising non-ionogenic dispersing groups; d) at least one isocyanate-reactive (meth)acryloyl-functional compound; e) optionally, at least one chain elongating agent comprising active hydrogen, and f) optionally, at least one compound comprising active hydrogen and ionic groups. Aqueous-base covering composition is useful especially for applying as a clear cover. Covers based on the proposed composition show resistance to water, solvents and scratches and flexibility and high adhesion also.

EFFECT: improved and valuable properties of composition.

15 cl, 12 tbl, 17 ex

The invention relates to compositions based on emulsified resins, curable by ultraviolet radiation, which includes: unmodified oligomers as the basis of composition, which determines the final properties of the cured product; curing agents consisting of polyfunctional monomers; photoinitiator initiating polymerization; additives to make the product special properties

The invention relates to the field of coatings, curing under the action of radiation of low energy in the wavelength range of 400-700 nm and used in such fields as dentistry, electronics, printing

FIELD: polymers, covering compositions.

SUBSTANCE: invention relates to photoactivating aqueous-base covering composition. The proposed composition comprises the following components: a)(meth)acryloyl-functional polyurethane dispersion wherein this (meth)acryloyl-functional polyurethane comprises from 5 to 18 weight % of alkylene-oxide groups and (meth)acryloyl functionality represents a value in the range from 2 to 40, and b) UV-initiating agent. The presence of reactive diluting agent in the covering composition is preferable. (Meth)acryloyl-functional polyurethane can be prepared by carrying out the following interactions: a) at least one organic polyisocyanate; b) optionally, at least one organic compound comprising at least two isocyanate-reactive groups and having an average molecular mass in the range from 400 to 6000 Da; c) at least one isocyanate-reactive and/or isocyanate-functional compound comprising non-ionogenic dispersing groups; d) at least one isocyanate-reactive (meth)acryloyl-functional compound; e) optionally, at least one chain elongating agent comprising active hydrogen, and f) optionally, at least one compound comprising active hydrogen and ionic groups. Aqueous-base covering composition is useful especially for applying as a clear cover. Covers based on the proposed composition show resistance to water, solvents and scratches and flexibility and high adhesion also.

EFFECT: improved and valuable properties of composition.

15 cl, 12 tbl, 17 ex

FIELD: powder covers.

SUBSTANCE: invention relates to a powder cover composition and to a method for its preparing that forms cover with reduced luster after hardening. Composition comprises one or some cross-linked basic polymers: cross-linked polyester, cross-linked polyurethane, cross-linked acrylated polyether and their combinations, about from 5 to 60 wt.-%; cross-linked acrylic polymer with solidification point about from 40°C to 100°C, and about 0.1 to 10 wt.-% of one or some free-radical initiating agents. Additional reducing luster and improved smoothness can be obtained by addition spheroidal particles to the powder cover composition. Proposed compositions can be used for making covers on metallic backings, such as vehicle bodies and on nonmetallic backings, such as backings made of pressed wood materials with impregnation used for making table tops of different species.

EFFECT: improved and valuable properties of covers.

21 cl, 4 tbl

FIELD: chemistry.

SUBSTANCE: aqueous composition for coatings has a rapid curing mechanism and allows cross-linking of poorly illuminated areas, the composition comprising (I) at least one polyisocyanate (A), (II) at least one polyurethane (B) containing from 0 to 0.53 mmole/g of active, according to Tserevitinov, hydrogen atoms and being a product of reaction of: (a) one or several polyisocyanates, (b1) one or more compounds with hydrophilising action having ion groups and/or groups transferable to ion groups, and/or non-ionic groups, (b2) one or more compounds capable of radical polymerisation and including unsaturated acrylate or methacrylate groups, (b3) if necessary, one or more polyols with an average molecular weight of 50-500 and a hydroxyl functionality more than or equal to 2 and less than or equal to 3, (b4) if necessary, one or more polyols with an average molecular weight of 500 to 13,000 g/mole and an average hydroxyl functionality of 1.5 to 2.5, and (b5) if necessary, one or more di- or polyamines, and (III) an initiator (C).

EFFECT: capable to cross-link poorly illuminated areas and to cause radical polymerisation.

8 cl, 15 ex, 8 tbl

FIELD: chemistry.

SUBSTANCE: powdered coating agent contains solid particles of a resin-polyurathane binding substance with equivalent mass of olefinic double bonds ranging from 200 to 2000 and content of silicon bonded in alkoxy silane groups ranging from 1 to 10 mass % and a photoinitiator. In the method of obtaining a single layered or multilayered coating on substrates, in particular when obtaining multilayered coating for transportation equipment and their components (car body or car body components coating), at least one layer of this coating is deposited from a powdered coating agent. In that case, solidification of at least one layer of the above mentioned powdered coating is achieved through free-radical polymerisation of olefinic double bonds when irradiated with high energy radiation and through formation of siloxane atomic bridges under the effect of moisture.

EFFECT: obtaining a powdered coating, which is hard, has scratch resistance and good resistance to chemical effects.

8 cl, 1 tbl

FIELD: chemistry.

SUBSTANCE: invention concerns method of obtaining polyurethanedi(met)acrylates applicable as binders for powder coatings applied on metal substrates, plastic parts, fiber-reinforced plastic parts. Polyurethanedi(met)acrylates are obtained by interaction of diisocyanate component, diol component and hydroxy-C2-C4-alkyl(met)acrylate at mol ratio of x:(x-1):2, where x takes any value from 2 to 5. 1,6-hexanediisocyanate comprises 50 to 80 mol % of diisocyanate component, and one or two diisocyanates selected out of defined diisocyanate group where mol content of respective diisocyanates amount to 100 mol % comprise(s) 20 to 50 mol %, so that each diisocyanate comprises at least 10 mol % of diisocyanate component. Diol component includes not more than four different diols, and at least one linear aliphatic alpha, omega-C2-C12-diol comprises 20 to 100 mol % of diol component, while at least one (cyclo)aliphatic diol different from linear aliphatic alpha, omega-C2-C12-diols comprises 0 to 80 mol %. Each diol of the diol component comprises at least 10 mol % of diol component, and mol content or respective diols amounts to 100 mol %. Due to the absence of solvent in polyurethanedi(met)acrylate production, further cleaning of end product is not required, thus increasing process product output.

EFFECT: higher acid resistance of coating films applied and solidified with the use of powder coatings containing claimed polyurethanedi(met)acrylates.

6 cl, 15 ex, 3 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to processing polyvinyl chloride through dispersion, particularly to production of highly filled adhesive plastisols used in making protective coatings in motor-car construction, as anticorrosion protection of inner surfaces of metal structures. The method of producing highly filled plastisol based on polyvinyl chloride involves successive addition and mixture in a mixer of di(2-ethylhexyl)phthalate, isopropylbenzene hydroperoxide, half of the given amount of kaolin, calcium strearate, polyvinyl chloride and the remaining amount of kaolin. Hexafunctional oligourethane acrylate, diatomite and NGZ-4 phosphate hydraulic fluid are added before adding polyvinyl chloride, and after adding the remaining amount of kaolin, a polysulphide oligomer - liquid thiocol II with weight ratio of SH groups of 1.7-2.6% and molecular weight of 2100 is added.

EFFECT: high degree of restoration of the thixotropic structure, extrusion, fire resistance and tensile strength of the polyvinyl chloride plastisol and the hardened material.

1 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to processing polyvinyl chloride through dispersion, particularly to production of highly filled adhesive plastisols used in making protective coatings in motor-car construction, as anticorrosion protection of inner surfaces of metal structures. The method of producing highly filled plastisol based on polyvinyl chloride involves successive addition and mixture in a mixer of di(2-ethylhexyl)phthalate, triethylene glycol dimethacrylate, isopropylbenzene hydroperoxide, half of the given amount of kaolin, calcium strearate, polyvinyl chloride and the remaining amount of kaolin. Hexafunctional oligourethane acrylate, diatomite and NGZ-4 phosphate hydraulic fluid are added before adding polyvinyl chloride, and after adding the remaining amount of kaolin, a polysulphide oligomer - liquid thiocol II with weight ratio of SH groups of 1.7-2.6% and molecular weight of 2100 is added.

EFFECT: high degree of restoration of the thixotropic structure, extrusion, fire resistance and tensile strength of the polyvinyl chloride plastisol and the hardened material.

1 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to compositions for protective coating for window glass. The invention discloses a composition which contains a) one or more film-forming resins which contain acrylic and/or methacrylic functional fragments; b) one or more reactive diluents which contain an acrylate functional group; c) one or more compounds which promote adhesion of the composition to glass, which contain a product of a Michael reaction, having four or more siloxane groups, at least one acrylate group and a tertiary amine group; d) one or more filler substances, capable of endowing compositions with wear-resistance in solidified state; and e) one or more compounds which can react with a film-forming resin, which contain at least one acid fragment.

EFFECT: composition ensures high adhesion of the coating to adhesive substances on a structure in the absence of an undercoat.

16 cl, 5 dwg, 28 tbl, 38 ex

FIELD: chemistry.

SUBSTANCE: radiation-curable primary coating composition contains an oligomer, a diluent monomer; a photoinitiator; an antioxidant; and an adhesion promoter; wherein said oligomer is the reaction product of: a hydroxyethyl acrylate; an aromatic isocyanate; an aliphatic isocyanate; a polyol; a catalyst; and an inhibitor. Said oligomer has number-average molecular weight ranging from at least 4000 g/mol to less than or equal to 15000 g/mol; and wherein said catalyst is selected from a group comprising dibutyl tin dilaurate; metal carboxylates, sulphonic acids; catalysts based on amines or organic bases, zirconium and titanium alkoxides and ionic liquid salts of phosphonium, imidazolium and pyridinium.

EFFECT: obtaining a hardened film of said radiation-curable primary coating composition.

6 cl

FIELD: chemistry.

SUBSTANCE: radiation-curable secondary coating composition contains a mixture of secondary coating oligomers which is mixed with a first diluent monomer; a second diluent monomer; an optional third diluent monomer; an antioxidant; a first photoinitiator; a second photoinitiator; and, optionally, a slide-enhancing additive or a mixture of slide-enhancing additives; wherein said mixture of secondary coating oligomers contains: α) Omega-oligomer; and β) Upsilon-oligomer; wherein said Omega-oligomer is synthesised from reaction of α1) hydroxyl-containing (meth)acrylate; α2) isocynate; α3) polyether polyol; and α4) tripropylene glycol; in the presence of α5) a polymerisation inhibitor; and α6) a catalyst; to obtain an Omega-oligomer; wherein said catalyst is selected from a group comprising copper naphthenate, cobalt naphthenate, zinc naphthenate, triethylamine, triethylenediamine, 2-methyltriethylenediamine, dibutyl tin dilaurate, metal carboxylates, sulphonic acids, catalysts based on amines or organic bases, zirconium and titanium alkoxides and ionic liquid salts of phosphonium, imidazolium and pyridinium; and wherein said Upsilon-oligomer is epoxy diacrylate. The method of applying the coating onto an optical fibre involves operation of a glass drawing column to obtain optical glass fibre; applying a radiation-curable primary coating composition onto said optical glass fibre; optional exposure of said radiation-curable primary coating composition to radiation in order to cure said coating; applying a radiation-curable secondary coating composition in paragraph 1 onto said optical glass fibre; and exposing said radiation-curable secondary coating composition to radiation in order to said coating.

EFFECT: obtaining optical fibre and a conductor having a cured secondary coating.

6 cl

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