Coating masses, process for their preparation and the use of selected two-component polyurethane systems as binding agents in this kind of coating masses.

The invention relates to an aqueous two-component polyurethane coating compositions, a process for its preparation and the use of selected two-component polyurethane systems, as binders for such coating compositions.

In the area of ​​surface technology environmental issues play a significant role. A particularly urgent problem is to reduce the amounts used for paints and coating materials of organic solvents.

In chemically crosslinking polyurethane lacquers, which in the coatings sector are of great importance due to their excellent properties, could not be dispensed with so far on organic solvents. The use of water instead of organic solvents in two-component polyurethane coatings based on polyisocyanates having free isocyanate groups seemed far not been possible because it is known that isocyanate groups react not only with alcoholic hydroxyl groups but also with water. In addition, of course, to the concentration, originating from the water, active hydrogen atoms in such systems, much higher than the concentration of hydroxyl groups of organic, NCO-reactive component, so that had to be assumed that in the ternary system / polyisocyanate / organic polyhydroxyl compound / water especially an isocyanate-water reaction with formation of urea and carbon dioxide formation occurs, which does not cause the one hand, to crosslink the organic polyhydroxyl compounds, and on the other hand for the foaming of the paint due to the approach Kohlendioxidbildund.

Although it is known from DE-OS 2,708,442 and DE-OS 3,529,249 already known aqueous polymer dispersions to add organic polyisocyanates to improve the property image, but it is in these plastics on the one hand not to organic polyhydroxyl compounds commonly used in polyurethane chemistry as reactants for polyisocyanates used type, and on the other hand, the effect described in these prior polyisocyanate addition to the aqueous polymer dispersions is presumably due to an envelope of the dispersed resin with the urea formed from polyisocyanate and water.

As has now been found, surprisingly, it is possible with the use of selected organic polyhydroxy compounds, that is, thereby to produce from polyhydroxy polyacrylates of the type described in detail below as a reaction partner for organic polyisocyanates with free isocyanate groups aqueous two-component polyurethane coating compositions, characterized in that the polyisocyanates containing free isocyanate groups in the aqueous polymer solution or dispersion is emulsified. The coating compositions of the invention described below have a pot life of several hours and harden to form high quality crosslinked films which are the varnish films previously obtained from solvent-based two-component polyurethane coatings comparable with respect to their property profile. This is for the above reasons highly surprising since one would have expected that such a selective reaction between the polyisocyanate and the dissolved or dispersed in water, hydroxyl-containing polymer does not take place.

The invention is, therefore, an optionally the customary auxiliaries and additives containing two-component coating compositions containing as binder components<ul><li>a) a polyol component consisting of at least one hydroxyl-containing polymer of olefinically unsaturated compounds and</li><li>b) a polyisocyanate component of a viscosity at 23 ° C from 50 to 10000 mPa.s, consisting of at least one organic polyisocyanate</li></ul> in an NCO / OH equivalent ratio of 0.5: 1 to 5: 1 is appropriate amounts, characterized in that component a) having an aqueous solution and / or dispersion of a hydroxyl polymer represents, in which the polyisocyanate component b is present emulsified) ,

The invention also provides a process for producing such a coating agent, which is characterized in that, in an aqueous solution or dispersion of one or more hydroxyl groups Direction polymer resins having a solubility and / or dispersibility effecting in water quantity of chemically incorporated sulphonate and / or carboxylate groups, a polyisocyanate component of a viscosity at 23 ° C from 50 to 10000 mPa.s, consisting of at least one organic polyisocyanate, is emulsified, the amount ratios of the two components to an NCO / OH equivalent ratio, based on the isocyanate groups of polyisocyanate component and the incorporated hydroxyl groups of the polymer component, of 0.5: 1 to 5: 1 correspond, and wherein the optionally used auxiliary substances and additives of the polymer solution and / or dispersion have been incorporated prior to addition of the polyisocyanate component.

The invention also provides the use of combinations of<ul><li>a) hydroxyl-containing polymers of olefinically unsaturated monomers with </li><li>b) organic polyisocyanates having a viscosity at 23 ° C from 50 to 10000 mPa.s</li></ul> in, an NCO / OH equivalent ratio of 0.5: 1 to 5: 1 corresponding quantities as binders in aqueous two-component coating compositions.

When component a) is hydroxyl, sulphonate and / or carboxylate groups, preferably carboxylate groups and optionally sulphonic acid and / or carboxyl groups, preferably carboxyl groups are polymers of olefinically unsaturated monomers, preferably a determinable by gel permeation chromatography molecular weight M_n (Number average) of 500 to 50,000, in particular 1,000 to 10,000, a hydroxyl value from 16.5 to 264, preferably 33 to 165 mg KOH / g solid resin, an acid number (based on the unneutralized sulfonic acid and / or carboxyl groups) of from 0 to 150, preferably from 0 to 100 mg KOH / g solid resin and a content of sulfonate and / or carboxylate groups 5-417, preferably 24-278 milliequivalents per 100 g solids comprise particular preference is it with these anionic groups are carboxylate groups.

The polymer resins a) are used in the preparation of the coating compositions of the invention generally in the form of 10 to 50, preferably 20 to 40 wt .-% aqueous solutions and / or dispersions are used, which generally have a viscosity of up to 10 , preferably 10⁵ 100 to 10,000 mPa.s / 23 ° C and pH values ​​of 5 to 10, preferably 6 to 9

Depending on the molecular weight of the polymers and their content of anionic groups or to free acid groups, especially carboxyl groups are in the aqueous, the polymers containing systems to true dispersions, colloidally or molecularly dispersions, but in general, so-called "partial dispersions", ie to aqueous systems which are partly molecularly in colloidal and partly.

The preparation of the hydroxyl-containing polymers is carried out by per se known copolymerization of olefinically unsaturated monomers, comprising as monomers both hydroxyl monomers and acid groups, that is, sulfonic acid groups or carboxyl groups, preferably carboxyl-containing monomers are copolymerized in general together with other monomers, according to which the present acid groups are at least partially neutralized.

The concomitant use of acid group-containing monomers is carried out for the purpose of incorporation of carboxyl and / or sulfonic acid groups into the copolymers which ensure the solubility or dispersibility of the polymers, especially after at least partial neutralization of the acid groups because of their hydrophilicity. The amount of associated "acidic" comonomers and the degree of neutralization of the first resultant "acidic" polymers corresponds to the statements made above with respect to the acid value and the content of sulfonate and / or carboxylate groups. In general, the "acidic" come comonomers in amounts of from 1 to 30, preferably 5 to 20 wt .-%, based on the total weight of the monomers used. When using less than 5 wt .-% of "acidic" monomers resulting in general even after complete neutralization of aqueous dispersions in which most a small proportion of polymer is molecularly dissolved. Going to higher levels of "acidic" monomers through at constant degree of neutralization, resulting rising shares in molecularly dissolved species, until finally wt .-% the colloidal components disappear at levels above about 12th

Suitable "acid" comonomers are in principle all olefinically unsaturated polymerizable compounds which contain at least one carboxyl and / or sulfonic acid group include such as olefinically unsaturated mono- or dicarboxylic acids in the molecular weight range of 72-207, such as acrylic acid, methacrylic acid, maleic acid, itaconic acid or sulfonic acid groups having olefinically unsaturated compounds such as 2-acrylamido-2-methyl propane sulfonic acid, or mixtures of such olefinically unsaturated acids.

Hydroxyl-containing monomers are used in amounts such that the hydroxyl numbers of the above-mentioned polymers result which contain 1 to 5 correspond to the rest generally a hydroxyl group content of the polymers of 0.5 to 8, preferably wt .-%. In general, the hydroxy functional comonomers are used in amounts of 3 to 75, preferably 6 to 47 wt .-% co-used, based on the total weight of the monomers employed. In addition, care must be taken, of course that the amount of hydroxy-functional monomers is selected so as part of the information provided, to form copolymers which have at least two hydroxyl groups on average per molecule.

Suitable hydroxyl-containing monomers are especially hydroxyalkyl esters of acrylic or methacrylic acid preferably having 2 to 4 carbon atoms in the alkyl group such as 2-hydroxyethyl acrylate or methacrylate, 2- or 3-hydroxypropyl acrylate or methacrylate, the isomeric hydroxybutyl acrylates or methacrylates and any mixtures of such monomers ,

A third group of olefinically unsaturated monomers that are used in the preparation of the copolymers generally, such olefinically unsaturated compounds may be mentioned, having neither acidic groups nor hydroxyl groups. These include, for example, esters of acrylic acid or of methacrylic acid with 1 to 18, preferably 1 to 8 carbon atoms in the alcohol radical, such as methyl acrylate, ethyl acrylate, isopropyl acrylate, n-propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, n-stearyl acrylate that these acrylates corresponding methacrylates , styrene, alkyl-substituted styrenes, acrylonitrile, methacrylonitrile, vinyl acetate or vinyl stearate, or any mixtures of such monomers. Comonomers containing epoxide groups such as glycidyl acrylate or methacrylate, or monomers such as N-methoxymethyl acrylamide or methacrylamide can be used in small quantities.

The monomers of the latter third group without acid and hydroxyl groups are generally used in amounts of up to 90 wt .-%, preferably 40 to 80 wt .-%, based on the total weight of monomers used.

The preparation of the polymers can be carried out by polymerization according to conventional methods. Preferably, the polymers are prepared in organic solution. The substance may have continuous or discontinuous polymerization. Of the batch process, the batch and the feed process may be mentioned, the latter being preferred. In the feed process, the solvent is presented alone or with a part of the monomer mixture, heated to the polymerization temperature, the polymerization is initiated in the case of initial monomer radical and the remaining monomer mixture together with an initiator mixture over a period of 1 to 10 hours, preferably 3 to 6 hours metered. Optionally is subsequently reactivated, by up to a conversion carry out the polymerization of at least 99%.

For example, aromatics such as benzene, toluene, xylene, chlorobenzene, esters such as ethyl acetate, butyl acetate, methyl glycol acetate, ethyl glycol acetate, methoxypropyl acetate, ethers such as butyl glycol, tetrahydrofuran, dioxane, Ethylglycolether, ketones such as acetone, methyl ethyl ketone, and halogenated solvents such as methylene chloride or trichloromonofluoroethane suitable solvents consideration.

The init oriented by radical polymerization can be triggered by initiators whose half-lives of the radical decay at 80 to 180 ° C 0.01 to 400 are min. In general, the copolymerization reaction is carried out in the stated temperature range, preferably between 100 and 160 ° C, under a pressure of from 10³ to 2 x 10⁴ mbar, where the exact polymerization temperature depends on the type of the initiator. The initiators are used in amounts of from 0.05 to 6 wt .-%, based on the total amount of monomers.

Suitable initiators include aliphatic azo compounds such as azoisobutyronitrile and peroxides such as dibenzoyl peroxide, t-butyl perpivalate, t-butyl per-2-ethylhexanoate, t-butyl perbenzoate, t-butyl hydroperoxide, di-t-butyl peroxide, cumene hydroperoxide and dicyclohexyl and dibenzyl peroxydicarbonate.

To control the molecular weight of the polymers, conventional regulators can be used, such as n-dodecyl, diisopropyl, di (methylentrimethylolpropan) xanthogen and thioglycol. They are added in amounts of not more than 3 wt .-% of the monomer mixture.

After completion of polymerization, the copolymers are transferred into an aqueous solution or dispersion. For this purpose, the organic polymer solution is introduced into a usually pre-heated water phase and at the same time the organic solvent by distillation, generally carried out under application of a vacuum, removed. In order to achieve good solubility or dispersibility, the water phase is generally required, a neutralizing agent such as inorganic bases, ammonia or amines, may be added. As inorganic bases, for example sodium hydroxide, the amines are used in addition to ammonia, trimethylamine, triethylamine, dimethylethanolamine. The neutralizing agent can also be used both in excess stoichiometric lower than, the aforementioned levels of sulfonate and / or carboxylate groups, in particular carboxylate groups and the above-mentioned acid values ​​result. In the case of complete neutralization of the acid groups present then the resulting acid number zero, while the content of sulfonate and / or carboxylate groups corresponding to the original content of sulphonic acid groups or carboxyl groups. In a partial neutralization, the contents of sulfonate and / or carboxylate groups in the amount of neutralizing agent used comply. Particularly when using a stoichiometric excess of neutralizing agent, however, it must be ensured that a distinct increase in viscosity can be done by the polyelectrolyte character of the polymers. The resulting aqueous solutions or dispersions have the abovementioned concentrations and viscosities and generally have a content of residual solvent of less than 5 wt .-%, preferably of less than 2 wt .-% to. The virtually complete removal also of higher boiling solvents as water is possible by azeotropic distillation.

The polyisocyanate component b) is any organic polyisocyanates with aliphatic, cycloaliphatic, araliphatic and / or aromatically bonded, free isocyanate groups which are liquid at room temperature. The polyisocyanate component b) has at 23 ° C generally have a viscosity from 50 to 10,000, preferably 50 to 1000 mPa · s. Particularly preferably, the polyisocyanate component b) polyisocyanates or polyisocyanate mixtures with exclusively aliphatically and / or cycloaliphatically bound isocyanate groups a lying 2.2 to 5.0 (average) NCO functionality and a viscosity at 23 ° C of 50 to 500 mPa.s

If necessary, the polyisocyanates can be mixed with small amounts of inert solvents in order to lower the viscosity to a value within the ranges mentioned. The amount of such solvents is a maximum such that wt .-% solvent, based on the amount present in the novel coating compositions ultimately obtained a maximum of 20 of water, which also optionally in the polymer or even solutions solvent present in the calculation received. Suitable additives for the polyisocyanates suitable solvents include aromatic hydrocarbons such as "solvent naphtha" or solvent of the above type exemplified.

As component b) suitable polyisocyanates are in particular the so-called "paint polyisocyanates" having aromatically or (cyclo) aliphatically bound isocyanate groups, the latter aliphatic polyisocyanates, as already stated, are particularly preferred.

Very suitable are, for example, "lacquer polyisocyanates" based on hexamethylene diisocyanate or on 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane (IPDI) and / or bis (isocyanato) methane, especially those which exclusively hexamethylene diisocyanate. "Lacquer polyisocyanates" based on these diisocyanates known per se containing biuret, urethane, uretdione and / or isocyanurate groups are having to understand derivatives of these diisocyanates that until after their manufacture in a known manner, preferably by distillation, from excess starting on a residual content of less than 0.5 wt .-% have been freed. Preferred, according to the invention to use aliphatic polyisocyanates include the above criteria, Biretgruppen polyisocyanates based on hexamethylene diisocyanate, such as those described by the processes of US Patents 3,124,605, 3,358,010, 3,903,126, 3,903,127, or 3 976 622 can be obtained, and the mixtures of N, N ', N-tris (6-isocyanato) biuret with minor amounts of its higher homologs, as well as meet the criteria mentioned cyclic trimers of hexamethylene diisocyanate, as described in US -PS 4,324,879 can be obtained, and the substantially N, N ', N-tris (6-isocyanato) isocyanurate mixed with minor amounts of its higher homologs. Particularly preferred are the corresponding criteria specified mixtures of uretdione and / or isocyanurate polyisocyanates based on hexamethylene diisocyanate, as are formed by catalytic oligomerization of hexamethylene diisocyanate using trialkyl. Particularly preferably, the latter mixtures with a viscosity at 23 ° C of 50 to 500 mPa.s and an 2.2 to 5.0 NCO functionality.

In accordance with the invention also suitable, but less preferred aromatic polyisocyanates are in particular "paint polyisocyanates" based on 2,4-diisocyanatotoluene or technical mixtures thereof with 2,6-diisocyanatotoluene or based on 4,4'-diisocyanatodiphenylmethane or mixtures with its isomers and / or higher homologues. Such aromatic lacquer polyisocyanates are, for example, isocyanates containing urethane groups as obtained by reacting excess amounts of 2,4-diisocyanatotoluene with polyhydric alcohols such as trimethylolpropane and subsequent distillative removal of the unreacted diisocyanate excess Further aromatic lacquer polyisocyanates are, for example, the trimers of the type exemplified monomeric diisocyanates, that is, the corresponding isocyanato-isocyanurates, which are also preferably freed by distillation from excess monomeric diisocyanates, subsequent to their preparation.

Basically possible is of course also possible to use unmodified polyisocyanates of the type exemplified above, if they comply with the statements made with respect to the viscosity.

The polyisocyanate component b) can moreover consist of mixtures of the polyisocyanates exemplified.

To prepare the ready-coating agent, the polyisocyanate component b) is emulsified in the aqueous dispersion of the polymers a), wherein the dissolved or dispersed polymer simultaneously assumes the function of an emulsifier for the added polyisocyanate. This is especially true for the preferred case of the use of hydrophilically modified polyisocyanates b). Basically possible, but less preferred is the use of hydrophilically modified polyisocyanates as a polyiso cyanate component b), which are self due to the built-ionic or nonionic hydrophilic centers.

The mixing can take place by simple stirring at room temperature. The amount of the polyisocyanate component is in this case dimensioned such that an NCO / OH equivalent ratio, based on the isocyanate groups of component B) and the alcoholic hydroxyl groups of component a) of 0.5: 1 to 5: 1, preferably 0.8: 1 to 2: 1 result.

Prior to the addition of the polyisocyanate component b) can the polymer component a), ie, the dispersion or solution of the polymers, the customary auxiliaries and additives of paint technology are incorporated. Etc. These include, for example, defoamers, leveling agents, pigments, dispersants for pigment distribution.

The resulting coating compositions are suitable for virtually all applications in which find today solventborne, solvent-free or other types of aqueous paint and coating systems with an increased property profile using, for example: coating practically all mineral building materials such as lime and / or cement-bound Patze , gypsum-containing surfaces, fiber-cement building materials, concrete; Painting and sealing of wood and wood-based materials such as chipboard, fibreboard and paper; Lacquering and coating of metallic surfaces; Coating and painting asphaltic or bituminous road surfaces; Painting and sealing of various plastics surfaces; moreover, they are suitable for surface bonding of various materials, with similar and dissimilar materials are joined together.

In the following examples, all percentages are percentages by weight.

Examples

Starting materials:

polyisocyanate 1

Mixture of 70 parts by weight of a uretdione, therefore dimerized hexamethylene diisocyanate containing two terminal, free NCO groups and 30 parts by weight of the substantially for N, N ', N-tris (6-isocyanato) isocyanurate trimerized hexamethylene diisocyanate in admixture with minor quantities of higher homologs of both products polyisocyanate 1 has in its 100% strength, ie solvent-free form supplied an average viscosity of 150 mPa.s / 23 ° C and an average content of free NCO groups of 22.5%.

polyisocyanate 2

N, N ', N-tris (6-isocyanato) biuret with minor amounts of its higher homologs. The 100% product has an average NCO content of 22.5 wt .-% and an average viscosity of about 3000 mPa.s / 23 ° C.

polyisocyanate 3

N, N ', N-tris (6-isocyanato) isocyanurate with minor amounts of higher homologues, as it can be obtained according to US Patent No. 4,324,879 The 100% product has a viscosity of about 3200 mPa.s / 23 ° C and an average NCO content of 21.5 at.

polyisocyanate 4

Polyisocyanate prepolymer which has been prepared by reacting 80 parts by weight Polyisocyanate 2 and 20 parts by weight of a saturated polyester of phthalic acid and propylene glycol having a hydroxyl group content of 2%. The prepolymer has 65% solution in solvent naphtha 100 / methoxypropyl (weight ratio of solvent = 4: 1) an NCO content of 10.4% and a viscosity of 1300 mPa.s / 23 ° C.

polyisocyanate 5

The polyisocyanate mixture of the diphenylmethane series, which as 100% substance having an NCO content of 31% and a viscosity of 120 mPa.s / 23 ° C.

Polymer resins A to H:

Preparation Method:

In a 3 1 stirred autoclave with a reflux condenser, effective stirrer and gas inlet and outlet, the original I (see. Table) is introduced and purged with nitrogen. Then, nitrogen is passed in a steady stream and heats the template with stirring at about 200 rev / min to an internal temperature of 110 ° C. Then the mixture II is metered in uniformly over the course of 4 hours. After completion of the addition is about 30 minutes. stirred and then reactivated with the mixture III. The reaction time is 6 hours. about 100 ml of residual monomers are then at a vacuum of about 200 to 400 mbar distilled off together with the solvent, butyl acetate. The amount distilled out is replaced by fresh solvent. Dissolved in the organic solvent, polymer resins possess also indicated in the table physico-chemical data.

In order to convert the organic solution in an aqueous solution or dispersion, the mixtures IV and heated with stirring to about 95 ° C in a 8 liter reactor. Then, the organic polymer solutions in the course of about 0.5 to 1 hour are metered and simultaneously removed butyl acetate by azeotropic distillation. The amount of water distilled off is replaced continuously. With an approximately 25% aqueous ammonia solution, or with N-dimethylethanolamine (Example H) is adjusted to a pH of 7 to 8 The physico-chemical data of the aqueous polymer solutions or dispersions are also listed in the table. The solvent content of the finally obtained aqueous dispersions part is always less than 2%.<tables id="tabl0001" num="0001"><table frame="all"><tgroup cols="9" colsep="1" rowsep="0"><colspec colnum="1" colname="col1" colwidth="17.50mm" /><colspec colnum="2" colname="col2" colwidth="17.50mm" /><colspec colnum="3" colname="col3" colwidth="17.50mm" /><colspec colnum="4" colname="col4" colwidth="17.50mm" /><colspec colnum="5" colname="col5" colwidth="17.50mm" /><colspec colnum="6" colname="col6" colwidth="17.50mm" /><colspec colnum="7" colname="col7" colwidth="17.50mm" /><colspec colnum="8" colname="col8" colwidth="17.50mm" /><colspec colnum="9" colname="col9" colwidth="17.50mm" /><thead valign="top"><row><entry namest="col1" nameend="col1" align="center">-</entry><entry namest="col2" nameend="col2" rowsep="0" align="center">A</entry><entry namest="col3" nameend="col3" rowsep="0" align="center">B</entry><entry namest="col4" nameend="col4" rowsep="0" align="center">C</entry><entry namest="col5" nameend="col5" rowsep="0" align="center">D</entry><entry namest="col6" nameend="col6" rowsep="0" align="center">e</entry><entry namest="col7" nameend="col7" rowsep="0" align="center">F</entry><entry namest="col8" nameend="col8" rowsep="0" align="center">G</entry><entry namest="col9" nameend="col9" rowsep="0" align="center">H</entry></row><row><entry namest="col1" nameend="col1" align="left"><u>I. template</u></entry><entry namest="col2" nameend="col2" /><entry namest="col3" nameend="col3" /><entry namest="col4" nameend="col4" /><entry namest="col5" nameend="col5" /><entry namest="col6" nameend="col6" /><entry namest="col7" nameend="col7" /><entry namest="col8" nameend="col8" /><entry namest="col9" nameend="col9" /></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">Butyl acetate (g)</entry><entry namest="col2" nameend="col2" align="char" char=",">900</entry><entry namest="col3" nameend="col3" align="char" char=",">900</entry><entry namest="col4" nameend="col4" align="char" char=",">900</entry><entry namest="col5" nameend="col5" align="char" char=",">900</entry><entry namest="col6" nameend="col6" align="char" char=",">900</entry><entry namest="col7" nameend="col7" align="char" char=",">900</entry><entry namest="col8" nameend="col8" align="char" char=",">900</entry><entry namest="col9" nameend="col9" align="char" char=",">900</entry></row></tbody></tgroup><tgroup cols="9" colsep="1" rowsep="0"><colspec colnum="1" colname="col1" colwidth="17.50mm" /><colspec colnum="2" colname="col2" colwidth="17.50mm" /><colspec colnum="3" colname="col3" colwidth="17.50mm" /><colspec colnum="4" colname="col4" colwidth="17.50mm" /><colspec colnum="5" colname="col5" colwidth="17.50mm" /><colspec colnum="6" colname="col6" colwidth="17.50mm" /><colspec colnum="7" colname="col7" colwidth="17.50mm" /><colspec colnum="8" colname="col8" colwidth="17.50mm" /><colspec colnum="9" colname="col9" colwidth="17.50mm" /><thead valign="top"><row><entry namest="col1" nameend="col1" align="left">II.</entry><entry namest="col2" nameend="col2" /><entry namest="col3" nameend="col3" /><entry namest="col4" nameend="col4" /><entry namest="col5" nameend="col5" /><entry namest="col6" nameend="col6" /><entry namest="col7" nameend="col7" /><entry namest="col8" nameend="col8" /><entry namest="col9" nameend="col9" /></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">Methacrylic acid 2-hydroxyethyl (g)</entry><entry namest="col2" nameend="col2" align="char" char=",">344</entry><entry namest="col3" nameend="col3" align="char" char=",">459</entry><entry namest="col4" nameend="col4" align="char" char=",">574</entry><entry namest="col5" nameend="col5" align="char" char=",">459</entry><entry namest="col6" nameend="col6" align="char" char=",">459</entry><entry namest="col7" nameend="col7" align="char" char=",">459</entry><entry namest="col8" nameend="col8" align="char" char=",">459</entry><entry namest="col9" nameend="col9" align="char" char=",">459</entry></row><row><entry namest="col1" nameend="col1" align="left">Methyl methacrylate (g)</entry><entry namest="col2" nameend="col2" align="char" char=",">323</entry><entry namest="col3" nameend="col3" align="char" char=",">266</entry><entry namest="col4" nameend="col4" align="char" char=",">208</entry><entry namest="col5" nameend="col5" align="char" char=",">191</entry><entry namest="col6" nameend="col6" align="char" char=",">116</entry><entry namest="col7" nameend="col7" align="char" char=",">381</entry><entry namest="col8" nameend="col8" align="char" char=",">231</entry><entry namest="col9" nameend="col9" align="char" char=",">381</entry></row><row><entry namest="col1" nameend="col1" align="left">Styrene (g)</entry><entry namest="col2" nameend="col2" align="char" char=",">323</entry><entry namest="col3" nameend="col3" align="char" char=",">266</entry><entry namest="col4" nameend="col4" align="char" char=",">208</entry><entry namest="col5" nameend="col5" align="char" char=",">191</entry><entry namest="col6" nameend="col6" align="char" char=",">116</entry><entry namest="col7" nameend="col7" align="char" char=",">-</entry><entry namest="col8" nameend="col8" align="char" char=",">-</entry><entry namest="col9" nameend="col9" align="char" char=",">-</entry></row><row><entry namest="col1" nameend="col1" align="left">Acrylic acid-n-butyl ester (g)</entry><entry namest="col2" nameend="col2" align="char" char=",">300</entry><entry namest="col3" nameend="col3" align="char" char=",">300</entry><entry namest="col4" nameend="col4" align="char" char=",">300</entry><entry namest="col5" nameend="col5" align="char" char=",">450</entry><entry namest="col6" nameend="col6" align="char" char=",">600</entry><entry namest="col7" nameend="col7" align="char" char=",">450</entry><entry namest="col8" nameend="col8" align="char" char=",">600</entry><entry namest="col9" nameend="col9" align="char" char=",">450</entry></row><row><entry namest="col1" nameend="col1" align="left">Acrylic acid (g)</entry><entry namest="col2" nameend="col2" align="char" char=",">150</entry><entry namest="col3" nameend="col3" align="char" char=",">150</entry><entry namest="col4" nameend="col4" align="char" char=",">150</entry><entry namest="col5" nameend="col5" align="char" char=",">150</entry><entry namest="col6" nameend="col6" align="char" char=",">150</entry><entry namest="col7" nameend="col7" align="char" char=",">150</entry><entry namest="col8" nameend="col8" align="char" char=",">150</entry><entry namest="col9" nameend="col9" align="char" char=",">150</entry></row><row><entry namest="col1" nameend="col1" align="left">Azoisobutyronitrile (g)</entry><entry namest="col2" nameend="col2" align="char" char=",">50</entry><entry namest="col3" nameend="col3" align="char" char=",">50</entry><entry namest="col4" nameend="col4" align="char" char=",">50</entry><entry namest="col5" nameend="col5" align="char" char=",">50</entry><entry namest="col6" nameend="col6" align="char" char=",">50</entry><entry namest="col7" nameend="col7" align="char" char=",">50</entry><entry namest="col8" nameend="col8" align="char" char=",">50</entry><entry namest="col9" nameend="col9" align="char" char=",">50</entry></row></tbody></tgroup><tgroup cols="9" colsep="1" rowsep="0"><colspec colnum="1" colname="col1" colwidth="17.50mm" /><colspec colnum="2" colname="col2" colwidth="17.50mm" /><colspec colnum="3" colname="col3" colwidth="17.50mm" /><colspec colnum="4" colname="col4" colwidth="17.50mm" /><colspec colnum="5" colname="col5" colwidth="17.50mm" /><colspec colnum="6" colname="col6" colwidth="17.50mm" /><colspec colnum="7" colname="col7" colwidth="17.50mm" /><colspec colnum="8" colname="col8" colwidth="17.50mm" /><colspec colnum="9" colname="col9" colwidth="17.50mm" /><thead valign="top"><row><entry namest="col1" nameend="col1" align="left">III.</entry><entry namest="col2" nameend="col2" /><entry namest="col3" nameend="col3" /><entry namest="col4" nameend="col4" /><entry namest="col5" nameend="col5" /><entry namest="col6" nameend="col6" /><entry namest="col7" nameend="col7" /><entry namest="col8" nameend="col8" /><entry namest="col9" nameend="col9" /></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">t-butyl peroctoate (g)</entry><entry namest="col2" nameend="col2" align="char" char=",">10</entry><entry namest="col3" nameend="col3" align="char" char=",">10</entry><entry namest="col4" nameend="col4" align="char" char=",">10</entry><entry namest="col5" nameend="col5" align="char" char=",">10</entry><entry namest="col6" nameend="col6" align="char" char=",">10</entry><entry namest="col7" nameend="col7" align="char" char=",">10</entry><entry namest="col8" nameend="col8" align="char" char=",">10</entry><entry namest="col9" nameend="col9" align="char" char=",">10</entry></row><row><entry namest="col1" nameend="col1" align="left">Butyl acetate (g)</entry><entry namest="col2" nameend="col2" align="char" char=",">100</entry><entry namest="col3" nameend="col3" align="char" char=",">100</entry><entry namest="col4" nameend="col4" align="char" char=",">100</entry><entry namest="col5" nameend="col5" align="char" char=",">100</entry><entry namest="col6" nameend="col6" align="char" char=",">100</entry><entry namest="col7" nameend="col7" align="char" char=",">100</entry><entry namest="col8" nameend="col8" align="char" char=",">100</entry><entry namest="col9" nameend="col9" align="char" char=",">100</entry></row><row><entry namest="col1" nameend="col1" align="left">Concentration (wt .-%)</entry><entry namest="col2" nameend="col2" align="char" char=",">63.7</entry><entry namest="col3" nameend="col3" align="char" char=",">65.3</entry><entry namest="col4" nameend="col4" align="char" char=",">64.4</entry><entry namest="col5" nameend="col5" align="char" char=",">58.8</entry><entry namest="col6" nameend="col6" align="char" char=",">58.6</entry><entry namest="col7" nameend="col7" align="char" char=",">60.9</entry><entry namest="col8" nameend="col8" align="char" char=",">58.9</entry><entry namest="col9" nameend="col9" align="char" char=",">59.1</entry></row><row><entry namest="col1" nameend="col1" align="left">Viscosity (Pa.s 23 ° C)</entry><entry namest="col2" nameend="col2" align="char" char=",">27.9</entry><entry namest="col3" nameend="col3" align="char" char=",">74.4</entry><entry namest="col4" nameend="col4" align="char" char=",">49.0</entry><entry namest="col5" nameend="col5" align="char" char=",">7.8</entry><entry namest="col6" nameend="col6" align="char" char=",">5.0</entry><entry namest="col7" nameend="col7" align="char" char=",">20.8</entry><entry namest="col8" nameend="col8" align="char" char=",">6.0</entry><entry namest="col9" nameend="col9" align="char" char=",">6.1</entry></row><row><entry namest="col1" nameend="col1" align="left">Hydroxyl (mg KOH / g solution)</entry><entry namest="col2" nameend="col2" align="char" char=",">62.7</entry><entry namest="col3" nameend="col3" align="char" char=",">82.8</entry><entry namest="col4" nameend="col4" align="char" char=",">95.3</entry><entry namest="col5" nameend="col5" align="char" char=",">80.3</entry><entry namest="col6" nameend="col6" align="char" char=",">77.7</entry><entry namest="col7" nameend="col7" align="char" char=",">80.8</entry><entry namest="col8" nameend="col8" align="char" char=",">79.7</entry><entry namest="col9" nameend="col9" align="char" char=",">79.9</entry></row><row><entry namest="col1" nameend="col1" align="left">Acid number (mg KOH / g solution)</entry><entry namest="col2" nameend="col2" align="char" char=",">47.3</entry><entry namest="col3" nameend="col3" align="char" char=",">46.8</entry><entry namest="col4" nameend="col4" align="char" char=",">44.6</entry><entry namest="col5" nameend="col5" align="char" char=",">46.1</entry><entry namest="col6" nameend="col6" align="char" char=",">46.1</entry><entry namest="col7" nameend="col7" align="char" char=",">48.6</entry><entry namest="col8" nameend="col8" align="char" char=",">46.6</entry><entry namest="col9" nameend="col9" align="char" char=",">46.5</entry></row></tbody></tgroup><tgroup cols="9" colsep="1" rowsep="0"><colspec colnum="1" colname="col1" colwidth="17.50mm" /><colspec colnum="2" colname="col2" colwidth="17.50mm" /><colspec colnum="3" colname="col3" colwidth="17.50mm" /><colspec colnum="4" colname="col4" colwidth="17.50mm" /><colspec colnum="5" colname="col5" colwidth="17.50mm" /><colspec colnum="6" colname="col6" colwidth="17.50mm" /><colspec colnum="7" colname="col7" colwidth="17.50mm" /><colspec colnum="8" colname="col8" colwidth="17.50mm" /><colspec colnum="9" colname="col9" colwidth="17.50mm" /><thead valign="top"><row><entry namest="col1" nameend="col1" align="left">IV.</entry><entry namest="col2" nameend="col2" /><entry namest="col3" nameend="col3" /><entry namest="col4" nameend="col4" /><entry namest="col5" nameend="col5" /><entry namest="col6" nameend="col6" /><entry namest="col7" nameend="col7" /><entry namest="col8" nameend="col8" /><entry namest="col9" nameend="col9" /></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">deionized water (g)</entry><entry namest="col2" nameend="col2" align="char" char=",">3500</entry><entry namest="col3" nameend="col3" align="char" char=",">3500</entry><entry namest="col4" nameend="col4" align="char" char=",">3500</entry><entry namest="col5" nameend="col5" align="char" char=",">3500</entry><entry namest="col6" nameend="col6" align="char" char=",">3500</entry><entry namest="col7" nameend="col7" align="char" char=",">3500</entry><entry namest="col8" nameend="col8" align="char" char=",">3500</entry><entry namest="col9" nameend="col9" align="char" char=",">3500</entry></row><row><entry namest="col1" nameend="col1" align="left">aqueous ammonia solution (25%) (g)</entry><entry namest="col2" nameend="col2" align="char" char=",">143</entry><entry namest="col3" nameend="col3" align="char" char=",">143</entry><entry namest="col4" nameend="col4" align="char" char=",">143</entry><entry namest="col5" nameend="col5" align="char" char=",">143</entry><entry namest="col6" nameend="col6" align="char" char=",">143</entry><entry namest="col7" nameend="col7" align="char" char=",">143</entry><entry namest="col8" nameend="col8" align="char" char=",">143-</entry><entry namest="col9" nameend="col9" align="char" char=",">-</entry></row><row><entry namest="col1" nameend="col1" align="left">N-dimethylethanolamine (g)</entry><entry namest="col2" nameend="col2" align="char" char=",">-</entry><entry namest="col3" nameend="col3" align="char" char=",">-</entry><entry namest="col4" nameend="col4" align="char" char=",">-</entry><entry namest="col5" nameend="col5" align="char" char=",">-</entry><entry namest="col6" nameend="col6" align="char" char=",">-</entry><entry namest="col7" nameend="col7" align="char" char=",">-</entry><entry namest="col8" nameend="col8" align="char" char=",">-</entry><entry namest="col9" nameend="col9" align="char" char=",">175</entry></row><row><entry namest="col1" nameend="col1" align="left">Concentration (wt .-%)</entry><entry namest="col2" nameend="col2" align="char" char=",">26.3</entry><entry namest="col3" nameend="col3" align="char" char=",">30.1</entry><entry namest="col4" nameend="col4" align="char" char=",">30.1</entry><entry namest="col5" nameend="col5" align="char" char=",">24.8</entry><entry namest="col6" nameend="col6" align="char" char=",">26.2</entry><entry namest="col7" nameend="col7" align="char" char=",">27.8</entry><entry namest="col8" nameend="col8" align="char" char=",">26.2</entry><entry namest="col9" nameend="col9" align="char" char=",">30.3</entry></row><row><entry namest="col1" nameend="col1" align="left">PH value</entry><entry namest="col2" nameend="col2" align="char" char=",">6.8</entry><entry namest="col3" nameend="col3" align="char" char=",">6.5</entry><entry namest="col4" nameend="col4" align="char" char=",">6.6</entry><entry namest="col5" nameend="col5" align="char" char=",">7.1</entry><entry namest="col6" nameend="col6" align="char" char=",">7.1</entry><entry namest="col7" nameend="col7" align="char" char=",">7.1</entry><entry namest="col8" nameend="col8" align="char" char=",">7.0</entry><entry namest="col9" nameend="col9" align="char" char=",">7.6</entry></row><row><entry namest="col1" nameend="col1" align="left">Viscosity * (Pa.s / 23 ° C)</entry><entry namest="col2" nameend="col2" align="char" char=",">-</entry><entry namest="col3" nameend="col3" align="char" char=",">-</entry><entry namest="col4" nameend="col4" align="char" char=",">-</entry><entry namest="col5" nameend="col5" align="char" char=",">0.97</entry><entry namest="col6" nameend="col6" align="char" char=",">4.6</entry><entry namest="col7" nameend="col7" align="char" char=",">5.7</entry><entry namest="col8" nameend="col8" align="char" char=",">1.8</entry><entry namest="col9" nameend="col9" align="char" char=",">-</entry></row><row><entry namest="col1" nameend="col1" align="left">Carboxylate (Mequiv./100 g solids)</entry><entry namest="col2" nameend="col2" align="char" char=",">139</entry><entry namest="col3" nameend="col3" align="char" char=",">139</entry><entry namest="col4" nameend="col4" align="char" char=",">139</entry><entry namest="col5" nameend="col5" align="char" char=",">139</entry><entry namest="col6" nameend="col6" align="char" char=",">139</entry><entry namest="col7" nameend="col7" align="char" char=",">139</entry><entry namest="col8" nameend="col8" align="char" char=",">139</entry><entry namest="col9" nameend="col9" align="char" char=",">131</entry></row><row><entry namest="col1" nameend="col1" align="left">Acid value (calculated) [mg KOH / g solid resin] (after neutralization)</entry><entry namest="col2" nameend="col2" align="char" char=",">0</entry><entry namest="col3" nameend="col3" align="char" char=",">0</entry><entry namest="col4" nameend="col4" align="char" char=",">0</entry><entry namest="col5" nameend="col5" align="char" char=",">0</entry><entry namest="col6" nameend="col6" align="char" char=",">0</entry><entry namest="col7" nameend="col7" align="char" char=",">0</entry><entry namest="col8" nameend="col8" align="char" char=",">0</entry><entry namest="col9" nameend="col9" align="char" char=",">4.4</entry></row></tbody></tgroup><tgroup cols="9" colsep="0" rowsep="0"><colspec colnum="1" colname="col1" colwidth="17.50mm" /><colspec colnum="2" colname="col2" colwidth="17.50mm" /><colspec colnum="3" colname="col3" colwidth="17.50mm" /><colspec colnum="4" colname="col4" colwidth="17.50mm" /><colspec colnum="5" colname="col5" colwidth="17.50mm" /><colspec colnum="6" colname="col6" colwidth="17.50mm" /><colspec colnum="7" colname="col7" colwidth="17.50mm" /><colspec colnum="8" colname="col8" colwidth="17.50mm" /><colspec colnum="9" colname="col9" colwidth="17.50mm" /><tbody valign="top"><row><entry namest="col1" nameend="col9" align="justify">* These are average values; the viscosities are not constant due to intrinsic viscosity.</entry></row></tbody></tgroup></table></tables>

example 1

100.0 parts by weight of polyhydroxyacrylate G having a solids content of 26.2 wt .-%, a viscosity of 1800 mPa.s at 23 ° C and a pH of 7.0 to 8.0 wt parts of demineralized water, 0.25 parts by weight of a commercial silicone-containing defoamer, (®Foamex 1488 Fa. Th. Goldschmidt AG, Essen), 0.3 parts by weight of a commercial dispersing (pigment dispersant a Fa. BASF AG , Ludwigshafen) and 19.0 parts by weight of titanium dioxide rutile mixed (Bayertitan® R-KB-4 from Bayer AG, Leverkusen) and about 20 minutes with a dissolver running at a speed of about 14 m / sec. dispersed. This gives a dispersion batch of virtually unlimited storage stability. a) after the addition of 11.7 parts by weight of polyisocyanate 1 to obtain a white-pigmented, water-dilutable two-component polyurethane paint, which is composed according to the invention as follows: <tables id="tabl0002" num="0002"><table frame="all"><tgroup cols="2" colsep="1" rowsep="0"><colspec colnum="1" colname="col1" colwidth="78.75mm" /><colspec colnum="2" colname="col2" colwidth="78.75mm" /><thead valign="top"><row><entry namest="col1" nameend="col1" /><entry namest="col2" nameend="col2" align="center">Wt .-%</entry></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">binder</entry><entry namest="col2" nameend="col2" align="char" char=",">27.21</entry></row><row><entry namest="col1" nameend="col1" align="left">pigment</entry><entry namest="col2" nameend="col2" align="char" char=",">13.61</entry></row><row><entry namest="col1" nameend="col1" align="left">aid</entry><entry namest="col2" nameend="col2" align="char" char=",">0.43</entry></row><row><entry namest="col1" nameend="col1" align="left">Total Solids</entry><entry namest="col2" nameend="col2" align="char" char=",">41,25</entry></row><row><entry namest="col1" nameend="col1" align="left">water</entry><entry namest="col2" nameend="col2" align="char" char=",">58,75</entry></row><row><entry namest="col1" nameend="col1" /><entry namest="col2" nameend="col2" align="char" char=",">100.00</entry></row></tbody></tgroup></table></tables> The ready-to-batch contains no organic solvents, the ratio NCO / OH groups is 1.0 and the processing time is about 4 hours. Films that were applied in a wet from 100 to 600 microns (corresponding to a dry film thickness 25-180 microns), dry within 30 to 120 minutes on a tack and defect-free film. The curing process is fully completed after 7 to 14 days. b) diluted to 50% solids by addition of 20.0 g of polyisocyanate 4, with 6 g of solvent naphtha 100, the abovementioned dispersion batch obtains a ready-white pigmented, water two-component polyurethane paint, which is composed according to the invention as follows: <tables id="tabl0003" num="0003"><table frame="all"><tgroup cols="2" colsep="1" rowsep="0"><colspec colnum="1" colname="col1" colwidth="78.75mm" /><colspec colnum="2" colname="col2" colwidth="78.75mm" /><thead valign="top"><row><entry namest="col1" nameend="col1" /><entry namest="col2" nameend="col2" align="center">Wt .-%</entry></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">binder</entry><entry namest="col2" nameend="col2" align="char" char=",">25,54</entry></row><row><entry namest="col1" nameend="col1" align="left">pigment</entry><entry namest="col2" nameend="col2" align="char" char=",">12.37</entry></row><row><entry namest="col1" nameend="col1" align="left">additive</entry><entry namest="col2" nameend="col2" align="char" char=",">0.35</entry></row><row><entry namest="col1" nameend="col1" align="left">Total Solids</entry><entry namest="col2" nameend="col2" align="char" char=",">38.26</entry></row><row><entry namest="col1" nameend="col1" align="left">water</entry><entry namest="col2" nameend="col2" align="char" char=",">53.27</entry></row><row><entry namest="col1" nameend="col1" align="left">Organic solver</entry><entry namest="col2" nameend="col2" align="char" char=",">8.47</entry></row><row><entry namest="col1" nameend="col1" /><entry namest="col2" nameend="col2" align="char" char=",">100.00</entry></row></tbody></tgroup></table></tables> The Global Approach contains a proportion of organic solvers of only 8.47 wt .-%. The ratio of NCO / OH groups is 1.0 and the processing time is given several hours. Films that are applied in a wet from 100 to 600 microns (corresponding to a dry film thickness 25-180 microns) dry within 30 to 120 minutes to a tack and defect-free film. The curing process is fully completed after 7 to 14 days. c) After the addition of 22.4 parts by weight of polyisocyanate 3, 50% solution in solvent naphtha 100 (= 11,2 parts by weight of solid) is obtained a white pigmented, water two-component polyurethane paint, which is composed according to the invention as follows: <tables id="tabl0004" num="0004"><table frame="all"><tgroup cols="2" colsep="1" rowsep="0"><colspec colnum="1" colname="col1" colwidth="78.75mm" /><colspec colnum="2" colname="col2" colwidth="78.75mm" /><thead valign="top"><row><entry namest="col1" nameend="col1" /><entry namest="col2" nameend="col2" align="center">Wt .-%</entry></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">binder</entry><entry namest="col2" nameend="col2" align="char" char=",">24,94</entry></row><row><entry namest="col1" nameend="col1" align="left">additive</entry><entry namest="col2" nameend="col2" align="char" char=",">0.37</entry></row><row><entry namest="col1" nameend="col1" align="left">pigment</entry><entry namest="col2" nameend="col2" align="char" char=",">12,67</entry></row><row><entry namest="col1" nameend="col1" align="left">Total Solids</entry><entry namest="col2" nameend="col2" align="char" char=",">37.98</entry></row><row><entry namest="col1" nameend="col1" align="left">water</entry><entry namest="col2" nameend="col2" align="char" char=",">54.55</entry></row><row><entry namest="col1" nameend="col1" align="left">Organic solver</entry><entry namest="col2" nameend="col2" align="char" char=",">7.47</entry></row><row><entry namest="col1" nameend="col1" /><entry namest="col2" nameend="col2" align="char" char=",">100.00</entry></row></tbody></tgroup></table></tables> The Global Approach contains a proportion of organic solvers of only 7.47 wt .-%. The ratio of NCO / OH groups is 1.0 and the processing time of several hours. Films that are applied in a wet from 100 to 600 microns (corresponding to 25 to 180 microns) dry film thickness, dry within 30 to 120 minutes of a tack and defect-free film. The curing process is fully completed after 7 to 14 days.

The cured films of Examples 1a to 1c can be characterized as follows: <tables id="tabl0005" num="0005"><table frame="all"><tgroup cols="4" colsep="1" rowsep="0"><colspec colnum="1" colname="col1" colwidth="39.37mm" /><colspec colnum="2" colname="col2" colwidth="39.37mm" /><colspec colnum="3" colname="col3" colwidth="39.37mm" /><colspec colnum="4" colname="col4" colwidth="39.37mm" /><thead valign="top"><row><entry namest="col1" nameend="col1" /><entry namest="col2" nameend="col2" align="left">1a</entry><entry namest="col3" nameend="col3" align="left">1b</entry><entry namest="col4" nameend="col4" align="left">1c</entry></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">Pendulum hardness according to DIN 53 157 (s)</entry><entry namest="col2" nameend="col2" align="right">75</entry><entry namest="col3" nameend="col3" align="right">75</entry><entry namest="col4" nameend="col4" align="right">85</entry></row><row><entry namest="col1" nameend="col1" align="left">Gloss according to DIN 67 530 60 ° angle</entry><entry namest="col2" nameend="col2" align="right">80</entry><entry namest="col3" nameend="col3" align="right">90</entry><entry namest="col4" nameend="col4" align="right">75</entry></row></tbody></tgroup><tgroup cols="4" colsep="1" rowsep="0"><colspec colnum="1" colname="col1" colwidth="39.37mm" /><colspec colnum="2" colname="col2" colwidth="39.37mm" /><colspec colnum="3" colname="col3" colwidth="39.37mm" /><colspec colnum="4" colname="col4" colwidth="39.37mm" /><thead valign="top"><row><entry namest="col1" nameend="col1" align="left">solver resistance</entry><entry namest="col2" nameend="col2" /><entry namest="col3" nameend="col3" /><entry namest="col4" nameend="col4" /></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">white spirit</entry><entry namest="col2" nameend="col2" align="left">very good</entry><entry namest="col3" nameend="col3" align="left">very good</entry><entry namest="col4" nameend="col4" align="left">very good</entry></row><row><entry namest="col1" nameend="col1" align="left">toluene</entry><entry namest="col2" nameend="col2" align="left">very good</entry><entry namest="col3" nameend="col3" align="left">very good</entry><entry namest="col4" nameend="col4" align="left">very good</entry></row><row><entry namest="col1" nameend="col1" align="left">methoxypropyl</entry><entry namest="col2" nameend="col2" align="left">well-moderately</entry><entry namest="col3" nameend="col3" align="left">Good</entry><entry namest="col4" nameend="col4" align="left">very good</entry></row><row><entry namest="col1" nameend="col1" align="left">acetone</entry><entry namest="col2" nameend="col2" align="left">moderate</entry><entry namest="col3" nameend="col3" align="left">moderate</entry><entry namest="col4" nameend="col4" align="left">moderate</entry></row><row><entry namest="col1" nameend="col1" align="left">ethanol</entry><entry namest="col2" nameend="col2" align="left">moderate</entry><entry namest="col3" nameend="col3" align="left">well-moderately</entry><entry namest="col4" nameend="col4" align="left">moderate</entry></row></tbody></tgroup></table></tables>

example 2

100 parts by weight of polyhydroxyacrylate G having a solids content of 26.2 wt .-%, a viscosity of 1800 mPa.s at 23 ° C and a pH of 7.0 to 8.0 parts by weight of demineralized water and 0.25 parts by weight of a commercial silicone-containing defoamer (®Foamex 1488 Fa. Th. Goldschmidt AG, Essen) homogeneously stirred.

The result is a caused by the defoamers slightly cloudy resin solution with an average flow viscosity according to DIN 53 211 200 seconds and virtually unlimited storage stability.

After stirring polyisocyanate 1 in such a way that in 4 different approaches, an NCO / OH ratio of<ul><li>a: 0.5 (addition of 5.57 wt Tlen polyisocyanate. 1</li><li>b: 1.0 (addition of 11.51 wt Tlen polyisocyanate. 1</li><li>c: 1.5 (addition of 17.26 wt Tlen polyisocyanate. 1</li><li>d: 2.0 (addition of 23.00 wt Tlen polyisocyanate. 1</li></ul> arises, is obtained ready-clearcoats, which are composed according to the invention as follows: <tables id="tabl0006" num="0006"><table frame="all"><tgroup cols="5" colsep="1" rowsep="0"><colspec colnum="1" colname="col1" colwidth="31.50mm" /><colspec colnum="2" colname="col2" colwidth="31.50mm" /><colspec colnum="3" colname="col3" colwidth="31.50mm" /><colspec colnum="4" colname="col4" colwidth="31.50mm" /><colspec colnum="5" colname="col5" colwidth="31.50mm" /><thead valign="top"><row><entry namest="col1" nameend="col1" /><entry namest="col2" nameend="col2" align="center">A</entry><entry namest="col3" nameend="col3" align="center">B</entry><entry namest="col4" nameend="col4" align="center">C</entry><entry namest="col5" nameend="col5" align="center">D</entry></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">NCO / OH =</entry><entry namest="col2" nameend="col2" align="char" char=",">0.5</entry><entry namest="col3" nameend="col3" align="char" char=",">1.0</entry><entry namest="col4" nameend="col4" align="char" char=",">1.5</entry><entry namest="col5" nameend="col5" align="char" char=",">2.0</entry></row><row><entry namest="col1" nameend="col1" align="left">Binder:</entry><entry namest="col2" nameend="col2" align="char" char=",">23,03</entry><entry namest="col3" nameend="col3" align="char" char=",">31,49</entry><entry namest="col4" nameend="col4" align="char" char=",">34,63</entry><entry namest="col5" nameend="col5" align="char" char=",">37,49</entry></row><row><entry namest="col1" nameend="col1" align="left">aids:</entry><entry namest="col2" nameend="col2" align="char" char=",">0.22</entry><entry namest="col3" nameend="col3" align="char" char=",">0.21</entry><entry namest="col4" nameend="col4" align="char" char=",">0.19</entry><entry namest="col5" nameend="col5" align="char" char=",">0.19</entry></row><row><entry namest="col1" nameend="col1" align="left">Total Solids:</entry><entry namest="col2" nameend="col2" align="char" char=",">28,25</entry><entry namest="col3" nameend="col3" align="char" char=",">31,70</entry><entry namest="col4" nameend="col4" align="char" char=",">34,83</entry><entry namest="col5" nameend="col5" align="char" char=",">37,68</entry></row><row><entry namest="col1" nameend="col1" align="left">Water:</entry><entry namest="col2" nameend="col2" align="char" char=",">71,75</entry><entry namest="col3" nameend="col3" align="char" char=",">68,30</entry><entry namest="col4" nameend="col4" align="char" char=",">65.17</entry><entry namest="col5" nameend="col5" align="char" char=",">62.32</entry></row><row><entry namest="col1" nameend="col1" align="left">Organic solver:</entry><entry namest="col2" nameend="col2" align="char" char=",">-</entry><entry namest="col3" nameend="col3" align="char" char=",">-</entry><entry namest="col4" nameend="col4" align="char" char=",">-</entry><entry namest="col5" nameend="col5" align="char" char=",">-</entry></row><row><entry namest="col1" nameend="col1" /><entry namest="col2" nameend="col2" align="char" char=",">100.0</entry><entry namest="col3" nameend="col3" align="char" char=",">100.0</entry><entry namest="col4" nameend="col4" align="char" char=",">100.0</entry><entry namest="col5" nameend="col5" align="char" char=",">100.0</entry></row></tbody></tgroup></table></tables>

to tack films of examples 2A to 2D, which, dried in a wet film thickness of 100 to 600 microns, were applied in accordance with a dry film thickness 25-180 microns within 30 to 120 minutes and trouble-free films. The curing process is fully completed after 7 to 14 days.<tables id="tabl0007" num="0007"><table frame="all"><tgroup cols="5" colsep="1" rowsep="0"><colspec colnum="1" colname="col1" colwidth="31.50mm" /><colspec colnum="2" colname="col2" colwidth="31.50mm" /><colspec colnum="3" colname="col3" colwidth="31.50mm" /><colspec colnum="4" colname="col4" colwidth="31.50mm" /><colspec colnum="5" colname="col5" colwidth="31.50mm" /><thead valign="top"><row><entry namest="col1" nameend="col1" /><entry namest="col2" nameend="col2" align="left">2A</entry><entry namest="col3" nameend="col3" align="left">2 B</entry><entry namest="col4" nameend="col4" align="left">2C</entry><entry namest="col5" nameend="col5" align="left">2D</entry></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">Gloss according to DIN 67 530 60 ° measuring angle</entry><entry namest="col2" nameend="col2" align="right">100</entry><entry namest="col3" nameend="col3" align="right">100</entry><entry namest="col4" nameend="col4" align="right">100</entry><entry namest="col5" nameend="col5" align="right">100</entry></row><row><entry namest="col1" nameend="col1" align="left">Pendulum hardness n. DIN (s)</entry><entry namest="col2" nameend="col2" align="right">50</entry><entry namest="col3" nameend="col3" align="right">60</entry><entry namest="col4" nameend="col4" align="right">85</entry><entry namest="col5" nameend="col5" align="right">100</entry></row></tbody></tgroup><tgroup cols="5" colsep="1" rowsep="0"><colspec colnum="1" colname="col1" colwidth="31.50mm" /><colspec colnum="2" colname="col2" colwidth="31.50mm" /><colspec colnum="3" colname="col3" colwidth="31.50mm" /><colspec colnum="4" colname="col4" colwidth="31.50mm" /><colspec colnum="5" colname="col5" colwidth="31.50mm" /><thead valign="top"><row><entry namest="col1" nameend="col1" align="left">solver resistance</entry><entry namest="col2" nameend="col2" /><entry namest="col3" nameend="col3" /><entry namest="col4" nameend="col4" /><entry namest="col5" nameend="col5" /></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">white spirit</entry><entry namest="col2" nameend="col2" align="left">very good</entry><entry namest="col3" nameend="col3" align="left">very good</entry><entry namest="col4" nameend="col4" align="left">very good</entry><entry namest="col5" nameend="col5" align="left">very good</entry></row><row><entry namest="col1" nameend="col1" align="left">toluene</entry><entry namest="col2" nameend="col2" align="left">moderate</entry><entry namest="col3" nameend="col3" align="left">Good</entry><entry namest="col4" nameend="col4" align="left">very good</entry><entry namest="col5" nameend="col5" align="left">very good</entry></row><row><entry namest="col1" nameend="col1" align="left">methoxypropyl</entry><entry namest="col2" nameend="col2" align="left">moderate</entry><entry namest="col3" nameend="col3" align="left">Good</entry><entry namest="col4" nameend="col4" align="left">Good</entry><entry namest="col5" nameend="col5" align="left">very good</entry></row><row><entry namest="col1" nameend="col1" align="left">acetone</entry><entry namest="col2" nameend="col2" align="left">moderate-bad</entry><entry namest="col3" nameend="col3" align="left">moderate-bad</entry><entry namest="col4" nameend="col4" align="left">moderate-bad</entry><entry namest="col5" nameend="col5" align="left">Good</entry></row><row><entry namest="col1" nameend="col1" align="left">ethanol</entry><entry namest="col2" nameend="col2" align="left">moderate-bad</entry><entry namest="col3" nameend="col3" align="left">moderate-bad</entry><entry namest="col4" nameend="col4" align="left">moderate</entry><entry namest="col5" nameend="col5" align="left">very good</entry></row></tbody></tgroup></table></tables>

example 3

100 parts by weight of polyhydroxyacrylate F with a solids content of 27.8 wt .-%, a viscosity of 5700 mPa.s at 23 ° C and a pH of 7.1 were demineralized with 8.0 parts by weight water, 0.25 parts by weight of a commercial silicone-containing defoamer (®Foamex 1488 Fa. Th. Goldschmidt AG, Essen), 0.3 parts by weight of a commercial dispersing (pigment dispersant a Fa. BASF, Ludwigshafen) and mixed 20.0 parts by weight of a commercially available titanium dioxide rutile type (Bayertitan® R-KB-4 from. BAYER AG, Leverkusen) and about 20 minutes with a dissolver running at a speed of about 14 m / sec. dispersed. This gives a dispersion batch of virtually unlimited storage stability. A. After the addition of 16.28 parts by weight of polyisocyanate 2 to obtain a ready-white pigmented, water-dilutable two-component polyurethane paint, which is composed according to the invention as follows: <tables id="tabl0008" num="0008"><table frame="all"><tgroup cols="2" colsep="1" rowsep="0"><colspec colnum="1" colname="col1" colwidth="78.75mm" /><colspec colnum="2" colname="col2" colwidth="78.75mm" /><thead valign="top"><row><entry namest="col1" nameend="col1" /><entry namest="col2" nameend="col2" align="center">Wt .-%</entry></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">binder</entry><entry namest="col2" nameend="col2" align="char" char=",">27.62</entry></row><row><entry namest="col1" nameend="col1" align="left">pigment</entry><entry namest="col2" nameend="col2" align="char" char=",">13.81</entry></row><row><entry namest="col1" nameend="col1" align="left">aid</entry><entry namest="col2" nameend="col2" align="char" char=",">0.38</entry></row><row><entry namest="col1" nameend="col1" align="left">Total Solids</entry><entry namest="col2" nameend="col2" align="char" char=",">41.81</entry></row><row><entry namest="col1" nameend="col1" align="left">water</entry><entry namest="col2" nameend="col2" align="char" char=",">55.38</entry></row><row><entry namest="col1" nameend="col1" align="left">Organic solver</entry><entry namest="col2" nameend="col2" align="char" char=",">2.81</entry></row><row><entry namest="col1" nameend="col1" /><entry namest="col2" nameend="col2" align="char" char=",">100.00</entry></row></tbody></tgroup></table></tables> The ready-to-batch contains only 2.81 wt .-% organic solvents. The ratio of NCO / OH groups is 1.0, a working time of several hours. With 180 microns wet thickness applied films (50 micron dry film equivalent) dry within 30 to 60 minutes to tack and trouble free. The curing process is fully completed after about 7 to 14 days. b. Using, as a hardening material for the pigment dispersion described polyisocyanate 1, the result is a ready-white paint, which is composed as follows:<tables id="tabl0009" num="0009"><table frame="all"><tgroup cols="2" colsep="1" rowsep="0"><colspec colnum="1" colname="col1" colwidth="78.75mm" /><colspec colnum="2" colname="col2" colwidth="78.75mm" /><thead valign="top"><row><entry namest="col1" nameend="col1" /><entry namest="col2" nameend="col2" align="center">Wt .-%</entry></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">binder</entry><entry namest="col2" nameend="col2" align="char" char=",">28,42</entry></row><row><entry namest="col1" nameend="col1" align="left">pigment</entry><entry namest="col2" nameend="col2" align="char" char=",">14,21</entry></row><row><entry namest="col1" nameend="col1" align="left">aid</entry><entry namest="col2" nameend="col2" align="char" char=",">0.39</entry></row><row><entry namest="col1" nameend="col1" align="left">Total Solids</entry><entry namest="col2" nameend="col2" align="char" char=",">43,02</entry></row><row><entry namest="col1" nameend="col1" align="left">water</entry><entry namest="col2" nameend="col2" align="char" char=",">56.98</entry></row><row><entry namest="col1" nameend="col1" /><entry namest="col2" nameend="col2" align="char" char=",">100.00</entry></row></tbody></tgroup></table></tables> The ready-to-two-component paint contains no organic solvents. The ratio of NCO / OH groups is 1.0, the processing is given over several hours. With 180 microns wet thickness applied films (corresponding to about 50 microns dry film) dry to tack and trouble-free within 30 to 60 minutes films. The curing process is fully completed after 7 to 14 days.

The film properties of the applied according to Example 3a and 3b films can be characterized as follows: <tables id="tabl0010" num="0010"><table frame="all"><tgroup cols="3" colsep="1" rowsep="0"><colspec colnum="1" colname="col1" colwidth="52.50mm" /><colspec colnum="2" colname="col2" colwidth="52.50mm" /><colspec colnum="3" colname="col3" colwidth="52.50mm" /><thead valign="top"><row><entry namest="col1" nameend="col1" /><entry namest="col2" nameend="col2" align="left">3a</entry><entry namest="col3" nameend="col3" align="left">3b</entry></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">Pendulum hardness (s), ca.</entry><entry namest="col2" nameend="col2" align="right">65</entry><entry namest="col3" nameend="col3" align="right">110</entry></row><row><entry namest="col1" nameend="col1" align="left">Gloss according to DIN 67 530 60 ° measuring angle</entry><entry namest="col2" nameend="col2" align="right">85</entry><entry namest="col3" nameend="col3" align="right">85</entry></row></tbody></tgroup><tgroup cols="3" colsep="1" rowsep="0"><colspec colnum="1" colname="col1" colwidth="52.50mm" /><colspec colnum="2" colname="col2" colwidth="52.50mm" /><colspec colnum="3" colname="col3" colwidth="52.50mm" /><thead valign="top"><row><entry namest="col1" nameend="col1" align="left">solver resistance</entry><entry namest="col2" nameend="col2" /><entry namest="col3" nameend="col3" /></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">white spirit</entry><entry namest="col2" nameend="col2" align="left">very good</entry><entry namest="col3" nameend="col3" align="left">very good</entry></row><row><entry namest="col1" nameend="col1" align="left">toluene</entry><entry namest="col2" nameend="col2" align="left">very good</entry><entry namest="col3" nameend="col3" align="left">very good</entry></row><row><entry namest="col1" nameend="col1" align="left">methoxypropyl</entry><entry namest="col2" nameend="col2" align="left">well-moderately</entry><entry namest="col3" nameend="col3" align="left">well-moderately</entry></row><row><entry namest="col1" nameend="col1" align="left">acetone</entry><entry namest="col2" nameend="col2" align="left">moderate</entry><entry namest="col3" nameend="col3" align="left">moderate</entry></row><row><entry namest="col1" nameend="col1" align="left">ethanol</entry><entry namest="col2" nameend="col2" align="left">moderate</entry><entry namest="col3" nameend="col3" align="left">moderate</entry></row></tbody></tgroup></table></tables>