Lacquer formulations
Abstract
Lacquer formulations containing: from 5 to 99.5 wt. % of solids of a polymer component or of a mixture of two or more physically or chemically crosslinking polymer components, (binder components and hardener components), from 0 to 80 wt. % of a low molecular weight component acting as solvent or of a mixture of such low molecular weight components, from 0.5 to 50 wt. % of a silanised, structurally modified pyrogenic silica to the surface of which there are attached alkylsilyl groups (SiC<SUB>n</SUB>H<SUB>2n+1</SUB>, where n=from 2 to 18) and/or dimethylsilyl groups and/or monomethylsilyl groups, from 0 to 10 wt. % of commercially available additives.
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1 claim: 1 independent, 0 dependent
- 1Lacquer formulations containing:• from 5 to 99.5 wt.% of solids of a polymer component or of a mixture of two or more physically or chemically crosslinking polymer components, • from 0 to 80 wt.% of a low molecular weight component acting as solvent or of a mixture of the low molecular weight components, • from 0.5 to 50 wt.% of a silanised, structurally modified pyrogenic silica to the surface of which there are attached alkylsilyl groups (SiC n H 2n+1 , where n = from 2 to 18) and/or dimethylsilyl groups and/or monomethylsilyl groups, • from 0 to 10 wt.% of commercially available additives.
71 paragraphs, as filed
0001The invention relates to lacquer formulations.
0002Lacquer formulations are used for sealing or coating surfaces. In the case of special surfaces such as, for example, surfaces of parquet floors or other floors, or motor vehicle bodies, special scratch resistance is desired.
0003The document <patcit id="pcit0001" dnum="EP0798349A"><text>EP 0 798 349</text></patcit> describes a coating agent for applying a protective coat and an impregnation both onto smooth and porous bases selected from brickwall, natural and ortificial stone, consisting of an active substance component, which can contain pyrogenic silica, a liquid vehicle component and of one or more usual additives, whereby the additive can be precipitated silica.
0004The document <patcit id="pcit0002" dnum="US5833967A"><text>US 5,833,967</text></patcit> describes a method of inforcing Keratin substances using colloidal silicic acid, which can be a pyrogenic silica.
0005The document <patcit id="pcit0003" dnum="DE3740139"><text>DE 37 40 139</text></patcit> describes a basic lacquer which contains pyrogenic silica as thixotropic agent.
0006<patcit id="pcit0004" dnum="DE19811790A1"><text>DE 198 11 790 A1</text></patcit>, corresponding to <patcit id="pcit0005" dnum="US6020419A"><text>US.A.6 020 419</text></patcit> describes improving the scratch resistance of transparent lacquer binders by the use of pyrogenic hydrophilic and/or hydrophobic silicas. In that case, the silica is incorporated into the binder using a special process.
0007It is a disadvantage that, with the known silicas, despite the use of a special dispersing device, the rheology of the lacquer system is affected to a very great extent and highly flawed lacquer surfaces are obtained (orange-peel effect).
0008The invention provides lacquer formulations containing <ul id="ul0001" list-style="bullet"><li>from 5 to 99.5 wt.%, preferably from 20 to 80 wt.%, particularly preferably from 35 to 70 wt.%, of solids of a polymer component or of a mixture of two or more physically or chemically crosslinking polymer components (binder components and hardener components),</li><li>from 0 to 80 wt.%, preferably from 20 to 70 wt.%, particularly preferably from 30 to 55 wt.%, of a low molecular weight component acting as solvent or of a mixture of the low molecular weight components,</li><li>from 0.5 to 50 wt.%, preferably from 1 to 25 wt.%, particularly preferably from 2 to 10 wt.%, of a silanised, structurally modified pyrogenic silica to the surface of which there are attached alkylsilyl groups (SiC<sub>n</sub>H<sub>2n+1</sub>, where n = from 2 to 18), preferably octylsilyl and/or hexadecylsilyl groups, and or dimethylsilyl and/or monomethylsilyl groups, preferably dimethylsilyl groups,</li><li>from 0 to 10 wt.% of commercially available additives. Which have a positive effect on the properties of a lacquer, such as, the rheological behaviour of the liquid system, stabilisation and dispersibility of fillers and pigments, appearance and flow of the lacquer surface.</li></ul>
0009As binders there may be used the resins conventional in lacquers and coatings technology, as are described, for example, in <nplcit id="ncit0001" npl-type="b"><text>Lackharze, Chemie, Eigenschaften und Anwendungen, Eds. D. Stoye, W. Freitag, Hanser Verlag, Munich, Vienna 1996</text></nplcit>. Examples which may be mentioned include, <i>inter alia</i>, polymers and copolymers of (meth)acrylic acid and their esters, optionally carrying further functional groups, with further olefinically unsaturated compounds, such as, for example, styrene; also polyether, polyester, polycarbonate, polyurethane and epoxy resins, as well as any desired mixtures of those polymers.
0010As polymeric organic compounds there are preferably used polymers carrying hydroxyl groups, for example polyacrylate, polyester, polycaprolactone, polyether, polycarbonate and polyurethane polyols and hydroxyfunctional epoxy resins, as well as any desired mixtures of those polymers. As particularly preferred polymeric organic compounds there are used aqueous or solvent-containing or solvent-free polyacrylate and polyester polyols, as well as any desired mixtures thereof. Suitable polyacrylate polyols are copolymers of hydroxyl-group-containing monomers with other olefinically unsaturated monomers, such as, for example, esters of (meth)acrylic acid, styrene, α-methylstyrene, vinyltoluene, vinyl esters, maleic and fumaric acid mono- and di-alkyl esters, α-olefins and other unsaturated oligomers and polymers.
0011Particularly suitable polyacrylate polyols have an average weight-average molecular weight, which can be determined by means of gel permeation chromatography (standard polystyrene), of from 2000 to 10,000 g/mol., preferably from 2500 to 50,000 g/mol. and particularly preferably from 3100 to 40,000 g/mol., a glass transition temperature TG of from -50°C to +100°C, preferably from -40°C to +90°C and particularly preferably -30°C (to +80°C), an acid number of < 30 mg KOH/g, preferably < 25 mg KOH/g, and a hydroxyl group content of from 0.5 to 14.0 wt.%, preferably from 0.5 to 10.0 wt.% and particularly preferably from 1.0 to 8.0 wt.%, and consist of <ol id="ol0001"><li>a) from 0 to 70 parts by weight, preferably from 5 to 70 parts by weight, of at least one unsaturated, aromatic monomer, such as styrene, methylstyrene or vinyltoluene,</li><li>b) from 0 to 70 parts by weight, preferably from 5 to 70 parts by weight, of at least one (cyclo)aliphatic ester of acrylic and/or methacrylic acid having from 1 to 18 carbon atoms in the (cyclo)alkyl radical,</li><li>c) from 4 to 95 parts by weight, preferably from 10 to 60 parts by weight, of at least one hydroxyalkyl ester of acrylic and/or methacrylic acid having from 2 to 4 carbon atoms in the hydroxyalkyl radical, and/or addition products of monoepoxides with acrylic and/or methacrylic acid,</li><li>d) from 0 to 10 parts by weight, preferably from 0.1 to 5 parts by weight, of at least one monoolefinically unsaturated mono- or di-carboxylic acid having from 3 to 7 carbon atoms, and/or at least one maleic acid or fumaric acid semi-ester having from 1 to 14 carbon atoms in the alcohol radical, and</li><li>e) from 0 to 30 parts by weight, preferably from 0 to 20 parts by weight, of further copolymerisable, olefinically (also polyolefinically) unsaturated monomeric and/or polymeric compounds.</li></ol>
0012The described hydroxyl-functional polyols can be used in both one-component and two-component lacquer systems together with the hardeners conventional in lacquers and coatings technology. There come into consideration as hardeners therefor, for example, polyisocyanates or polyisocyanates blocked with cleaving agents such as methyl ethyl ketoxime, caprolactam, malonic acid esters, triazole or 2,5-dimethylpyrazole, or (partially) etherified melamine-formaldehyde resins, as are described, for example, in <nplcit id="ncit0002" npl-type="b"><text>Lackharze, Chemie, Eigenschaften und Anwendungen, Eds. D. Stoye, W. Freitag, Hanser Verlag, Munich, Vienna 1996</text></nplcit>.
0013Preference is given to the use of the aqueous or solvent-containing binders according to the invention in two-component systems together with polyisocyanates based on hexamethylene diisocyanate, isophorone diisocyanate, 4,4-diisocyanatodicyclohexylmethane, tetramethylene diisocyanate, 2-methylpentamethylene diisocyanate, 2,2,4-and 2,4,4-trimethylhexamethylene diisocyanate (THDI), 1,4-diisocyanato-cyclohexane, 3-isocyanatomethyl-1-methyl-1-isocyanatocyclohexane (IMCI), a,a,a',a'-tetramethyl-m- or -p-xylylene diisocyanate (TMXDI), 1,4- and 1,3-xylylene diisocyanate (XDI), hexahydroxylylene diisocyanate (H6-XDI) and/or mixtures thereof and optionally their variants rendered hydrophilic for aqueous binders, as are described, for example, in <patcit id="pcit0006" dnum="DE4136618A"><text>DE-A 41 36 618</text></patcit>.
0014Particular preference is given, however, to polyisocyanates based on hexamethylene diisocyanate, isophorone diisocyanate and 4,4-diisocyanatodicyclohexylmethane.
0015Such polyisocyanates are used as hardeners in high-quality polyurethane lacquers which have outstanding resistance to chemicals and a high degree of gloss.
0016The conventional solvents are such as aromatic, aliphatic, araliphatic or cycloaliphatic hydrocarbons, partially or completely halogenated aromatic, aliphatic, araliphatic or cycloaliphatic hydrocarbons, alcohols, such as, for example, methanol, ethanol, isopropanol, butanol, benzyl alcohol, diacetone alcohol, esters, such as, for example, ethyl acetate, propyl acetate, butyl acetate, ether esters, such as, for example, methoxypropyl acetate or butyl glycol acetate, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as, for example, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxite, N-methylpyrrolidone; further solvents are water, liquid acid esters, such as, for example, phosphoric acid dibutyl ester, phosphoric acid tributyl ester, sulfonic acid esters, borates or derivatives of silica, for example tetraethoxysilane, methyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, glycidyloxypropyltrimethoxysilane, glycidyloxypropyltriethoxysilane.
0017If those solvents are used as dispersing media for the silicas according to the invention, further substances may be added to those materials that are used. Preference is given to those substances which are also provided for subsequent further use or which improve the deagglomeration or the properties, for example the stability, of the deagglomerated materials.
0018Particular preference is given to oligomeric or polymeric organic compounds, such as, for example, the above-mentioned resins and binders conventional in lacquers and coatings technology.
0019It is also possible to use in the dispersing medium amounts of the combination resins used in multi-component systems, such as, for example, the amine and melamine resins acting as hardeners, polyisocyanates, the adducts, referred to as blocked polyisocyanates, consisting of aromatic or aliphatic polyisocyanates and so-called cleaving agents, such as methyl ethyl ketoxime, caprolactam, malonic acid esters or triazole and 2,5-dimethylpyrazole. For procedures in which water is used as a substantial constituent of the dispersing medium, suitable additives are especially compounds which are soluble in or compatible with water, such as, for example, partially or completely saponified polyvinyl acetate, or variants of the above-mentioned classes of compounds which have been rendered hydrophilic. Further additives which are suitable and which are preferably used in aqueous media are, for example, silica sol and the sols of metallic oxides of the elements aluminium, titanium, zirconium, tantalum and tin.
0020As low molecular weight additives by means of which it is possible, for example, to achieve stabilisation of the deagglomerated silicas according to the invention against further agglomeration, there are suitable in principle all compounds which are used for stabilising nanoscale materials prepared by other means, for example by one of the methods mentioned above. Mention may be made of, for example, hydrolysable compounds carrying silane groups, such as alkoxysilanes or chlorosilanes. Particular amphiphilic compounds may also be used. The solvents and additives that are suitable for the preparation of the dispersing medium can be mixed with one another as desired.
0021The lacquer binders according to the invention can be mixed with any conventional hardeners (combinations) to produce coatings.
0022The lacquer formulations according to the invention are transparent lacquer formulations containing pyrogenic, structurally modified silicas, the silicas according to the invention having an extremely small effect on the rheology of the lacquer formulation while at the same time exhibiting increased resistance of the lacquer surface to scratching.
0023The lacquer formulations according to the invention are particularly suitable for the production of clear lacquers, because significant improvements in the properties, such as an improvement in scratch resistance, can be achieved thereby while transparency and a high degree of gloss are retained. Typical clear lacquer applications in which the lacquer formulations according to the invention lead to particularly marked advantages are, for example, the series and repair lacquering of motor vehicles, and the wear-resistant coating of parquet floors and other floors.
0024In addition, owing to the structural modification, the pyrogenic silicas have a reduced tendency to dust formation, and incorporation into the lacquer binders is simplified.
0025The following two tables contain an overview of the production and the physicochemical data of the comparison silicas and the silicas according to the invention used in the Examples. <tables id="tabl0001" num="0001"><table frame="all"><title><b><u style="single">Table 1:</u></b> Overview of the preparation of the comparison silicas and of the silicas according to the invention (Examples)</title><tgroup cols="4"><colspec colnum="1" colname="col1" colwidth="40mm" /><colspec colnum="2" colname="col2" colwidth="43mm" /><colspec colnum="3" colname="col3" colwidth="41mm" /><colspec colnum="4" colname="col4" colwidth="43mm" /><thead><row><entry valign="top"><b>Description</b></entry><entry align="center" valign="top"><b>Group attached to the surface</b></entry><entry align="center" valign="top"><b>Structural modification</b></entry><entry align="center" valign="top"><b>Milling after structural modification</b></entry></row></thead><tbody><row><entry>Comparison silica 1</entry><entry align="center">Hexadecylsilyl</entry><entry align="center">No</entry><entry align="center">-</entry></row><row><entry>Comparison silica 2</entry><entry align="center">Octylsilyl</entry><entry align="center">No</entry><entry align="center">-</entry></row><row><entry>Comparison silica 3</entry><entry align="center">Dimethylsilyl</entry><entry align="center">No</entry><entry align="center">-</entry></row><row><entry>Comparison silica 4</entry><entry align="center">Dimethylsilyl</entry><entry align="center">No</entry><entry align="center">-</entry></row><row><entry>Silica 1</entry><entry align="center">Hexadecylsilyl</entry><entry align="center">Yes</entry><entry align="center">Yes</entry></row><row><entry>Silica 2</entry><entry align="center">Hexadecylsilyl</entry><entry align="center">Yes</entry><entry align="center">No</entry></row><row><entry>Silica 3</entry><entry align="center">Octylsilyl</entry><entry align="center">Yes</entry><entry align="center">Yes</entry></row><row><entry>Silica 4</entry><entry align="center">Octylsilyl</entry><entry align="center">Yes</entry><entry align="center">No</entry></row><row><entry>Silica 5</entry><entry align="center">Dimethylsilyl</entry><entry align="center">Yes</entry><entry align="center">No</entry></row><row><entry>Silica 6</entry><entry align="center">Dimethylsilyl</entry><entry align="center">Yes</entry><entry align="center">No</entry></row><row><entry>Silica 7</entry><entry align="center">Dimethylsilyl</entry><entry align="center">Yes</entry><entry align="center">No</entry></row><row><entry>Silica 8</entry><entry align="center">Dimethylsilyl</entry><entry align="center">Yes</entry><entry align="center">No</entry></row></tbody></tgroup></table></tables><tables id="tabl0002" num="0002"><table frame="all"><title><b><u style="single">Table 2:</u></b> Physicochemical data of the comparison silicas and of the silicas according to the invention (Examples)</title><tgroup cols="8"><colspec colnum="1" colname="col1" colwidth="22mm" /><colspec colnum="2" colname="col2" colwidth="20mm" /><colspec colnum="3" colname="col3" colwidth="22mm" /><colspec colnum="4" colname="col4" colwidth="22mm" /><colspec colnum="5" colname="col5" colwidth="17mm" /><colspec colnum="6" colname="col6" colwidth="22mm" /><colspec colnum="7" colname="col7" colwidth="23mm" /><colspec colnum="8" colname="col8" colwidth="21mm" /><thead><row valign="middle"><entry>Description</entry><entry align="center">Tamped density [g/l]</entry><entry align="center">Loss on drying [%]</entry><entry align="center">Ignition loss[%]</entry><entry align="center">pH value</entry><entry align="center">C content [%]</entry><entry align="center">DBP adsorption [%]</entry><entry align="center">Specific BET surface area [m<sup>2</sup>/g]</entry></row></thead><tbody><row><entry>Comparison silica 1</entry><entry align="center">57</entry><entry align="char" char=".">0.5</entry><entry align="char" char=".">1.8</entry><entry align="char" char="." charoff="11">4.6</entry><entry align="char" char=".">1.2</entry><entry align="center">302</entry><entry align="center">195</entry></row><row><entry>Comparison silica 2</entry><entry align="center">51</entry><entry align="char" char=".">0.6</entry><entry align="char" char=".">6.8</entry><entry align="char" char="." charoff="11">5.3</entry><entry align="char" char=".">5.4</entry><entry align="center">236</entry><entry align="center">175</entry></row><row><entry>Comparison silica 3</entry><entry align="center">64</entry><entry align="char" char=".">0.1</entry><entry align="char" char=".">0.5</entry><entry align="char" char="." charoff="11">4.0</entry><entry align="char" char=".">0.8</entry><entry align="center">243</entry><entry align="center">113</entry></row><row><entry>Comparison silica 4</entry><entry align="center">67</entry><entry align="char" char=".">0.5</entry><entry align="char" char=".">0.6</entry><entry align="char" char="." charoff="11">4.8</entry><entry align="char" char=".">1.0</entry><entry align="center">256</entry><entry align="center">165</entry></row><row><entry>Silica 1</entry><entry align="center">123</entry><entry align="char" char=".">0.7</entry><entry align="char" char=".">2.6</entry><entry align="char" char="." charoff="11">6.0</entry><entry align="char" char=".">1.4</entry><entry align="center">208</entry><entry align="center">197</entry></row><row><entry>Silica 2</entry><entry align="center">146</entry><entry align="char" char=".">1.1</entry><entry align="char" char=".">2.3</entry><entry align="char" char="." charoff="11">5.8</entry><entry align="char" char=".">1.4</entry><entry align="center">192</entry><entry align="center">195</entry></row><row><entry>Silica 3</entry><entry align="center">240</entry><entry align="char" char=".">0.8</entry><entry align="char" char=".">6.7</entry><entry align="char" char="." charoff="11">4.8</entry><entry align="char" char=".">5.3</entry><entry align="center">87</entry><entry align="center">169</entry></row><row><entry>Silica 4</entry><entry align="center">322</entry><entry align="char" char=".">0.3</entry><entry align="char" char=".">6.9</entry><entry align="char" char="." charoff="11">6.0</entry><entry align="char" char=".">5.3</entry><entry align="center">not determinable</entry><entry align="center">172</entry></row><row><entry>Silica 5</entry><entry align="center">236</entry><entry align="char" char=".">0.1</entry><entry align="char" char=".">0.6</entry><entry align="char" char="." charoff="11">4.0</entry><entry align="char" char=".">0.8</entry><entry align="center">127</entry><entry align="center">115</entry></row><row><entry>Silica 6</entry><entry align="center">204</entry><entry align="char" char=".">0.1</entry><entry align="char" char=".">0.6</entry><entry align="char" char="." charoff="11">3.9</entry><entry align="char" char=".">0.8</entry><entry align="center">137</entry><entry align="center">116</entry></row><row><entry>Silica 7</entry><entry align="center">223</entry><entry align="char" char=".">0.3</entry><entry align="char" char=".">0.7</entry><entry align="char" char="." charoff="11">4.2</entry><entry align="char" char=".">1.0</entry><entry align="center">160</entry><entry align="center">169</entry></row><row><entry>Silica 8</entry><entry align="center">186</entry><entry align="char" char=".">0.3</entry><entry align="char" char=".">0.7</entry><entry align="char" char="." charoff="11">4.2</entry><entry align="char" char=".">1.1</entry><entry align="center">152</entry><entry align="center">171</entry></row></tbody></tgroup></table></tables>
Example 1:
0026A conventional 2-component polyurethane lacquer was used for investigating the improvement in scratch resistance. The recipe for the lacquer and the preparation, including application, thereof are summarised hereinbelow:
Recipe 1:
0027<tables id="tabl0003" num="0003"><table frame="all"><tgroup cols="2"><colspec colnum="1" colname="col1" colwidth="103mm" /><colspec colnum="2" colname="col2" colwidth="27mm" /><thead><row><entry valign="top">Material to be ground</entry><entry valign="top">Parts by weight</entry></row></thead><tbody><row rowsep="0"><entry>Acrylate resin, 50 % in xylene/ethyl benzene 3:1</entry><entry>53.3</entry></row><row rowsep="0"><entry>Butyl acetate 98 %</entry><entry>6.7</entry></row><row rowsep="0"><entry>Xylene</entry><entry>6.7</entry></row><row><entry>Silica</entry><entry>5.0</entry></row><row><entry align="right">∑</entry><entry>71.7</entry></row></tbody></tgroup><tgroup cols="2"><colspec colnum="1" colname="col1" colwidth="103mm" /><colspec colnum="2" colname="col2" colwidth="27mm" /><thead><row><entry valign="top">Making up into a lacquer</entry><entry valign="top" /></row></thead><tbody><row rowsep="0"><entry>Acrylate resin, 50 % in xylene/ethyl benzene 3:1</entry><entry>1.1</entry></row><row rowsep="0"><entry>Xylene</entry><entry>12.2</entry></row><row rowsep="0"><entry>Ethoxypropyl acetate</entry><entry>1.5</entry></row><row rowsep="0"><entry>Butyl glycol acetate</entry><entry>1.5</entry></row><row rowsep="0"><entry>Butyl acetate 98 %</entry><entry>-</entry></row><row><entry>Aliphatic polyisocyanate, 75 % in 1-methoxypropyl acetate-2/xylene 1:1</entry><entry>17.0</entry></row><row><entry align="right">∑</entry><entry>105.0</entry></row></tbody></tgroup></table></tables><tables id="tabl0004" num="0004"><table frame="none"><tgroup cols="2" colsep="0" rowsep="0"><colspec colnum="1" colname="col1" colwidth="54mm" /><colspec colnum="2" colname="col2" colwidth="15mm" /><tbody><row><entry>Binder concentration:</entry><entry>40 %</entry></row><row><entry>Silica calculated on material</entry><entry /></row><row><entry>to be ground (FK):</entry><entry>18.8 %</entry></row><row><entry>Silica calculated on lacquer (total) :</entry><entry>5.0 %</entry></row><row><entry>Silica calculated on lacquer (FK):</entry><entry>12.5 %</entry></row></tbody></tgroup></table></tables>
Preparation and application of the lacquers
0028The binder is mixed with the solvents. For preliminary dispersion, the silica is then incorporated into that mixture using a dissolver (plate ∅ 45 mm) and predispersed for 5 minutes at 2000 rpm. The mixture is dispersed in a laboratory bead mill for 30 minutes at 2500 rpm and 60 % pump capacity using glass beads (∅ 1 mm). The dispersed material is checked using a grindometer, 25 µm, according to DIN ISO 1524. It must be smaller than 10 µm.
0029The ground material is made up into a lacquer according to the recipe, the components being mixed by means of a blade-type stirrer at 2000 rpm. The hardener is incorporated in the same manner.
0030After adjusting the lacquers to spraying viscosity according to DIN 53411, the lacquers are applied by means of spray application to black-lacquered metal sheets, e.g. DT 36 (Q-Panel) (layer thickness about 40-50 µm). After spraying, the metal sheets are dried for 24 hours at room temperature and then for 2 hours in a drying oven at 70°C.
Scratching tests:
0031By means of a scouring- and washing-resistance testing machine (Erichsen, pig-bristle brush), the metal sheets are scoured using a quartz/water suspension (100 g of water + 1 g of Marlon<sup>®</sup> A 350, 0.25 % + 5 g of Sikro<sup>®</sup> F500) and also using a CaCO<sub>3</sub>/water mixture (100 g of water + 1 g of Marlon<sup>®</sup> A 350, 0.25 % + 5 g of Millicarb<sup>®</sup> BG). The gloss before scouring and 10 minutes after scouring is determined using a reflectometer (angle of irradiation 20°).
0032Table 3: next page
0033Because of their substantially lower rheological activity as compared with the comparison silicas, all the silicas according to the invention can be used in high concentrations without impairing the appearance of the lacquer surface. In addition, the silicas according to the invention exhibit a substantial improvement in the scratch resistance of the lacquer surfaces. <tables id="tabl0005" num="0005"><table frame="all"><title><u style="single">Table 3a:</u> Summary of the relevant lacquer-related properties of the liquid lacquers and of the applied and dried films</title><tgroup cols="9"><colspec colnum="1" colname="col1" colwidth="66mm" /><colspec colnum="2" colname="col2" colwidth="29mm" /><colspec colnum="3" colname="col3" colwidth="12mm" /><colspec colnum="4" colname="col4" colwidth="12mm" /><colspec colnum="5" colname="col5" colwidth="35mm" /><colspec colnum="6" colname="col6" colwidth="31mm" /><colspec colnum="7" colname="col7" colwidth="12mm" /><colspec colnum="8" colname="col8" colwidth="12mm" /><colspec colnum="9" colname="col9" colwidth="35mm" /><thead><row><entry valign="top" /><entry align="center" valign="top"><b>Comparison S1</b></entry><entry align="center" valign="top"><b>S 1</b></entry><entry align="center" valign="top"><b>S 2</b></entry><entry align="center" valign="top"><b>Reference without S</b></entry><entry align="center" valign="top"><b>Comparison S2</b></entry><entry align="center" valign="top"><b>S 3</b></entry><entry align="center" valign="top"><b>S 4</b></entry><entry align="center" valign="top"><b>Reference without S</b></entry></row></thead><tbody><row><entry><b>Grindometer value [µm]</b></entry><entry align="center">< 10</entry><entry align="center">< 10</entry><entry align="center">< 10</entry><entry align="center">< 10</entry><entry align="center">< 10</entry><entry align="center">< 10</entry><entry align="center">< 10</entry><entry align="center">/</entry></row><row rowsep="0"><entry><b>Viscosity (ground material) [mPas]</b></entry><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /></row><row rowsep="0"><entry align="right"><b>6 rpm</b></entry><entry align="center">409</entry><entry align="center">210</entry><entry align="center">220</entry><entry align="center">/</entry><entry align="center">5670</entry><entry align="center">935</entry><entry align="center">832</entry><entry align="center">/</entry></row><row><entry align="right"><b>60 rpm</b></entry><entry align="center">407</entry><entry align="center">210</entry><entry align="center">212</entry><entry align="center">/</entry><entry align="center">1260</entry><entry align="center">409</entry><entry align="center">407</entry><entry align="center">/</entry></row><row rowsep="0"><entry><b>Viscosity (lacquer+hardener) [mPas]</b></entry><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /></row><row rowsep="0"><entry align="right"><b>6 rpm</b></entry><entry align="center">120</entry><entry align="center">80</entry><entry align="center">80</entry><entry align="center">60</entry><entry align="center">446</entry><entry align="center">195</entry><entry align="center">175</entry><entry align="center">55</entry></row><row><entry align="right"><b>60 rpm</b></entry><entry align="center">113</entry><entry align="center">82</entry><entry align="center">82</entry><entry align="center">61</entry><entry align="center">194</entry><entry align="center">146</entry><entry align="center">144</entry><entry align="center">64</entry></row><row><entry><b>Flow</b></entry><entry align="center">poor fine cracks</entry><entry align="center">o. k.</entry><entry align="center">o. k.</entry><entry align="center">o. k.</entry><entry align="center">orange-peel effect</entry><entry align="center">o. k.</entry><entry align="center">o. k.</entry><entry align="center">o. k.</entry></row><row><entry colsep="0"><b>Scratch resistance</b></entry><entry colsep="0" align="center" /><entry colsep="0" align="center" /><entry colsep="0" align="center" /><entry colsep="0" align="center" /><entry colsep="0" align="center" /><entry colsep="0" align="center" /><entry colsep="0" align="center" /><entry colsep="0" align="center" /></row><row><entry><b>20° reflectometer value before scratching</b></entry><entry align="center">81</entry><entry align="center">89.5</entry><entry align="center">89.1</entry><entry align="center">91.3</entry><entry align="center">38</entry><entry align="center">85.5</entry><entry align="center">85.3</entry><entry align="center">91.7</entry></row><row><entry><b>Haze before scratching</b></entry><entry align="center">101</entry><entry align="center">9</entry><entry align="center">12</entry><entry align="center">2</entry><entry align="center">423</entry><entry align="center">18</entry><entry align="center">19</entry><entry align="center">2</entry></row><row rowsep="0"><entry><b>40 strokes with Sikron F 500</b></entry><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /></row><row><entry align="right"><b>residual gloss [%]</b></entry><entry align="center">83.4</entry><entry align="center">88.5</entry><entry align="center">90.7</entry><entry align="center">51.8</entry><entry align="center">/</entry><entry align="center">80.4</entry><entry align="center">84.3</entry><entry align="center">56.1</entry></row></tbody></tgroup></table></tables><tables id="tabl0006" num="0006"><table frame="all"><title><u style="single">Table 3b:</u> Summary of the relevant lacquer-related properties of the liquid lacquers and of the applied and dried films</title><tgroup cols="9"><colspec colnum="1" colname="col1" colwidth="66mm" /><colspec colnum="2" colname="col2" colwidth="31mm" /><colspec colnum="3" colname="col3" colwidth="12mm" /><colspec colnum="4" colname="col4" colwidth="12mm" /><colspec colnum="5" colname="col5" colwidth="35mm" /><colspec colnum="6" colname="col6" colwidth="31mm" /><colspec colnum="7" colname="col7" colwidth="12mm" /><colspec colnum="8" colname="col8" colwidth="12mm" /><colspec colnum="9" colname="col9" colwidth="35mm" /><thead><row><entry valign="top" /><entry align="center" valign="top"><b>Comparison S3</b></entry><entry align="center" valign="top"><b>S 5</b></entry><entry align="center" valign="top"><b>S 6</b></entry><entry align="center" valign="top"><b>Reference without S</b></entry><entry align="center" valign="top"><b>Comparison S4</b></entry><entry align="center" valign="top"><b>S 7</b></entry><entry align="center" valign="top"><b>S 8</b></entry><entry align="center" valign="top"><b>Reference without S</b></entry></row></thead><tbody><row><entry><b>Grindometer value [µm]</b></entry><entry align="center">< 10</entry><entry align="center">< 10</entry><entry align="center">< 10</entry><entry align="center">/</entry><entry align="center">< 10</entry><entry align="center">< 10</entry><entry align="center">< 10</entry><entry align="center">/</entry></row><row rowsep="0"><entry><b>Viscosity (ground material) [mPas]</b></entry><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /></row><row rowsep="0"><entry align="right"><b>6 rpm</b></entry><entry align="center">4710</entry><entry align="center">421</entry><entry align="center">772</entry><entry align="center">571</entry><entry align="center">4990</entry><entry align="center">802</entry><entry align="center">772</entry><entry align="center">55</entry></row><row><entry align="right"><b>60 rpm</b></entry><entry align="center">1120</entry><entry align="center">210</entry><entry align="center">264</entry><entry align="center">225</entry><entry align="center">1200</entry><entry align="center">279</entry><entry align="center">264</entry><entry align="center">52</entry></row><row rowsep="0"><entry><b>Viscosity (lacquer+hardener) [mPas]</b></entry><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /></row><row rowsep="0"><entry align="right"><b>6 rpm</b></entry><entry align="center">882</entry><entry align="center">105</entry><entry align="center">210</entry><entry align="center">135</entry><entry align="center">857</entry><entry align="center">235</entry><entry align="center">105</entry><entry align="center">70</entry></row><row><entry align="right"><b>60 rpm</b></entry><entry align="center">239</entry><entry align="center">75</entry><entry align="center">92</entry><entry align="center">79</entry><entry align="center">242</entry><entry align="center">100</entry><entry align="center">26</entry><entry align="center">37</entry></row><row><entry><b>Flow</b></entry><entry align="center">orange-peel effect</entry><entry align="center">o. k.</entry><entry align="center">o. k.</entry><entry align="center">o. k.</entry><entry align="center">orange-peel effect</entry><entry align="center">o. k.</entry><entry align="center">o. k.</entry><entry align="center">o. k.</entry></row><row><entry colsep="0"><b>Scratch resistance</b></entry><entry colsep="0" align="center" /><entry colsep="0" align="center" /><entry colsep="0" align="center" /><entry colsep="0" align="center" /><entry colsep="0" align="center" /><entry colsep="0" align="center" /><entry colsep="0" align="center" /><entry colsep="0" align="center" /></row><row><entry><b>20° reflectometer value before scratching</b></entry><entry align="center">39.0</entry><entry align="center">83.4</entry><entry align="center">83.5</entry><entry align="center">88.8</entry><entry align="center">67.2</entry><entry align="center">84.2</entry><entry align="center">82.6</entry><entry align="center">89.3</entry></row><row><entry><b>Haze before scratching</b></entry><entry align="center">430</entry><entry align="center">30</entry><entry align="center">40</entry><entry align="center">3</entry><entry align="center">235</entry><entry align="center">18</entry><entry align="center">10</entry><entry align="center">2</entry></row><row rowsep="0"><entry><b>40 strokes with Sikron F 500</b></entry><entry morerows="1" rowsep="1" align="center" valign="middle">/</entry><entry morerows="1" rowsep="1" align="center" valign="middle">83.7</entry><entry morerows="1" rowsep="1" align="center" valign="middle">82.3</entry><entry morerows="1" rowsep="1" align="center" valign="middle">56.0</entry><entry morerows="1" rowsep="1" align="center" valign="middle">/</entry><entry morerows="1" rowsep="1" align="center" valign="middle">74.7</entry><entry morerows="1" rowsep="1" align="center" valign="middle">80.4</entry><entry morerows="1" rowsep="1" align="center" valign="middle">47.2</entry></row><row><entry align="right"><b>residual gloss</b> [%]</entry></row></tbody></tgroup></table></tables>
Example 2
0034In this Example, the effect of structural modification has been investigated with reference to a high solids 2K PUR clear lacquer. The recipe for the lacquer and the preparation, including application and testing, thereof are summarised hereinbelow:
Recipe 2:
0035<tables id="tabl0007" num="0007"><table frame="all"><tgroup cols="2"><colspec colnum="1" colname="col1" colwidth="77mm" /><colspec colnum="2" colname="col2" colwidth="27mm" /><thead><row><entry valign="top">Material to be ground</entry><entry align="center" valign="top">Parts by weight</entry></row></thead><tbody><row rowsep="0"><entry>Acrylic copolymer, modified with synthetic fatty acids,</entry><entry align="center" /></row><row rowsep="0"><entry>70 % in n-butyl acetate</entry><entry align="center">61.0</entry></row><row rowsep="0"><entry>Butyl acetate 98 %</entry><entry align="center">7.3</entry></row><row rowsep="0"><entry>Methoxypropyl acetate</entry><entry align="center">1.7</entry></row><row rowsep="0"><entry>Solvesso<sup>®</sup> 100</entry><entry align="center">2.0</entry></row><row rowsep="0"><entry>Xylene</entry><entry align="center">2.0</entry></row><row rowsep="0"><entry>Baysilon<sup>®</sup> OL 17, 10 % in xylene (silicone oil)</entry><entry align="center">0.7</entry></row><row><entry>Silica</entry><entry align="center">5.0</entry></row><row><entry align="right">∑</entry><entry align="center">79.7</entry></row></tbody></tgroup><tgroup cols="2"><colspec colnum="1" colname="col1" colwidth="77mm" /><colspec colnum="2" colname="col2" colwidth="27mm" /><thead><row><entry valign="top">Making up into a lacquer (hardener)</entry><entry align="center" valign="top" /></row></thead><tbody><row rowsep="0"><entry>Aliphatic polyisocyanate, 90 % in n-butyl</entry><entry align="center" /></row><row rowsep="0"><entry>acetate</entry><entry align="center">22.3</entry></row><row rowsep="0"><entry>Butyl acetate 98 %</entry><entry align="center">2.0</entry></row><row><entry>Solvesso<sup>®</sup> 100</entry><entry align="center">1.0</entry></row><row><entry align="right">∑</entry><entry align="center">105.0</entry></row></tbody></tgroup></table></tables><tables id="tabl0008" num="0008"><table frame="none"><tgroup cols="2" colsep="0" rowsep="0"><colspec colnum="1" colname="col1" colwidth="52mm" /><colspec colnum="2" colname="col2" colwidth="15mm" align="right" /><tbody><row><entry>Binder concentration:</entry><entry>62.8 %</entry></row><row><entry>Silica calculated on material</entry><entry /></row><row><entry>to be ground (FK):</entry><entry>11.7 %</entry></row><row><entry>Silica calculated on lacquer (total):</entry><entry>5.0 %</entry></row><row><entry>Silica calculated on lacquer (FK):</entry><entry>8.0 %</entry></row></tbody></tgroup></table></tables>
Preparation and application of the lacquers
0036The binder is mixed with the solvents. For preliminary dispersion, the silica is then incorporated into that mixture using a dissolver (plate ∅ 45 mm) and predispersed for 5 minutes at 2000 rpm. The mixture is dispersed in a laboratory bead mill for 30 minutes at 2500 rpm and 60 % pump capacity using glass beads (∅ 1 mm). The dispersed material is checked using a grindometer, 25 µm, according to DIN ISO 1524. It must be smaller than 10 µm.
0037The ground material is made up into a lacquer according to the recipe, the components being mixed by means of a blade-type stirrer at 2000 rpm. The hardener is incorporated in the same manner.
0038After adjusting the lacquers to spraying viscosity according to DIN 53411, the lacquers are applied by means of spray application to black-lacquered metal sheets, e.g. DT 36 (Q-Panel) (layer thickness 40-50 µm). After spraying, the metal sheets are dried for 24 hours at room temperature and then for 2 hours in a drying oven at 70°C.
Scratching tests:
0039By means of a scouring- and washing-resistance testing machine (Erichsen, pig-bristle brush), the metal sheets are scoured using a quartz/water suspension (100 g of water + 1 g of Marlon<sup>®</sup> A 350, 0.25 % + 5 g of Sikron<sup>®</sup> F500). The gloss before scouring and 10 minutes after scouring is determined using a reflectometer (angle of irradiation 20°). <tables id="tabl0009" num="0009"><table frame="all"><title><u style="single">Table 4:</u> Summary of the relevant lacquer-related properties of the liquid lacquers and of the applied and dried films</title><tgroup cols="9"><colspec colnum="1" colname="col1" colwidth="57mm" /><colspec colnum="2" colname="col2" colwidth="31mm" /><colspec colnum="3" colname="col3" colwidth="12mm" /><colspec colnum="4" colname="col4" colwidth="12mm" /><colspec colnum="5" colname="col5" colwidth="35mm" /><colspec colnum="6" colname="col6" colwidth="40mm" /><colspec colnum="7" colname="col7" colwidth="12mm" /><colspec colnum="8" colname="col8" colwidth="12mm" /><colspec colnum="9" colname="col9" colwidth="35mm" /><thead><row><entry valign="top" /><entry align="center" valign="top"><b>Comparison S1</b></entry><entry align="center" valign="top"><b>S 1</b></entry><entry align="center" valign="top"><b>S 2</b></entry><entry align="center" valign="top"><b>Reference without S</b></entry><entry align="center" valign="top"><b>Comparison S4</b></entry><entry align="center" valign="top"><b>S 7</b></entry><entry align="center" valign="top"><b>S 8</b></entry><entry align="center" valign="top"><b>Reference without S</b></entry></row></thead><tbody><row><entry><b>Grindometer value [µm]</b></entry><entry align="center">< 10</entry><entry align="center">< 10</entry><entry align="center">< 10</entry><entry align="center">/</entry><entry align="center">< 10</entry><entry align="center">< 10</entry><entry align="center">< 10</entry><entry align="center">/</entry></row><row rowsep="0"><entry><b>Viscosity (ground material) [mPas]</b></entry><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /></row><row rowsep="0"><entry align="right"><b>6 rpm</b></entry><entry align="center">767</entry><entry align="center">376</entry><entry align="center">376</entry><entry align="center">205</entry><entry align="center">6200</entry><entry align="center">1500</entry><entry align="center">541</entry><entry align="center">140</entry></row><row><entry align="right"><b>60 rpm</b></entry><entry align="center">717</entry><entry align="center">359</entry><entry align="center">361</entry><entry align="center">205</entry><entry align="center">2100</entry><entry align="center">900</entry><entry align="center">559</entry><entry align="center">195</entry></row><row rowsep="0"><entry><b>Viscosity (lacquer+hardener) [mPas]</b></entry><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /></row><row rowsep="0"><entry align="right"><b>6 rpm</b></entry><entry align="center">459</entry><entry align="center">279</entry><entry align="center">281</entry><entry align="center">120</entry><entry align="center">3821</entry><entry align="center">1041</entry><entry align="center">497</entry><entry align="center">167</entry></row><row><entry align="right"><b>60 rpm</b></entry><entry align="center">399</entry><entry align="center">272</entry><entry align="center">274</entry><entry align="center">120</entry><entry align="center">1320</entry><entry align="center">666</entry><entry align="center">446</entry><entry align="center">195</entry></row><row><entry><b>Flow</b></entry><entry align="center">poor (fine "cracks")</entry><entry align="center">o.k.</entry><entry align="center">o. k.</entry><entry align="center">o. k.</entry><entry align="center">pronounced orange peel</entry><entry align="center">o. k.</entry><entry align="center">o. k.</entry><entry align="center">o. k.</entry></row><row><entry colsep="0"><b>Scratch resistance</b></entry><entry colsep="0" align="center" /><entry colsep="0" align="center" /><entry colsep="0" align="center" /><entry colsep="0" align="center" /><entry colsep="0" align="center" /><entry colsep="0" align="center" /><entry colsep="0" align="center" /><entry colsep="0" align="center" /></row><row><entry><b>20° reflectometer value before scratching value</b></entry><entry align="center">82.3</entry><entry align="center">86.5</entry><entry align="center">86.3</entry><entry align="center">88.2</entry><entry align="center">81.0</entry><entry align="center">83.5</entry><entry align="center">82.8</entry><entry align="center">88.0</entry></row><row><entry><b>Haze before scratching</b></entry><entry align="center">3</entry><entry align="center">4</entry><entry align="center">4</entry><entry align="center">2</entry><entry align="center">25</entry><entry align="center">5</entry><entry align="center">6</entry><entry align="center">2</entry></row><row rowsep="0"><entry><b>40 strokes with Sikron F 500</b></entry><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /></row><row><entry align="right"><b>residual gloss [%]</b></entry><entry align="center">63.2</entry><entry align="center">78.2</entry><entry align="center">75.4</entry><entry align="center">30.2</entry><entry align="center" /><entry align="center">94.3</entry><entry align="center">93.4</entry><entry align="center">82.0</entry></row></tbody></tgroup></table></tables>
0040Because of their substantially lower rheological activity as compared with the comparison silicas 1 and 4, the silicas 1 + 2 and 7 + 8 according to the invention can be used in high concentrations without impairing the appearance of the lacquer surface. In addition, the silicas according to the invention exhibit a substantial improvement in the scratch resistance of the lacquer surface.
Example 3:
0041A conventional 2-component polyurethane lacquer was used for investigating the improvement in scratch resistance. The recipe for the lacquer and the preparation, including application, thereof are summarised hereinbelow:
Recipe 3
0042<tables id="tabl0010" num="0010"><table frame="all"><tgroup cols="2"><colspec colnum="1" colname="col1" colwidth="103mm" /><colspec colnum="2" colname="col2" colwidth="27mm" /><thead><row><entry valign="top">Material to be ground</entry><entry align="center" valign="top">Parts by weight</entry></row></thead><tbody><row rowsep="0"><entry>Acrylic copolymer, modified with synthetic fatty acids, 60 % solution</entry><entry align="center">43.4</entry></row><row rowsep="0"><entry>Butyl acetate 98 %</entry><entry align="center">17.8</entry></row><row rowsep="0"><entry>Xylene</entry><entry align="center">3.9</entry></row><row><entry>Silica</entry><entry align="center">5.0</entry></row><row><entry align="right">∑</entry><entry align="center">70.7</entry></row></tbody></tgroup><tgroup cols="2"><colspec colnum="1" colname="col1" colwidth="103mm" /><colspec colnum="2" colname="col2" colwidth="27mm" /><thead><row><entry valign="top">Making up into a lacquer</entry><entry align="center" valign="top" /></row></thead><tbody><row rowsep="0"><entry>Xylene</entry><entry align="center">11.3</entry></row><row rowsep="0"><entry>Ethoxypropyl acetate</entry><entry align="center">3.4</entry></row><row rowsep="0"><entry>Butyl glycol acetate</entry><entry align="center">1.6</entry></row><row rowsep="0"><entry /><entry align="center" /></row><row><entry>Aliphatic polyisocyanate, 75 % in 1-methoxypropyl acetate-2/xylene 1:1</entry><entry align="center">18.6</entry></row><row><entry align="right">∑</entry><entry align="center">105.0</entry></row></tbody></tgroup></table></tables><tables id="tabl0011" num="0011"><table frame="none"><tgroup cols="2" colsep="0" rowsep="0"><colspec colnum="1" colname="col1" colwidth="52mm" /><colspec colnum="2" colname="col2" colwidth="15mm" /><tbody><row><entry>Binder concentration:</entry><entry>40 %</entry></row><row><entry>Silica calcuated on material</entry><entry /></row><row><entry>to be ground (FK):</entry><entry>19.2 %</entry></row><row><entry>Silica calculated on lacquer (total):</entry><entry>5.0 %</entry></row><row><entry>Silica calculated on lacquer (FK):</entry><entry>12.5 %</entry></row></tbody></tgroup></table></tables>
Preparation and application of the lacquers
0043The binder is mixed with the solvents. For preliminary dispersion, the silica is then incorporated into that mixture using a dissolver (plate ∅ 45 mm) and predispersed for 5 minutes at 2000 rpm. The mixture is dispersed in a laboratory bead mill for 30 minutes at 2500 rpm and 60 % pump capacity using glass beads (∅ 1 mm). The dispersed material is checked using a grindometer, 25 µm, according to DIN ISO 1524. It must be smaller than 10 µm.
0044The ground material is made up into a lacquer according to the recipe, the components being mixed by means of a blade-type stirrer at 2000 rpm. The hardener is stirred in in the same manner.
0045After adjusting the lacquers to spraying viscosity according to DIN 53411, the lacquers are applied by means of spray application to black-lacquered metal sheets, e.g. DT 36 (Q-Panel) (layer thickness about 40-50 µm). After spraying, the metal sheets are dried for 24 hours at room temperature and then for 2 hours in a drying oven at 70°C.
Scratching tests:
0046By means of a scouring- and washing-resistance testing machine (Erichsen, pig-bristle brush), the metal sheets are scoured using a quartz/water suspension (100 g of water + 1 g of Marlon<sup>®</sup> A 350, 0.25 % + 5 g of Sikron<sup>®</sup> F500). The gloss before scouring and 10 minutes after scouring is determined using a reflectometer (angle of irradiation 20°).
0047Table 5: see next page
0048Because of their substantially lower rheological activity as compared with the comparison silicas 1 and 2, the silicas 1 + 2 and 3 + 4 according to the invention can be used in high concentrations without impairing the appearance of the lacquer surface. In addition, the silicas according to the invention exhibit a substantial improvement in the scratch resistance of the lacquer surface. <tables id="tabl0012" num="0012"><table frame="all"><title><u style="single">Table 5:</u> Summary of the relevant lacquer-related properties of the liquid lacquers and of the applied and dried films</title><tgroup cols="10"><colspec colnum="1" colname="col1" colwidth="35mm" /><colspec colnum="2" colname="col2" colwidth="34mm" /><colspec colnum="3" colname="col3" colwidth="16mm" /><colspec colnum="4" colname="col4" colwidth="16mm" /><colspec colnum="5" colname="col5" colwidth="35mm" /><colspec colnum="6" colname="col6" colwidth="10mm" /><colspec colnum="7" colname="col7" colwidth="35mm" /><colspec colnum="8" colname="col8" colwidth="16mm" /><colspec colnum="9" colname="col9" colwidth="16mm" /><colspec colnum="10" colname="col10" colwidth="35mm" /><thead><row valign="middle"><entry /><entry align="center"><b>Comparison silica 1</b></entry><entry align="center"><b>Silica 1</b></entry><entry align="center"><b>Silica 2</b></entry><entry align="center"><b>Reference without silica</b></entry><entry align="center" /><entry align="center"><b>Comparison silica 2</b></entry><entry align="center"><b>Silica 3</b></entry><entry align="center"><b>Silica 4</b></entry><entry align="center"><b>Reference without silica</b></entry></row></thead><tbody><row><entry><b>Grindometer value [µm]</b></entry><entry align="center">< 10</entry><entry align="center">< 10</entry><entry align="center">< 10</entry><entry align="center">/</entry><entry align="center" /><entry align="center">< 10</entry><entry align="center">< 10</entry><entry align="center">< 10</entry><entry align="center">/</entry></row><row rowsep="0"><entry><b>Viscosity (ground material) [mPas]</b></entry><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /></row><row rowsep="0"><entry align="right"><b>6 rpm</b></entry><entry align="center">409</entry><entry align="center">210</entry><entry align="center">220</entry><entry align="center">/</entry><entry align="center" /><entry align="center">5670</entry><entry align="center">935</entry><entry align="center">832</entry><entry align="center">/</entry></row><row><entry align="right"><b>60 rpm</b></entry><entry align="center">407</entry><entry align="center">210</entry><entry align="center">212</entry><entry align="center">/</entry><entry align="center" /><entry align="center">1260</entry><entry align="center">409</entry><entry align="center">407</entry><entry align="center">/</entry></row><row rowsep="0"><entry><b>Viscosity (lacquer+hardener) [mPas]</b></entry><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /></row><row rowsep="0"><entry align="right"><b>6 rpm</b></entry><entry align="center">120</entry><entry align="center">80</entry><entry align="center">80</entry><entry align="center">60</entry><entry align="center" /><entry align="center">446</entry><entry align="center">195</entry><entry align="center">175</entry><entry align="center">55</entry></row><row><entry align="right"><b>60 rpm</b></entry><entry align="center">113</entry><entry align="center">82</entry><entry align="center">82</entry><entry align="center">61</entry><entry align="center" /><entry align="center">194</entry><entry align="center">146</entry><entry align="center">144</entry><entry align="center">64</entry></row><row><entry><b>Flow</b></entry><entry align="center">poor fine cracks</entry><entry align="center">o. k.</entry><entry align="center">o. k.</entry><entry align="center">o. k.</entry><entry align="center" /><entry align="center">orange-peel effect</entry><entry align="center">o. k.</entry><entry align="center">o. k.</entry><entry align="center">o. k.</entry></row><row><entry colsep="0"><b>Scratch resistance</b></entry><entry colsep="0" align="center" /><entry colsep="0" align="center" /><entry colsep="0" align="center" /><entry colsep="0" align="center" /><entry colsep="0" align="center" /><entry colsep="0" align="center" /><entry colsep="0" align="center" /><entry colsep="0" align="center" /><entry colsep="0" align="center" /></row><row><entry><b>20° reflectometer value before scratching</b></entry><entry align="center">81</entry><entry align="center">89.5</entry><entry align="center">89.1</entry><entry align="center">91.3</entry><entry align="center" /><entry align="center">38</entry><entry align="center">85.5</entry><entry align="center">85.3</entry><entry align="center">91.7</entry></row><row><entry><b>Haze before scratching</b></entry><entry align="center">101</entry><entry align="center">9</entry><entry align="center">12</entry><entry align="center">2</entry><entry align="center" /><entry align="center">423</entry><entry align="center">18</entry><entry align="center">19</entry><entry align="center">2</entry></row><row rowsep="0"><entry><b>40 strokes with Sikron F 500</b></entry><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /></row><row><entry align="right"><b>residual gloss</b></entry><entry align="center">83.4</entry><entry align="center">88.5</entry><entry align="center">90.7</entry><entry align="center">51.8</entry><entry align="center" /><entry align="center">/</entry><entry align="center">80.4</entry><entry align="center">84.3</entry><entry align="center">56.1</entry></row></tbody></tgroup></table></tables>
Example 4
0049Direct comparison of the silicas according to the invention with a scratch-resistant lacquer according to <patcit id="pcit0007" dnum="DE19811790A1"><text>DE 198 11 790 A1</text></patcit>, in which AEROSIL<sup>®</sup> R 972 is used to improve the scratch resistance.
Recipe 4
0050<tables id="tabl0013" num="0013"><table frame="all"><tgroup cols="3"><colspec colnum="1" colname="col1" colwidth="82mm" /><colspec colnum="2" colname="col2" colwidth="20mm" /><colspec colnum="3" colname="col3" colwidth="58mm" /><thead><row><entry valign="top" /><entry align="center" valign="top"><b>prior art 1)</b></entry><entry align="center" valign="top"><b>Silicas according to the invention 2)</b></entry></row><row><entry valign="top"><b>Material to be ground</b></entry><entry align="center" valign="top" /><entry align="center" valign="top" /></row></thead><tbody><row><entry>Desmophen<sup>®</sup> A 2009/1</entry><entry align="center" /><entry align="center">190.2</entry></row><row><entry>Methoxypropyl acetate : Solvesso<sup>®</sup> 100 1:1</entry><entry align="center" /><entry align="center">36.8</entry></row><row><entry>Silica</entry><entry align="center" /><entry align="center">23.0</entry></row><row><entry align="right">∑</entry><entry align="center" /><entry align="center">250.0</entry></row></tbody></tgroup><tgroup cols="3"><colspec colnum="1" colname="col1" colwidth="82mm" /><colspec colnum="2" colname="col2" colwidth="20mm" /><colspec colnum="3" colname="col3" colwidth="58mm" /><thead><row><entry valign="top"><b>Making up into a lacquer</b></entry><entry align="center" valign="top" /><entry align="center" valign="top" /></row></thead><tbody><row><entry>Desmophen<sup>®</sup> A #A YEP4-55A, contains AEROSIL R 972</entry><entry align="center">96.0</entry><entry align="center">-</entry></row><row><entry>Ground material</entry><entry align="center">-</entry><entry align="center">48.9</entry></row><row><entry>Desmophen<sup>®</sup> 2009/1</entry><entry align="center">-</entry><entry align="center">24.9</entry></row><row><entry>OL 17, 10 % in MPA</entry><entry align="center">-</entry><entry align="center">-</entry></row><row><entry>Modaflow<sup>®</sup> 1 % in MPA</entry><entry align="center">-</entry><entry align="center">-</entry></row><row><entry>MPA : Solvesso<sup>®</sup> 100 1:1</entry><entry align="center">11.6</entry><entry align="center">33.8</entry></row><row><entry>Butyl glycol acetate</entry><entry align="center">10.5</entry><entry align="center">10.5</entry></row><row><entry>Byketol<sup>®</sup> OK</entry><entry align="center">7.5</entry><entry align="center">7.5</entry></row><row><entry>Byk<sup>®</sup> 141</entry><entry align="center">0.8</entry><entry align="center">0.8</entry></row></tbody></tgroup><tgroup cols="3"><colspec colnum="1" colname="col1" colwidth="82mm" /><colspec colnum="2" colname="col2" colwidth="20mm" /><colspec colnum="3" colname="col3" colwidth="58mm" /><thead><row><entry valign="top"><b>Addition of hardener</b></entry><entry align="center" valign="top" /><entry align="center" valign="top" /></row></thead><tbody><row><entry>Desmodur<sup>®</sup> N 3390</entry><entry align="center">23.6</entry><entry align="center">23.6</entry></row><row><entry align="right">∑</entry><entry align="center">150.0</entry><entry align="center">150.0</entry></row></tbody></tgroup></table></tables>
Preparation and application of the lacquers
0051<ol id="ol0002"><li>1) The comparison silica 1 is incorporated into the binder according to <patcit id="pcit0008" dnum="DE19811790A1"><text>DE 198 11 790 A1</text></patcit> by means of a jet disperser.</li><li>2) The binder is mixed with the solvents. For preliminary dispersion, the silica is then incorporated into that mixture using a dissolver (plate ∅ 45 mm) and predispersed for 5 minutes at 2000 rpm. The mixture is dispersed in a laboratory bead mill for 30 minutes at 2500 rpm and 60 % pump capacity using glass beads (∅ 1 mm). The dispersed material is checked using a grindometer, 25 µm, according to DIN ISO 1524. It must be smaller than 10 µm.</li></ol>
0052The ground material is made up into a lacquer corresponding to 1) or 2) according to the recipe, the components being mixed by means of a blade-type stirrer at 2000 rpm. The hardener is stirred in in the same manner.
0053After adjusting the lacquers to spraying viscosity according to DIN 53411, the lacquers are applied by means of spray application to black-lacquered metal sheets, e.g. DT 36 (Q-Panel) (layer thickness about 40-50 µm). After spraying, the metal sheets are dried for 24 hours at room temperature and then for 2 hours in a drying oven at 70°C.
Scratching tests:
0054By means of a scouring- and washing-resistance testing machine (Erichsen, pig-bristle brush), the metal sheets are scoured using a CaCO<sub>3</sub>/water suspension (100 g of water + 1 g of Marlon<sup>®</sup> A 350, 0.25 % + 5 g of CaCO<sub>3</sub> Millicarb). The gloss before scouring and 10 minutes after scouring is determined using a reflectometer (angle of irradiation 20°). <tables id="tabl0014" num="0014"><table frame="all"><title><u style="single">Table 6:</u> Summary of the relevant lacquer-related properties of the liquid lacquers and of the applied and dried films</title><tgroup cols="6"><colspec colnum="1" colname="col1" colwidth="37mm" /><colspec colnum="2" colname="col2" colwidth="25mm" /><colspec colnum="3" colname="col3" colwidth="24mm" /><colspec colnum="4" colname="col4" colwidth="24mm" /><colspec colnum="5" colname="col5" colwidth="24mm" /><colspec colnum="6" colname="col6" colwidth="36mm" /><thead><row><entry valign="top" /><entry align="center" valign="top"><b>Prior art</b></entry><entry align="center" valign="top"><b>Silica 1</b></entry><entry align="center" valign="top"><b>Silica 5</b></entry><entry align="center" valign="top"><b>Silica 8</b></entry><entry align="center" valign="top"><b>Reference without S</b></entry></row></thead><tbody><row><entry><b>Grindometer value [µm] value</b></entry><entry align="center">< 10</entry><entry align="center" /><entry align="center">< 10 < 10</entry><entry align="center">< 10</entry><entry align="center">/</entry></row><row rowsep="0"><entry><b>Viscosity (ground material)</b></entry><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /></row><row rowsep="0"><entry align="right"><b>6 rpm</b></entry><entry align="center">58</entry><entry align="center">30</entry><entry align="center">30</entry><entry align="center">26</entry><entry align="center">30</entry></row><row><entry align="right"><b>60 rpm</b></entry><entry align="center">48</entry><entry align="center">43</entry><entry align="center">43</entry><entry align="center">33</entry><entry align="center">40</entry></row><row><entry><b>Surface</b></entry><entry align="center">orange peel</entry><entry align="center">o.k.</entry><entry align="center">o.k.</entry><entry align="center">o.k.</entry><entry align="center">o.k.</entry></row><row><entry><b>20° reflectometer value before scratching</b></entry><entry align="center">88.0</entry><entry align="center">86.5</entry><entry align="center">90.2</entry><entry align="center">89.6</entry><entry align="center">98.5</entry></row><row rowsep="0"><entry><b>100 strokes with Millicarb</b></entry><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /></row><row><entry align="right"><b>residual gloss</b></entry><entry align="center">88.3</entry><entry align="center">96.3</entry><entry align="center">95.4</entry><entry align="center">97.1</entry><entry align="center">59.6</entry></row></tbody></tgroup></table></tables>
0055It is found that, by the use of the silicas according to the invention, a substantially greater improvement in the residual gloss after scratching of the lacquer surface is achieved than in the case of the prior art. In addition, owing to their low rheological activity, the silicas according to the invention do not cause an orange-peel effect.
Every citation, both ways
| Document | Relation | Office | Cited during |
|---|---|---|---|
| US2002077388A1 | Cites | United States of America | Examiner |
| US5959005A | Cites | United States of America | Examiner |
| US6193795B1 | Cites | United States of America | Examiner |
| EP0798349A | Cites | European Patent Office (EPO) | – |
| DE3740139A | Cites | Germany | – |
| US5833967A | Cites | United States of America | – |
| US5959005A | Cites | United States of America | – |
| US6020419A | Cites | United States of America | – |
| US2002077388A | Cites | United States of America | – |
| US6193795B | Cites | United States of America | – |
20 members in 13 offices
Priority claims3
| Document | Office | Kind | Date |
|---|---|---|---|
| 10239425 | Germany | – | |
| 10239425 | Germany | A | |
| 0308330 | European Patent Office (EPO) | W |
Members20
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|---|---|---|---|
| CA2496936A1 | Canada | A1 | |
| DE10239425A1 | Germany | A1 | |
| WO2004020536A1 | World Intellectual Property Organization (WIPO) | A1 | |
| AU2003250187A1 | Australia | A1 | |
| EP1539890A1 | European Patent Office (EPO) | A1 | |
| KR20050059129A | Republic of Korea | A | |
| BR0313815A | Brazil | A | |
| CN1678698A | China | A | |
| JP2005536612A | Japan | A | |
| US2006009545A1 | United States of America | A1 | |
| KR100720852B1 | Republic of Korea | B1 | |
| CA2496936C | Canada | C | |
| EP1539890B1This record | European Patent Office (EPO) | B1 | |
| AT430786T | Austria | T | |
| ATE430786T1 | Austria | T1 | |
| DE60327538D1 | Germany | D1 | |
| PT1539890E | Portugal | E | |
| ES2326317T3 | Spain | T3 | |
| CN101712847A | China | A | |
| JP2012158765A | Japan | A |
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Numbers
- Publication
- 1539890
- Application
- 37908266
Titles3
- German
- LACKE
- English
- LACQUER FORMULATIONS
- French
- FORMULATIONS DE LAQUES
Classification
- CPC, 6
- C09C1/3684
- C08G18/6254
- C08G18/627
- C08K9/06
- C09D175/04
- C09D7/62
- IPC, 9
- C09D7 12
- C09C1 30
- C08G18 62
- C08K9 06
- C09C1 36
- C09C3 12
- C09D7 62
- C09D175 04
- C09D201 00
Designated states27
- Contracting states, 27
- Austria
- Belgium
- Bulgaria
- Switzerland
- Cyprus
- Czechia
- Germany
- Denmark
- Estonia
- Spain
- Finland
- France
- United Kingdom
- Greece
- Hungary
- Ireland
- Italy
- Liechtenstein
- Luxembourg
- Monaco
- Netherlands (Kingdom of the)
- Portugal
- Romania
- Sweden
and 3 moreShow fewer
- Slovenia
- Slovakia
- Türkiye