Brilliant goniochromatic pigments based on iron oxide platelets bearing multiple coatings

The present invention relates to novel goniochromatic luster pigments based on multiply coated iron oxide platelets, the at least one layer packet of<sl><li>A) a colorless coating having a refractive index n ≤ 1.8 and</li><li>B) a colorless coating having a refractive index n ≥ 2.0</li></sl>exhibit.

Furthermore, the invention relates to the preparation of these luster pigments and to their use for coloring paints, printing inks, Inks, plastics, glasses, ceramic products and preparations decorative cosmetics.

Luster or effect pigments are used in many areas of technology used, for example in automotive coatings, decorative Coating, plastics pigmentation, in paints, printing inks, especially security printing inks, and cosmetics.

Their optical effect is based on the directed reflection of Light at predominantly sheetlike, mutually parallel oriented, metallic or strongly refractive pigment particles. produce Depending on the composition of the pigment platelets Interference, reflection and absorption phenomena create angle-dependent Color and lightness.

Due to their optical effects nichtkopierbaren win this Pigments also increasingly important for the production of Forgeryproofness as banknotes, checks, Debit cards, credit cards, tax stamps, postage stamps, rail and Airline tickets, phone cards, lottery tickets, gift certificates, ID cards and identification cards.

Markings, which were made with the effect pigments, and the absence of these markings or their alteration, for example, in a color copy (disappearance of color flops and Glitter), are safe unaided, naked eye recognizable and so make it easy to distinguish the original from the copy.

Of particular interest are goniochromatic luster pigments, which an angle-dependent color change between several intensive Interference colors and hence an attractive color play show.

Heretofore, a number of goniochromatic luster pigments metallic base known about physical vapor deposition (US-A-3,438,796 and 5,135,812) or by coating of metal platelets by gas phase decomposition of volatile precursor (CVD = chemical vapor deposition) or by wet chemical Coating the metal platelets (EP-A-668 329, EP-A-708 154 and WO-A-96/34917) are prepared.

Goniochromatic luster pigments based on transparent, silicate Substrates coated or iron (III) oxide platelets are described in DE-A-196 18 569 and EP-A-753 545th

The known luster pigments differ from the invention Pigments by the nature of the substrate material and / or the applied coatings.

The invention had the object of further goniochromatic provide luster pigments which are notable for advantageous application properties distinguished.

Accordingly the goniochromatic initially defined Luster pigments found.

Furthermore, a method for preparing these luster pigments found which is characterized in that the Coatings (A) and (B) independently of one another either wet-chemically by hydrolytic decomposition of organic or inorganic Metal compounds or by gas phase decomposition of volatile, organic or inorganic metal compounds on the iron oxide platelets applied.

In addition, a method for manufacturing according to the invention was Luster pigments found on the basis of magnetite, which characterized in that<sl><li>a) Iron (III) oxide platelets initially with the coatings (A) and (B) has and the coated platelets then treated at 150 to 600 ° C with hydrogen or </li><li>b) the iron (III) oxide platelets initially at 150 to 600 ° C with a reducing gas and the treated magnetite obtained then with the coatings (A) and (B) occupied.</li></sl>

Finally, the use of the luster pigments of the invention for coloring paints, printing inks, inks, plastics, Glasses, ceramic products and preparations of decorative Cosmetics found.

based The goniochromatic luster pigments of the invention on multiply coated iron oxide platelets.

Examples of preferred substrate materials are platy α-iron (III) oxide (α-Fe₂O₃, Hematite), the silicon- (EP-A-14,382), aluminum (EP-A-68 311) or aluminum and manganese (EP-A-265 820) may be doped, and platelet-shaped iron (II / III) oxide (Fe₃O₄, Magnetite), which also referred to the may be doped metals.

The iron oxide platelets invention are highly refractive. you Refractive index n is generally ≥ 2.0, preferably ≥ 2.4. The optionally doped iron (III) oxide platelets are for visible light depending on the wavelength considered substantially transparent virtually impermeable to, while the Magnetite substantially opaque are.

The size of the iron oxide platelets is not critical per se and can be matched to the particular application. In the Usually have platelet average largest diameters of about 1 to 50 microns, preferably 5 to 20 microns. The thickness of the platelets is generally from 0.1 to 1 micron, preferably about 0.3 microns. Their specific free surface area (BET) is usually 0.5 to 15 m²/ G, particularly 1 to 12 m²/G.

The luster pigments of the invention have a colorless low refractive Coating (A) in combination with a colorless high refractive coating (B) on. You can buy several same or various combinations (layer packets) (A) + (B), but is preferably coating with just one layer packet (A) + (B).

The colorless low refractive coating (A) has a refractive index n ≤ 1.8, preferably ≤ 1.6, and in the visible wavelength range an absorption constant k = 0th

The layer material (A) are any low-index colorless substances that a durable film on the iron oxide platelets can be applied, inorganic Materials are preferred.

Especially suitable are for example metal oxides and metal oxide hydrates such as silicon oxide, silicon oxide hydrate, aluminum oxide, aluminum oxide hydrate and mixtures thereof, with silicon oxide (hydrate) is preferred is.

The geometric layer thickness of the coating (A) is generally 50 to 800 nm, preferably 100 to 600 nm. Since the Layer (A) essentially determines the interference colors of the invention Pigments determines it has a particularly pronounced Farbenspiel facing and therefore preferred luster pigments only one layer packet (A) + (B), a minimum layer thickness of about 200 nm. If multiple (eg, 2, 3 or 4) layer packets (A) + (B) present, the layer thickness of (A) is preferably at 50 to 200 nm.

With increasing layer thickness of (A) are the dry pigment powder in the plan several times in succession, the interference colors watching Blue-green-gold-red-violet, which starting with the second order blue, the angular dependence of the hue increases. However, the interference colors are only in the dry state visible and disappear when wet or in the paint completely. The additional coating with (B), the optically variable layer visible in varnishes.

The colorless high refractive coating (B) has a refractive index n ≥ 2.0, in particular ≥ 2.4, and in the visible wavelength range an absorption constant k = 0th

The layer material (B) are all highly refractive colorless substance occupied a durable film on the with (A) Iron oxide platelets may be applied, is suitable.

Particularly suitable besides metal sulfides such as zinc sulfide are also here especially metal oxides and metal oxide hydrates, such as titanium dioxide, Titanium oxide hydrate, zirconium dioxide, zirconium oxide hydrate, Tin dioxide, tin oxide hydrate, zinc oxide, zinc oxide hydrate and their Mixtures with titanium dioxide and titanium oxide hydrate and their Mixtures with up to about 5 wt .-% of other metal oxides, in particular Tin dioxide, are preferred. Titanium dioxide can also together used with low refractive colorless metal oxides , when the refractive index of these blends is ≥ 2.0.

The coating (B) preferably has a lower layer thickness than the coating (A). Preferred geometric layer thicknesses are for the coating (B) about 5 to 50 nm, particularly 10 to 40 nm.

The inventively preferred, essentially of titanium dioxide existing coating (B) preferably has an optical Layer thickness of ≤ 100 nm, ie in itself and silvery still shows no interference effects.

The luster pigments of the invention are distinguished by good Hiding power, high brightness values, strong and extremely angle-dependent Interference colors and "silky ausehen" in appliqued Form and the uniform, homogeneous and filmy Construction of their interference-capable coating. inventive Luster pigments give oxide platelets based on iron (III) particularly strong red and gold tones, vibrant blues and greens can be obtained in particular based on magnetite.

In the process for producing the luster pigments of the invention the coatings (A) and (B) are independently either wet-chemically by hydrolytic decomposition of organic or inorganic metal salts or by gas phase decomposition (CVD) of suitable volatile metal compounds applied.

Of course, both approaches can arbitrarily for preparing the individual layers are combined. If both applied coatings wet chemically, so it is unnecessary to intermediate drying the surface coated with (A) iron oxide platelets; becomes uses the same reaction medium, as can also the intermediate isolation . omitted Accordingly, the intermediate isolation usually also in the implementation of both coating steps not required by the CVD method.

layers to produce the silicon and / or aluminum oxide (hydrate) (A) are the wet chemical and the CVD preparation route likewise suitable.

In the wet-chemical variant may be advantageous according to the EP-A-668 329 method described proceed in the organic silicon and / or aluminum compounds in which bound the organic radicals bonded via oxygen atoms to the metal are, in the presence of iron oxide platelets and an organic Solvent in which the metal compounds soluble are and which is miscible with water, are hydrolyzed.

The preferred embodiment consists in the hydrolysis of the Metal alkoxides (especially tetraethoxysilane and aluminum triisopropoxide) in the presence of an alcohol (especially isopropanol) and aqueous ammonia as a catalyst.

The process is in accordance with the process described in EP-A-668 329 The method preferably followed in which iron oxide platelets, Isopropanol, water and ammonia submits this mixture with stirring at 40 to 80 ° C, especially 60 to 70 ° C, heated and a solution of the metal in isopropanol continuously metered. After stirring for usually about 1 to 15 h the mixture is cooled to room temperature and isolated the coated pigment by filtration and drying.

Silicon oxide (hydrate) coatings (A) can also advantageously starting from alkali metal silicates, especially sodium silicate, be generated.

The process involves the expediently so that the iron oxide platelets suspended in water, the suspension to about 20 to 100 ° C, preferably 40 to 80 ° C, heated with a base (especially an alkali metal such as potassium hydroxide or sodium hydroxide) or an acid (eg nitric acid) has a pH-value of in usually 4 to 9, preferably 6.5 to 8.5, particularly about 7.5, is established and the alkali metal silicate solution with simultaneous Adding an aqueous inorganic acid such as hydrochloric acid, especially a dilute hydrochloric acid, for keeping the pH metered. Optionally, stirred a few minutes to 2 h.

In CVD-variant, according to the process described in EP-A-708 154 Process proceed. Here are silanes that at least contain one alkanoyloxy in the gas phase with water vapor and, if the silanes and alkyl or phenyl radicals, Oxygen in the presence of the fluidized iron oxide platelets decomposed.

Preferred silanes have alkoxy and alkanoyloxy, is more preferably di-tert-butoxydiacetoxysilane.

To carry out the CVD variant is recommended as generally customary for CVD process using a fluidized bed reactor. The iron oxide platelets are in the reactor under fluidization (Turbulence) with an inert gas such as nitrogen fluidized to the desired reaction temperature (typically 100 to 600 ° C, preferably 150 to 300 ° C), silane and water vapor (And optionally oxygen) are then using inert Carrier gas streams (advantageously part-streams of the fluidizing gas) from upstream vaporizer vessels introduced via separate nozzles, the silane concentration being advantageously in ≤ Vol .-% preferably ≤ 2 Vol .-%, based on the total amount of gas in the reactor, is maintained. The amount of water vapor should be at least the stoichiometrically required for hydrolysis of the silane amount but correspond, preferable is 10 to 100 times that amount.

Also the deposition of coatings (B) is on both the CVD way and wet chemically possible.

For the CVD variant can be used as starting compounds are , Metal, metal halides, and organometallics. Prefers are those compounds which at temperatures up to 200 ° C have a sufficiently high vapor pressure to a simple to ensure evaporation possible without decomposition.

The alcoholates aromatic alkoxides such as phenoxides come and Benzylalkoholate and aliphatic, especially C₁-C₄alcoholates as n-, iso- and tert-butanolates, preferably methanolate and Ethanolates, and in particular n-and iso-propoxides and also their Mixtures.

When metal halides the chlorides are preferred.

Organometallics can eg metal, particularly those with up to 4 carbon atoms in the alkyl chain, Metallalkenyle, metal aryls, be Metallarylalkyle and Metallalkylalkenyle.

Examples which may be mentioned as suitable starting materials:<ul><li>Alkoxides such as titanium tetraethoxide, titanium tetra-isopropoxide and N- and in particular mixtures of titanium tetraethoxide and titanium tetraisopropoxide, preferably in a molar ratio of about 1: 1, which is characterized by low evaporation temperatures (120 ° C) and low decomposition temperatures (Hydrolysis with steam at about 200 ° C possible) are distinguished, and zirconium n- and isopropoxide;</li><li>Halides such as titanium tetrachloride, zirconium tetrachloride and tin tetrachloride;</li><li>Organyl as tin tetramethyl, tin tetra-n-butyl and zinc diethyl.</li></ul>

The decomposition of these metal compounds filmy about to the coated with (A) iron oxide platelets depositing metal oxide layers is advantageously carried out also in a fluidized bed reactor, and in the case of the alcoholates and the halides Water vapor and in the case of oxygen as an additional organyls The reaction gas is employed. Suitable decomposition temperatures are generally from 100 to 600 ° C, preferably 150 to 300 ° C (Alkoxides), 150 to 350 ° C (halides) or 300 to 500 ° C (Organyl).

coatings Analogous to the metal oxide (hydrate) (A), the metal oxide (hydrate) layers (B) likewise wet-chemically by hydrolysis metal alcoholates (eg of titanium ethoxide) in an alcoholic Medium or preferably by hydrolysis of inorganic Metal salts, in particular halides, preferably chlorides, be applied in aqueous suspension.

For deposition of the preferred titanium dioxide layers (B) can be advantageously proceed by the with an aqueous suspension (A) -coated iron oxide platelets at usually 50 to 100 ° C, preferably 70 to 80 ° C, heated with a base (especially an alkali metal such as potassium hydroxide or sodium hydroxide) or an acid preferably a pH of generally 0.5 to 5, 1.5 to 2.5, particularly about 2.2, is established and Titanium tetrachloride solution with simultaneous addition of base to Maintenance of the pH-value added.

Both the deposited from the gas phase and the wet-chemical Titanium oxide (hydrate) is crystallized incompletely. The amorphous portions can by calcination of the isolated (and dried) pigment in crystalline form, usually in the Anatase, are transferred. These heating the pigment generally about 1 to 4 hours at 400 to 1000 ° C. Should the Titanium dioxide coating (B) after calcination in the rutile modification present, so it is recommended that the titanium oxide (hydrate) by co-depositing tin oxide (hydrate) with about 0.5 to dope to 10 wt .-% tin dioxide, which of the formation Rutile favors.

The luster pigments based on magnetite invention can advantageously by subsequent reduction with (A) and (B) coated iron (III) oxide platelets with hydrogen be prepared (a) as laid likewise inventive Manufacturing process).

Suitable reduction temperatures are noted in typically 150 to 600 ° C, especially at 200 to 500 ° C.

One can also produce based on magnetite luster pigments, by reducing oxide platelets initially iron (III) and the magnetite obtained then with (A) and (B) coated (b), of the inventive production method.

The reduction of the iron (III) oxide platelets preferably is with reducing gases such as hydrogen made, said reduction temperatures from 150 to 600 ° C, in particular 200 to 500 ° C, are functional. At temperatures ≥ 600 ° C containing formed Magnetite increasing proportions of metallic iron. The increased magnetization of these pigments can be targeted as Another safety feature be exploited.

The reduction is in both process variants expediently rendered inert in an oven in which a mixing of the substrate is possible, carried out. For example were on a laboratory scale, a rotary kiln, ie a flask of quartz glass, which is rotated by a motor, with Gas supply and discharge lines is provided in the axis of rotation and a clamshell oven is heated, and for continuous Process on an industrial scale, a rotary kiln having internals for pigment mixing and gas supply and called dissipation.

Using the manufacturing method according to the invention can multiply coated luster pigments in a simple manner in large Quantities are produced reproducibly. There are completely coated pigment particles with high quality of the individual coatings (Homogeneous, filmlike).

The luster pigments of the invention are advantageous for many purposes, such as the coloring of plastics, glasses, ceramic Products, decorative cosmetic preparations and especially coatings, and inks, including security printing inks. When applying the pressure are all industry-standard Printing processes, for example screen printing, intaglio printing, bronze, Flexo and offset printing suitable.

For these applications, the pigments of the invention can be also beneficial in admixture with transparent and opaque white, colored and black pigments and also conventional Luster pigments based on metal oxide Mica and metal pigments and known goniochromatic using luster pigments.

Examples

Manufacture and use of luster pigments according to the invention

To assess the coloristic properties of the pigments obtained in each case 0.4g pigment in 3.6 g of a polyester mixing varnish with 21 Wt .-% solids and stirred for 2 minutes in a Red Devil® dispersed. With a blade (200 .mu.m wet film thickness, simple doctoring) were then the pigmented paints on a black and white cardboard made. Measurement of CIELAB values was carried out after drying of the film with a gonio-spectrophotometer Multi Flash (Fa. Optronics) at an angle difference from 20 ° to 115 ° to the specular angle against a black background. The reported color coordinates relate to the standard illuminant D65. L is the lightness, a * the red or green content and b * the blue or yellow portion, H is the hue angle and C chroma. With this measuring device is only one part of the color game, namely essentially the color of paint in supervisory detected.

example 1

<sl><li>a) 20 kg of a copper-colored, doped with aluminum and manganese, platelet-like iron (III) oxide pigment (average Particle diameter 18 microns; Paliocrom® Copper L3000, BASF) were mixed in a 1.5 m³Stirred tank in a mixture of 305 l strength isopropanol 80 kg of water and 8 kg of a 25 wt .-% aqueous ammonia solution heated with stirring to 60 ° C. Then were a mixture of 125 kg and 125 kg of tetraethoxysilane strength isopropanol and, in parallel 28.1 kg of a 3 wt .-% aqueous Anmoniaklösung metered. The progress of the Coating was followed by regular sampling. After stirring for 2 h and cooling the Suspension was filtered, the product washed with water and dried under reduced pressure at 80 ° C. The dried SiO₂-coated pigment exhibited in air in supervision an orange interference color which in oblique view flopped toward gold.</li><li>b) 1 kg of the SiO₂-coated and dried product was in a fluidized bed reactor under fluidization with a total 1800 l / h of nitrogen heated to 200 ° C. Then a Part of the fluidizing gas (400 l / h) heated to 50 ° C over a Water seal and another part of the fluidizing gas (400 l / h) a temperature-controlled to 120 ° C template with a mixture of Titanium tetraethoxide and titanium tetraisopropoxide (molar ratio 1: 1, titanate IPET passed Huls).. Within about were 8 h so 150 ml of Titanalkoholatgemisches portions transferred into the fluidized bed reactor and to be the pigment flakes which deposited TiO₂ implemented.</li></sl>

The pigment obtained had a silicon content of 26.5 wt .-% and a titanium content of 2.1 wt .-%. An electron microscope Investigation (sectional TEM) revealed a gemometrische SiO₂Layer thickness of about 400 nm and a geometrical TiO₂Layer thickness of about 35 nm. Applied in varnish, showed the Pigment an angle-dependent color play from bluish red to Gold at a high brightness level.<tables><table><tgroup cols="6"><tbody><row><entry namest="1" nameend="6">Colorimetric data of pigment obtained:</entry></row><row><entry align="center">Measuring angle in °</entry><entry align="center">L</entry><entry align="center">a *</entry><entry align="center">b *</entry><entry align="center">C</entry><entry align="center">H</entry></row><row><entry align="center">20</entry><entry align="center">78,99</entry><entry align="center">51.87</entry><entry align="center">-6,64</entry><entry align="center">52,29</entry><entry align="center">352.7</entry></row><row><entry align="center">25</entry><entry align="center">67.98</entry><entry align="center">47.39</entry><entry align="center">-3.21</entry><entry align="center">47.5</entry><entry align="center">356.1</entry></row><row><entry align="center">35</entry><entry align="center">50,27</entry><entry align="center">37,83</entry><entry align="center">4.17</entry><entry align="center">38,06</entry><entry align="center">6.29</entry></row><row><entry align="center">45</entry><entry align="center">38.74</entry><entry align="center">31,14</entry><entry align="center">9.93</entry><entry align="center">32.69</entry><entry align="center">17,69</entry></row><row><entry align="center">55</entry><entry align="center">31.62</entry><entry align="center">27.58</entry><entry align="center">13,63</entry><entry align="center">30,77</entry><entry align="center">26.3</entry></row><row><entry align="center">65</entry><entry align="center">26,11</entry><entry align="center">25,26</entry><entry align="center">16.2</entry><entry align="center">30,01</entry><entry align="center">32,68</entry></row><row><entry align="center">75</entry><entry align="center">24,98</entry><entry align="center">24.9</entry><entry align="center">16,53</entry><entry align="center">29,89</entry><entry align="center">33,58</entry></row><row><entry align="center">115</entry><entry align="center">21,99</entry><entry align="center">25.1</entry><entry align="center">18,66</entry><entry align="center">31,27</entry><entry align="center">36.62</entry></row></tbody></tgroup></table></tables>

example 2

1 kg of the SiO₂-coated and dried product from Example 1a) was similar to Example 1b) in the fluidized bed reactor Using 300 ml of Titanalkoholatgemisches with TiO₂ coated.

The pigment obtained had a silicon content of 24.2 wt .-% and a titanium content of 5.7 wt .-%. An electron microscope Investigation (sectional TEM) revealed a geometric SiO₂Layer thickness of about 400 nm and a geometrical TiO₂Layer thickness of approximately 75 nm. Applied in varnish, showed the Pigment an angle-dependent color play from weak blue over strong violet to gold at a high brightness level. <tables><table><tgroup cols="6"><tbody><row><entry namest="1" nameend="6">Colorimetric data of pigment obtained:</entry></row><row><entry align="center">Measuring angle in °</entry><entry align="center">L</entry><entry align="center">a *</entry><entry align="center">b *</entry><entry align="center">C</entry><entry align="center">H</entry></row><row><entry align="center">20</entry><entry align="center">80,39</entry><entry align="center">43.8</entry><entry align="center">-19.43</entry><entry align="center">47.92</entry><entry align="center">336.08</entry></row><row><entry align="center">25</entry><entry align="center">69.86</entry><entry align="center">37,43</entry><entry align="center">-13.35</entry><entry align="center">39,74</entry><entry align="center">340.36</entry></row><row><entry align="center">35</entry><entry align="center">53,05</entry><entry align="center">27,15</entry><entry align="center">-1.35</entry><entry align="center">27.18</entry><entry align="center">357.16</entry></row><row><entry align="center">45</entry><entry align="center">42.17</entry><entry align="center">22,32</entry><entry align="center">6.71</entry><entry align="center">23.3</entry><entry align="center">16.7</entry></row><row><entry align="center">55</entry><entry align="center">35,49</entry><entry align="center">20.76</entry><entry align="center">11,05</entry><entry align="center">23.52</entry><entry align="center">28,02</entry></row><row><entry align="center">65</entry><entry align="center">30,16</entry><entry align="center">20,15</entry><entry align="center">13,27</entry><entry align="center">24,13</entry><entry align="center">33,35</entry></row><row><entry align="center">75</entry><entry align="center">29,05</entry><entry align="center">19,98</entry><entry align="center">13,47</entry><entry align="center">24.1</entry><entry align="center">33,99</entry></row><row><entry align="center">115</entry><entry align="center">26,09</entry><entry align="center">19.74</entry><entry align="center">14,29</entry><entry align="center">24,37</entry><entry align="center">35.9</entry></row></tbody></tgroup></table></tables>

example 3

75 g of the pigment from Example 2 were mixed in a rotary kiln inert by 30 minutes passing 10 l / h of nitrogen and simultaneously heated to 350 ° C. Then the inert gas flow were admixed with 5 l / h of hydrogen. After 10 min, the temperature was increased to 400 ° C. Subsequently, the hydrogen content was on 10 l / h and increased the nitrogen content of 5 l / h lowered. After were finally 1 h 15 l / h of hydrogen (without a stream of nitrogen) passed through the pigment. After about 5 hours, the hydrogen stream was turned off, and the pigment was under a nitrogen stream 15 l / h cooled to room temperature.

The reduced pigment had a silicon content of 24.8 wt .-%, a titanium content of 5.9 wt .-% and a Iron (II) content of 11.2 wt .-% (total iron 22.1 wt .-%). in the applied paint, the pigment showed a strong angle-dependent Farbenspiel from blue to violet.<tables><table><tgroup cols="6"><tbody><row><entry namest="1" nameend="6">Colorimetric data of pigment obtained:</entry></row><row><entry align="center">measuring angle</entry></row><row><entry align="center">in</entry><entry align="center">L</entry><entry align="center">a *</entry><entry align="center">b *</entry><entry align="center">C</entry><entry align="center">H</entry></row><row><entry align="center">20</entry><entry align="center">81.44</entry><entry align="center">42.69</entry><entry align="center">-18.61</entry><entry align="center">46.57</entry><entry align="center">-23.56</entry></row><row><entry align="center">25</entry><entry align="center">71.86</entry><entry align="center">36.39</entry><entry align="center">-13.5</entry><entry align="center">38.82</entry><entry align="center">-20.35</entry></row><row><entry align="center">35</entry><entry align="center">55,37</entry><entry align="center">26.38</entry><entry align="center">-2.59</entry><entry align="center">26.5</entry><entry align="center">-5.6</entry></row><row><entry align="center">45</entry><entry align="center">44.06</entry><entry align="center">21,67</entry><entry align="center">5.36</entry><entry align="center">22,32</entry><entry align="center">13,89</entry></row><row><entry align="center">55</entry><entry align="center">36.82</entry><entry align="center">20,35</entry><entry align="center">10,11</entry><entry align="center">22,72</entry><entry align="center">26.41</entry></row><row><entry align="center">65</entry><entry align="center">30,88</entry><entry align="center">20,14</entry><entry align="center">12,97</entry><entry align="center">23,95</entry><entry align="center">32,77</entry></row><row><entry align="center">75</entry><entry align="center">29,77</entry><entry align="center">19,98</entry><entry align="center">13,29</entry><entry align="center">24</entry><entry align="center">33.64</entry></row><row><entry align="center">115</entry><entry align="center">26.4</entry><entry align="center">20,14</entry><entry align="center">14.33</entry><entry align="center">24,72</entry><entry align="center">35.44</entry></row></tbody></tgroup></table></tables>