Mixtures of thermoplastic polydiorganosiloxan-polycarbonate block copolymers with polytetrafluoroethylene polymers.

0001The present invention relates to mixtures consisting of<ul id="ul0001" list-style="none"><li>A) 80 wt .-% - 99 wt .-%, preferably 82 wt .-% - 97 wt .-% of thermoplastic polydiorganosiloxane-polycarbonate block copolymers, with average molecular weight <o ostyle="single">M</o>w from 10,000 to 200,000 and with a content of aromatic carbonate structural units between 70% by weight and 99% by weight and a content of diorganosiloxy units between 30% by weight and 1% by weight, the block copolymers starting from α, ω-Bishydroxyaryloxypolydiorganosiloxanen, with a degree of polymerization Pπ from 5 to 100 and</li><li>B) 20% by weight to 1% by weight, preferably 18% by weight to 3% by weight, of polytetrafluoroethylene polymers having an average particle diameter of 0.1 μm to 700 μm, preferably of 0.2 μm to 600 μm and one <o ostyle="single">M</o>_n (Number average molecular weight) from 4,000 to 900,000, preferably from 50,000 to 800,000, and optionally effective amounts of stabilizers, pigments, flow agents, mold release agents and / or reinforcing materials, the sum of the percentages by weight of components A) and B) in each case being 100% by weight .</li></ul>

0002The preferred <o ostyle="single">M</o>w of the block copolymers is between 20,000 and 80,000; the preferred content of carbonate structural units is between 80% by weight and 97% by weight, the preferred content of polydiorganosiloxane blocks is between 20% by weight and 3% by weight and the preferred degree of polymerization of the polydiorganosiloxane blocks is between 5 and 80.

0003Component A can also be a mixture of polydiorgano-polycarbonate block copolymers with other siloxane-free, aromatic, thermoplastic polycarbonates, the total content of diorganosiloxy units in these mixtures again being between 1% by weight and 30% by weight, preferably between 3 % And 20% by weight.

0004Mixtures of polycarbonates with polytetrafluoroethylene in amounts of 0.05% to 20% are known from US Pat. No. 3,005,795. They have a particularly favorable flow behavior in the melt, but still show the tendency towards stress corrosion cracking which is characteristic of polycarbonates when exposed to fuels for Otto engines and have normal rigidity.

0005From GB-PS 93 89 31 plain bearings made of filled polycarbonates are known. Among other things, plastics can be used as fillers and polytetrafluoroethylene as preferred plastics. (Page 1, lines 50-56 of the GB-PS). The amount of filler can be up to 40% by volume of the polycarbonate.

0006DE-OS 1 494 288 discloses a method for producing lubrication-free plain bearings. Here, thermoplastic materials are mixed with 10 to 36 wt .-% of polytetrafluoroethylene fibers. Polycarbonates are also suitable as thermoplastics.

0007US Pat. No. 3,294,871 discloses a process for the production of thermoplastics containing polytetrafluoroethylene, the content of polytetrafluoroethylene being 10% by weight to 20% by weight. Polycarbonates are also suitable as thermoplastics.

0008From US Pat. Nos. 3,651,174 and 3,742,085, thermostable polycarbonates are known which contain mixtures of polytetrafluoroethylene and organosiloxane polymers.

0009Polymer Letters Edition, vol. 12, pages 247-252, (1974) describes the influence of short siloxane blocks in polycarbonate-siloxane block polymers. It can be seen from this that siloxane blocks improve the low-temperature toughness of the polycarbonate.

0010Flame-retardant molding compositions are also known which contain polysiloxane-polycarbonate block copolymers and polytetrafluoroethylene. (See for example EP-OS 0 174 493, DOS 3 615 768, DOS 3 617 511, DOS 3 628 904 and DOS 3 629 546).

0011However, such mixtures relate to molding compositions with fire protection equipment, which also contain considerable amounts of copolymers and phosphoric acid esters.

0012Compared to the prior art, the mixtures according to the invention have a much greater rigidity.

0013The polydiorganosiloxane-polycarbonate block copolymers according to component A) which can be used according to the invention are those based on the diphenols of the formula (I) and the formula (I a)<chemistry id="chem0001" num="0001"><img file="EP0382004A2_D0001.tif" /></chemistry> wherein R¹ are the same or different and are Cl, Br or CH₃, p is zero, 1 or 2, A is a single bond C₁-C₅-alkylene, a C₂-C₅-alkylidene, a C₅-C₆-cycloalkylidene, -S- or -SO₂-, n = 1 or zero, the R are the same or different and a linear C₁-C₂₀ -Alkyl, branched C₃-C₂₀-alkyl or C₆-C₂₀-aryl, preferably CH₃ and m is an integer between 5 and 100, preferably between 5 and 80, and the proportion by weight of diphenols of the formula (I a) in the copolycarbonates is in each case such that the content of diorganosiloxy units<chemistry id="chem0002" num="0002"><img file="EP0382004A2_D0002.tif" /></chemistry> in the copolycarbonate used for component A is between 1 and 30% by weight, preferably between 3 and 20% by weight.

0014The content of aromatic carbonate structural units<chemistry id="chem0003" num="0003"><img file="EP0382004A2_D0003.tif" /></chemistry> corresponds to the complementary amount from 99 to 70 wt .-%, preferably from 97 to 80 wt .-%.

0015Other, siloxane-free thermoplastic, aromatic polycarbonates are preferably those which contain only those of the formula (I) incorporated as diphenols.

0016In cases in which component (A) is a mixture of siloxane-containing polycarbonates and siloxane-free polycarbonates, the siloxane-containing polycarbonates can also contain a content of diorganosiloxy units of more than 30% by weight, provided that they are mixed with the siloxane-free polycarbonates the content in the polycarbonate mixture in turn is between 1 and 30% by weight.

0017The diphenols of the formula (I) are either known from the literature or can be prepared by processes known from the literature.

0018Polydiorganosiloxanes with hydroxyaryloxy end groups of the formula (I a) are also known (see, for example, US Pat. No. 3,419,634) or can be prepared by processes known from the literature.

0019The preparation of the polydiorganosiloxane-polycarbonate block copolymers according to component A) which is suitable according to the invention is known from the literature and can be carried out, for example, with phosgene by the phase interface process or with phosgene by the process in a homogeneous phase (the so-called pyridine process), the molecular weight to be set in each case being known by a appropriate amount of known chain terminators is achieved. [Regarding polydiorganosiloxane-containing polycarbonates, see e.g. B. DE-OS 3 334 782 (Le A 22 594)].

0020Suitable chain terminators are e.g. B. phenol or p-tert-butylphenol, but also long-chain alkylphenols such as 4- (1,3-tetramethyl-butyl) phenol according to DE-OS 2 842 005 (Le A 19 006) or monoalkylphenols or dialkylphenols with a total of 8 to 20 C atoms in the alkyl substituents according to German patent application P 3 506 472.2 (Le A 23 654), such as p-nonylphenol, 2,5-di-tert-butylphenol, p-tert-octylphenol, p-dodecylphenol, 2- (3,5-dimethylheptyl) phenol and 4- (3,5-dimethylheptyl) phenol. The amount of chain terminators to be used is generally between 0.5 and 10 mol%, based on the sum of the diphenols (II) and (II a) used in each case.

0021The polycarbonates according to component A) which are suitable according to the invention have average weight-average molecular weights (<o ostyle="single">M</o>w, measured z. B. by ultracentrifugation or scattered light measurement) from 10,000 to 200,000, preferably from 20,000 to 80,000.

0022Siloxane-free thermoplastic, aromatic polycarbonates are also known from the literature.

0023Suitable diphenols for the preparation of the polycarbonates are, for example, hydroquinone, resorcinol, dihydroxydiphenyls, bis (hydroxyphenyl) alkanes, bis (hydroxyphenyl) cycloalkanes, bis (hydroxyphenyl) sulfides, bis (hydroxyphenyl) ethers, bis ( hydroxyphenyl) ketones, bis (-hydroxyphenyl) sulfoxides, bis (hydroxyphenyl) sulfones and α, α′-bis (hydroxyphenyl) diisopropylbenzenes and their ring-alkylated and ring-halogenated compounds. These and other diphenols are e.g. B. in US Pat. Nos. 3,028,365, 3,272,601, 3,148,172, 3,062,781, 2,991,273, 3,271,367, 2,999,835, 2,970,131 and 2,999,846, in German Offenlegungsschriften 1,570,703,2 063 050, 2 063 052, 2 211 956, 2 211 957, French Patent 1,561,518 and in the monograph by H. Schnell, "Chemistry and Physics of Polycarbonates", Interscience Publishers, New York.

0024Preferred diphenols are e.g. B. 4,4'-dihydroxydiphenyl, 2,4-bis (4-hydroxyphenyl) -2-methylbutane, α, α'-bis (4-hydroxyphenyl) -p-diisopropylbenzene, 2,2-bis (3-methyl -4-hydroxyphenyl) propane, 2,2-bis (3-chloro-4-hydroxyphenyl) propane, bis (3,5-dimethyl-4-hydroxyphenyl methane, bis (3,5-dimethyl-4 -hydroxyphenyl) sulfone, 2,4-bis (3,5-dimethyl-4-hydroxyphenyl) -2-methylbutane, 1,1-bis (3,5-dimethyl-4-hydroxyphenyl) cyclohexane and α, α'-bis (3,5-dimethyl-4-hydroxyphenyl) -p-diisopropylbenzene.

0025Particularly preferred diphenols are e.g. B. 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, 2,2-bis (3,5-dichloro -4-hydroxyphenyl) propane, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane and 1,1-bis (4-hydroxyphenyl) cyclohexane.

0026Suitable diphenols of the formula (I a) are those in which R is methyl, ethyl, propyl, n-butyl, tert-butyl and phenyl.

0027Preferred diphenols of the formula (Ia) are those of the formula (I b)<chemistry id="chem0004" num="0004"><img file="EP0382004A2_D0004.tif" /></chemistry> where the R's are the same and have the meaning given above, that is to say methyl etc. and phenyl and m is in turn an integer between 5 and 100, preferably between 20 and 80.

0028The siloxane-containing and siloxane-free polycarbonates according to component A) which are suitable according to the invention can be branched in a known manner, preferably by incorporating from 0.05 to 2.0 mol%, based on the sum of the diphenols used, of three or more as tri-functional compounds, e.g. B. those with three or more than three phenolic OH groups (see for example DE-OS 33 47 071 (Le A 22 802)).

0029Preferred polydiorganosiloxane-polycarbonate block copolymers are copolycarbonates of the diphenols of the formula (I) with diphenols of the formula (I a).

0030The polydiorganosiloxane-polycarbonate block polymers suitable according to the invention can also be characterized by their relative solution viscosities of 1.16 to 1.5, where η_rel is measured in CH₂Cl₂ at 25 ° C and a concentration of 0.5 g per 100 ml of solution.

0031The particle shape of the polytetrafluorethylene suitable according to the invention can be round, fibrous, but also irregular.

0032The production, processing and properties of polytetrafluoroethylene (PTFE) are described, for example, in Ullmanns Encyklopadie der Technische Chemie, 4th edition, volume 19, p. 89 f, Verlag Chemie, Weinheim, 1980.

0033The publications Kunststoffe Hoechst, "Hostaflon", edition July 1984, also provide information about polytetrafluorethylene. "Teflon" by DuPont de Nemours, June 1987 edition.

0034The mixtures according to the invention from components A) and B) can be prepared in the melt in conventional mixing units. Extruders and kneaders should be mentioned as such. The temperature and pressure conditions are the usual for the mixing of thermoplastics.

0035A particular possibility of blending consists in the synthesis of the polydiorganosiloxane-polycarbonate block copolymers in the presence of the amount of polytetrafluoroethylene to be blended in accordance with component B) and the subsequent customary workup and isolation of component A) from the reaction mixture, or in the metered addition of the polytetrafluoroethylene in the amount to be mixed to a solution of the block polymer in conventional solvents, such as CH₂Cl₂, intimate mixing and subsequent precipitation of the mixture from A) and B). A suitable precipitant is acetone. Methanol can also be used.

0036The present invention thus also relates to a process for the preparation of the mixtures according to the invention consisting of components A) and B), which is characterized in that either the components A) and B) are mixed in the amount to be mixed in conventional mixing units via the melt of Component A) mixed and isolated at usual temperatures and pressures, or component A) is synthesized in the presence of the amount of component B) to be mixed and then component A) is then worked up and isolated in the customary manner, or component B) is metered in to the amount to be mixed in a solution of component A) in customary solvents mixed and then the mixture of A) and B) precipitates.

0037With the mixing of components A) and B), the stabilizers, pigments, flow agents, mold release agents and reinforcing materials customary for the polycarbonates can be incorporated in the customary amounts.

0038Suitable additives are, for example, glass fibers, carbon fibers of organic or inorganic polymers, calcium carbonate, talc, silica gel, quartz powder, fatty acid esters, phosphite stabilizers, carbon black and TiO₂.

0039The present invention thus also relates to a process for the preparation of the mixtures according to the invention consisting of A) and B) and at least one additive selected from the group of stabilizers, pigments, flow aids, mold release agents and reinforcing materials, characterized in that they are incorporated into the inventive Mixing of component A) with B) is included.

0040The molding compositions according to the invention can be processed to give moldings, semifinished products and foils on customary processing machines, such as injection molding and extrusion systems.

0041The mixtures according to the invention are used as molding compositions or moldings in mechanical engineering.

Examples:

0042The compositions of the mixtures according to the invention produced and their properties are summarized in Table 1. The mixtures were compounded in a twin-screw extruder type ZSK 32 from Werner and Pfleiderer.

0043The following siloxane-polycarbonate block copolymers (abbreviated SiCoPC) were produced to produce the molding compositions according to the invention:

SiCoPC I:

Approx. 10% by weight siloxane blocks in polycarbonate

0044According to Example 2 a of DOS 3 334 782, α, ω-bis-hydroxy-aryloxy-polysiloxanes are prepared: 1140 (5 moles.) Are added to a vessel provided with a cooler, drying tube, dropping funnel, stirrer and distillation bridge ) Parts by weight of bisphenol A and 22400 parts by weight of chlorobenzene. Under reflux and stirring, a solution of 3068 (1 mol) parts by weight of α, ω-bisacetoxypolydimethylsiloxane P_n = 40, added in 5600 parts by weight of chlorobenzene. Subsequently, about a third of the amount of solvent is distilled off, the acetic acid formed in the reaction passing over as an azeotropic mixture with the chlorobenzene. Yield: 97% of theory.

0045From this, the SiCoPC was produced according to Example 3 of DOS 3 334 782:

0046The tenth part of the solution from Example 2a is in a reaction flask equipped with a stirrer, phosgene inlet tube, reflux condenser, internal thermometer and dropping funnel, with 2280 parts by weight of bisphenol A, 1010 parts by weight of sodium hydroxide, 31100 parts by weight of water, 13500 Parts by weight of dichloromethane and 10700 parts by weight of chlorobenzene and 25 parts by weight of phenol were added. 1646 parts by weight of phosgene are introduced at room temperature, the pH being kept between 12 and 13 by adding 45% sodium hydroxide solution. The initiation takes about an hour. Then 8 parts by weight of triethylamine are added and the mixture is stirred at pH 12 to 13 for a further 45 minutes. The cocondensate is worked up according to methods common to polycarbonate.

0047The material obtained had the relative solution viscosity (η_rel) 1.288 (measured in dichloromethane at 25 ° C and a concentration of 0.5 g SiCoPC) in 100 ml solution). The material contained 9.9% by weight of siloxane.

SiCoPC II:

Granulate mixture of a) 20% by weight SiCoPC based on 50% by weight siloxane blocks and 50% by weight bisphenol A homopolycarbonate and b) 80% by weight bisphenol A homopolycarbonate (η

rel

of this latter PC part 1,293).

0048The SiCoPC with a content of 50% by weight of siloxane blocks was produced as follows:

0049The solution of Example 2 a of DOS 3,334,782, containing 2,966.4 g of siloxane, was 1 521.6 g of bisphenol A, 9.5 g of phenol as a chain terminator, 1,000 g of NaOH as a 45% strength aqueous solution, 35 l Water and 10 l each of dichloromethane and chlorobenzene are added and 1,600 g of phosgene are introduced with vigorous stirring at room temperature, the pH of the aqueous phase is kept between 12 and 13 with NaOH. The introduction of the phosgene took about 1 hour. Then 9 g of N-ethylpiperidine were added and 45 min. stirred at pH 12-13. The batch was worked up in the manner customary for polycarbonate at the end by extruder degassing. The cocondensate obtained had a relative solution viscosity of 1.297, measured in CH₂Cl₂ at a concentration of 0.5 g of product in 100 ml of solution.

0050The mixture with the bisphenol A homopolycarbonate in a ratio of 20 to 80 was carried out in a tumble mixer.

0051A bisphenol A homopolycarbonate with a relative solution viscosity of 1,287 was used as the polycarbonate (PC in the table).

0052The following grades from Hoechst AG were used as finely divided polytetrafluoroethylene (PTFE): Hostaflon TF 2027 (I) and 1740 (II). The average particle size was approx. 550 or 40 µm; the densities were 2.1 to 2.2 g / cm³.

0053Teflon 30-N (III) from DuPont with an average particle size of 0.23 µm was used, the density of which is between 2.1 and 2.2 g / cm³.

0054The mixtures according to Examples 2 and 5 to 10 were prepared by compounding in a twin-screw extruder from Werner and Pfleiderer.

0055The mixtures according to Examples 11 and 12 were prepared by metering the polytetrafluoroethylene into a solution of component A) in CH₂Cl₂, intimately mixing and precipitating with acetone.

0056To assess the fuel resistance, test rods (manufactured by injection molding) with the dimensions 80 x 10 x 4 mm were subjected to the stencil test (W. Kaufmann, determination of the chemical resistance of plastics under mechanical tension, Kunststoffe 65 (1976), pp. 155-157). Edge fiber strains of 1% were set. According to DIN 51 604, part 1, a mixture of; 50 vol% toluene 30 vol.% ISO octane 15 vol.% Diisobutylene 5 vol% ethanol

0057The test was carried out as follows:

1. cycle

0058Place a cotton ball soaked in the test liquid on the bending templates with the sample applied and leave for 15 minutes. Let the sample flash off for 15 minutes.

2nd Cycle:

0059corresponds to the 1st cycle.

Evaluation:

0060At the end of the 2nd cycle, the sample taken from the template is viewed with the naked eye and evaluated as follows: <tables id="tabl0001" num="0001"><table frame="all"><tgroup cols="2" colsep="1" rowsep="0"><colspec colnum="1" colname="col1" colwidth="78.75mm" /><colspec colnum="2" colname="col2" colwidth="78.75mm" /><thead valign="top"><row><entry namest="col1" nameend="col1" align="left"><u style="single">step</u></entry><entry namest="col2" nameend="col2" align="left"><u style="single">feature</u></entry></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="right">1</entry><entry namest="col2" nameend="col2" align="left">no visible change</entry></row><row><entry namest="col1" nameend="col1" align="right">2</entry><entry namest="col2" nameend="col2" align="left">Matted surface</entry></row><row><entry namest="col1" nameend="col1" align="right">3</entry><entry namest="col2" nameend="col2" align="left">fine cracks</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="right">4</entry><entry namest="col2" nameend="col2" align="left">strong cracks, breakage</entry></row></tbody></tgroup></table></tables>

0061The modulus of elasticity is to be understood as the tensile modulus of elasticity in accordance with DIN 53 457. It characterizes the stiffness.

0062To measure the coefficient of sliding friction ng, the measuring method used is described below in the absence of a DIN standard. Fig. 1 is a schematic representation of the measuring device for the sliding friction coefficient ng. In Fig. 1 mean 1 = weight, 2 = test, 3 = sample, 4 = sample holder, FN = normal force and FT = tangential force.

0063A steel friction ring (ST 50) with a diameter of 85 mm is driven by a step gear. The circumferential, ie the friction speed of the ring can be adjusted in 12 steps from 0.065 m / s to 5.8 m / s. The speed is preferred 1 m / s.

0064Two measurements each with friction rings with a roughness of R_T = 0.8 µm (max. Roughness depth) / R_a = 0.2 µm (arithmetic mean) and R_T = 3.1 µm / R_a = 1.5 µm performed.

0065The sample to be examined with the cross-section of approx. 4 x 6 mm is clamped in a sample holder which is connected to a force measuring bottle, on which it can exert tensile forces. Weights hang on the other side of the carrier, which generate the desired contact pressure of the sample on the rotating friction ring. The frictional force increases with increasing contact pressure and is registered by the force measuring plate.

0066The coefficient of friction results from the quotient of contact pressure (normal force) and friction force (tangential force): the contact pressure generates a contact pressure of 1 N / mm². due to the thermal properties of samples and measuring equipment as well as contact pressure, coefficient of friction and peripheral speed, the friction surface heats up to thermal equilibrium. This temperature is detected by the sensor on the surface of the friction ring. An XY recorder records the coefficient of friction as a function of temperature for a certain peripheral speed during the generally one-hour friction test.

0067The Izod impact strength was measured in accordance with ASTM D 256. <tables id="tabl0002" num="0002"><table frame="all"><title>Table 1</title><tgroup cols="12" colsep="1" rowsep="0"><colspec colnum="1" colname="col1" colwidth="13.12mm" /><colspec colnum="2" colname="col2" colwidth="13.12mm" /><colspec colnum="3" colname="col3" colwidth="13.12mm" /><colspec colnum="4" colname="col4" colwidth="13.12mm" /><colspec colnum="5" colname="col5" colwidth="13.12mm" /><colspec colnum="6" colname="col6" colwidth="13.12mm" /><colspec colnum="7" colname="col7" colwidth="13.12mm" /><colspec colnum="8" colname="col8" colwidth="13.12mm" /><colspec colnum="9" colname="col9" colwidth="13.12mm" /><colspec colnum="10" colname="col10" colwidth="13.12mm" /><colspec colnum="11" colname="col11" colwidth="13.12mm" /><colspec colnum="12" colname="col12" colwidth="13.12mm" /><thead valign="top"><row><entry namest="col1" nameend="col1" align="left">Example No.</entry><entry namest="col2" nameend="col3" align="center">SiCoPC, wt .-%</entry><entry namest="col4" nameend="col4" align="center">PC wt%</entry><entry namest="col5" nameend="col7" align="left">PTFE,% by weight</entry><entry namest="col8" nameend="col8" align="center">Fuel strength level</entry><entry namest="col9" nameend="col9" align="center">Modulus of elasticity [MPa]</entry><entry namest="col10" nameend="col10" align="center">Sliding friction coefficient; µg</entry><entry namest="col11" nameend="col11" align="center">When measuring reached max. Temp- [° C]</entry><entry namest="col12" nameend="col12" align="center">Notched impact strength according to Izod [J / m] at 23 ° C</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" /><entry namest="col2" nameend="col2" align="left">I.</entry><entry namest="col3" nameend="col3" align="left">II</entry><entry namest="col4" nameend="col4" /><entry namest="col5" nameend="col5" align="left">I.</entry><entry namest="col6" nameend="col6" align="center">II</entry><entry namest="col7" nameend="col7" align="center">III</entry><entry namest="col8" nameend="col8" /><entry namest="col9" nameend="col9" /><entry namest="col10" nameend="col10" /><entry namest="col11" nameend="col11" /><entry namest="col12" nameend="col12" /></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="right">1 *</entry><entry namest="col2" nameend="col2" /><entry namest="col3" nameend="col3" /><entry namest="col4" nameend="col4" align="right">100</entry><entry namest="col5" nameend="col5" align="right">-</entry><entry namest="col6" nameend="col6" align="right">-</entry><entry namest="col7" nameend="col7" align="right">-</entry><entry namest="col8" nameend="col8" align="right">4</entry><entry namest="col9" nameend="col9" align="right">2329</entry><entry namest="col10" nameend="col10" align="char" char=",">0,40</entry><entry namest="col11" nameend="col11" align="right">40</entry><entry namest="col12" nameend="col12" align="right">860</entry></row><row><entry namest="col1" nameend="col1" align="right">2 *</entry><entry namest="col2" nameend="col2" /><entry namest="col3" nameend="col3" /><entry namest="col4" nameend="col4" align="right">90</entry><entry namest="col5" nameend="col5" align="right">10</entry><entry namest="col6" nameend="col6" align="right">-</entry><entry namest="col7" nameend="col7" align="right">-</entry><entry namest="col8" nameend="col8" align="right">4</entry><entry namest="col9" nameend="col9" align="right">2358</entry><entry namest="col10" nameend="col10" align="char" char=",">0,37</entry><entry namest="col11" nameend="col11" align="right">40</entry><entry namest="col12" nameend="col12" align="right">463</entry></row><row><entry namest="col1" nameend="col1" align="right">3 *</entry><entry namest="col2" nameend="col2" align="right">100</entry><entry namest="col3" nameend="col3" /><entry namest="col4" nameend="col4" align="right">-</entry><entry namest="col5" nameend="col5" align="right">-</entry><entry namest="col6" nameend="col6" align="right">-</entry><entry namest="col7" nameend="col7" align="right">-</entry><entry namest="col8" nameend="col8" align="right">4</entry><entry namest="col9" nameend="col9" align="right">1996</entry><entry namest="col10" nameend="col10" align="char" char=",">0,53</entry><entry namest="col11" nameend="col11" align="right">48</entry><entry namest="col12" nameend="col12" align="right">897</entry></row><row><entry namest="col1" nameend="col1" align="right">4 *</entry><entry namest="col2" nameend="col2" /><entry namest="col3" nameend="col3" align="right">100</entry><entry namest="col4" nameend="col4" align="right">-</entry><entry namest="col5" nameend="col5" align="right">-</entry><entry namest="col6" nameend="col6" align="right">-</entry><entry namest="col7" nameend="col7" align="right">-</entry><entry namest="col8" nameend="col8" align="right">4</entry><entry namest="col9" nameend="col9" align="right">2008</entry><entry namest="col10" nameend="col10" align="char" char=",">0,55</entry><entry namest="col11" nameend="col11" align="right">49</entry><entry namest="col12" nameend="col12" align="right">883</entry></row><row><entry namest="col1" nameend="col1" align="right">5</entry><entry namest="col2" nameend="col2" align="right">93</entry><entry namest="col3" nameend="col3" /><entry namest="col4" nameend="col4" align="right">-</entry><entry namest="col5" nameend="col5" align="right">7</entry><entry namest="col6" nameend="col6" align="right">-</entry><entry namest="col7" nameend="col7" align="right">-</entry><entry namest="col8" nameend="col8" align="right">2</entry><entry namest="col9" nameend="col9" align="right">2746</entry><entry namest="col10" nameend="col10" align="char" char=",">0,32</entry><entry namest="col11" nameend="col11" align="right">40</entry><entry namest="col12" nameend="col12" align="right">536</entry></row><row><entry namest="col1" nameend="col1" align="right">6</entry><entry namest="col2" nameend="col2" /><entry namest="col3" nameend="col3" align="right">93</entry><entry namest="col4" nameend="col4" align="right">-</entry><entry namest="col5" nameend="col5" align="right">7</entry><entry namest="col6" nameend="col6" align="right">-</entry><entry namest="col7" nameend="col7" align="right">-</entry><entry namest="col8" nameend="col8" align="right">2</entry><entry namest="col9" nameend="col9" align="right">2753</entry><entry namest="col10" nameend="col10" align="char" char=",">0,31</entry><entry namest="col11" nameend="col11" align="right">42</entry><entry namest="col12" nameend="col12" align="right">489</entry></row><row><entry namest="col1" nameend="col1" align="right">7</entry><entry namest="col2" nameend="col2" align="right">93</entry><entry namest="col3" nameend="col3" /><entry namest="col4" nameend="col4" align="right">-</entry><entry namest="col5" nameend="col5" align="right">-</entry><entry namest="col6" nameend="col6" align="right">7</entry><entry namest="col7" nameend="col7" align="right">-</entry><entry namest="col8" nameend="col8" align="right">2</entry><entry namest="col9" nameend="col9" align="right">2739</entry><entry namest="col10" nameend="col10" align="char" char=",">0,31</entry><entry namest="col11" nameend="col11" align="right">40</entry><entry namest="col12" nameend="col12" align="right">541</entry></row><row><entry namest="col1" nameend="col1" align="right">8</entry><entry namest="col2" nameend="col2" align="right">93</entry><entry namest="col3" nameend="col3" /><entry namest="col4" nameend="col4" align="right">-</entry><entry namest="col5" nameend="col5" align="right">-</entry><entry namest="col6" nameend="col6" align="right">-</entry><entry namest="col7" nameend="col7" align="right">7</entry><entry namest="col8" nameend="col8" align="right">2</entry><entry namest="col9" nameend="col9" align="right">2743</entry><entry namest="col10" nameend="col10" align="char" char=",">0,26</entry><entry namest="col11" nameend="col11" align="right">38</entry><entry namest="col12" nameend="col12" align="right">526</entry></row><row><entry namest="col1" nameend="col1" align="right">9</entry><entry namest="col2" nameend="col2" align="right">85</entry><entry namest="col3" nameend="col3" /><entry namest="col4" nameend="col4" align="right">-</entry><entry namest="col5" nameend="col5" align="right">15</entry><entry namest="col6" nameend="col6" align="right">-</entry><entry namest="col7" nameend="col7" align="right">-</entry><entry namest="col8" nameend="col8" align="right">1 - 2</entry><entry namest="col9" nameend="col9" align="right">2917</entry><entry namest="col10" nameend="col10" align="char" char=",">0,27</entry><entry namest="col11" nameend="col11" align="right">35</entry><entry namest="col12" nameend="col12" align="right">356</entry></row><row><entry namest="col1" nameend="col1" align="right">10</entry><entry namest="col2" nameend="col2" /><entry namest="col3" nameend="col3" align="right">85</entry><entry namest="col4" nameend="col4" align="right">-</entry><entry namest="col5" nameend="col5" align="right">-</entry><entry namest="col6" nameend="col6" align="right">15</entry><entry namest="col7" nameend="col7" align="right">-</entry><entry namest="col8" nameend="col8" align="right">2</entry><entry namest="col9" nameend="col9" align="right">2873</entry><entry namest="col10" nameend="col10" align="char" char=",">0,28</entry><entry namest="col11" nameend="col11" align="right">35</entry><entry namest="col12" nameend="col12" align="right">374</entry></row><row><entry namest="col1" nameend="col1" align="right">11</entry><entry namest="col2" nameend="col2" align="right">93</entry><entry namest="col3" nameend="col3" /><entry namest="col4" nameend="col4" /><entry namest="col5" nameend="col5" align="right">7</entry><entry namest="col6" nameend="col6" align="right">-</entry><entry namest="col7" nameend="col7" align="right">-</entry><entry namest="col8" nameend="col8" align="right">2</entry><entry namest="col9" nameend="col9" align="right">3068</entry><entry namest="col10" nameend="col10" align="char" char=",">0,26</entry><entry namest="col11" nameend="col11" align="right">34</entry><entry namest="col12" nameend="col12" align="right">518</entry></row><row><entry namest="col1" nameend="col1" align="right">12</entry><entry namest="col2" nameend="col2" /><entry namest="col3" nameend="col3" align="right">93</entry><entry namest="col4" nameend="col4" /><entry namest="col5" nameend="col5" align="right">-</entry><entry namest="col6" nameend="col6" align="right">7</entry><entry namest="col7" nameend="col7" align="right">-</entry><entry namest="col8" nameend="col8" align="right">2</entry><entry namest="col9" nameend="col9" align="right">3107</entry><entry namest="col10" nameend="col10" align="char" char=",">0,27</entry><entry namest="col11" nameend="col11" align="right">32</entry><entry namest="col12" nameend="col12" align="right">493</entry></row><row rowsep="1"><entry namest="col1" nameend="col12" align="justify">Examples marked with an asterisk are for comparison</entry></row></tbody></tgroup></table></tables>