Optical elements.

The present invention relates to optical contact objects made from optionally crosslinked copolymers based on siloxanyl and fluoro- (meth) acrylates.

Optical contact objects in the context of the present invention are preferably contact lenses and scleral shells.

The contact lenses on the market can be divided into hard and soft materials. The soft lenses, which sit close to the eye, must have a high oxygen permeability, since the oxygen supply takes place to a particular extent via the atmosphere. This is achieved through a very high proportion of water (hydrogel lenses) or the use of highly permeable silicones that are hydrophilized on the surface.

Hard contact lens materials offer the advantage that in addition to permeation through the lens, the eye can also be supplied with oxygen by exchanging the tear fluid, since the lenses float on the eye. A prerequisite for this is sufficient hydrophilicity of the material, which enables the lens to be wetted by the tear fluid.

Another advantage of hard lenses is their extremely easy maintenance. Due to the low water content, the risk of cloudiness due to protein and lipoid deposits and bacterial contamination is greatly reduced (OC Geyer, Kontakt-Linsen - aber correctly, Schnetztor Verlag, Konstanz, 1979).

Hard contact lens materials made from crosslinked copolymers based on siloxanyl methacrylic acid esters and / or fluorine methacrylates are known (US Pat. No. 3,808,178; WO 86/04342). Compared to polymethyl methacrylate, these materials are characterized by a significantly higher oxygen permeability.

Disadvantages of the materials described above, however, are the unsatisfactory surface properties. The high silicon and fluorine content leads to poor surface wettability, which reduces the wearing comfort of the lens.

Subsequent hydrophilization of the surface, for example by corona discharge or plasma treatment, improves the wettability for a short time, but after long wear the lens loses its good compatibility, since the very thin hydrophilic layer is destroyed by mechanical and enzymatic stress.

Another disadvantage of hard materials based on siloxanyl methacrylates is the lack of long-term stability. Under the influence of light and enzymatic degradation, the surfaces weather and there are microcracks that severely impair the optical properties.

In order to improve the hydrophilicity of the materials, hydrophilic monomers can be used as comonomers [DE-A 3 329 722; Polym. Technology Corp. (09/30/82)]. However, these have a relatively high water absorption, which increases the risk of lipoid deposits. In addition, the polymers soften and are therefore more difficult to process and have insufficient radius stability.

There have been found optical contact objects made from optionally crosslinked copolymers, which are characterized in that they are the comonomers of the components<ul id="ul0001" list-style="none"><li>A) 5 to 40 wt .-% of a 2-N- (alkyl-perfluoroalkylsulfonamido) alkyl (meth) acrylate of the formula<chemistry id="chem0001" num="0001"><img file="EP0306756A2_D0001.tif" /></chemistry> in the R¹ H, CH₃, R² H, lower alkyl, cycloalkyl, aryl, n is a number from 1 to 6, m is a number from 0 to 11 mean,</li><li>B) 5 to 60% by weight of a siloxanyl (meth) acrylic acid ester or a mixture of different siloxanyl (meth) acrylic acid esters,</li><li>C) optionally up to 65% by weight of a non-hydrophilic vinyl monomer,</li><li>D) optionally up to 20% by weight of a hydrophilic vinyl monomer and</li><li>E) optionally up to 10% by weight of a bis- or polyfunctional vinyl monomer not covered by B)</li></ul> contained in the polymer, the sum of the percentages by weight A) to E) being 100.

Surprisingly, the contact optical objects according to the invention have excellent oxygen permeability, combined with good wettability, low water absorption and high long-term stability.

Monomers of component A) are generally 2- (N-alkyl-perfluoroalkylsulfonamido) alkyl (meth) acrylates of the formula I.

Lower alkyl generally means branched and unbranched hydrocarbon radicals having 1 to 6 carbon atoms. Examples include methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, t-butyl, pentyl, iso-pentyl, neopentyl, n-hexyl and iso-hexyl. Methyl, ethyl and isopropyl are particularly preferred, and methyl is particularly preferred.

Cycloalkyl generally means cyclic hydrocarbon radicals having 5 to 9 carbon atoms. Examples include cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl. Cyclopentyl and cyclohexyl are preferred, particularly preferably cyclohexyl.

Aryl generally means an aromatic hydrocarbon radical having 6 to 12 carbon atoms. Examples include phenyl, naphthyl, biphenylyl and benzyl. Preferred aryl radicals are phenyl and benzyl.

The 2- (N-alkyl-perfluoroalkylsulfonamido) alkyl (meth) acrylates are known and can be prepared from the corresponding perfluoroalkylsulfonamides by reaction with corresponding halohydrins and subsequent esterification with (meth) acrylic acid (US Pat. No. 2,803,615). Preferred 2- (N-alkyl-perfluoroalkylsulfonamido) alkyl (meth) acrylates are 2- (N-methyl-perfluorobutylsulfonamido) ethyl methacrylate and 2- (N-methyl-perfluorooctylsulfonamido) ethyl methacrylate. 2- (N-Methyl-Perfluorobutylsulfonamido) ethyl methacrylate (C₄FM)&gt; is particularly preferred

The contact optical articles according to the invention can generally contain 5 to 50% by weight, preferably 10 to 40% by weight and particularly preferably 10 to 30% by weight of the fluoromonomer in the polymer.

Monomers of component B) are generally siloxanyl (meth) acrylates such as:<ul id="ul0002" list-style="none"><li>1. Compounds of the formula<chemistry id="chem0002" num="0002"><img file="EP0306756A2_D0002.tif" /></chemistry> in the m represents 0 or 1, n stands for a number from 1 to 3, R³, R⁴ and R⁵ are the same or different and are alkoxy, lower alkyl, cycloalkyl, aryl, trimethylsiloxy, polysiloxy or the rest<chemistry id="chem0003" num="0003"><img file="EP0306756A2_D0003.tif" /></chemistry> stands in the n, R³, R⁴ have the meanings given above, and X represents hydroxy, acetoxy, alkoxy, amino, mercapto, glycidoxy or carboxy.</li><li>2nd Compounds of the formula<chemistry id="chem0004" num="0004"><img file="EP0306756A2_D0004.tif" /></chemistry> in the m and n independently represent a number from 1 to 3, R³, R⁴ and R⁵ are the same or different and are alkoxy, lower alkyl, cycloalkyl, aryl, trimethylsiloxy, polysiloxy or the rest<chemistry id="chem0005" num="0005"><img file="EP0306756A2_D0005.tif" /></chemistry> stand in the n, R³, R⁴ have the meanings given above, and X represents hydroxy, acetoxy, alkoxy, amino, mercapto, glycidoxy or carboxy.</li><li>3rd Compounds of the formula<chemistry id="chem0006" num="0006"><img file="EP0306756A2_D0006.tif" /></chemistry> in the n stands for a number from 1 to 3, R³, R⁴ and R⁵ are the same or different and are alkoxy, lower alkyl, cycloalkyl, aryl, trimethylsiloxy, polysiloxy or the rest<chemistry id="chem0007" num="0007"><img file="EP0306756A2_D0007.tif" /></chemistry> stand in the n, R³, R⁴ have the meanings given above, and X represents hydroxy, acetoxy, alkoxy, amino, mercapto, glycidoxy or carboxy, and R⁶ represents lower alkyl or cycloalkyl.</li><li>4th Compounds of the formula<chemistry id="chem0008" num="0008"><img file="EP0306756A2_D0008.tif" /></chemistry> in the n stands for a number from 1 to 3, R³, R⁴ and R⁵ are the same or different and are alkoxy, lower alkyl, cycloalkyl, aryl, trimethylsiloxy, polysiloxy or the rest<chemistry id="chem0009" num="0009"><img file="EP0306756A2_D0009.tif" /></chemistry> stand in the n, R³, R⁴ have the meanings given above, and X represents hydroxy, acetoxy, alkoxy, amino, mercapto, glycidoxy or carboxy, R⁶ represents H, lower alkyl or cycloalkyl, Y for O, S or the rest<chemistry id="chem0010" num="0010"><img file="EP0306756A2_D0010.tif" /></chemistry> stands in the R⁶ has the meaning given above, and Z represents a divalent C₂ to C₂₄ alkylene, C₅ to C₉ cycloalkylene, C₆ to C₁₂ arylene or a divalent radical having 7 to 24 carbon atoms from alkylene, cycloalkylene and / or arylene groups.</li></ul>

Lower alkyl generally means branched and unbranched hydrocarbon radicals having 1 to 6 carbon atoms. Examples include methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, t-butyl, pentyl, iso-pentyl, neopentyl, n-hexyl and iso-hexyl. Methyl, ethyl and Isopropyl and particularly preferably listed methyl.

Cyclic hydrocarbon radicals having 5 to 9 carbon atoms may generally be mentioned as cycloalkyl. Examples include cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl. Cyclopentyl and cyclohexyl are preferred, and cyclohexyl is particularly preferred.

Alkoxy generally means an oxygen-bonded straight-chain or branched hydrocarbon radical having 1 to about 8 carbon atoms. Lower alkoxy having 1 to about 6 carbon atoms is preferred. Examples include methoxy, ethoxy, propoxy, iso-propoxy, butoxy, iso-butoxy, tert-butoxy, pentoxy, iso-pentoxy, hexoxy and iso-hexoxy. Methoxy and ethoxy are particularly preferred.

Aryl generally means an aromatic hydrocarbon radical having 6 to 12 carbon atoms. Examples include phenyl, naphthyl, biphenylyl and benzyl. Preferred aryl radicals are phenyl and benzyl.

Divalent alkylene (Z) generally means a divalent unbranched or branched hydrocarbon chain with 2 to 24 carbon atoms. Alkylene radicals having 6 to 9 carbon atoms are preferred. Examples include methylene, ethylene, trimethylene, tetramethylene, pentamethylene, 2,2-dimethyltrimethylene, hexamethylene and 2,2,4-trimethylhexamethylene. Hexamethylene and 2,2,4-trimethylhexamethylene are particularly preferred.

Divalent cycloalkylene (Z) generally means a divalent cyclic hydrocarbon radical with 5 to 9 carbon atoms.

Examples include cyclopentylene, cyclohexylene, cycloheptylene and cyclooctylene. Cyclopentylene and cyclohexylene are preferred. Cyclohexylene is particularly preferred.

Divalent arylene (Z) generally means a divalent aromatic hydrocarbon radical with 6 to 12 carbon atoms. Phenylene, naphthylene and biphenylene radicals are preferred. The phenylene radical is particularly preferred.

Divalent radicals with 7 to 24 carbon atoms from alkylene, cycloalkylene and / or arylene groups are, for example, methylene-di-p-phenylene and 2,2-propylene-di-p-phenylene.

Polysiloxyl generally means straight-chain or branched, preferably branched, polysiloxy radicals of the general formula<chemistry id="chem0011" num="0011"><img file="EP0306756A2_D0011.tif" /></chemistry> in the n stands for a number from 1 to 3, R³, R⁴ and R⁵ are the same or different and are alkoxy, lower alkyl, cycloalkyl, aryl, trimethylsiloxy or the rest<chemistry id="chem0012" num="0012"><img file="EP0306756A2_D0012.tif" /></chemistry> stand in the n, R³, R⁴ have the meanings given above, and X represents hydroxy, acetoxy, alkoxy, amino, mercapto, glycidoxy or carboxy, and the factors a, b, c are determined as follows: a + b + c - 1. 0 ≦ a ≦ 0.8; 0 ≦ b ≦ 0.8 and 0 ≦ c ≦ 0.8.

Siloxanyl (meth) acrylic acid esters of the formula II can be, for example: γ-methacryloxypropyltrimethoxysilane (MEMO):<chemistry id="chem0013" num="0013"><img file="EP0306756A2_D0013.tif" /></chemistry> and its derivatives, such as: γ-methacryloxypropyl-tris (trimethylsiloxy) silane (TRIS):<chemistry id="chem0014" num="0014"><img file="EP0306756A2_D0014.tif" /></chemistry> 1,3-bis (γ-methacryloxypropyl) -1,1,3,3-tetra (trimethylsiloxy) disiloxane (TETRA):<chemistry id="chem0015" num="0015"><img file="EP0306756A2_D0015.tif" /></chemistry> γ-methacryloxypropyl-tris (3-acetoxypropyldimethylsiloxy) silane (ATRIS):<chemistry id="chem0016" num="0016"><img file="EP0306756A2_D0016.tif" /></chemistry> and γ-methacryloxypropyl-bis- (trimethylsiloxy) - (3-acetoxypropyldimethylsiloxy) silane. γ-methacryloxypropyl bis (3-acetoxypropyldimethylsiloxy) trimethylsiloxy) silane. γ-methacryloxypropyl-tris (3-hydroxypropyldimethylsiloxy) silane (HTRIS), γ-methacryloxypropyl-bis- (3-hydroxypropyldimethylsiloxy) - (trimethylsiloxy) silane and γ-methacryloxypropyl-bis (trimethylsiloxy) - (3-hydroxypropyldimethylsiloxy) silane.

The compounds can be prepared from γ-methacryloxypropyltrimethoxysilane and the corresponding functionalized chlorosiloxides or acetoxysilanes by hydrolysis (DE-A 3,244,877; DE-A 3,309,631).

Further known siloxanyl methacrylates of the formula II are, for example: Hydrolysis products of the reaction of δ-methacryloxypropyltrimethoxysilane with dichlorodimethylsilane and chlorotrimethylsilane (DE-A 3,329,722), γ-methacryloxypropylpentamethyldisiloxane (US 3,808,178) and γ-methacryloxypropyldimethyl (nonamethyltetrasiloxanyl) silane (US 4,303,772).

Siloxanyl methacrylates of the formula III are, for example, reaction products of β-allyloxyethyl methacrylate with polysiloxanes containing SiH groups (EP-A 130,731).

Siloxanyl methacrylates of the formula IV can be prepared by reacting isocyanatoethyl methacrylate with hydroxy- or aminoalkyl-terminated polysiloxanes (EP-A 127.321; Yu X., Nagarajan HRJ Appl.Pol. Sci. <u style="single">30</u>, 2115 (1985).

Examples of compounds of the formula V are silicone methacrylate macromers which can be prepared by reacting hydroxyalkyl-terminated polysiloxanes such as, for example, polydimethylsiloxane-triol with 1-isocyanatomethyl-5-isocyanato-1,3,3-trimethylcyclohexane and β-hydroxyethyl methacrylate. The methacrylic radical in the compounds of the formula V is linked to the polysiloxane via urethane, thiourethane, urea or amide functions (Cameron EG, Chisholm MS Polymer 1985,<u style="single">26</u>(3), 437; US 4,136,250; EP-A 109.355).

Preferred siloxanyl methacrylates are:

γ-methacryloxypropyltrimethoxysilane (MEMO), γ-methacryloxypropyl-tris (trimethylsiloxy) silane (TRIS), 1,3-bis (γ-methacryloxypropyl) -1,1,3,3-tetra (trimethylsiloxy) disiloxane (TETRA), γ-methacryloxypropyl-tris (3-acetoxypropyldimethylsiloxy) silane (ATRIS), γ-methacryloxypropyl-tris (3-hydroxypropyldimethylsiloxy) silane (HTRIS) and mixtures thereof. Mixtures of TRIS, ATRIS, HTRIS and C4FM are particularly preferred.

The contact optical objects according to the invention generally contain 5 to 60% by weight of siloxanyl methacrylate. They preferably contain 10 to 55% by weight, and particularly preferably 20 to 40% by weight, of the monomers in the polymer.

The contact optical objects according to the invention may optionally contain non-hydrophilic vinyl monomers as component C). Preferred vinyl monomers are, for example, (meth) acrylic acid derivatives such as C₁ to C₁₂ alkyl or cycloalkyl esters of (meth) acrylic acid.

Examples include: Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (iso) bornyl (meth) acrylate, bicycloheptanyl (meth) acrylate and cyclohexyl (meth ) acrylate. A particularly preferred vinyl monomer is methyl methacrylate.

The contact optical objects according to the invention generally contain up to 65% by weight of non-hydrophilic vinyl monomers. They preferably contain 10 to 60% by weight and particularly preferably 20 to 55% by weight of the monomers in the polymer.

The contact optical objects according to the invention can optionally contain, as component D), hydrophilic vinyl monomers. Preferred vinyl monomers are, for example, N-vinyl lactams and vinyl amides and (meth) acrylic acid derivatives.

Examples of vinyl lactams are N-vinylpyrrolidone and (meth) acrylic acid derivatives are (meth) acrylic acid and (meth) acrylamides.

Particularly preferred hydrophilic vinyl monomers are N-vinylpyrrolidone and N-vinyl-N-methylacetamide.

The contact optical objects according to the invention optionally contain up to 20% by weight of hydrophilic vinyl monomers. They preferably contain up to 10% by weight and particularly preferably up to 5% by weight of the monomers in the polymer.

The contact optical objects according to the invention can optionally contain bi- or polyfunctional vinyl monomers as crosslinker component E). Here are, for example, bi- or polyfunctional methacrylic acid esters such as ethylene glycol dimethacrylate, propylene glycol dimethacrylate, diethylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, trimethylolpropane trimethacrylate, allyl methacrylate, vinyl methacrylate, (meth) acrylic acid ester^2.6] decane derivatives (cf. DE-A 2.931.925) and bisphenol A dimethacrylate, and bi- or polyfunctional vinyl or allyl crosslinking agents such as butanediol divinyl ether, divinyl ethylene urea, divinyl propylene urea, divinyl benzene, triallyl cyanurate, triallyl isocyanurate, diethylene glycol bis (3, allyl itaconate), diallyl carbonate 3′-ethylidene bis (N-vinyl-2-pyrrolidone), diallyl maleate, diallyl fumarate, dimethallyl fumarate, dimethallyl maleate, diallyl diglycolate, diallyl oxalate, diallyl adipate, diallyl succinate, Diallylazelate, divinyl adipate, triallyl trimellitate and N, N-diallymelamine called. In addition, bis- or polyfunctional siloxanyl methacrylates such as 1,3-bis (γ-methacryloxypropyl) -1,1,3,3-tetra (trimethylsiloxy) disiloxane and 1,3-bis (γ-methacryloxypropyl) -1.1 , 3,3-tetramethyldisiloxane listed.

Particularly preferred crosslinkers are dimethacrylates such as ethylene glycol dimethacrylate and mixtures thereof.

The contact optical objects according to the invention generally contain 0 to 10% by weight of crosslinking agents. They preferably contain 0.1 to 5% by weight.

A process for the production of contact-optical objects has been found, which is characterized in that<ul id="ul0003" list-style="none"><li>A) 5 to 40 parts by weight of a 2- (N-alkyl-perfluoroalkylsulfonamido) alkyl (meth) acrylate of the formula<chemistry id="chem0017" num="0017"><img file="EP0306756A2_D0017.tif" /></chemistry> in the R¹ H, CH₃, R² H, lower alkyl, cycloalkyl, aryl, n is a number from 1 to 6, m is a number from 0 to 11 mean,</li><li>B) 5 to 60 parts by weight of a (meth) acrylic acid ester or a mixture of different polyorganosiloxane (meth) acrylic acid esters,</li><li>C) optionally up to 60 parts by weight of a non-hydrophilic vinyl monomer,</li><li>D) optionally up to 20 parts by weight of a hydrophilic vinyl monomer and</li><li>E) optionally up to 10 parts by weight of a bi- or polyfunctional vinyl monomer not covered by B)</li></ul> polymerized in the presence of a radical initiator.

Peroxides such as dibenzoyl peroxide, dilauroyl peroxide or azo compounds such as azoisobutyronitrile can be used as free radical initiators. Photoini tiators such as 2,2-dimethoxy-2-phenylacetophenone, diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone or benzoin propyl or isobutyl ether can be used as polymerization initiators.

A preferred embodiment of the method according to the invention is the polymerization as bulk polymerization in plate chambers, glass tubes, plastic tubes or cups. The embodiment is preferably selected in plate chambers or from polyolefin tubes or cells.

The materials thus obtained contain practically no water-extractable components. Their water content after hydration is, depending on the proportion of the hydrophilic monomers, 0.5 to 2% by weight (based on the hydrated state).

The wetting contact angles are in the range of 68 to 75 °, and the oxygen permeability amounts to values ​​of 300 to 1250 cm³O₂ / (m² · 24h · bar).

The Shore D hardness of 70 to 85 ensure good processability and scratch resistance comparable to that of polymethyl methacrylate materials.

The surfaces of the contact lenses made from the materials according to the invention show no microcracking in the xenon test after 1000 hours of irradiation under the electron beam scanning microscope.

Because of the high oxygen permeability, the good wettability and the excellent stability, contact lenses made from the material according to the invention are particularly suitable as VT lenses (extended wear lenses). Biological tests have shown that there is no irritation on the rabbit eye without interruption over a period of 30 days and that the lenses remain fog-free and without deposits.

A particular advantage of the contact optical objects according to the invention is the very good wettability with very high oxygen permeability at the same time. This effect of 2- (N-alkyl-perfluoroalkylsulfonamido) alkyl (meth) acrylate is all the more surprising since the fluoromonomers have hitherto been used to make the surfaces of plastics, leather, metals and textiles oil and water-repellent (US 2,803, 615; US 3,100,180).

Examples 1 to 18

The radical polymerizations were carried out in polypropylene tubes (ø 12 mm).

Monomer mixtures of the components<ul id="ul0004" list-style="none"><li>A) 2- (N-alkyl-perfluoroalkylsulfonamido) alkyl (meth) acrylate,</li><li>B) siloxane (meth) acrylate,</li><li>C) non-hydrophilic vinyl monomer,</li><li>D) hydrophilic vinyl monomer and</li><li>E) bi- or polyfunctional vinyl monomer</li></ul> with the compositions listed in Table 1 were degassed and transferred into the polymerization vessels with the exclusion of air.

The polymerizations were started photochemically and irradiated with UV fluorescent light at 40 ° C. for 24 h.

Thereafter, UV light was irradiated for a further three days, the mold was removed and then annealed at 80 ° C. in a drying cabinet for one day. Blanks were made from the cylindrical shapes and contact lenses were made from them by turning and polishing.

Shore hardness measurement:

The Shore D values ​​(according to DIN 53 505) of the materials were determined in the dry state. For this purpose, roughly 7 mm thick blanks are turned and ground flat.

The <u style="single">Water-wetting contact angle</u> were determined with a video system. The mean values ​​from 10 dynamic contact angles, which were determined in a time range of 10 seconds, are given.

The <u style="single">Oxygen permeability</u> were determined by mass spectroscopy. With a partial pressure difference of one bar, oxygen was forced through samples of approx. 1.5 mm thickness and 12 mm ø over a period of 24 h. The measurements were carried out at 35 ° C, a relative humidity of 100% and an additional humidification of the material with a drop of H₂O.

The transmissibilities are standardized to a sample thickness of 1 mm.<tables id="tabl0001" num="0001"><img file="EP0306756A2_D0018.tif" /></tables><tables id="tabl0002" num="0002"><img file="EP0306756A2_D0019.tif" /></tables><tables id="tabl0003" num="0003"><table frame="all"><title>Table 2</title><tgroup cols="5" colsep="1" rowsep="0"><colspec colnum="1" colname="col1" colwidth="31.50mm" /><colspec colnum="2" colname="col2" colwidth="31.50mm" /><colspec colnum="3" colname="col3" colwidth="31.50mm" /><colspec colnum="4" colname="col4" colwidth="31.50mm" /><colspec colnum="5" colname="col5" colwidth="31.50mm" /><thead valign="top"><row><entry namest="col1" nameend="col5" align="center">Physical properties of the materials</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="center">E.g.</entry><entry namest="col2" nameend="col2" align="center">Shore-D</entry><entry namest="col3" nameend="col3" align="center">H₂O [%]</entry><entry namest="col4" nameend="col4" align="center">φ [°]</entry><entry namest="col5" nameend="col5" align="center">O₂ permeability [cm³O₂ / m² · 24h · bar)]</entry></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="right">1</entry><entry namest="col2" nameend="col2" align="right">80</entry><entry namest="col3" nameend="col3" align="char" char=".">1.5</entry><entry namest="col4" nameend="col4" align="right">75</entry><entry namest="col5" nameend="col5" align="right">1059</entry></row><row><entry namest="col1" nameend="col1" align="right">2</entry><entry namest="col2" nameend="col2" align="right">80</entry><entry namest="col3" nameend="col3" align="char" char=".">1.4</entry><entry namest="col4" nameend="col4" align="right">86</entry><entry namest="col5" nameend="col5" align="right">705</entry></row><row><entry namest="col1" nameend="col1" align="right">3</entry><entry namest="col2" nameend="col2" align="right">81</entry><entry namest="col3" nameend="col3" align="char" char=".">1.5</entry><entry namest="col4" nameend="col4" align="right">74</entry><entry namest="col5" nameend="col5" align="right">813</entry></row><row><entry namest="col1" nameend="col1" align="right">4</entry><entry namest="col2" nameend="col2" align="right">84</entry><entry namest="col3" nameend="col3" align="char" char=".">1.0</entry><entry namest="col4" nameend="col4" align="right">70</entry><entry namest="col5" nameend="col5" align="right">280</entry></row><row><entry namest="col1" nameend="col1" align="right">5</entry><entry namest="col2" nameend="col2" align="right">82</entry><entry namest="col3" nameend="col3" align="char" char=".">2.0</entry><entry namest="col4" nameend="col4" align="right">76</entry><entry namest="col5" nameend="col5" align="right">318</entry></row><row><entry namest="col1" nameend="col1" align="right">6</entry><entry namest="col2" nameend="col2" align="right">75</entry><entry namest="col3" nameend="col3" align="char" char=".">2.7</entry><entry namest="col4" nameend="col4" align="right">76</entry><entry namest="col5" nameend="col5" align="right">800</entry></row><row><entry namest="col1" nameend="col1" align="right">7</entry><entry namest="col2" nameend="col2" align="right">83</entry><entry namest="col3" nameend="col3" align="char" char=".">0.7</entry><entry namest="col4" nameend="col4" align="right">73</entry><entry namest="col5" nameend="col5" align="right">650</entry></row><row><entry namest="col1" nameend="col1" align="right">8</entry><entry namest="col2" nameend="col2" align="right">82</entry><entry namest="col3" nameend="col3" align="char" char=".">1.2</entry><entry namest="col4" nameend="col4" align="right">74</entry><entry namest="col5" nameend="col5" align="right">740</entry></row><row><entry namest="col1" nameend="col1" align="right">9</entry><entry namest="col2" nameend="col2" align="right">83</entry><entry namest="col3" nameend="col3" align="char" char=".">1.8</entry><entry namest="col4" nameend="col4" align="right">74</entry><entry namest="col5" nameend="col5" align="right">760</entry></row><row><entry namest="col1" nameend="col1" align="right">10</entry><entry namest="col2" nameend="col2" align="right">83</entry><entry namest="col3" nameend="col3" align="char" char=".">2.1</entry><entry namest="col4" nameend="col4" align="right">75</entry><entry namest="col5" nameend="col5" align="right">800</entry></row><row><entry namest="col1" nameend="col1" align="right">11</entry><entry namest="col2" nameend="col2" align="right">83</entry><entry namest="col3" nameend="col3" align="char" char=".">1.0</entry><entry namest="col4" nameend="col4" align="right">74</entry><entry namest="col5" nameend="col5" align="right">630</entry></row><row><entry namest="col1" nameend="col1" align="right">12</entry><entry namest="col2" nameend="col2" align="right">82</entry><entry namest="col3" nameend="col3" align="char" char=".">1.3</entry><entry namest="col4" nameend="col4" align="right">74</entry><entry namest="col5" nameend="col5" align="right">640</entry></row><row><entry namest="col1" nameend="col1" align="right">13</entry><entry namest="col2" nameend="col2" align="right">82</entry><entry namest="col3" nameend="col3" align="char" char=".">1.6</entry><entry namest="col4" nameend="col4" align="right">75</entry><entry namest="col5" nameend="col5" align="right">750</entry></row><row><entry namest="col1" nameend="col1" align="right">14</entry><entry namest="col2" nameend="col2" align="right">78</entry><entry namest="col3" nameend="col3" align="char" char=".">1.5</entry><entry namest="col4" nameend="col4" align="right">80</entry><entry namest="col5" nameend="col5" align="right">310</entry></row><row><entry namest="col1" nameend="col1" align="right">15</entry><entry namest="col2" nameend="col2" align="right">80</entry><entry namest="col3" nameend="col3" align="char" char=".">1.4</entry><entry namest="col4" nameend="col4" align="right">79</entry><entry namest="col5" nameend="col5" align="right">510</entry></row><row><entry namest="col1" nameend="col1" align="right">16</entry><entry namest="col2" nameend="col2" align="right">76</entry><entry namest="col3" nameend="col3" align="char" char=".">1.1</entry><entry namest="col4" nameend="col4" align="right">70</entry><entry namest="col5" nameend="col5" align="right">630</entry></row><row><entry namest="col1" nameend="col1" align="right">17</entry><entry namest="col2" nameend="col2" align="right">79</entry><entry namest="col3" nameend="col3" align="char" char=".">1.9</entry><entry namest="col4" nameend="col4" align="right">75</entry><entry namest="col5" nameend="col5" align="right">760</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="right">18</entry><entry namest="col2" nameend="col2" align="right">79</entry><entry namest="col3" nameend="col3" align="char" char=".">1.1</entry><entry namest="col4" nameend="col4" align="right">70</entry><entry namest="col5" nameend="col5" align="right">515</entry></row></tbody></tgroup></table></tables>