Alkyl silicones as pigment coatings

Abstract

The present invention is directed to a specific class on pigment reactive silicone polymers that contain both higher alkyl groups and reactive trialkoxy silanes present in the backbone of a specific silicone polymer. By carefully selecting the proper reactive silicone polymer and treating the pigment with said polymer a surprisingly stable and efficient coating is applied the pigment, most importantly ZnO and TiO.sub.2 as to render photo stability and alter solubility of the pigment in a variety of solvents.

Claims

1. A reactive silicone polymer having the following structure: ##STR00030## wherein: c is an integer ranging from 10 to 25; R is a mixture of: a) an alkyl having the following structure:
(CH.sub.2).sub.xCH.sub.3 wherein: x is an integer ranging from 7 to 21; and b) a silane having a structure selected from the group consisting of i. CH.sub.2CH.sub.2Si(OCH.sub.3).sub.3 ii. CH.sub.2CH.sub.2Si(OCH.sub.2CH.sub.3).sub.3.

2. The reactive silicone of claim 1 where ##STR00031## wherein: c is 10; R is a mixture of CH.sub.2CH.sub.2Si(OCH.sub.3).sub.3 and alkyl wherein x is 7.

3. The reactive silicone of claim 1 where in ##STR00032## wherein: c is 25; R is a mixture of CH.sub.2CH.sub.2Si(OCH.sub.3).sub.3 and alkyl wherein x is 7.

4. The reactive silicone of claim 1 where in ##STR00033## wherein: c is 10; R is a mixture of CH.sub.2CH.sub.2Si(OCH.sub.3).sub.3 and alkyl having 22 carbon atoms.

5. The reactive silicone of claim 1 where in ##STR00034## wherein: c is 25; R is a mixture of CH.sub.2CH.sub.2Si(OCH.sub.3).sub.3 and alkyl having 22 carbon atoms.

6. The reactive silicone of claim 1 where in ##STR00035## wherein: c is 10; R is a mixture of CH.sub.2CH.sub.2Si(OCH.sub.2CH.sub.3).sub.3 and alkyl wherein x is 7.

7. The reactive silicone of claim 1 where in ##STR00036## wherein: c is 25; R is a mixture of CH.sub.2CH.sub.2Si(OCH.sub.2CH.sub.3).sub.3 and alkyl wherein x is 7.

8. The reactive silicone of claim 1 where in ##STR00037## wherein: c is 10; R is a mixture of CH.sub.2CH.sub.2Si(OCH.sub.2CH.sub.3).sub.3 and alkyl having 22 carbon atoms.

9. The reactive silicone of claim 1 where in ##STR00038## wherein: c is 25; R is a mixture of CH.sub.2CH.sub.2Si(OCH.sub.2CH.sub.3).sub.3 and alkyl having 22 carbon atoms.

10. The reactive silicone of claim 1 where in ##STR00039## wherein: c is 10; R is a mixture of CH.sub.2CH.sub.2Si(OCH.sub.3).sub.3 and alkyl wherein x is 15.

11. The reactive silicone of claim 1 where in ##STR00040## wherein: c is 25; R is a mixture of CH.sub.2CH.sub.2Si(OCH.sub.3).sub.3 and alkyl wherein x is 15.

12. The reactive silicone of claim 1 where in ##STR00041## wherein: c is 10; R is a mixture of CH.sub.2CH.sub.2Si(OCH.sub.3).sub.3 and alkyl having 15 carbon atoms.

13. The reactive silicone of claim 1 where in ##STR00042## wherein: c is 25; R is a mixture of CH.sub.2CH.sub.2Si(OCH.sub.3).sub.3 and alkyl having 15 carbon atoms.

14. The reactive silicone of claim 1 where in ##STR00043## wherein: c is 10; R is a mixture of CH.sub.2CH.sub.2Si(OCH.sub.2CH.sub.3).sub.3 and alkyl wherein x is 15.

15. The reactive silicone of claim 1 where in ##STR00044## wherein: c is 25; R is a mixture of CH.sub.2CH.sub.2Si(OCH.sub.2CH.sub.3).sub.3 and alkyl wherein x is 15.

16. The reactive silicone of claim 1 where in ##STR00045## wherein: c is 10; R is a mixture of CH.sub.2CH.sub.2Si(OCH.sub.2CH.sub.3).sub.3 and alkyl having 15 carbon atoms.

17. The reactive silicone of claim 1 where in ##STR00046## wherein: c is 25; R is a mixture of CH.sub.2CH.sub.2Si(OCH.sub.2CH.sub.3).sub.3 and alkyl having 15 carbon atoms.

18. A process for coating zinc oxide with the reactive silicone of claim 1 which comprises: i. mixing the reactive silicone and zinc oxide together; ii. heating the mixture to a temperature of between 40 C. and 100 C.; iii. holding the temperature of said mixture for two to ten hours, generating methanol or ethanol.

19. A reactive silicone polymer composition the following structure: ##STR00047## wherein: a is an integer ranging from 0 to 150; b is an integer ranging from 1 to 10; R is a mixture of: a) an alkyl having the following structure:
(CH.sub.2).sub.xCH.sub.3 wherein: x is an integer ranging from 7 to 21; and b) A silane having a structure selected from the groups consisting of: i. CH.sub.2CH.sub.2Si(OCH.sub.3).sub.3 ii. CH.sub.2CH.sub.2Si(OCH.sub.2CH.sub.3).sub.3.

20. The reactive silicone of claim 19 wherein: a is 2; b is 1; R is a mixture of CH.sub.2CH.sub.2Si(OCH.sub.3).sub.3 and alkyl wherein x is 7.

21. The reactive silicone of claim 19 wherein: a is 2; b is 1; R is a mixture of CH.sub.2CH.sub.2Si(OCH.sub.2CH.sub.3).sub.3 and alkyl wherein x is 7.

22. The reactive silicone of claim 19 wherein: a is 2; b is 1; R is a mixture of CH.sub.2CH.sub.2Si(OCH.sub.3).sub.3 and alkyl wherein x is 15.

23. The reactive silicone of claim 19 wherein: a is 2; b is 1; R is a mixture of CH.sub.2CH.sub.2Si(OCH.sub.2CH.sub.3).sub.3 and alkyl wherein x is 15.

24. The reactive silicone of claim 19 wherein: a is 2; b is 1; R is a mixture of CH.sub.2CH.sub.2Si(OCH.sub.3).sub.3 and alkyl wherein x is 21.

25. The reactive silicone of claim 19 wherein: a is 2; b is 1; R is a mixture of CH.sub.2CH.sub.2Si(OCH.sub.2CH.sub.3).sub.3 and alkyl wherein x is 21.

26. The reactive silicone of claim 19 wherein: a is 20; b is 10; R is a mixture of CH.sub.2CH.sub.2Si(OCH.sub.3).sub.3 and alkyl wherein x is 7.

27. The reactive silicone of claim 19 wherein: a is 20; b is 10; R is a mixture of CH.sub.2CH.sub.2Si(OCH.sub.2CH.sub.3).sub.3 and alkyl wherein x is 7.

28. The reactive silicone of claim 19 wherein: a is 20; b is 10; R is a mixture of CH.sub.2CH.sub.2Si(OCH.sub.3).sub.3 and alkyl wherein x is 15.

29. The reactive silicone of claim 19 wherein: a is 20; b is 10; R is a mixture of CH.sub.2CH.sub.2Si(OCH.sub.2CH.sub.3).sub.3 and alkyl wherein x is 15.

30. The reactive silicone of claim 19 wherein: a is 20; b is 10; R is a mixture of CH.sub.2CH.sub.2Si(OCH.sub.3).sub.3 and alkyl wherein x is 21.

31. The reactive silicone of claim 19 wherein: a is 20; b is 10; R is a mixture of CH.sub.2CH.sub.2Si(OCH.sub.2CH.sub.3).sub.3 and alkyl wherein x is 21.

32. The reactive silicone of claim 19 wherein: a is 150; b is 3; R is a mixture of CH.sub.2CH.sub.2Si(OCH.sub.3).sub.3 and alkyl wherein x is 7.

33. The reactive silicone of claim 19 wherein: a is 150; b is 3; R is a mixture of CH.sub.2CH.sub.2Si(OCH.sub.2CH.sub.3).sub.3 and alkyl wherein x is 7.

34. The reactive silicone of claim 19 wherein: a is 150; b is 3; R is a mixture of CH.sub.2CH.sub.2Si(OCH.sub.3).sub.3 and alkyl wherein x is 15.

35. The reactive silicone of claim 19 wherein: a is 150; b is 3; R is a mixture of CH.sub.2CH.sub.2Si(OCH.sub.2CH.sub.3).sub.3 and alkyl wherein x is 15.

36. The reactive silicone of claim 19 wherein: a is 150; b is 3; R is a mixture of CH.sub.2CH.sub.2Si(OCH.sub.3).sub.3 and alkyl wherein x is 21.

37. The process for coating zinc oxide with the reactive silicone of claim 19 comprises: iv. mixing the reactive silicone and zinc oxide together; v. heating the mixture to a temperature of between 40 C. and 100 C.; vi. holding the temperature of said mixture for two to ten hours, generating methanol or ethanol.

Description

SUMMARY OF THE INVENTION

Detailed Description of the Invention

(1) The present invention is directed to a series of pigment reactive silicone polymers having the following structure:

(2) ##STR00002##

(3) wherein:

(4) a is an integer ranging from 0 to 150;

(5) b is an integer ranging from 1 to 10;

(6) R is independently selected from the groups consisting of: a) an alkyl having the following structure:
(CH.sub.2).sub.xCH.sub.3 wherein: x is an integer ranging from 7 to 21; b) A silane independently selected from the groups having the following structure: i. a silane derived from vinyltrimethoxysilane having the structure:

(7) ##STR00003## ii. a silane derived from triethoxyvinylsilane having the following structure:

(8) ##STR00004## and mixtures thereof:

(9) Another aspect of the present invention is directed to a series of silicone polymers having the following structure:

(10) ##STR00005##

(11) wherein:

(12) c is an integer ranging from 10 to 25;

(13) R is independently selected from the groups consisting of: a) an alkyl having the following structure:
(CH.sub.2).sub.xCH.sub.3 wherein: x is an integer ranging from 7 to 21; b) a silane independently selected from the groups having the following structure: i. A silane derived from vinyltrimethoxysilane having the structure:

(14) ##STR00006## ii. a silane derived from triethoxyvinylsilane having the following structure:

(15) ##STR00007## and mixtures thereof:

(16) The present invention also discloses (a) a process for hydrophobizing the surface of zinc oxide with a specific type of reactive silicone, and (b) a novel hydrophobic zinc oxide composition. Additionally, water may be added to the mixture of the reactive silicone and zinc oxide mixture prior to heating. The concentration will be between 1 and 10% water.

(17) It has been found that highly effective system for hydrophobizing zinc oxide makes use of a silicone compound conforming to the following structure:

(18) ##STR00008##

(19) wherein:

(20) a is an integer ranging from 0 to 150;

(21) b is an integer ranging from 1 to 10;

(22) R is independently selected from the groups consisting of: c) an alkyl having the following structure:
(CH.sub.2).sub.xCH.sub.3 wherein: x is an integer ranging from 7 to 21; d) A silane independently selected from the groups having the following structure: j. a silane derived from vinyltrimethoxysilane having the structure:

(23) ##STR00009## iii. a silane derived from triethoxyvinylsilane having the following structure:

(24) ##STR00010## and mixtures thereof:

(25) Another aspect of the present invention is directed to a series of silicone polymers having the following structure:

(26) ##STR00011##

(27) wherein:

(28) c is an integer ranging from 10 to 25;

(29) R is independently selected from the groups consisting of: c) an alkyl having the following structure:
(CH.sub.2).sub.xCH.sub.3 wherein: x is an integer ranging from 7 to 21; d) a silane independently selected from the groups having the following structure: j. A silane derived from vinyltrimethoxysilane having the structure:

(30) ##STR00012## ii. a silane derived from triethoxyvinylsilane having the following structure:

(31) ##STR00013## and mixtures thereof.

(32) The zinc hydrophobizing process comprises; contacting zinc oxide with an effective hydrophobizing concentration of a silicone which conforms to the following structure:

(33) ##STR00014##

(34) wherein:

(35) a is an integer ranging from 0 to 150;

(36) b is an integer ranging from 1 to 10;

(37) R is independently selected from the groups consisting of: e) an alkyl having the following structure:
(CH.sub.2).sub.xCH.sub.3 wherein: x is an integer ranging from 7 to 21; f) A silane independently selected from the groups having the following structure: k. a silane derived from vinyltrimethoxysilane having the structure:

(38) ##STR00015## iv. a silane derived from triethoxyvinylsilane having the following structure:

(39) ##STR00016## and mixtures thereof:

(40) Another aspect of the present invention is directed to a series of silicone polymers having the following structure:

(41) ##STR00017##

(42) wherein:

(43) c is an integer ranging from 10 to 25;

(44) R is independently selected from the groups consisting of: e) an alkyl having the following structure:
(CH.sub.2).sub.xCH.sub.3 wherein: x is an integer ranging from 7 to 21; f) a silane independently selected from the groups having the following structure: k. A silane derived from vinyltrimethoxysilane having the structure:

(45) ##STR00018## ii. a silane derived from triethoxyvinylsilane having the following structure:

(46) ##STR00019## and mixtures thereof:
then heating the mixture to a temperature of between 40 C. and 100 C., for two to ten hours.

(47) The product so produced surprisingly is hydrophobic and maintains the desirable performance characteristics making the zinc oxide useful in many applications including as a sun screen.

(48) Process

(49) The compounds of the present invention are prepared by contacting zinc oxide with an effective hydrophobizing concentration (generally between 0.1% and 25% by weight of the total formulation) of a silicone which conforms to the following structure:

(50) ##STR00020##

(51) wherein:

(52) a is an integer ranging from 0 to 150;

(53) b is an integer ranging from 1 to 10;

(54) R is independently selected from the groups consisting of: g) an alkyl having the following structure:
(CH.sub.2).sub.xCH.sub.3 wherein: x is an integer ranging from 7 to 21; h) A silane independently selected from the groups having the following structure: 1. a silane derived from vinyltrimethoxysilane having the structure:

(55) ##STR00021## v. a silane derived from triethoxyvinylsilane having the following structure:

(56) ##STR00022## and mixtures thereof:

(57) Another aspect of the present invention is directed to a series of silicone polymers having the following structure:

(58) ##STR00023##

(59) wherein:

(60) c is an integer ranging from 10 to 25;

(61) R is independently selected from the groups consisting of: g) an alkyl having the following structure:
(CH.sub.2).sub.xCH.sub.3 wherein: x is an integer ranging from 7 to 21; h) a silane independently selected from the groups having the following structure: 1. A silane derived from vinyltrimethoxysilane having the structure:

(62) ##STR00024## ii. a silane derived from triethoxyvinylsilane having the following structure:

(63) ##STR00025## and mixtures thereof:
then heating the intermediate to a temperature of between 40 C. and 100 C., for between 2 hr and 10 hr. During this time alcohol is removed. The reaction is considered complete when 97% of the theoretical alcohol is removed. The quantity of alcohol removed is considered more important than the time at which the material is held at temperature.

(64) When R is CH.sub.3, the alcohol removed is methanol. When R is CH.sub.2CH.sub.3 the alcohol removed is ethanol.

(65) The zinc oxide is coated dry. The silicone can be applied by simply mixing it with the zinc oxide, or in a preferred method using traditional methods for applying liquids to solids like a V blender.

(66) Raw Materials

(67) Internal Silicone Hydride

(68) Internal silicone hydrides are commercially available from a variety of sources including Siltech Corporation, Toronto, Ontario, Canada. They have the structure of:

(69) TABLE-US-00001 Molecular Weight Example A b (g/mol) 1 2 1 370.5 2 150 3 11,619.4 3 0 4 404.0 4 8 4 996.8 5 24 8 2,583.6 6 20 10 2,407.4 7 100 10 8,335.4

(70) Terminal Silicone Hydride

(71) Terminal silicone hydrides are commercially available from a variety of sources including Siltech Corporation, Toronto, Ontario, Canada. They have the structure of:

(72) TABLE-US-00002 Molecular Weight Example c (g/mol) 8 10 816.1 9 15 1,186.6 10 25 1,852.5

Example 11

(73) Vinyltrimethoxysilane is commercially available from a variety of sources including Sigma-Aldrich and has the following structure:

(74) ##STR00028## C.A.S. number: 2768-02-7

Example 12

(75) Triehoxyvinylsilane is commercially available from a variety of sources including Sigma-Aldrich and has the following structure:

(76) ##STR00029## C.A.S. number: 78-08-0

Examples

(77) Alpha-Olefin

(78) Alpha-olefins are hydrocarbons with a primary double bond. They are available from a variety of sources including . . . they have the following structure:

(79) TABLE-US-00003 CH.sub.3(CH.sub.2).sub.dCHCH.sub.2 Molecular Weight Example d (g/mol) 13 8 154.0 14 12 210.0 15 16 266.0 16 18 294.0 17 22 350.0 18 26 406.0

(80) TABLE-US-00004 Internal Silane Polymer Silicone Hydride Example 11 Alpha-Olefin Example Example Grams Grams Example Grams 19 1 139.81 60.19 20 2 89.98 35.22 13 74.80 21 2 82.06 48.17 14 69.77 22 2 85.12 66.63 18 48.25 23 3 82.11 117.89 24 3 77.03 82.94 14 40.04 25 3 65.91 47.31 15 86.79 26 3 50.53 18.14 17 131.33 27 4 126.43 73.57 28 4 115.52 50.41 16 34.07 29 4 125.01 36.37 13 38.63 30 4 102.77 14.95 15 82.28 31 5 138.03 61.97 32 5 137.70 54.10 13 8.21 33 5 129.06 28.97 14 42.96 34 5 92.76 5.21 18 102.04 35 6 124.35 75.65 36 6 122.10 66.19 14 11.72 37 6 107.90 32.49 15 59.61 38 6 84.43 5.09 17 110.48 39 7 170.11 29.89 40 7 168.88 26.44 16 4.68 41 7 160.44 13.96 13 25.60 42 7 143.34 2.49 15 54.17

(81) TABLE-US-00005 Internal Silane Polymer with Triethoxthyvinylsilane Silicone Hydride Example 12 Alpha-Olefin Example Example Grams Grams Example Grams 43 1 128.60 71.40 44 2 85.62 43.21 13 71.17 45 2 76.71 58.07 14 65.22 46 2 77.63 58.07 18 65.22 47 3 70.14 129.86 48 3 68.77 95.49 14 35.74 49 3 61.68 95.49 15 35.74 50 3 49.24 22.79 17 127.97 51 4 114.26 85.74 52 4 107.66 60.59 16 31.75 53 4 118.75 44.56 13 36.69 54 4 100.60 18.87 15 80.53 55 5 126.66 73.34 56 5 127.69 64.70 13 7.61 57 5 123.87 35.86 14 40.27 58 5 92.06 6.66 18 101.27 59 6 112.07 87.93 60 6 111.42 77.89 14 10.69 61 6 103.05 40.02 15 56.93 62 6 83.82 6.51 17 109.67 63 7 163.05 36.05 64 7 162.65 32.84 16 4.51 65 7 157.27 17.64 13 25.09 66 7 142.82 3.20 15 53.97

(82) TABLE-US-00006 Mixed alkyl Silane polymer Silicone Hydride Siloxane Alpha-Olefin Ex- Ex- Ex- Ex- Ex- am- am- am- am- am- ple ple Grams ple Grams ple Grams ple Grams 67 2 80.41 12 40.59 13 33.42 14 45.58 68 3 56.46 12 26.14 15 55.77 16 61.64 69 4 110.16 12 62.00 13 8.51 17 19.34 70 5 119.07 12 34.47 13 14.19 17 32.26 71 6 102.76 12 15.96 14 35.86 15 45.42 72 7 146.27 12 6.56 15 18.67 18 28.50 73 2 84.25 11 32.97 13 35.02 14 47.75 74 3 58.17 11 20.88 15 57.45 16 63.50 75 4 118.40 11 51.67 13 9.15 17 20.79 76 5 123.87 11 27.81 13 14.77 17 33.56 77 6 104.64 11 12.60 14 36.51 15 46.25 78 7 147.35 11 5.13 15 18.81 18 28.71

(83) TABLE-US-00007 Terminal Silane Polymer Silicone Hydride Silane Alpha-Olefin Example Example Grams Example Grams Example Grams 79 8 145.65 11 54.35 80 8 135.03 12 64.97 81 9 159.16 11 49.73 82 9 150.27 12 28.23 83 10 171.77 11 28.23 84 10 165.02 12 34.98 85 8 144.49 11 28.24 13 27.27 86 8 138.82 12 34.99 13 26.19 87 8 137.67 11 26.91 14 35.43 88 8 132.51 12 33.40 14 34.10 89 8 131.46 11 25.69 15 42.85 90 8 118.73 12 42.57 15 38.70 91 8 128.56 11 25.13 16 46.31 92 8 116.36 12 41.72 16 41.92 93 8 123.13 11 24.06 17 52.81 94 8 111.89 12 40.12 17 47.99 95 8 118.14 11 23.09 18 58.77 96 8 107.76 12 38.63 18 53.61 97 9 158.20 11 21.27 13 20.53 98 9 153.48 12 26.61 13 19.92 99 9 152.51 11 20.50 14 26.99 100 9 148.11 12 25.68 14 26.21 101 9 147.21 11 19.79 15 33.00 102 9 135.98 12 33.53 15 30.48 103 9 144.70 11 19.45 16 35.85 104 9 133.84 12 33.00 16 33.16 105 9 139.92 11 18.81 17 41.27 106 9 129.74 12 31.99 17 38.27 107 9 135.45 11 18.21 18 46.34 108 9 125.89 12 31.04 18 43.07 109 10 171.05 11 14.73 13 14.22 110 10 167.48 12 18.60 13 13.92 111 10 166.74 11 14.36 14 18.90 112 10 163.35 12 18.14 14 18.52 113 10 162.64 11 14.00 15 23.35 114 10 153.66 12 24.27 15 22.06 115 10 160.67 11 13.83 16 25.50 116 10 151.90 12 23.99 16 24.11 117 10 156.86 11 13.51 17 29.64 118 10 148.49 12 23.45 17 28.05 119 10 153.23 11 13.19 18 33.58 120 10 145.23 12 22.94 18 31.83

(84) TABLE-US-00008 Preparation of the Pigment Reactive silicone Polymers of the Present Invention Vinyl Trimethoxyl Silane Example Example Grams ZnO 121 19 1.0 99.0 122 20 2.0 98.0 123 21 1.0 99.0 124 22 2.0 98.0 125 23 1.0 99.0 126 24 2.0 98.0 127 25 1.0 99.0 128 26 2.0 98.0 129 27 1.0 99.0 130 28 2.0 98.0 131 29 1.0 99.0 132 30 2.0 98.0 133 31 1.0 99.0 134 32 2.0 98.0 135 33 1.0 99.0 136 34 2.0 98.0 137 35 1.0 99.0 138 36 2.0 98.0 139 37 1.0 99.0 140 38 2.0 98.0 141 39 1.0 99.0 142 40 2.0 98.0 143 41 1.0 99.0 144 42 2.0 98.0 145 43 1.0 99.0 146 44 2.0 98.0 147 45 1.0 99.0 148 46 2.0 98.0 149 47 1.0 99.0 150 48 2.0 98.0 151 49 1.0 99.0 152 50 2.0 98.0 153 51 1.0 99.0 154 52 2.0 98.0 155 53 1.0 99.0 156 54 2.0 98.0 157 55 1.0 99.0 158 56 2.0 98.0 159 57 1.0 99.0 160 58 2.0 98.0 161 59 1.0 99.0 162 60 2.0 98.0 163 61 1.0 99.0 164 62 2.0 98.0 165 63 1.0 99.0 166 64 2.0 98.0 167 65 1.0 99.0 168 66 2.0 98.0 169 67 1.0 99.0 170 68 2.0 98.0 171 69 1.0 99.0 172 70 2.0 98.0 173 71 1.0 99.0 174 72 2.0 98.0 175 73 1.0 99.0 176 74 2.0 98.0 177 75 1.0 99.0 178 76 2.0 98.0 179 77 1.0 99.0 180 78 2.0 98.0 181 79 1.0 99.0 182 80 2.0 98.0 182 81 1.0 99.0 183 82 2.0 98.0 184 83 1.0 99.0 185 84 2.0 98.0 186 85 1.0 99.0 187 86 2.0 98.0 188 87 1.0 99.0 189 88 2.0 98.0 190 89 1.0 99.0 191 90 2.0 98.0 192 91 1.0 99.0 192 92 2.0 98.0 193 93 1.0 99.0 194 94 2.0 98.0 195 95 1.0 99.0 196 96 2.0 98.0 197 97 1.0 99.0 198 98 2.0 98.0 199 99 1.0 99.0 200 100 2.0 98.0 201 101 1.0 99.0 202 102 2.0 98.0 203 103 1.0 99.0 204 104 2.0 98.0 205 105 1.0 99.0 206 106 2.0 98.0 207 107 1.0 99.0 208 108 2.0 98.0 209 109 1.0 99.0 210 110 2.0 98.0 211 111 2.0 98.0 212 112 1.0 99.0 213 113 2.0 98.0 214 114 1.0 99.0 215 115 2.0 98.0 216 116 1.0 99.0 217 117 2.0 98.0 218 118 1.0 99.0 219 119 2.0 98.0 220 120 1.0 99.0

(85) While the illustrative embodiments of the invention have been described with particularity, it will be understood that various other modifications will be apparent to and can be readily made by those skilled in the art without departing from the spirit and scope of the invention. Accordingly, it is not intended that the scope of the claims appended hereto be limited to the examples and descriptions set forth hereinabove but rather that the claims be construed as encompassing all the features of patentable novelty which reside in the present invention, including all features which would be treated as equivalents thereof by those skilled in the art to which the invention pertains.