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It is difficult to provide abrasion resistance coatings with both good coatability, optical clarity and the ability to be tinted after application of the coating to a transparent substrate, such as an ophthalmic lens. An abrasion-resistant coating that adheres well to the substrate and is clear, transparent, colorless, and free of visible specks comprises a solvent, an epoxy resin composition, an aminosilane, and an hydrocarbyltrihydrocarboxysilane, such as an alkyltrialkoxysilane. The aminosilane may be a partially hydrolyzed aminosilane that is effectively blocked from reacting with the epoxy resin composition at ambient temperature. The coating composition is applied to the substrate and then treated to remove any block from the hydrolyzable aminosilane such that the aminosilane and the epoxy resin composition react to form an abrasion-resistant coating. The coating is also controllably tintable and is strongly adherent to the substrate even after tinting or exposure to heat and humidity.
1. A method for applying a mar resistant coating to a surface of an ophthalmic lens comprising the steps of:
a) providing a first solution of at least one amino silane, at least one epoxy resin and at least one hydrocarbyltrihydrocarbyloxy silane and allowing the combination to react;
b) applying the reacted combination onto said surface as a coating and allowing the coating to dry; and
c) applying a tinting dye to the dried coating to tint the coating.
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8. A method for applying a mar resistant coating to a surface of a polymeric ophthalmic lens comprising the steps of:
c) providing a first solution of at least one amino silane and one additional ingredient selected from the group consisting of an epoxy resin and a hydrocarbyltrihydrocarbyloxy silane and hydrolyzing at least one ingredient of the first solution, thereby forming a second solution;
d) adding to the second solution a hydrocarbyltrihydrocarbyloxy silane or an epoxy resin, thereby forming a third solution, and allowing ingredients among the third solution to react to form a fourth solution;
i. applying the fourth solution onto said surface of a polymeric ophthalmic lens as a coating and allowing the coating to dry; and
e) applying a tinting dye to the dried coating to tint the coating.
1. Field of the Invention
The present invention relates generally to coating compositions, and more particularly, to polyorganosiloxane compositions forming mar-resistant coatings on substrates and to controlling the tintability of the mar-resistant coatings after formation on a substrate.
2. Background of the Art
A variety of substrates, including those made of glass, plastic, metal, or concrete, are usefully coated with protective films. It is generally desirable that protective film coatings have good weathering properties, strong adhesion to the substrate, as well as resistance to thermal shock, mechanical shock, heat, humidity, and common chemicals. It is also desirable that the protective film coatings be practical to apply, dry, and cure. These properties are more difficult to achieve when the protective film coating is applied to polymeric or plastic substrates than when applied to many other substrates because of the greater susceptibility of these synthetic substrates, especially where the need for mar resistance is highest.
Some plastic substrates are desirable substitutes for glass due to a lower density than glass, economically advantageous fabrications, and breakage resistance. However, commercially available plastic substrates tend to have a reduced resistance to surface damage such as abrasion, marring, and scratching when compared to glass. Therefore, protective film coatings for plastic substrates are of particular interest to a wide range of industries where plastics are used.
Several technical approaches have been attempted in an effort to coat plastic substrates to improve resistance to abrasion, marring and scratching of the plastic substrates. Among the various classes of materials used to provide protection to polymeric substrates have been polysiloxanes, epoxy resins, acrylic (both acryloyl and methacryloyl) resins, urethanes, titanate esters, and ambifunctional polymeric compositions with multiple classes of polymer functionalities (e.g., acryloylsilanes, epoxysilanes, etc.). In particular, substantial work has been carried out to develop coatings of polyorganosiloxanes cross-linked by a condensation of silane or silanol groups.
U.S. Pat. No. 3,837,876 (Mayasumi et al.) describes a reaction of an aminosilane with an epoxysilane to produce a substance dissolvable in a solvent. Once dissolved, the substance was applied to various substrates to coat the substrates and form a mar-resistant coating on the surface.
U.S. Pat. No. 3,166,527 (Ender) describes mixing an epoxysilane with an aminosilane to make an unpolymerized mixture and a polymerized mixture. Each of the mixtures was applied to a surface to coat the surface. The coating made by each mixture was cured either by standing at ambient temperature or by heating.
U.S. Pat. No. 3,961,977 (Koda) describes a use of an aminoalkoxysilane hydrolyzed within a range of 10 to 40% of hydroxyl groups and an epoxyalkoxysilane to make a coating mixture. The hydrolyzed aminoalkoxysilane and epoxyalkoxysilane were dissolved in a solvent. Solvents described included a ketone.
U.S. Pat. No. 4,378,250 (Treadway) describes the use of ketones or aldehydes in making a mar-resistant coating. In particular, Treadway describes hydrolyzing at least two different silane materials to above 40% hydrolysis to form a reaction mixture. Treadway also describes adding the ketone to the reaction mixture to form a ketimine. The reaction mixture is then applied to a substrate and cured.
U.S. Pat. No. 5,786,032 describes a process for manufacturing an abrasion-resistant coating that adheres well to the substrate and is clear, transparent, colorless, and free of visible specs. The coating is also highly tintable and is strongly adherent to the substrate even after tinting or exposure to heat and humidity. The process comprises partially hydrolyzing an aminosilane having hydrolyzable groups to form an aminosilane hydrolyzate; adding a non-silane epoxy prepolymer to the aminosilane hydrolyzate to form a first mixture; partially polymerizing the first mixture to form a second mixture; adding a solvent to the second mixture to form a third mixture; applying the third mixture to a substrate and curing the third mixture on the substrate to make the tintable and abrasion resistant coating. The first mixture may consist essentially of the aminosilane hydrolyzate and the non-silane epoxy prepolymer. Although this composition provided a unique capability of mar-resistance and tintability after formation, the coating tended to be too tintable with certain materials, making application of a full range of colors to a single lens type more difficult.
The present invention comprises an abrasion-resistant coating that adheres well to the substrate and is clear, transparent, colorless, and free of visible specs. The coating is also controllably tintable and is strongly adherent to the substrate even after tinting or exposure to heat and humidity. The coating composition includes a solvent, an epoxy resin composition, an aminosilane, and an hydrocarbyltrihydrocarboxysilane, such as an alkyltrialkoxysilane. The aminosilane may be a partially hydrolyzed aminosilane that is effectively blocked from reacting with the epoxy resin composition at ambient temperature. The coating composition is applied to the substrate and then treated to remove any block from the hydrolyzable aminosilane such that the aminosilane and the epoxy resin composition react to form an abrasion-resistant coating.
It is not easy to modify only a single significant property of a film without adverse modification of other properties of films. This is particularly true where some significant properties of the film are related by the underlying nature of the properties or the components of the film that contribute to these properties. This is particularly the case when dealing with a film such as an abrasion resistant mar-resistant coating where many of the properties are tied to the structure of the polymeric network. For example, both chemical resistance and mar resistance are in part tied to the tightness and surface organization of the polymer chains. To whatever degree that tightness and organization is altered to modify one property, the other property is likely to be affected. There is also no assurance that one property can be adjusted within the desired range while maintaining one or a myriad of properties that are necessary for a specific type of commercial product. Such is the case where the high quality, tintable mar-resistant coating of the prior art represented by U.S. Pat. No. 5,786,032 was found to have too rapid a rate of absorption of dye from tinting solutions. Even having discovered this limitation on the use of that composition, there was no assurance that any chemical modification of the composition could have been predicted to provide reduced tintability, maintain an acceptable level of abrasion resistance, and maintain the high level of optical quality and other attributes essential across a wide range of properties that are necessary in a composition to be used as a coating on an ophthalmic lens.
The present invention includes a coating composition that includes a solvent, an epoxy resin that undergoes epoxy polymerization, and an aminosilane in combination with 2 to 60% by weight of a hydrocarbyltrihydrocarbyloxysilane. A particularly desirable coating composition utilizes a partially hydrolyzed aminosilane that is effectively blocked from reacting with the epoxy resin at ambient temperature to provide an exceptionally durable coating that is cross-linked by silanol condensation in combination with the hydrocarboxytrihydrocarbyloxysilane. The present invention also includes a method for making a coating cross-linked by silanol condensation that includes partially hydrolyzing an aminosilane to a degree that is greater than 10% of complete molar reaction, mixing the partially hydrolyzed aminosilane with an agent blocking epoxy polymerization such as a ketone or an aldehyde to form a ketimine thereby blocking later epoxy polymerization until desired by heating, adding an epoxy resin (including either or both of a non-silane epoxy resin or epoxysilane resin) to the ketimine along with the hydrocarbyltrialkoxysilane to form a mixture, partially polymerizing and/or further hydrolyzing the mixture by heating to provide body to the mixture, adding a solvent to provide to the polymerized mixture a proper viscosity for coating (and during this step or after this step or earlier adding the hydrocarbyltrialkoxysilane), and adding a surfactant to provide uniform coating characteristics. The composition is then coated and dried and/or cured on a substrate such as an ophthalmic lens.
Suitable non-silane epoxy resins include any compound containing a glycidyl or 3,4-epoxycyclohexyl, 3,4-epoxycyclopentyl group thereon (the latter often referred to as epoxycyclohexyl or epoxycyclopentyl groups), but which are free of reactive silane groups. These epoxy groups are represented by the formulae:
where R1 and R2 include hydrogen, alkyl, aryl, alkoxy, alkoxyalkyl, alkoxyaryl, or other relatively stable organic moieties. Diepoxy, triepoxy, or polyepoxy compounds with the epoxies separated by alkyl, etheric, or alkyletheric linkages may also be used. This class of compounds is well known in the polymer art. The term epoxy resin is conventionally used to refer to any composition having compounds with polymerizable epoxy groups (e.g., glycidyl or 3,4-epoxycyclohexyl or 3,4-epoxycyclopentyl groups). These compounds may be monomeric compounds, oligomeric compounds or polymeric compounds as long as they have a polymerizable epoxy group (or functionality therein). In fact, the term epoxy resin is most conventionally used to refer to compositions comprising monomeric epoxy functional compounds.
The epoxy functional silanes usually excluded from the practice of the invention of U.S. Pat. No. 5,786,032, but which may be included as minor component (less than 50% by weight contribution to the final polymer solids, less than 30%, less than 20%, less than 10%, less than 5%, and less than 1%, including 0% by weight contribution to the final polymer solids) supplemental comonomers may be described by the formula:
wherein R1O, R2O, and R3O are independently selected from aliphatic groups or aromatic groups which complete a silane on the Si (silicon) atom, preferably alkyl groups or phenyl groups, and more preferably unsubstituted alkyl groups,
n is as described above, and
EP represents a glycidyl (e.g., glycidoxy) or cyclohexaneoxide (epoxycyclohexyl) or cyclopentaneoxide (epoxycyclopentyl) epoxy polymerizable group.
It is well recognized within the art that some substitution of the compounds used in forming the compositions is not only tolerable, but in some instances highly desirable.
Where the term group is used to refer to a substitutent or nucleus, that term is specifically inclusive of both substituted and unsubstituted substituents or nuclei. For example, the term alkyl group refers to not only the pure hydrocarbon within the definition of alkyl (e.g., methyl ethyl, octyl, isooctyl, dodecyl, etc.), but also those materials within the art recognized as substituted alkyls, such as monosubstituted haloalkyl, hydroxyalkyl, ether groups (e.g., �CH2�O�CH2�, etc.), and the like. Where the chemical group is used without description of a group or described as a moiety, such as with ethyl or hexyl moiety, or decyl, that phrase excludes substitution.
A great number of aminoalkylalkoxysilane precursors are known and suitable for conversion to the alkine-bridged bis-(aminosilane) for use in the present invention. Many suitable aminoalkylalkoxysilane precursors may be represented by the structure of below:
wherein R1O, R2O, R3O and n are as defined above, R1, R2, and R3 are independently monovalent hydrocarbon radical (e.g., alkyl and other aliphatic radicals, especially alkyl groups and most particularly methyl and ethyl), Q is a hydrogen or other halide reactive group, or halide non-reactive group (e.g., alkyl or aryl), and R4 is selected from hydrogen, aliphatic and phenyl groups, alkyl of from 1 to 20 carbon atoms or especially alkyl groups of from 1 to 4 carbon atoms. Were the group R4 an alkoxy group, the compounds of Formula (II) would be within the scope of Formula (I). For example, many known and suitable aminoalkyltrialkoxysilanes useful as precursors for the first component are as follows:
beta-aminoethyltriethoxysilane, beta-aminoethyltrimethoxysilane, beta-aminoethyltriethoxysilane, beta-aminoethyltributoxysilane, beta-aminoethyltripropoxysilane, alpha-aminoethyltrimethoxysilane, alpha-aminoethyltriethoxysilane, gamma-aminopropyltrimethoxysilane, gamma-aminopropyltriethoxysilane, gamma-aminopropyltributoxysilane, gamma-aminopropyltripropoxysilane, beta-aminopropyltrimethoxysilane, beta-aminopropyltriethoxysilane, beta-aminopropyltripropoxysilane, beta-aminopropyltributoxysilane, alpha-aminopropyltrimethoxysilane, alpha-aminopropyltriethoxysilane, alpha-aminopropyltributoxysilane, alpha-aminopropyltripropoxysilane, N-aminomethylaminoethyltrimethoxysilane, N-aminomethylaminomethyltripropoxysilane, N-aminomethyl-beta-aminoethyltrimethoxysilane, N-aminomethyl-beta-aminoethyltriethoxysilane, N-aminoethyl-beta-aminoethyltripropoxysilane, N-aminomethyl-gamma-aminopropyltrimethoxysilane, N-aminomethyl-gamma-aminopropytriethoxysilane, N-aminomethyl-gamma-aminopropyltripropoxysilane, N-aminomethyl-beta-aminopropyltrimethoxysilane, N-aminomethyl-beta-aminopropyltriethoxysilane, N-aminomethyl-beta-aminopropyltripropoxysilane, N-aminopropyltripropoxysilane, N-aminopropyltrimethoxysilane, N-(beta-aminoethyl)-beta-aminoethyltrimethoxysilane, N-(beta-aminoethyl)-beta-aminoethyltriethoxysilane, N-(beta-aminoethyl)-beta-aminoethyltripropoxysilane, N-(beta-aminoethyl)-beta-aminoethyltrimethoxysilane, N-(beta-aminoethyl)-alpha-aminoethyltriethoxysilane, N-(beta-aminoethyl)-alpha-aminoethyltripropoxysilane, N-(beta-aminoethyl)-beta-aminopropyltrimethoxysilane, N-(beta-aminoethyl)-gamma-aminopropyltriethoxysilane, N-(beta-aminoethyl)-gamma-aminopropyltripropoxysilane, N-(beta-aminoethyl)-gamma-aminopropyltrimethoxysilane, N-(beta-aminoethyl)-beta-aminopropyltriethoxysilane, N-(beta-aminoethyl)-beta-aminopropyltripropoxysilane, N-(gamma-aminopropyl)-beta-aminoethyltrimethoxysilane, N-(gamma-aminopropyl)-beta-aminoethyltriethoxysilane, N-(gamma-aminopropyl)-beta-aminoethyltripropoxysilane, N-methylaminopropyltrimethoxysilane, beta-aminopropylmethyldiethoxysilane, gamma-diethylenetriaminopropyltriethoxysilane. The N-beta and N-gamma alternatives are less preferred materials within the class of materials useful in the practice of the present invention.
Coatings may also be formed where the aminosilane is a hydrolyzed (which includes partial hydrolysis) product of a compound of one of the formulae:
wherein R1, R2, and R3 are independently selected from alkyl groups of 1 to 4 carbon atoms or phenyl groups,
R4 is selected from hydrogen, phenyl groups, and alkyl of from 1 to 4 carbon atoms, R20 is defined as hydrogen, alkyl of from 1 to 4 carbon atoms, or phenyl, and
n is 1, 2, 3 or 4,
p is 2, 3 or 4,
q is 0 or 1,
o is 0 or 1, and
m is 1, 2, 3 or 4,
wherein q plus m is 1 or 2, o is 1 only when all aminosilane groups are bonded to the other alkine groups, and when p is 4, both m and o are zero.
Suitable aminosilanes also include compounds having the general formula:
where each R is independently selected from aliphatic or aromatic groups, especially aliphatic or aromatic hydrocarbon groups, such that the aminosilane can be any stable mix of substituents or combination of substituents at the various positions within the aminosilane of alkyl groups, alkoxy groups, alkyl ether groups, alkylamino groups or other combination of carbon, hydrogen and hetero atoms. One particularly preferred component, due to availability and price, is gamma-aminopropyltriethoxysilane.
The additional novel component of the present invention is a hydrocarbyltrihydrocarbyloxysilane, including alkyltrihydrocarbyloxysilane, phenyltrihydrocarbyloxysilane, alkyltrialkoxysilane, and phenyltrialkoxysilane. The term hydrocarbyl represents any moiety bonded to another atom directly through a carbon atom, and the term hydrocarbyloxy represents any moiety bonded to another atom through the oxygen of a �C�O� group. Many suitable hydrocarbyltrihydrocarbyloxysilanes may be represented by the general formula below:
wherein R11O, R12O, and R3O are independently selected from aliphatic groups or aromatic groups which complete a silane on the Si (silicon) atom, wherein R11, R12, and R13 preferably represent alkyl groups (of 1 to 8 carbon atoms, 1 to 4 carbon atoms, or 1 to 2 carbon atoms) or phenyl groups, and more preferably unsubstituted alkyl groups of the described chain lengths,
The aminoalkylalkoxysilane precursor (and if present, the epoxyalkylalkoxysilane precursor) may be preferably partially hydrolyzed in forming compositions of the present invention. The hydrolyzates may actually be in a gel form rather than easily flowing liquid, depending upon the degree of hydrolysis.
Hydrolysis refers to the initial products of reaction of water with alkoxy groups of the aminoalkylalkoxysilane precursor and/or of the epoxyalkylalkoxysilane precursor. Silanols are relatively unstable and tend to condense spontaneously. Thus, the simultaneous hydrolysis of a mixture of different silanes is normally referred to as co-hydrolysis, and a hydrolyzate refers to the end product of hydrolysis where some condensation has normally occurred during the hydrolysis reaction, so that homopolymers or copolymers are formed.
The reagent or precursor compounds of the aminosilanes used in the practice of the present invention include at least two, and usually three, alkoxy groups covalently bonded to a silicon atom. Each of these reagents may be partially hydrolyzed to form the partial hydrolyzate thereof by adding enough water to hydrolyze greater than 10% or 20% by number of the two or three available alkoxy groups, and more preferably having enough water to hydrolyze more than about 40% of these alkoxy groups.
Partial hydrolysis of the aminoalkylalkoxysilane precursor may be performed by adding enough water to hydrolyze an amount of the available alkoxy groups, and an approximately equal amount of a water soluble alcohol, such as ethanol or methanol, may be added to aid solubility. The mixture may be equilibrated, or ripened, for a sufficient period of time to effect the partial hydrolysis. The partial hydrolysis may be performed either by stripping off volatiles, such as the volatile alcohol by product of the hydrolysis, or not.
As a basic background to the practice of the present invention, the following underlying reactions and processes are believed to occur. The aminosilane reagent, herein described as Silane-N-H2 for simplicity, is reacted with a halogen substituted alkane, e.g., dichloromethane, trichloromethane, dibromomethane, tribromomethane, 1,2-dichloroethane, 1,2-dichloro-1,2-dibromoethene, etc. Iodo counterparts of these compounds (with 100% iodine substituents or partial iodine substitution) are also useful within the practice of the present invention. Dichloromethane will be used in the schematic to exemplify the reaction without limiting then scope of the invention. In reacting the Silane-NH2 with the halogenated alkane, the following reaction occurs:
This reaction generates a new reactant that can provide a higher crosslink density than the original aminosilane. It is desirable to keep the alkine or alkylene bridging group as small as possible (e.g., methine is most preferred and ethylene is next preferred).
The underlying method of use of the compositions and materials of the present invention may be summarized as follows. At least one aminosilane (10 to 60% by weight reactive ingredients within the solution), at least one epoxy resin (10 to 60% by weight total reactive ingredients within the solution) and at least one hydrocarbyltrihydrocarbyloxysilane (in an amount of from 2 to 60% by total reactive ingredients within the solution) are mixed into a coating composition and applied to a substrate. The hydrolyzable ingredients (e.g., any component comprising a silane group) may be hydrolyzed at any stage during the process (e.g., before admixture with any other ingredients, after admixture with one ingredient, or after admixture of all ingredients). It is desirable to be able to control the hydrolysis reaction for individual ingredients, so one skilled in the art would be most likely to choose a process where the individual hydrolyzable components are separately hydrolyzed before admixture with other ingredients. For an example of a particularly desirable description of a generally applicable process, an aminosilane is hydrolyzed, as described above. This is preferably performed with an alcohol, especially a lower molecular weight lower carbon chain length alcohol, such as 2-propanol. This can be done by combining the aminosilane and deionized water with stirring (e.g., at ambient temperature, although this may be varied up or down). These ingredients are allowed to react overnight or a shorter time if heated or catalyzed. The 2-propanol is then added and allowed to react for 3 hours with stirring (e.g., again at ambient temperature). The hydrocarbyltricarbyloxysilane is then mixed with deionized water with stirring (under ambient conditions) and allowed to react overnight. This step could be conveniently done at the same time as the hydrolysis of the aminosilane. The hydrolyzed aminosilane (with 2-propanol) and the epoxy compound, or epoxy compounds, are combined with stirring, heated to 95� F. to 158� F. (e.g., 122� F.), removed from heat, and held for enough time for the reaction to occur to a desirable level (e.g., 3.25 minutes). The temperature of the hot plate used to heat the mixture was 284� F. (140� C.). Immediately after the mixture reached a temperature of 122� F. (50� C.), the flask was removed from the hot plate and placed on a stirring plate at ambient temperature. The exotherm of the reaction caused the mixture to reach a temperature of 135� F. (57� C.). After two minutes, the hydrolyzed methyltrimethoxysilane was added. At the end of the 3.25 minutes, a quench was added comprising methyl ethyl ketone, ethanol, and Fluorad� FC-430 fluorosurfactant. This was allowed to react for 5 minutes at ambient conditions before cooling to 50� F. (10� C.). Polycarbonate lenses were coated when this solution was cooled to 50� F. (10� C.), although sometimes the coating is stored at 14� F. (−10� C.) in a freezer before being warmed at ambient conditions to 50� F. (10� C.) and applied. The coated lenses are preferably precured for twenty minutes at 180� F. (82� C.) and then cured for 4 hours at 250� F. (121� C.).
The preferred coatings of this invention can last for as long as 14 days in a freezer environment at 14� F. (−10� C.) and still produce consistent results. The solution will remain viable for 48 hours at ambient temperature. By proper adjustment of ingredients as specifically shown in the following examples, the following range of properties may be easily achieved:
The coating composition of the present invention is formed by combining an aminosilane as described above (which as an option may also include the alkine-bridged bis-aminosilanes of U.S. Pat. No. 6,057,040 which may also be referred to as a bis-silane-amino-methide, the methide group including substituted methide, especially methyl methide or ethylene as the bridging group) with an epoxy resin. Longer chain bridging groups such as propyl or butyl can be made on the aminosilane, but these add a softness to the polymer coating which may not be desirable for mar resistant coatings. These optional longer chain alkine-bridged bis-aminosilanes may be good additives where some modest flexibility is desired without having to add a non-crosslinkable monomer which would add only to flexibility and could be more erratic in its effects as compared to the longer chain alkine bridged bis-aminosilane. If necessary or desired, a solvent may be provided to adjust the composition to the proper coating viscosity for the method of application. When the coating is applied to a substrate, it can be polymerized and hardened in an oven. The resulting coating is crosslinked by silanol condensation and by the alkylation of the aminosilane to provide an exceptionally durable coating perhaps due to the latter crosslinking reaction which would provide higher crosslink density (i.e., a lower crosslink equivalent weight) thereby resulting in better scratch resistance than would otherwise be possible. In addition, a range of tint values and shorter tinting times can be produced by suitable variations of the proportions of epoxy to aminosilane components. There are numerous classes of catalysts, which may also be used to improve the speed or manner of crosslinking and curing of the polymerizable groups. For example, perfluorinated alkylsulfonyl methides (and their amide counterparts) are known to be active catalysts for the silane condensation and for epoxy polymerization. Photoinitators such as the onium catalysts with complex fluorinated anions (e.g., triphenylsulfonium hexafluoroantimonate, diphenyliodonium tetrafluoroborate, phenylthiophenylsulfonium hexafluoroantimonate) are known photinitators for both the epoxy polymerization and the silane condensation reactions.
Copolymerizable monomers, oligomers, or polymers may also be present in the compositions of the present invention as well as fillers, adjuvants and conventional additives. For example, additional silane monomers, epoxy monomers or other crosslinkable materials may be present, such as titanate esters, acrylatesilanes (e.g., 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane), and the like. Caution should be exercised in these options to assure that the crosslink density is not severely diminished, which would worsen hardness of the surface of the coating, or that other physical parameters are not adversely affected, as by the addition of softness or too great flexibility to the material composition of the coating. Additives to the compositions which would be particularly useful would include UV absorbers, such as benzophenones, as well as dyes, pigments, flow control agents, antistatic agents, surfactants, and the like.
The coating composition of the present invention is particularly suitable for coating plastic substrates such as transmissive sheets, windows, face guards, sports lenses, eye guards, and ophthalmic lenses. In particular, the coating composition provides an abrasion-resistant and mar-resistant coating for polycarbonate ophthalmic lenses.
The coating composition of the present invention is controllably tintable. The coating composition may be used to formulate a coating for a substrate such as an ophthalmic lens, which tints many times darker than coatings with compositions having two or more different silanes. It is surprising to note that the original disclosure of U.S. Pat. No. 5,786,032 stated that a �. . . presence of two different silanes is believed to render the composition of the coating ponderous. Also, the composition having two or more different silanes has a limited dye tintability range obtainable by varying the ratio of epoxy to amino groups within the bounds of allowable abrasion resistance.� (Column 2, lines 43-53). The present invention actually has found that the addition of a specific class of silanes, e.g., hydrocarbyltrihydrocarbyloxysilanes, such as hydrocarbyltrialkoxysilanes, hydrocarbyltriphenoxyoxysilanes, alkyl- or phenyl-trialkoxysilanes, and alkyl- or phenyltriphenoxysilanes act to control the tintability of the finished coating while maintaining a satisfactory level of mar-resistance and maintaining the critical optical qualities essential for an ophthalmic element.
The method of the present invention is usable to provide a tintable coating for substrates such as ophthalmic lenses. In particular, the method may further include steps of coating a substrate with the coating composition and contacting the coating with a dye to impart a tint to the coating. The method has an increased versatility and efficiency for tinting lenses over methods presently available. A wide range of tint values and shorter tinting times with tinting baths may be produced by suitable variations of the proportions of epoxy and aminosilane components of the composition of the present invention.
Any suitable solvents may be used in the coating composition including, for example, alcohols, aldehydes, ketones, glycol ethers, and esters. One preferred solvent is a mixture of methyl ethyl ketone and ethanol. The particular step at which solvent is added in the method of making the composition is not critical.
In one embodiment, the composition preferably also includes a surfactant, used as a flow-controlling agent for regulating film thickness and enhancing the cosmetic appearance of the coated article. One commonly available fluorosurfactant is Fluorad� FC-430, available from 3M of Saint Paul, Minn.
When the coating is applied to a substrate, the coating can be polymerized and hardened in an oven. Heat removes the blocking agent so that epoxy polymerization can take place.
The examples set forth below are intended for illustrative purposes and should not be construed as limiting the invention in any way.
1,000 grams of gamma-propylaminotriethoxysilane was added to 150 grams of water to form a mixture, which was heated to 95� F. (35� C.) and stirred for an hour. The temperature of the mixture reached approximately 176� F. (80� C.). The resultant solution was allowed to stand for at least two hours. This will be called Solution A.
A quantity of cyclohexanedimethylol diglycidyl ether was set aside and will be called Solution B.
A quantity of 100 grams of Fluorad� FC-430 fluorosurfactant, manufactured by 3M of Saint Paul, Minn., were dissolved in 900 grams of methyl ethyl ketone, and labeled Solution C.
A quantity of 1,000 grams of solution A was added to 256 grams of solution B to form a mixture. The mixture was heated with stirring to 127� F. (53� C.) and components were allowed to react for 10 minutes. The reaction was then quenched with the addition of a mixture of 1,500 grams of methyl ethyl ketone, 64 grams of Solution C and 570 grams of ethanol. The quenched mixture was cooled down to 50� F. (10� C.). Polycarbonate lenses were dip coated with the cooled mixture, held at 150� F. (66� C.) for 20 minutes, and cured for 4 hours in an oven at 250� F. (121� C.).
Adhesion was tested by ASTM D3359. Abrasion was tested by 5 strokes of a steel wool mass weighted with a 32-ounce weight. If no scratches are observed, the coating passed. The lenses were tested for adhesion and abrasion. The lenses displayed acceptable adhesion and abrasion. The lenses were dyed for five minutes in BPI Molecular Catalytic Black�, a dye from Brain Power, Inc., of Miami, Fla., and were found to have a total light transmission of 3%.
Solution A in these examples comprises the same Solution A used in the comparative examples, and Solution B comprises the same Solution B used in the comparative examples.
Solution C was made by combining 74.07 parts by weight of the hydrolyzed aminosilane of Solution A and 11.11 parts by weight deionized water with stirring. These were allowed to react overnight. The following morning, 14.82 parts by weight 2-propanol was added and the solution was allowed to react for three hours with stirring.
Solution D was made from 73.57 parts by weight methyltrimethoxysilane and 26.43 parts by weight deionized water with stirring. The solution was allowed to react overnight.
The coating solution was prepared by combining ingredients in their desired proportions in the following manner. Solutions C and D were combined in amounts sufficient to provide the proportions shown in the Tables and Examples. The additions were done in a manner as follows. The hydrolyzed aminosilane with 2-propanol and the epoxy (in this case, cyclohexanedimethylol diglycidyl ether) are combined with stirring, heated to 122� F. (50� C.), and held for 3.25 minutes. This is done by immediately removing the solution from heat when a temperature of 122� F. (50� C.) has been reached. At the end of 3.25 minutes, the temperature reached 135� F. (57� C.). After two minutes, the hydrolyzed methyltrimethoxysilane was added. After 3.25 minutes, the quench, which contains methyl ethyl ketone, ethanol, and Fluorad� FC-430 fluorosurfactant, is added. This mixture is allowed to mix at ambient conditions for about five minutes before cooling to 50� F. (10� C.). Lenses are coated with the composition when it has reached 50� F. (10� C.). The coated lenses are precured for 20 minutes at 180� F. (82� C.) and then cured for four hours at 250� F. (121� C.).
The following data result from a comparison of the composition of Example 3 from U.S. Pat. No. 5,786,032, with various amounts of the hydrolyzed methyltrimethoxysilane (as described above) added to the composition.
The molar ratio referred to in the following table of comparative examples is that of 3-aminopropyltriethoxysilane to methyltrimethoxysilane.
CR-39 is a registered trademark of PPG Industries, Pittsburgh, Pa.
The ability of the hydrocarbyltrihydrocarbyloxysilanes to provide the specific type and quality of properties with respect to retention of abrasion resistance, improved tintability and optical qualities was proven to be unique when numerous materials were attempted for use in the practice of the invention. To show this, the following list of unsuccessful attempts is shown:
As can be seen from this list, a wide variety of compositions thought to be compatible with the mar-resistant compositions of U.S. Pat. No. 5,786,032 were evaluated unsuccessfully. The fact that only a single class of additives that were tried provided acceptable results establishes the uniqueness of the materials found in the practice of the present invention.
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Fort Worth leaders unhappy that rider went to the extreme on bridge
City officials say they're studying ways to discourage people from using the West Seventh Street bridge for unintended purposes in light of a stunt cyclist riding over the bridge's arches Saturday afternoon.
"It is a beautiful and safe structure when used properly and for its intended purpose," Bill Begley, a city spokesman, said in a emailed statement Monday afternoon. "That said, we discourage residents to participate in risky behaviors like that of the BMX rider this weekend."
Professional BMX stunt rider Mat Olson told the Star-Telegram that he had contemplated the stunt since the bridge was being constructed and thought it would help get his name in the public.
"You can turn anything into an obstacle with a little bit of an imagination," said Olson, who performs with a professional stunt team at events like the Texas State Fair.
Begley emphasized that the bridge should not be used as a prop for stunts.
"The arches of the bridge were not designed for that purpose, and climbing, walking or riding a bicycle or skateboard on them is a dangerous endeavor," Begley said. "We are studying ways to reinforce that message, but in the meantime we encourage residents to use and enjoy the new structure safely and in the method it was designed and built for."
Fellow riders and friends assisted Olson by placing plywood supports in between the arches, and a professional film crew was on hand to record the feat. Travis Baker, a Fort Worth man who had been riding his bike when he saw a small crowd and stopped to investigate, recorded the stunt on his cellphone, which he shared with the Star-Telegram.
That video has since gone viral, and more than 60,000 people had viewed it on the Star-Telegram's YouTube account as of 4 p.m. Monday.
While the stunt has apparently garnered Olson the attention he craved, not everyone was pleased.
Olson said Fort Worth police were waiting for him at the end of the bridge as he finished. He said he was given a warning by the officers.
Begley said general traffic laws apply to bicyclists unless specifically exempted.
For example, he said, the Texas Transportation Code requires a bike rider to generally ride as near as practicable to the edge of the roadway.
"The edge of the roadway doesn't include the arch support of the roadway," Begley said. "But police officers have discretion to write or not write tickets, and these officers chose to not write a ticket."
Local Spotlight
Join the Discussion
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subset: commoncrawl


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Instant Confirmation
Sandra & Len, the owners, have refurbished the property revealing many original features. Accommodation consists of 4 generous double/twin/single en suite bedrooms all with large showers and sumptuous superking sized double beds.
Banbury, in North Oxfordshire, is a thriving town, well known for its popular nursery rhyme 'Ride a Cock Horse to Banbury Cross'.
Banbury has many new shops and a wide selection of restaurants to meet all budgets and tastes. Markets are held every Thursday and Saturday with a Farmers Market being held on the 1st Friday of every month.
An ideal base for business as Banbury is just off the M40, it is also a very good centre for pleasure, exploring the surrounding areas by car, train, bicycle or on foot. We also have many lovely National Trust houses in the area which are all easily accessable by car or bus.
A minimum of 48 hours notice is required for all cancellations. Deposit is non refundable within 48 hours.
Electric car charging station available for our guests to recharge their car whilst staying at Treetops
Treetops Guest House


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Samuel Ray Griffin, 55, of Pathfork, passed away Wednesday, May 14, 2014, at the Harlan App. Reg. Hospital following a long illness. Born June 13, 1958 in Pathfork, he had lived here all of his life. Samuel worked as a Security Guard for American Security and believed in the Baptist faith.
He was preceded in death by his parents, Dan Griffin and Cassie Johnson Griffin; three brothers, Robert Griffin, Dan Griffin, Jr., Harmon Griffin; and one grandson, Lucas Bradley Griffin.
Left to mourn his passing is his loving wife of 34 years, Sharon Earls Griffin, Pathfork; son and daughter-in-law, Sam and Amy Griffin, Pathfork; three sisters, Cassie Stewart and husband Jimmy and Mildred Hensley all of Pathfork and Pamela Atkins, Corbin, KY; three brothers, Jim Griffin and wife, Sylvia; Joe Griffin and wife, Barbara; Paul Griffin and wife, Tammy, all of Pathfork.
Also surviving are three grandchildren, Robert Griffin, Middlesboro; and Matthew and Kelsey Gray, Pathfork and host of nieces, nephews, cousins and friends.
Visitation will be after 4 p.m. Sunday at the Pathfork Baptist Church.
Funeral services will be 1 p.m. Monday, May 19, 2014, at the church with Reverend James Green and Reverend J.C. Craig officiating.
Burial will be in the Tackett Hill Cemetery, Blackmont, KY.
Friends and family will serve as pallbearers.
Loyall Funeral Home is in charge of his arrangements.


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On select Tuesdays, Cameras@Lembeh Resort – the first and only dedicated photo & video center in Lembeh Strait with full time on site photo pro – will feature Tips and Techniques by Photo Pro Sascha Janson. Sascha will offer up …Read More
Posts Tagged 'Nudibranchs'
Here's the second part of the March of the Nudis. There are lots of different species of nudis and sea slugs here in Lembeh. Check them all out and see how many you recognise!Read More
This March is all about nudis, so here's the first part featuring both, common and rare nudibranchs of the Lembeh Strait. We have a lot of different species here. Have you seen all of these?Read More
Attention divers: some very unusual, weird and beautiful critters inside! A sea moth, tozeuma shrimp with eggs peeking out (can you spot them?), a tambja nudibranch with a surprise hitch-hiker on its backside, a close-up of the startlingly beautiful sand-diver's …Read More
Our Photo Pro is back with a new episode of critter awesomeness for you. Watch for incredible close-ups of charismatic animals such as the blue-ring octopus, ornate goby, and juvenile star puffer fish – you can see their eyes moving, …Read More
The first video of the year shows some of the incredible highlights of 2014. It was hard to pick the scenes because there was so much great stuff, but here are some memorable moments for you to enjoy. Meanwhile, in …Read More
Each trip to Lembeh Resort and diving with Critters@Lembeh is a new experience. The resort and dive center is constantly improving their facilities to make their guests feel comfortable. Returning to Lembeh Resort and …Read More
Who is Steve Fish? Yes, his last name really is Fish! If you are a frequent traveler to Indonesia you may have heard of Steve. Although Steve has …Read More
It's an underwater party and all your favorite critters are there – anemone fish, blue-ringed octopus, ornate ghost pipefish with eggs (yes, children are welcome at this party!), various frogfishes and a graceful free-swimming ribbon eel. Also keep your eyes peeled …Read More
We have been unusually fortunate these past few weeks in Lembeh with many sightings of mating blue rings, a beautiful red weedy rhinopias, and baby flamboyant cuttlefishes hatching, all of which are beautifully captured in this week's episode. As an extra cute …Read More
Awesome dive operation
All staff is worried about how we are doing, if everything is how we expected. They are really interested in making our experience as good as possible.The most amazing thing is the photography support, which is outstanding.
That was …
Have you ever seen a frogfish do the splits? Harlequin shrimps, ghost pipefish and an extremely cute baby coconut octopus in a shell round out this latest, greatest Critters of the Lembeh Strait episode!Read More
Siren Song of the Mantis Temptress
For those of you who have been diving in Lembeh Strait, maybe you already know how crazy-powerful and violent mantis shrimps are, either spearing or …Read More
The last weeks were pretty "HAIRY" – watch our latest episode to find out what else happened in the Strait.Read More
Some of the highlights of the latest episode of "Critters of the Lembeh Strait" include hairy frogfish, some of them in pairs, another mototi octopus and the tiny Doto ussi Ortea (a nudibranch). Also keep an eye out for the …Read More
Finally, after almost 2 years of diving the Lembeh Strait and not seeing this critter with my own eyes, I got to see it and got some footage: THE POISON OCELLATE OCTOPUS (Octopus mototi). As if that wasn't enough, a …Read More
Immerse yourself in the beauty of Lembeh scuba diving by watching our in-house Photo Pro's most recent video: catch a glimpse of how a porcelain crab filters the currents for a yummy snack and at the end of the video, …Read More
Incredible experience! Excellent dives! One of the best dive centers at Lembeh! I definitely come back soon!
Check out Ricardo Castillo's on our website for more of his photos.
Read More
Our first ever workshop focused on capturing haunting images of the wide variety of nudibranchs that thrive here in Lembeh Strait was a huge success! Participants and staff enjoyed learning about nudibranchs and their behaviour with Dr. David Behrens, one …Read More
How often is it that you experience something remarkable, do it again, and it's as amazing or even more amazing than it was the first time? Traveling halfway around the world to Lembeh Resort and completing my second stay there, …Read More
Doris Vierkötter from Alam Batu Beach Bungalow Resort, Bali and Danny Charlton from Critters@Lembeh get together each year as friends. Oddly enough their meeting place is not near their respective tropical paradises but in cold Dusseldorf, Germany for the BOOT …Read More
Tracey Winholt and her husband recently had a great trip at Lembeh Resort and Critters@Lembeh. See what Tracey has to say:
I can't say enough about the convenience and beauty of this resort. It is definitely built for divers! The meals were …Read More
Our Photo Pro Sascha Janson put together this collection of fresh critters from last week. Watch for the different varieties of nudibranchs, a common lion fish moving its spines in a unique way, and a mantis shrimp swimming in the water column to …Read More
Our Photo-Pro, Steve Fish, recently purchased a new rental DSLR rig and yesterday was his "test run". Since Steve started the photo center in Lembeh, he has only shot video using continuous light which allows him to shoot both …Read More
Welcome to episode 26 of Fresh Critters At Lembeh. This was an exceptionally good week for crustaceans with cool shrimps, crabs and squat lobsters showing up everywhere. Nudibranchs are still hot and once again we have hatching Flamboyant …Read More
Welcome to episode 25 of Fresh Critters At Lembeh. Diving is still hot for Nudis, Crustaceans, Frogfish (four Hairy's today!) and of course, Cephalopods are still plentiful.Read More
November was a terrific month of diving at Lembeh Resort. Our guides were at their best and found loads of rare and exotic creatures. It wasn't just a good month for critters though, it was also a good …Read More
This week we had three boats of divers spot Blue Ring Octopus. One boat saw two Blue Rings, and the other two boats also saw Mimic Octopus, Algae Octopus and a Wonderpus with eggs! It was also a …Read More
This is our third time to Lembeh Resort in the past year. The hotel and dive staff make it seem like a second home for us. Everyone greets us by name and welcomes us back. …Read More
Our new weekly web video is now online. This wee, in episode 17 of Fresh Critters at Lembeh, we once again have loads of fantastic creatures. Cephalopods are still hot, especially at Aer Bajo, and some rare Nudibranchs …Read More


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Global Dossier Task Force Meeting in Suzhou, China
On January 21 and 22, 2015, the 2nd Global Dossier Task Force (GDTF) Meeting was held in Suzhou, China. The purpose of the meeting was for the IP5 Offices (JPO, USPTO, EPO, KIPO, and SIPO), WIPO, and IP user groups (JIPA, AIPLA, IPO, Business Europe, KINPA, and PPAC) to gather to discuss the future plan for the Global Dossier, while having user needs reflected therein.
- JIPA Representatives to Vietnam and Indonesia
- Int'l Committee trip to Singapore and The Philippines
- Greetings for the New Year 2015
- JIPA Trademark Committee: Participation in the 3rd TM5 Meeting
- Int'l Committee trip to Istanbul, Turkey
- Int'l Committee trip to UAE and Saudi Arabia
- 2014 Opinion Exchange with Patent Examiners from India and Brazil
- Participation in the 21st Session of the WIPO-SCP, Switzerland
- Attendance as JIPA Speakers at WIPO Meetings in Morocco, Zimbabwe and South Africa - WIPO Japan Funds -
Last Update 2015/03/13 16:33


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Thunderbird Inn - Mackinaw City, Straits of Mackinac
146 Old Us 31 - Straits of Mackinac1-877-662-6988
Searching for convenient motel rates in Mackinaw City? Take a look at Thunderbird Inn!
This Mackinaw City motel offers an indoor pool and laundry facilities.
Knowledgeable staff available at the front desk 24 hours-a-day and can provide tour/ticket assistance, express check-in and express check-out. Planning a meeting? This motel has a meeting room, as well as a business center. Free Wi-Fi is provided. Coffee is available in the lobby so you can sit back and relax with a hot cup. Other amenities include a ferry terminal shuttle.
We show TripAdvisor reviews for new Venere hotels that haven't been reviewed yet
Check Availability at Thunderbird Inn
Breakfast at Thunderbird Inn
A free hot/cold buffet breakfast is available between 6:30 AM and 9 AM.
Facilities at Thunderbird Inn
- Business Center
- Meeting Room
- Dogs allowed
- Entire property is non-smoking
- Laundry room
- Indoor swimming pool
- Internet/Email services
- City tour
- Front desk - 24 hour
- Shuttle service
- Free parking
Know before you go
- A resort fee is included in the total price displayed.
- Children 12 years old and younger stay free when occupying the parent or guardian's room, using existing bedding.
- The property has connecting/adjoining rooms, which are subject to availability and can be requested by contacting the property using the number on the booking confirmation.
- The property allows pets in specific rooms only and has other pet restrictions (surcharges apply and can be found in the Fees section). Guests can arrange to bring pets by contacting the property directly, using the contact information on the booking confirmation.
Check-in: after 4 PM.
Check-out: before 11 AM.
PolicyExtra-person charges may apply and vary depending on hotel policy.
Government-issued photo identification and a credit card or cash deposit are required at check-in for incidental charges.
Special requests are subject to availability upon check-in and may incur additional charges. Special requests cannot be guaranteed.
City tax and/or any other fees charged by the hotel
The following fees and deposits are charged by the property at time of service, check-in, or check-out.
- Pet fee: USD 25.00 per accommodation, per stay
- Crib (infant bed) fee: USD 10.00 per stay
- Rollaway bed fee: USD 10 per stay
The above list may not be comprehensive. Fees and deposits may not include tax and are subject to change.
Renovation and closuresThe following facilities are closed seasonally each year. They will be closed from 13 October to 15 May:
- Swimming pool
Thunderbird Inn is also known as
Best Western Mackinaw City
Mackinaw City Best Western
Best Western Thunderbird Hotel
Room Details
Thunderbird Inn has 48 guest rooms, all with climate control and free local calls. Cable TV channels offer entertainment at the end of a busy day. Corporate travelers visiting the Mackinaw City area will benefit from free wireless high-speed Internet access as well as phones. A good night's sleep in pillowtop mattresses will have visitors waking up refreshed and well-rested throughout their holiday or business trip.
Private bathrooms are outfitted with shower/tub combinations and complimentary toiletries. Refrigerators, irons/ironing boards, coffee/tea makers and hair dryers are supplied in each room to facilitate basic travel needs. Additional comforts include air conditioning.
Accommodation Services
- Telephone
- Air conditioning
- Mini fridge
- Coffee and tea maker
- Hairdryer in each room
- In-room ironing facilities
- Cable TV
- Individually controlled air conditioning
- Wireless Internet access
Distances from Thunderbird InnAnimal Tracks Adventure Golf - 1 km / 0.6 mi
Mackinaw Manor Haunted Mansion - 1.1 km / 0.7 mi
Spy Quest Laser Maze - 1.1 km / 0.7 mi
Mackinaw Bridge Museum - 1.2 km / 0.8 mi
Icebreaker Mackinaw Maritime Museum - 1.3 km / 0.8 mi
Mackinaw City Dock - 1.3 km / 0.8 mi
Wawatam Park - 1.5 km / 0.9 mi
Old Mackinac Point Lighthouse - 1.8 km / 1.1 mi
Colonial Michilimackinac Park - 1.8 km / 1.1 mi
Mackinac Bridge - 1.9 km / 1.2 mi
Jack Pine Lumberjack Show - 2.6 km / 1.6 mi
Mackinaw Heritage Village - 3.3 km / 2 mi
McGulpin Point Lighthouse - 3.8 km / 2.4 mi
Headlands International Dark Sky Park - 4.1 km / 2.5 mi
Historic Mill Creek Discovery Park - 5.3 km / 3.3 mi
The preferred airport for Thunderbird Inn is Pellston, MI (PLN-Pellston Regional) - 22.6 km / 14 mi.
Distances are calculated in a straight line from the property's location to the point of interest or airport and may not reflect actual travel distance.
Distances are displayed to the nearest 0.1 mile and kilometer.
Transportation services Thunderbird Inn
- Shuttle service
- Free parking
We have the accommodation you need, all over the world
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- • Park Hotel Bad Salzig - Boppard, Germany
- • Comfort Inn Saint Pierre - Paris, France
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- • Holiday Inn Express Pittsburgh North - Pittsburgh, USA
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- • Six-Fours-les-Plages Hotels, France
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- • Totnes Hotels, United Kingdom
- • Castiglione Messer Raimondo Hotels, Italy
- • Laugarvatn Hotels, Iceland


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NPR Story
Sandy's Effects 'Staggering' To New York's Economy
Originally published on Fri November 9, 2012 12:46 pm
The governor of New York, Andrew Cuomo, also held a press conference yesterday, and gave a warning that Sandy could end up costing his state $33 billion in economic damage, which could worsen the state's already-perilous fiscal situation.
NPR's Jim Zarroli reports.
JIM ZARROLI, BYLINE: Cuomo said the initial estimates are that the storm will cost the region $50 billion in lost economic activity and infrastructure damage. And he said two-thirds of that will be borne by New York.
GOVERNOR ANDREW CUOMO: That is a staggering number, especially with the financial situation that we've been in.
ZARROLI: Like many states New York was left with massive fiscal problems as a result of the economic slowdown. Cuomo said yesterday that the state had closed a $10 billion budget gap over the past two years - a huge amount of money.
CUOMO: We're looking at an additional $1 billion deficit on the state side, maybe higher after what's happened.
ZARROLI: The situation is much the same in New Jersey. Tax revenues were already less than projected before the storm hit. In the aftermath of Sandy economic activity is likely to slow further, which can bring down revenues even more.
Weeks after Hurricane Katrina, Louisiana was forced to make sharp cuts in state spending, but the state received a large infusion of federal money which eventually offset the losses.
New Jersey Governor Chris Christie has said federal spending should eventually alleviate any fiscal problems his state faces as a result of the storm. Christie notes that many residents and businesses will get payouts from their insurance companies which will also help ease the state's economic pain.
Jim Zarroli, NPR News. Transcript provided by NPR, Copyright NPR.


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Download I Too Had A Love Story Read Online from our fatest mirrorSegal - Love Story (text) - OTSM-TRIZ Technologies Center
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God's Love in Creation ... as you read Genesis 1 and 2, make the creation story personal to yourself. ... for animals too; ...
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Date added: March 5, 2015 - Views: 1
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Tyndale House Publishers, Inc. Carol Stream, Illinois While the World Watched A Birmingham Bombing Survivor Comes of Age during the Civil Rights Movement
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Ghost of the Lagoon ... story he had not heard before. The old man's voice dropped to a whisper. ... love to win that reward!"
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Date added: December 25, 2011 - Views: 78
Responding to Poetry Through Writing is an excerpt from Writing ... My story on Monday ... They had read some poems about grandmas which had spurred them on to talk ...
Date added: October 15, 2011 - Views: 16
I love my old pony, my calico pony, If you want to buy him, ... This little piggie had roast beef This little piggie had none This little piggie went wee, ...
Date added: May 14, 2012 - Views: 5
Albert Camus . THE PLAGUE ... Rieux remembered having read somewhere that the plague spared weak constitutions and chose its victims chiefly among ... too, had to ...
Date added: December 25, 2012 - Views: 259
"Our first big event for Family Reading Week was a milestone too, as we had about 70 ... • To record an original story and illustration ... children love to read
Date added: May 12, 2013 - Views: 3
... Every Hero Has a Story Picture Books Page 1 of 14 ... toward impatience and love of snow caused him to lose this tail. ... she tells how she too, had
Date added: October 24, 2011 - Views: 14
Dillard/An American Childhood . of words. ... they had been throwing snowballs. ... too, for I had, ...
Date added: May 19, 2012 - Views: 5
Short Story by Cynthia Rylant ... As you read "A Crush," keep these questions in mind ... Dolores had never been in love, nor had anyone ever been in love with
Date added: December 29, 2013 - Views: 5
Theodore Boone, Kid Lawyer ... But it has a love story, adventure ... unexpected conclusion which was a delight for me to read. This story was written for 7th ...
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... Whoever you Are by Mem ... • Read the story so all children can see the pictures ... laugh, hurts, joys, love, pain, and blood. • Record the words in ...
Date added: February 4, 2013 - Views: 9
The Diamond as Big as the Ritz ... I've never had a boy in love with me in all ... and he would love her until the day he was too old for loving−−but he could not ...
Date added: November 16, 2013 - Views: 1
By Flannery O'Connor ... to love em if you want em to work for you. When they come in the ... She had read that pigs were the most intelligent
Date added: May 18, 2012 - Views: 13


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Information, Insight and Analysis for the Global Business of Interactive Gaming
Receive the latest iGaming news
The world famous Grand National racing festival will soon be upon UK betting enthusiasts so iGaming Business and Blueclaw decided to look at the search presence of operators and affiliates within that segment.
Virtual games specialist Kiron Interactive has been awarded a remote supplier's licence by the UK Gambling Commission.
Mobile and tablet casino operator LeoVegas Gaming has opted to sign up with games development and content marketplace Odobo.
Payment solutions provider Global Payments has set its sights on expanding its international ecommerce business after completing the acquisition of payment gateway Realex Payments.
Gaming operator Mansion Group has confirmed that its current chief operating officer Sagi Lahav is to replace Guy Gussarsky as chief executive officer.
Poker Players' Alliance says RAWA bill should be rejected for good while anti-igaming proponents repeat claims of dangers linked to online gambling.
CEO Anna Sainsbury explains positives of geolocation services and debunks claims of igaming opponents in Washington DC presentation.
Esports attract huge audiences and for the igaming sector offer operators and betting platforms the possibility of promoting peer-to-peer bets. However, beyond the opportunities for online betting entrepreneurs to harness the potential offered by these huge player numbers, it is worth wondering whether e-sports can enter the commercial mainstream.
Sweden remains a key market for Nordic operators such as Unibet, Betsson and Mr Green and in many ways offers an optimal environment: minimal regulation and taxation and a population keen on gambling. However, those companies appear reluctant to divulge much detail about their activities there, but with regulation at least 18 months off, will some investors be tempted to take a punt early on one of those operators?
Gaimerz launched in August of last year as a platform that matches up video gamers to play against one another for money or free-play. The peer-to-peer betting model has been tried before but with the profile of esports on the rise and the potential of huge liquidity numbers, iGaming Business spoke with Gaimerz co-founder Martyn Denney about why he believes his company combines flexibility and transparency and has the right model at the right time.
Spain's licensed betting operators expect to have recorded some €20m in stakes during last Sunday's Barcelona-Real Madrid clasico, but for former Juego Online chief executive Dina Niron, operators are still waiting for the roll out of online slots later this year.
bwin party's results announcement yesterday were not overly positive but at least the group can fall back on its sportsbook platform to turn things round. However, all the hard work that is going on indoors needs to translate into performance.
William Hill and Ladbrokes share some similarities but when it comes to online betting and gaming, they move in totally different circles. And following its results announcement that it would pay a dividend in 2015 without increasing online marketing spend, Ladbrokes has its work cut out if it wants to make a dent in its arch-rival's lead. Scott Longley goes through the figures.


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Serra Pelada is a high grade gold-platinum-palladium deposit located in the mineral and mining prolific Carajas region in Para State, northern Brazil and is operated by Colossus Minerals Inc. (TSX:CSI). The existing infrastructure and accessibility to the site are excellent due to the close proximity of a number of major mines. During the 1980's, Serra Pelada hosted the largest ever gold rush in Latin America with up to 80,000 artisanal miners producing 2 million ounces of gold, plus platinum and palladium, from a hand dug open pit.
Serra Pelada Royalty
Sandstorm has a 0.4% net smelter returns royalty ("NSR") on the production from Serra Pelada. Sandstorm previously held a palladium stream on the mine which was converted to a NSR and common shares during a restructuring of Colossus Minerals.


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Search Results for 'PRP Flexo releases new estimating program'
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Published September 25, 2012
Customers can now generate their own estimates, 24 hours a day, seven days a week. Read More »
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With the increased demand for environmentally sustainable consumables, the all important flexo plate continues to evolve. Read More »
By Steve Katz, Editor
Published November 21, 2013
Improved technology has an increasing number of converters adding digital presses. Read More »
Published July 10, 2012
Labelexpo Americas 2012 takes place September 11-13 at the Donald E. Stephens Convention Center in Rosemont, IL, USA, just outside of Chicago. Read More »
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Care, handling and the performance of a new generation of these critical press components. Read More »
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Confidence and optimism permeated the halls of the show's largest edition to date. Read More »
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The show of the year featured evolutionary technologies for converters eager to expand into new markets. Read More »


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Erik and Mallory Arthun
Jerry and Bobbie Graham of Fifty Lakes, Minn., and Dean and Peggy Arthun of Roscoe, Mont., are pleased to announce the marriage of their children, Mallory Jo Graham and Dr. Erik Norden Arthun, who were married on Sunday, May 27, 2012, at Breezy Point Resort in Breezy Point.
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Reader comments are listed below. Comments are currently closed and new comments are no longer being accepted.
Does the economist employ any editors? It appears that you may have used one of your "lowliest" authors to compose this poorly written article.
I am bothered by some references in the article of employees being referred to as reckless and lowliest. I find these comments to be rather insensitive to a business that prides itself with a theme of TEAM. Also, the article focuses around the Lincolnshire, IL plant yet the picture is from another Honeywell plant. The stock chart is not even correct.
"Even the lowliest worker is expected each month to come up with two implementable ideas for doing things better." I am also troubled by the use of the words "lowliest worker" in this statement as it may lead some people to believe that the company views individuals in lower-paying positions as a group of workers who do not typically contribute or are incapable of contributing value added ideas or suggestions, when in reality the exact opposite is true. Honeywell is an organization with a very diverse workforce where employees from various backgrounds and cultures who have different values and beliefs come together as a team to create the entire organization. Those differences are acknowledged and celebrated by Honeywell and are a direct result of improved creativity and innovative problem solving and is why we are where we are today.
Honeywell Aerospace is notorious for age discrimination and treating their older engineers very badly. They might be the new darling of Wall St but they are a dreadful company to work for.
That is indeed one of the most poorly-researched and written articles I read on Economist. On my personal scale it's about 4% of a proper case study, if Economist wanted to talk about successful tranformaton.
Great success story. I wasn't sure what Lean Six Sigma was so I did a bit of research and found this helpful resource: http://www.goleansixsigma.com/what-is-lean-six-sigma/
While America is becoming just consuming country, Honeywell is solid American manuafacturer. That's why Cote is on Obama's one of the advisory committee. Without manufacturing and export, US might end us like Greece. SO what world needs is more companies like Honeywell.
Just a technical remark:
You stated that "[Honeywell] had been left disorientated by a 2001 ruling of the European Union, on antitrust grounds, to forbid its planned acquisition by General Electric (GE)".
In fact, the merger was blocked by the European Commission as the antitrust authority of the European Union.
For a deeper look see pages 78 f.:
I have no idea how this company can be profiled without discussing this suit: http://techcrunch.com/2012/02/07/honeywell-vs-nest-when-the-establishmen...
Yes, understood. I was responding on LinkedIn. I'll provide that reference.
No one here knows who you are, so how do you expect them to find your LinkedIn reading list?
My friends at Honeywell demonstrate NA manufacturing is alive and well with a myriad of ways to be competitive. My favored Honeywell lesson learned is a major part of the HOS system - Sales and Operations Planning(S & OP)! For anyone interested - the book is on my LinkedIn reading list.
Hi Gregger,
my Linkedin is
http://www.linkedin.com/in/richardhlucas Please send me a link invite.
This article was very interesting. I am sanding it to my business partners, start ups and management teams.
I don't agree with the idea its wrong to use words like "lowly". We all know that the CFO, CMO CEO are higher status jobs than the marketing intern.. The important lesson is that Honeywell is interested in the low lever staff not that they are looked down on.
The Economist's use of plain blunt English is a huge asset.
I fully agree with the comments and points raised by A Loyal Employee. A resolve of issues and many manufacturing problems are implemented and resolved ultimately at the factory floor level by the work of many diverse employees within honeywell who pocess great skills, experience and knowlege for this to happen in the first place which I would regard as the most Important part of the six sigma process!! . The reference made by this article of this person as a "lowest worker" and Not mentioned as part of a team are a bit insensitive.
Politics in New Zealand: A Winston win
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Harry Reid's retirement: Republicans get their wish
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A collection of news and information related to Karate published by this site and its partners.
Top Karate Articles
Displaying items 78-79
First, Obama gets a Nobel Peace Prize for nothing; now, a tae kwon do black belt after zero kicksStory | Nov 19, 2009And not even a medium bow for receiving it....
Halloween scenes without the screamsStory | Oct 7, 2004 | 4:48 AMSome people just don't crave scary movies come Halloween. Have no fear, there is a wide variety of films out there that will still set the mood for the spooky holiday, but won't leave viewers trembling under the covers into the wee hours of Nov. 1. "A...


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a combination of smooth and silky generally used to define the coat of a cat.
Damn that cat is smilky
by kingofthieves February 17, 2008
2 more definitions
Top Definition
Excessively large, and usually sloppy, tities. Although traditionally white in color, "Smilkies" can come in all flavors (e.g. Chocolate smilkies)
Hey, check out those smilkies on Lindsay Lohan
by Lindsay Lohan November 03, 2004
Not just smooth and silky, but smilky.
J: I was waxing this fine poon last night, dizamn that shit was smilky.
by duplikit January 29, 2003


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GOP Makes outdated video game to gain support for senate andidatesUPDATED 4:03 PM EDT Aug 26, 2014
The National Republican Senatorial Committee is trying to get support for candidates with a video game that looks so old, Abe Lincoln could have played it. Mara Montalbano (@maramontalbano) shows us.
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Doctor insights on:
Snorting Clonazepam 1mg
I took 7, 1mg clonazepams over a span of 8 days. I took my last one last night (Thurs) and I have a UA test on tues. Will it show?
No: Half life of Clonazepam is 12 hours. If you can help it please do not take Clonazepam any more. ...Read moreGet help now ›
Clonazepam (Definition)
Klonopin (clonazepam) belongs to a class of medications called benzodiazepines. They are also referred to as sedative-hypnotics & anxiolytics. These medications are used for a variety of indications to include anxiety, insomnia, muscle spasm, seizure, & alcohol withdrawal. All benzodiazepines including Clonazepam are potentially habit forming. Alcohol should be ...Read more
What medications do u recommend for clonazepam withdrawal?..Im taking 1mg per day, recently down to .75 mg ..Thx
A ways to go, yet: You have a slow and gradual way to go. Your physician, who knows you and your condition best, is the best one to develop a taper schedule with you. Compounding pharmacies may be needed to prepare certain dosing increments. Klonopin is quite potent, and even small reductions can result in symptoms. Hopefully your basic anxiety is under good control with non-pharmaceutical methods. Good luck! ...Read moreGet help now ›
How fast can I stop taking 1mg of clonazepam if I have been taking it for 1year for anxiety?
Taper: I would taper it over a couple of weeks. Take 3/4 for 5 days, 1/2 for 5 days, 1/4 for 5 days and then stop. That will prevent any physical withdrawal. Of more concern would be recurrence of the underlying anxiety. Many antidepressants work well for anxiety (e.g. Paxil, mirtazepine, and effexor). ...Read moreGet help now ›
I'm on Clonazepam 1mg and it makes me feel tired throughout the day. I do not take it every day. Would a shorter lasting benzo be a good option?
Not necessarily: Clonazepam has more than it's fair share of sedating side effects. Valium has less even though it is even longer acting. Mos of the shorter acting agents are also less sedating but if you are taking the pills regularly and not as needed, you may not want to sacrifice stability ...Read moreGet help now ›
Would taking 1mg or 2mg of clonazepam help with my bad social anxiety?
Can, not best: Clonazepam is usually too sedating for daytime use. In addition to psychotherapy, you usually start out with a serotonin reuptake inhibitor (ssri) (like zoloft, prozac) and since it takes at least 3 weeks for the ssri to start to work, at the same time, you may start with a less sedating tranquilizer, like Ativan (lorazepam) or xanax (alprazolam) to help until the ssri is working enough to stop it. ...Read moreGet help now ›
Clonazepam and moods. I am wondering if taking 1mg-2mg per day would be possible considering the effects it has on moods (depressive)?
I am not sure what : You are asking. You should not take Klonopin unless it is prescribed for a legitimate anxiety disorder. The dose you are talking about is average. . While it is a central nervous system depressant, that does not mean that it is a mood depressant. I have seen reports of that, but they have to be rare because in clinical practice i just don't encounter it. At high doses that are used in europe iit is actually used as a mood stabilizerfor bipolar depression and mania.A central nervous system depressant is a medication that can potentially suppress the breathing drive and cause difficulties in that regard.It is not a reference to mood depressing effects.Best wishes. Make sure that you are also involved in therapy. ...Read moreGet help now ›
If i have been on 1mg of clonazepam for 4 months,does tapering down to 0.5mg seem like normal protocol?
Yes!: If you have been taking 1mg per day only the reducing to .5 mg for a few weeks is a reasonable way to taper your dose! However, it's important to discuss this with the physician who prescribed this for you to decide if indeed a dose reduction is really needed ...Read moreGet help now ›
How long does it take 1mg of clonazepam to exit your urine for a drug test?
Benzodiazepines: One to six weeks. It varies widely for a variety of reasons. If there has been more than a one time use i caution people that benzos stay positive for weeks not just one week. ...Read moreGet help now ›
Taking clonazepam for 1 month, 1mg twice a day. Some days three times. Last dose was 1/29 in the evening when can I drink alcohol?
No: This is a long lasting medication. I would wait ten days. ...Read moreGet help now ›
Diagnosed with occipital nueralga, prescribed norco for pain, also taking clonazepam 1mg. Is it safe to take together or spaced apart?
Depends on tolerance: And on how many norco. Starting doses of Clonazepam are in the 0.25- 0.5 mg range, so 1 mg is a hefty dose for this very potent drug. It takes Klonopin about 2 hours to peak, and hydrocodone peaks in an hour or less, so i would time the doses to not have the peaks overlap. There are effective drugs for neuropathic pain (like gabapentin, pregabilin, antidepressants) that don't get you "hooked.". ...Read moreGet help now ›
Klonopin (Definition)
Klonopin is a long-acting benzodiazepine which is a kind of sleep-inducing drug (anti-anxiety drug, psychiatric drug) and a blood pressure drug which is a ...Read more
Flumazenil (Definition)
Flumazenil is a long-acting benzodiazepine which is a kind of sleep-inducing drug ...Read more
- Talk to a doctor live online for free
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Registration takes less than 1 minute.
The commissioner's new term runs through June 30, 2018.
Top executives described initiatives to improve flow of cargo off docks at the nation's two largest ports during the TPM conference in Long Beach.
Speaking to an LA Chamber event in Washington, the official who brokered the Feb. 23 labor deal said LA Mayor Garcetti and Port Director Seroka were instrumental in solving the crisis-level contract talks.
The German ocean carrier said its financial results were impacted by costs from merger with Chilean liner CSAV.
ConAgra and Lululemon said they expect shipment delays for several more months as a result of West Coast port congestion.
The new container service will connect ports in China, Taiwan and South Korea with Mexico, Colombia, Peru and Chile.


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You should be able to find many good places to eat on this strip. Having a car makes getting around easy, but driver beware. Trinidad drivers are nuts!
If you own or manage Western Main Road, register now for free tools to enhance your listing, attract new reviews, and respond to reviewers.


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Astrobiologist Receives Paleontological Society MedalJanuary 3, 2013 / Posted by: Daniella Scalice
Please join the NASA Astrobiology Program in congratulating Bill Schopf on receiving the Paleontological Society Medal, the most prestigious honor bestowed by the Paleontological Society. He received the honor on November 4, 2012, at the Geological Society of America's annual meeting. A member of the NAI for over ten years, Schopf is Professor of Paleobiology in the Department of Earth and Space Sciences at UCLA, and the author of Cradle of Life: The Discovery of Earth's Earliest Fossils.
- A Robotic Sentinel to Monitor Remote Lakes
- SAM's First Wet Chemistry Experiment
- Curiosity Finds Biologically Useful Nitrogen
- FameLab: Looking Ahead to Stony Brook
- Linking Supernovae and Planet Formation
- Titan's Atmosphere Created as Gases Escaped Core
- Astrobiologists Named Geochemistry Fellows
- Chris Reinhard, 2015 Alfred P. Sloan Foundation Fellow
- Mars Once Had More Water Than Earth's Arctic Ocean
- NASA Ames Reproduces the Building Blocks of Life in Laboratory


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Click here to print the obituary below
Norma Pauline Kliewer Dick Loving wife, mother, grandmother, great grandmother passed away in the early hours on Februaury 11, 2013. She was born in Reedley, Ca on November 19, 1930, to Paul and Caroline Kliewer. She was a retired administrator for Clovis Unified Schools, where she worked for 28 years. During her career as an educator, Norma presided as California Reading Association President from 1975-1976. After retirement, she founded the Library Media Credential / Masters Program at Fresno Pacific University. Her passion for education inspired many. She was an outstanding educator and received many honors and awards for her contributions to reading literacy. She was a member of the Fresno First Baptist Church family for over 50 years. She is survived by her husband Don of 63 years, Carol and Robert Vix of Minot, North Dakota, Rebecca and Dan Skaling of San Dimas, Kathleen and Mark Condie of Visalia, five grandchildren and eight great-grandchildren. She was preceded in death by her parents and sisters, Josephine Kroeker and Dorothy Kliewer. Memorial Service to be held at 1:00 Wednesday, February 20, 2013 at Fresno First Baptist Church, 1400 E. Saginaw. Remembrances can be made to the FPU Norma P. Dick Scholarship Fund at Fresno Pacific University 1717 S. Chestnut Ave., Fresno California, 93702-4709, or online at
to_give. Condolences may be offered at
Arrangements by Miller Memorial Chapel.
Funeral Home
Miller Memorial Chapel
1120 West Goshen Ave
Visalia, CA 93291
(559) 732-8371
Published in Visalia Times-Delta and Tulare Adv-Register on Feb. 16, 2013