text:
|N·mero de publicaci¾n
|Tipo de publicaci¾n
|N·mero de solicitud
|Fecha de publicaci¾n
|11 Dic 2001
|Fecha de presentaci¾n
|6 Feb 2001
|Fecha de prioridad
|22 Dic 1998
|Tambiķn publicado como
|N·mero de publicaci¾n
|Ulrich B. Holeschovsky, Jeffrey L. Robbins, Harry Stefanou, Leah Langsdorf, David Gibala, Robert R. Pollock
|Cesionario original
|Bayer Antwerp N.V.
|Exportar cita
|BiBTeX, EndNote, RefMan
|Citas de patentes (12), Citada por (17), Clasificaciones (19), Eventos legales (3)
|Enlaces externos: USPTO, Cesi¾n de USPTO, Espacenet
This is a divisional of copending application Ser. No. 09/219,166 filed on Dec. 22, 1998.
The present invention pertains to a process for preparing tufted carpeting in which polyurethane adhesives are used, and to a process where the curing of the adhesive-coated carpet may be achieved face up.
Carpets are generally produced by tufting carpet yarns into a primary backing, the tufts being secured in the primary backing through use of a "precoat" or "tuft bind" adhesive. The greige good thus prepared may optionally be coated with adhesive and secured to a secondary backing, generally of polypropylene or jute. Key properties of the carpeting produced by these processes are tuft bind, the strength required to pull tufts from the primary backing, and delamination strength, the force required to separate the secondary backing from the carpet.
High values of tuft bind are obtained from high strength adhesives which thoroughly wet out both the tufts and the primary backing. In order to achieve suitable delamination strength, the secondary backing must be in intimate contact with the tufted yarn/primary backing ("greige good") during the curing process, and a sufficient amount of adhesive which ensures complete wet out of the tufted fibers and secondary backing and which promote a good marriage between these components must be used.
In the past, SBR latex has been almost exclusively used as both the tuft bind adhesive and the laminating adhesive. The latex may be applied by numerous methods, such as the indirect applicator (pan application) which is now used infrequently, and "direct" methods, these involving roll over flatbed or roll over roll processes, either as a single unitary process, or in series as a tandem process. Regardless of the actual method used, the reverse of the greige good is coated with a precoat of adhesive, and the secondary backing, also coated with adhesive, is married to the greige good, and cured. In these processes, the carpets are coated face down, but cured "face up", i.e., with the aesthetic side of the carpet uppermost.
While SBR latex has been the adhesive of choice, carpet prepared from SBR latex also exhibits numerous deficiencies. For example, the tensile strength and hydrolytic stability of SBR latexes is less than desired, and SBR polymers are less durable than desired. Greige goods in which SBR latexes are used as tuft bind adhesives are subject to "rewicking". Moreover, use of SBR latexes requires the evaporation of large quantities of water during cure, a process which is energy intensive. Polyurethane adhesives are capable of forming a laminate with superior tuft bind and delamination strength, as well as improving other desirable physical properties. However, technical problems have prevented widespread use of polyurethanes despite the increased performance potential.
Substitution of reactive polyurethane systems for latex laminating adhesives has not been straight forward, and has required numerous process modifications. For example, conventional latex maintains its tackiness and viscosity during processing, even in the curing oven. Following application of latex adhesive, the back-side of the greige goods is faced downward. A coat of additional latex is applied to the secondary backing by a skip roll. As a result of the latex properties, good temporary adherence of the secondary backing to the greige goods is obtained. In the curing oven, the latex viscosity does not drop significantly as water evaporates. Thus, the secondary backing satisfactorily adheres to the greige goods, and dripping of latex from the bottom of the laminate into the oven does not occur.
With polyurethanes, however, the single adhesive application common with latex has not been found operable. Polyurethane froth adhesives are not as inherently tacky as SBR latex. Following application of polyurethane adhesive to the greige good and the working of the adhesive into the tufts by means of a closely spaced doctor bar or similar device, a considerable additional amount of polyurethane must be applied from a second puddle in order to provide enough adhesive to temporarily adhere the secondary backing. Even with this additional adhesive, the slow advancement of the adhesive and its low level of tack does not allow for the desired adherence between the greige goods and secondary backing.
In the curing oven, polyurethanes generally exhibit a considerable initial decrease in viscosity prior to cure. As a result, unless the carpet laminating line is run with the greige goods reverse side uppermost, considerable loss of polyurethane into the curing oven would occur. Moreover, if sufficient initial adherence of secondary backing to the greige good has not been obtained, separation of the secondary backing may occur during this period of low viscosity. The viscosity of the polyurethane adhesive may decrease to only 10% of its initial value prior to the viscosity rising as the catalyzed urethane-forming reaction begins to exert its effect. The period of greatest viscosity decrease is often exhibited over the temperature range of ambient to 70░ C. where the polyurethane catalysts are not optimally active.
Due to the decrease in viscosity exhibited by polyurethane adhesives, carpets employing polyurethane adhesives cannot be cured "face up" with or without a secondary backing. The low viscosity allows the adhesive to drip to the floor of the oven or oven belt, eventually creating a buildup which must be removed; causing smoke and odor to be produced; and creating a risk of fire. Addition of secondary backing can minimize the dripping, but generally does not alleviate it altogether. Moreover, the low viscosity of the adhesive may allow the secondary backing to sag and pull away from the carpet, and migration of low viscosity polyurethane through the relatively large holes of the backing create drips and runs which render the carpet commercially unacceptable. These problems have proven to be major obstacles to acceptance of polyurethane adhesives in carpet manufacturing. The capital investment required to convert conventional latex adhesive lines to polyurethane adhesive lines, where the carpet runs face down in the oven, is considerable.
Simply raising the viscosity of the reactive polyurethane adhesive, for example by employing more viscous polyols or prepolymers can assist in lowering dripping and running. However, the higher viscosity impedes impregnation and wet-out of tuft ends and primary backing. Tuft bind then suffers considerably.
It would be desirable to employ a polyurethane adhesive in the manufacture of carpets which exhibits good tuft bind while able to be run on carpet manufacturing lines "face up", as practiced with conventional latex adhesive carpet manufacturing equipment, without dripping or running due to changes in viscosity in the cure oven. It has now been surprisingly discovered that polyurethane adhesives containing non-Newtonian thickeners and/or thickeners which cause the polyurethane viscosity to be less sensitive to temperature changes, are suitable for accomplishing the above objectives. It has further been discovered that the use of a surface viscosifying means, preferably a non-advancing viscosifying composition, particularly when employing a secondary backing, are useful as well, either alone or in conjunction with non-Newtonian thickened systems or temperature insensitive systems.
FIG. 1 illustrates a typical latex-based carpet laminating process, and one embodiment of the subject process when modified as described herein.
FIG. 2 illustrates a two puddle polyurethane-based carpet laminating system.
FIG. 3 illustrates a further embodiment of the subject invention.
FIGS. 3a-3 c illustrates use of several optional viscosifying means of the subject invention.
The various embodiments of the subject invention may best be understood following a description of the drawings, which have been simplified for ease of understanding.
FIG. 1 illustrates a typical, commercial, SBR latex-based carpet laminating process. In the dashed box labeled 1, preliminary carpet operations such as correction of bowing and skewing, which do not form a part of the coating and/or laminating processes per se, are practiced. The greige good 3, with carpet exterior 5 uppermost and the reverse side 7 to which tuft bind adhesive must be applied lowermost, is redirected by means of rollers 9 to place the reverse side of the greige goods under puddle 11, which is supplied with latex adhesive through supply line 13. Doctor blade or gauge bar 12, in conjunction with platen 17, adjusts the amount of latex applied, and assists also in forcing the latex into the tuft ends. The carpet is then redirected by roller 21. Secondary backing 23 is supplied from supply roll 25 and directed by rollers 27 across skip roll 29, which rotates in trough 31 filled with additional latex. Skip roll 29 and trough 31 together comprise a "skip coater". The skip coated secondary backing 33 is pressed onto the latex adhesive-coated greige goods 35 by their travel through marriage rolls 37. The carpet then passes through curing oven 39 where water is removed from the latex, and the latex cures, adhering tufts and secondary backing to form a laminated carpet. The carpet cures face up. If non-laminated carpet is desired, the secondary backing lamination steps are eliminated.
FIG. 2 illustrates a commercial two puddle polyurethane system. Dashed box 1 provides the same carpet preparation activities as in FIG. 1. To the reverse side 7 of the greige goods, polyurethane is applied from puddle 8, supplied with polyurethane froth adhesive through supply line 10. Doctor blade 12, in cooperation with platen 14, limits the applied weight of polyurethane and forces it into the greige goods. The "puddle" collects prior to the doctor blade. Following the first puddle 8 is second polyurethane adhesive puddle 16, supplied with frothed polyurethane adhesive from supply line 18. Doctor blade 20, in conjunction with platen 22, adjusts the thickness of the deposited adhesive. While the first doctor blade 12 substantially contacts the reverse of the greige good, the second doctor blade is spaced a distance away to allow enough adhesive to be deposited to temporarily (prior to cure) bind the secondary backing, when a secondary backing is desired. The secondary backing 23, supplied from supply roll 25, contacts the adhesive-coated greige good below roller 36. Prior to entry into the curing oven, press rollers 38 assist in maintaining stable contact between the secondary backing and the greige goods. Curing the laminate is accomplished by curing oven 39. Note that the carpet is cured face side down.
FIG. 1 also serves to illustrate one embodiment of the subject invention, except that instead of puddle 11 delivering latex to the carpet back, the puddle supplies and polyurethane adhesive, as was employed in FIG. 2. However, unlike FIG. 2, it must be emphasized that the carpet is cured in FIG. 1 by passing face up through the curing oven 39. A further difference between the subject invention process and prior art latex processes is that the skip coater 31 will contain a non-advancing viscosifying composition rather than further latex as in a latex adhesive-based process. For example, the viscosifying composition may contain a polyol with relatively high levels of tin and amine catalysts.
In FIG. 3, carpet is produced as in FIG. 1, in accordance with the subject invention, but without secondary backing. Thus the secondary backing roll, skip coater, and associated elements of FIG. 1 are absent. In FIG. 3, surface viscosifying means 3 a-3 c are optionally used.
In FIG. 3a, a very reactive viscosifying composition, or one containing significant amounts of urethane promoting catalyst, 10, is sprayed from spray nozzle 12 onto the surface of the adhesive 8 coating the primary backing 4 and tuft ends 6 of tufts 2. The fast reacting and/or catalyst loaded composition causes viscous or cured layer 16 to be formed on the surface of adhesive 8.
In FIG. 3b, an alternative method of applying the composition used in FIG. 4a employs a skip coater having a reservoir 28 which contains the viscosifying composition 32, applied to the surface of the polyurethane adhesive 8 by skip roll 26. The composition causes partially or fully cured layer 18 to be formed.
In FIG. 3c, a spray nozzle 12 supplies a photocurable composition as a mist 10 to the surface of polyurethane adhesive 8. Ultraviolet lamp 20 cures or partially cures the photocurable composition to form a viscous to solid film 18. In an alternative embodiment, the polyurethane adhesive composition may itself contain photocurable monomers and associated photoinitiator, or a photoactivated polyurethane catalyst, in which case the additional composition sprayed onto the polyurethane adhesive 8 by spray nozzle 12 becomes superfluous or optional. Ultraviolet lamp 20, or another actinic radiation generating device such as a laser, electron beam, etc., is used to expose the surface of the polyurethane adhesive, which cures at its surface, as a result.
In all of the foregoing embodiments, the Figures have been simplified for ease of viewing and understanding. In commercial embodiments, various tension controlling devices, tenter frames, drive motors, etc., will be required, as is well known to those skilled in the art. Depending upon the adhesive viscosities, weight pickup desired, depth of tufting through the primary backing, and other well known factors, additional coating stations or additional doctor blades, nip rolls, impregnation rollers, and the like may be required for any particular application. Design and fabrication of such devices is within the skill of the art.
The polyurethane adhesive systems of the subject invention must be formulated and/or processed so as to eliminate dripping, running, etc., when used in a face up carpet manufacturing configuration. There are three methods of achieving these objectives, which may be employed separately or may be employed together. In the first method, a non-Newtonian thickener is added to the reactive polyurethane, which is generally in the form of a filled froth. The non-Newtonian thickener raises the viscosity, but the viscosity is highly shear dependent. For example, under high shear rates, the viscosity is low. Such high shear rates occur at the point of adhesive application, for example at doctor bars, impregnation rollers, etc. The low viscosity under these conditions allows the reactive polyurethane to thoroughly penetrate exposed tufts and primary backing, ensuring adequate tuft bind. Under conditions of low shear, however, for example while traversing the curing oven, the viscosity is quite high.
A second method enabling processing of urethane adhesives face up is to employ a polyurethane reactive system which contains an additive which causes the viscosity decrease with increasing temperature to be less severe then if the additive were not present. Such an additive may be called a viscosity index improver. Among the possible additives which are suitable as viscosity index improvers are the same additives as the non-Newtonian thickeners.
It has been surprisingly discovered that the decrease in viscosity which occurs as the temperature rises is far less severe than in other systems not employing non-Newtonian thickeners. For example, whereas a conventional mineral filled polyurethane adhesive may exhibit loss of 85% or more of its room temperature viscosity when heated to 70░ C., the non-Newtonian thickened formulations of the present invention exhibit only a 25% loss in viscosity under the same circumstances. Suitability of a targeted additive as a viscosity index improver may be addressed by measuring the viscosities of otherwise identical polyurethane adhesives, one of which contains the additives, and one which does not. An additive which causes the change (decrease) in viscosity between 25░ C. and 70░ C. to be reduced is an index improving additive. As previously mentioned, some viscosity index improving additives may also be non-Newtonian thickeners, but this is not necessarily the case.
The third method of enabling face up carpet manufacture using polyurethane adhesives is to markedly increase the surface viscosity of the adhesive, for example, by formation of a cured or partially cured layer of adhesive on the carpet bottom. This layer prevents liquid adhesive from dripping through, acting as a film or "shield". The thin, partially cured skin, film, or surface layer may be formed by any means which results in at least a partial cure of the exposed adhesive surface or development of a highly viscous or solid surface. One method is to employ photoactive catalysts in the polyurethane. Since the actinic radiation which renders photocatalysts active, generally ultraviolet (UV) light, cannot penetrate deeply into the reactive polyurethane adhesive froth owing to its cellular nature and presence of mineral filler, only a surface cure is effected.
A further means of viscosifying the adhesive surface is to spray or coat the adhesive with a very reactive formulation which rapidly cures in and of itself, or which causes local cure of the polyurethane adhesive. An example of the former is a rapidly crosslinkable composition such as a di- or triacrylate either neat or dissolved in solvent, and containing a free radical initiator or photoinitiator. Preferably, any such crosslinkable compositions contain monomers and oligomers of relatively low volatility. Glycerol triacrylate is one example of such a low volatility monomer, which may be used in combination with a soluble peroxide or azo-type catalyst, or a photocatalyst such as the Irgacure« catalysts available from Ciba Geigy.
To ensure adherence of the photopolymerized coating with the carpet adhesive, monomers which are reactive with the polyurethane adhesive may be used. Examples are isocyanatoethylmethacrylate, hydroxyethylacrylate, and 1-(t-butylisocyanato)-3-isopropenylbenzene. Such monomers may be used in conjunction with other unsaturated compounds, particularly those with multiple unsaturation such as bisacrylates, divinylethers, etc., or alone. They may also be added to the polyurethane adhesive to imbue the latter with photocuring ability.
A yet further means of viscosifying the adhesive is to spray the adhesive with a solution which rapidly reacts with or catalyzes the reaction of the polyurethane adhesive at its surface. Examples of solutions which can rapidly react are solutions of amines and alkanolamines, for example an aqueous solution of ethylene diamine. Examples of compositions which can case local catalysis are ethylene glycol solutions of tin, tertiary amine, or bismuth polyurethane catalysts. When secondary backings are utilized, non-advancing viscosifying skip coats containing elevated catalyst levels and/or highly reactive species may be used, the skip coat contacting the secondary backing prior to its marriage to the adhesive-coated greige good. Skip coating may also be used to apply reactive or catalytic compositions to the polyurethane adhesive surface when secondary backings are not used.
Except for the non-Newtonian fillers, viscosity index improvers, and photocatalysts when present, the polyurethane adhesives of the subject invention are conventional. In general, these contain one or more polyoxyalkylene polyols, a di- or polyisocyanate, curing catalysts, cell control agents (frothing surfactants), mineral fillers, dyes, pigments, etc. Often, the polyol and isocyanate components may be prereacted to form an isocyanate-terminated prepolymer or quasi-prepolymer. Mixtures of polyols, isocyanates, and prepolymers and/or quasi-prepolymers are also useful.
Examples of suitable preferred isocyanates are toluene diisocyanate (TDI) and methylene diphenylene diisocyanate (MDI), and their mixtures. MDI need not be used in the form of the pure or nearly pure 4,4′-isomer. Modified isocyanates such as urethane- and carbodiimide-modified isocyanates, particularly the former, may be used. Polymeric and crude MDI containing tri- and higher functional isocyanates may be used as well. Isocyanate-terminated prepolymers and quasi-prepolymers are also useful. It is preferable that the isocyanate index be maintained between 90 and 120, with indexes in the range of 95 to 110 more preferable.
The polyols useful are well known and may have average nominal functionalities ranging from about 2 to about 8, preferably in the range of 2 to 3. The polyols may be polytetramethylene ether glycols (PTMEG), hydroxyl-functional polyester polyols, or preferably polyoxypropylene polyols which may be homopolymeric or may be a copolymer containing other copolymerizable monomers such as ethylene oxide, butylene oxide, oxetane, etc. Polyoxyalkylene polyols may be prepared by base catalyzed oxyalkylation of suitably hydric initiator molecules, and may advantageously be low or ultra-low unsaturation polyols having levels of intrinsic unsaturation less than about 0.015 meq/g, preferably lower than 0.010 meq/g, and most preferably with maximum unsaturation in the range of 0.002 to 0.007 meq/g. The polyols may have equivalent weights of from about 300 Da to about 10,000 Da, preferably 1000 Da to 4000 Da, and most preferably in the range of 1500 Da to 2500 Da. The polyoxyalkylene copolymer polyols may be block, random, block-random, or any other configuration. In one shot systems, polyols with high primary hydroxyl content are especially preferred.
Isocyanate-terminated prepolymers useful herein may be prepared by conventional methodology, preferably at somewhat elevated temperature. The free isocyanate content may range from about 1 weight percent or below to about 35 weight percent or higher, more preferably 2 weight percent to about 30 weight percent, yet more preferably 6 weight percent to about 25 weight percent, and most preferably in the range of 8 weight percent to about 20 weight percent. The polyol component used to prepare the prepolymers may be one of the polyols previously described, or a lower molecular weight glycol or oligomeric glycol or polyol.
For the polyurethane systems destined for use in puddles to supply polyurethane adhesive to the greige good, a catalyst which is effective to cure the adhesive in the curing oven is necessary. However, the catalyst must not cause undue advancement of the adhesive in the puddle. For this reason, all but the most minor amounts of highly active urethane catalysts such as the various tin compounds and tertiary amines, are generally avoided. However, such catalysts may be used in conjunction with delaying compounds such as those disclosed in U.S. Pat. No. 3,635,906, herein incorporated by reference. Latent catalysts which activate at elevated temperatures, i.e., iron diacetylacetonate and nickel diacetylacetonate, are preferred. The amounts of such catalysts used should be an effective amount, i.e., an amount which provides for substantially full cure in the curing oven while exhibiting minimum advancement in the puddle.
The mineral fillers are those conventionally used, generally ground limestone, dolomite, alumina trihydrate, etc. The fillers are of relatively large particle size, for example commonly in the range of 15 μm to 40 μm, and thus have low specific (BET) surface area. The surface area of such fillers is, in general, less than 5 m2/g. Amounts of filler vary quite widely, but amounts of from 50 parts filler per 100 parts polyol or adhesive to 500 parts filler per 100 parts polyol or adhesive have been used. Amounts of from about 100 parts per 100 parts polyol to 300 parts per 100 parts polyol are typical. It should be noted that these fillers do not cause any substantial non-Newtonian behavior.
The non-Newtonian thickeners may be any thickener which exhibits a substantial inverse relationship between shear and viscosity. In general, inorganic particulates having BET surface areas greater than about 10 m2/g, preferably greater than 40 m2/g, more preferably greater than 100 m2/g, and yet more preferably 200 m2/g or more, are suitable. The thickeners may be hydrophobic or hydrophilic in nature. Examples include precipitated calcium carbonate, finely divided clays, preferably smectite or "layered" clays, and precipitated and "fumed" silicas, i.e., silicas produced by flame pyrolysis processes and the like. Such thickeners are well known and available from numerous sources, including General Electric, Dow Corning Silicones, Wacker-Chemie GmbH and Wacker Silicones Corporation, Rhone-Poulenc, and Degussa, among others. Inorganic thickeners are used in amounts which preferably at least double the resting viscosity as opposed to the viscosity exhibited under a shear rate of 50 sec−1. More preferably, the rest viscosity at 25░ C. is more than three times the viscosity at a shear rate of 50 sec−1 or more, most preferably more than ten times this viscosity. Preferably, amounts of about 0.25 to 20 parts per 100 parts of the B-side, more preferably 1 to 2 parts of inorganic non-Newtonian thickener are used.
Since the action of non-Newtonian particulate thickeners is due, at least in part, to surface infractions, the nature of the surface will cause the amount of thickener as well as its overall effect to vary somewhat. However, adjustment of the amount of thickener can be easily accomplished. For example, thickeners with a relatively hydrophilic surface (organophobic) may be less effective than hydropholic thickeners having the same size and morphology. Some fillers, i.e., fumed silicas, may tend to aggregate and subsequently agglomerate.
Fillers such as fumed silica tend to have relatively small particle sizes, and are highly efficient non-Newtonian thickeners. For example, Aerosil« 200, with an average particle size of 0.012 μm (12 nm) is only required in amounts of 1 o 2 weight percent to be effective, whereas precipitated and surface treated calcium carbonate, with an average particle size of 0.15 μm, approximately an order of magnitude larger, requires 5-20 weight percent to be effective, these weight percents based on the weight of the isocyanate reactive components. In general, average particle size must be less than 1 μm, preferably less than 0.3 μm, and most preferably less than 0.1 μm.
Organic thickeners which display non-Newtonian characteristics are also useful. An expedient way to test a particular thickener for its non-Newtonian thickening ability is to add the thickener to a target polyurethane adhesive "B-side" (resin side), and measure its viscosity at different levels of shear. Thickeners which exhibit a substantial inverse relationship between viscosity and shear are non-Newtonian. Candidate thickeners include the various vegetable gums, i.e. carrageenan, tragacanth, acacia, guar, and the like; modified celluloses, e.g., carboxymethylcellulose, carboxypropylcellulose, hydroxymethylcellulose, and the like; polyacrylic acid polymers and copolymers with acrylates and other unsaturated monomers, e.g., the Carbopol™ and Acrysol™ thickeners; very high molecular weight polyethers, such as high molecular weight polyoxyethylene glycol, and the like. Associative thickeners may be particularly effective. Associative thickeners are molecules which have a hydrophobic or non-polar portion and a hydrophilic, polar, or ionic portion. In solution, the non-polar portions tend to associate with each other, as do the hydrophilic, polar, or ionic portions, forming extraordinarily long "associative" chains and networks. The interactions are easily broken by shear, however, and thus the molecules exhibit decidedly non-Newtonian behavior. Combinations of organic non-Newtonian and inorganic non-Newtonian thickeners may be used as well. Examples of non-Newtonian thickeners may be found in U.S. Pat. Nos. 4,709,099 and 4,649,224. It is possible to tailor the properties of certain of the polyols to serve as non-Newtonian thickeners.
For the aspect of the subject invention where local, surface viscosity is raised, the subject invention process preferably employs a secondary backing along with a non-advancing, viscosifying composition, preferably in the form of a non-advancing skip coat.
The skip coat composition may take several distinct forms. Skip coating has been used before in latex adhesive systems, but has not been used in polyurethane systems due to the problem of the polyurethane setting up in the skip roll trough. In the present invention, this problem is circumvented by employing a "non-advancing skip coat." By the term "non-advancing" is meant that the skip coat composition, by itself, exhibits very little increase in viscosity over the life of the composition in the trough, i.e., is not a "self-curing" composition. Compositions within the scope of the invention will not cure until contacted with the polyurethane adhesive coating on the greige good or until subjected to photocuring. The skip coat compositions, while in the skip roll trough, will thus exhibit little or no increase in viscosity, the skip coat weight will remain substantially constant, and there will be no need to remove accumulated gel or polymer from the skip coat trough.
The skip coat composition, or in general, the viscosifying composition as it will hereinafter be termed, may contain a "polyurethane reactive composition", or a curable film-forming composition. By "polyurethane reactive composition" is meant a composition which will become part of the overall polyurethane adhesive system by virtue of being a component of that system, by reacting with a component of that system, or by catalyzing reaction of the system. Thus, for example, the viscosifying composition may comprise an isocyanate-terminated prepolymer or quasi-prepolymer; or a mixture of polyols, i.e., polyoxyalkylene polyols, polyester polyols, polytetramethylene ether glycols, polycaprolactone diols, and the like; amino-functional polyoxyalkylene polyethers; one or more low molecular weight glycols and/or aminoalcohols; and even in some cases, may be water. When isocyanate-functional components are used in the viscosifying composition, it is preferred that a nitrogen blanket or its equivalent be used to prevent reaction with atmospheric moisture.
The viscosifying composition will also, in general, be an "adherence promoting composition." In this sense, the viscosifying composition, when applied to the secondary backing, will exhibit greater initial adhesion to the polyurethane adhesive-coated greige good than that obtained by a viscosifying composition-free secondary backing, and greater than that obtained from a skip coat which has the same composition as the greige good polyurethane adhesive when used in the same areal weight as the viscosifying compositions of the present invention.
The viscosifying composition functions to increase adhesion between the polyurethane adhesive-coated greige good and the secondary backing by providing a composition which promotes rapid and at least local cure of the greige good adhesive such that the latter's viscosity and/or tack is increased, or itself cures to become highly viscous or solid. The increase in tack/viscosity encourages initial adhesion of secondary backing to the greige good. Increased initial adhesion in turn promotes superior lamination strength in the cured carpet laminate. Most importantly, the increase in viscosity enables adhesive-coated greige good to be cured face-up without running or dripping.
The viscosifying compositions may also include a catalyst, provided that the catalyst does not catalyze the advancement of the skip coating composition. For example, a viscosifying composition employing isocyanate-terminated polyoxyalkylene polyol-derived prepolymers may include a urethane catalyst, but should not include an isocyanate trimerization catalyst. The former cannot cause substantial advancement of the skip coat composition isocyanate-terminated prepolymer as there is no hydroxyl-functional compound in the skip coat with which to react to form urethane linkages. However, trimerization catalysts are to be avoided as these may catalyze isocyanurate formation from trimerization of the free isocyanate groups of the prepolymer. Viscous polyoxyalkylene polyol or polyester polyol viscosifying compositions may include both urethane or isocyanurate catalysts, however.
The viscosifying compositions may also comprise relatively low viscosity components which contain active urethane catalysts. For example, the viscosifying composition may comprise one or more relatively low molecular weight and therefore low viscosity alkylene glycols, low molecular weight monomeric or oligomeric polyols, or alkanolamines. Examples include alkylene glycols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 2-methyl-1,3-propanediol and the like; polyols such as glycerol, sorbitol, trimethylolpropane, and their oligomeric oxyalkylation products; and alkanolamines such as mono-, di-, and trialkanolamines. Examples of the latter are monoethanolamine, monopropanolamine, diethanolamine, triethanolamine, and the like. Water may also be used, either alone or in conjunction with other ingredients. Mixtures of low viscosity glycols, polyols, etc., may be used, as may be one or more of these with minor amounts of high molecular weight, viscous polyols and other polymers.
To provide the desired viscosity increasing function, low viscosity viscosifying compositions must contain functional groups highly reactive with isocyanate groups, e.g., primary amino groups, and/or must contain a highly active catalyst, as opposed to a latent catalyst. Examples of highly active catalysts are those catalysts known to one skilled in the art as highly effective in catalyzing the urethane reaction, for example tin catalysts, particularly tin octoate, dibutyltin diacetate, dibutyltin dilaurate, dimethyltin diacetate, and the like. Bismuth compounds are highly active. Tertiary amines are also suitable. For example, a highly effective low viscosity viscosifying composition may be formulated from ethylene glycol and dibutyltin dilaurate. Application of only relatively small amounts of such a skip coat to the secondary backing and contact with the adhesive of the greige good will cause rapid advancement, viscosification, and tack development on the adhesive, promoting firm initial adherence of the secondary backing to the greige good, and development of much higher viscosity or even solidification at the surface of the polyurethane adhesive, i.e., the interface between the adhesive and secondary backing. The same composition may be sprayed or skip coated onto the adhesive itself when a secondary backing is not to be used.
For those viscosifying compositions described above which are sprayable, such as catalyst-containing ethylene glycol mixtures, water/amine mixtures, etc., these may be sprayed onto the advancing polyurethane adhesive-coated carpet back by suitable atomizers, spray heads or guns, etc., and may be used without a secondary backing. In such cases, the sprayed-on viscosifying composition rapidly reacts at the surface of the polyurethane adhesive, partially or even fully curing the latter at its surface. Thus, this aspect of the invention may be used without any secondary backing.
The polyurethane systems employed in puddles as "precoat adhesives", "tuft bind adhesives", or "greige good adhesives" are preferred to have indices at least near stoichiometric, i.e. in the range of 90-120, but are preferably somewhat over indexed. It is preferable that the index exceed 101, and more preferably be in the range of 103 to 120. Under-indexed systems are not preferred, as tuft bind may suffer. Areal weight of the precoat adhesive advantageously ranges from 20 oz/yd2 to 50 oz/yd2, and more preferably 25 oz/yd2 to 40 oz/yd2. However, these amounts are not limiting.
The precoat adhesive to be applied to the greige good preferably contains a relatively high amount of filler, for example amounts of 30 parts by weight to 350 parts by weight relative to the weight of the polyol, more preferably 50 parts by weight to 500 parts by weight. Further details with respect to formulations and mixing methods for froth foam may be had by reference to U.S. Pat. No. 5,604,267 and the references cited therein. Suitable fillers are ground or microcrystalline limestone, dolomite, barite, aluminum hydroxide, and the like.
The viscosifying composition is desirably used in considerably lesser quantities in areal weight relative to the amount of precoat adhesive. For example, with isocyanate-reactive viscosifying compositions, the applied viscosifying composition areal weight is preferably 0.05 to 1 oz/yd2 (1.7 to 33 g/m2), more preferably 0.2 to 0.5 oz/yd2 (6.7 to 16.7 g/m2), these quantities, again, not limiting. When isocyanate-functional viscosifying compositions are utilized, larger areal weights are tolerable, as any excess isocyanate-functionality left after marriage of greige good and secondary backing and cure between the respective reactive components will further react in the cure oven and/or with atmospheric moisture. In such cases, the preferred range is 0.05 to 2.5 oz/yd2 (1.7 to 83.4 g/m2), more preferably 0.2 to 1.0 oz/yd2 (6.7 to 33 g/m2). However, both larger and smaller amounts of all types of viscosifying compositions may be used as required by the particular greige good, greige good adhesive, and other raw material process parameters.
When isocyanate-reactive viscosifying compositions are used, the skip coat isocyanate-reactive functionality may be of greater reactivity than the isocyanate-reactive functionality of the adhesive. For example, when the adhesive contains a high secondary hydroxyl-functionality polyol, a polyol with considerable primary hydroxyl functionality may be used in the viscosifying compositions. In the same manner, if a primary hydroxyl polyol is used in the adhesive, e.g. one with 30% primary hydroxyl groups, a polyol with higher primary hydroxyl content may be used in the viscosifying composition. It is also possible to use amine-terminated polyols, aliphatic glycols, alkanolamines, aliphatic diamines, and the like, as well as water in the viscosifying compositions as more reactive isocyanate-reactive compounds. For example, it is possible to utilize mixtures of water and a catalyst, for example an amine catalyst, which facilitates the reaction of water with the isocyanate group. Hydroxyl-, amino-, and both hydroxyl- and amino-functional compounds having molecular weights below about 300 Da may advantageously be used.
Catalyst present in the viscosifying composition should be of sufficient type and amount that a relatively rapid cure rate is achieved following marriage of the greige good and secondary backing or application of the viscosifying composition to the surface of the polyurethane adhesive. The catalyst may constitute up to 10 weight percent of the skip coat, more preferably 0.5 to 7 weight percent, and most preferably 2 to 6 weight percent.
When sprayed onto the adhesive in the absence of attachment of secondary backing the amount of sprayed-on formulation is generally the same or less than the amount employed with a secondary backing. In such cases, adherence of secondary backing is not a consideration, and the amount of viscosifying composition formulation is only that necessary to cause sufficient local, surface cure so as to eliminate dripping, running, etc.
By the term "skip coat" as used herein is meant a coating applied to the secondary backing in most minor amount relative to the weight of adhesive applied to the greige good. By the term "viscosifying composition" is meant a formulation suitable for use as a skip coat when employing a secondary backing or which is useful for spraying onto the polyurethane adhesive for surface cure when a secondary backing is not to be used. By the term "complimentarily reactive" is meant a skip coat or viscosifying composition which is reactive with excess unreacted functionality of the adhesive, i.e. has complimentary functionality. For example, in an over-indexed adhesive with excess isocyanate functionality, a complimentarily reactive viscosifying composition will contain isocyanate-reactive functionality. Unless indicated otherwise, the use of "adhesive" in the claims refers to the precoat or tuft bind adhesive applied to the greige good which will subsequently contact the secondary backing, or which will be surface cured as described herein. This adhesive may be a liquid, may be a froth foam, or may be a foamable system, unless otherwise limited. Molecular weights and equivalent weights herein are expressed as number average molecular and equivalent weights in Daltons (Da).
The formulations presented herein may also be used in conjunction with additional non-froth adhesives/foam layers. For example, it is possible to apply a tuft bind adhesive, for example a relatively fluid froth or a liquid adhesive of relatively low viscosity to more effectively wet out the tufts in the backing side of the greige good followed by application of a further adhesive as a second layer to the greige good. More than one froth foam may be used similarly, for example froth foams containing differing filler content. In addition to or in lieu of froth foams, foams containing a volatile blowing agent or a reactive blowing agent such as water may be used.
The B-side (resin side) components of the polyurethane froth adhesives of Table 1 were mixed together. Comparative Example C1 is a typical polyurethane adhesive B-side formulation employing 180 parts filler to 100 parts polyol. Example 1 is the same formulation as Comparative Example 1, but contains 1.5 parts (per 280 parts) of Aerosil« (Degussa) fumed silica as a non-Newtonian thickener.
The viscosities were measured with a CSL2-500 rheometer (TA Instruments) using parallel plates. The viscosities at various shear rates are also presented in Table 1.
Atlantis ™ Q1000 Polyol1
Diethylene Glycol
Calcium Carbonate
Aluminum Trihydrate
Aerosil 200 (Degussa)
SHEAR RATE, sec−1
VISCOSITY [cps]
VISCOSITY [cps]
not det.
1Lyondell Chemical
These data illustrate the shear thinning characteristic that is imparted by the thickening agent, in this case fumed silica. Without fumed silica, the viscosity is essentially independent of the shear rate. When a non-Newtonian thickener, in this case, fumed silica, is added, the viscosity becomes highly dependent on shear. At low shear rates, the viscosity increases dramatically compared to the formulation that does not contain thickener. At high shear rates, the viscosities are substantially the same. This means that both formulations behave very similarly when subjected to the high shear encountered under a doctor bar, in terms of their ability to penetrate the greige good and the carpet fibers. Once the coated greige good has passed under the doctor bar all the shear is removed, and the viscosity of the formulation containing the thickener increases from around 12,000 to more than 200,000 cps. The higher viscosity reduces the tendency of the froth to leak out of the greige good once the greige good is inverted and passed through the curing oven. Note, that the conventional fillers are much too large in particle size (35 μm and 20 μm, respectively) to act as non-Newtonian thickeners: the viscosity at 0.54 sec−1 is only some 25% more than that at 174 sec−1, and is actually lower than the viscosity at 3.7 sec−1.
A second, and most important aspect of the subject invention process lies in the use of additives which minimize the viscosity decrease at increasing temperature. This is illustrated by the data presented in Table 2, where the effect is caused by the same non-Newtonian thickeners employed in Example 1. However, other viscosity index improvers will also be acceptable. To demonstrate the effect of temperature on viscosity, viscosity measurements were made with a Brookfield viscometer using an S95 T-bar spindle as the measurement probe.
Viscosities, sec−1
Example 1
Comparative Example C1
The results presented in Table 2 indicate that the viscosity of the non-Newtonian thickened composition is not affected greatly by temperature. The viscosity at 70░ C. is only 25.2% less then the viscosity at 25░ C. However, the Comparative Example, containing no non-Newtonian thickener, exhibited an 88.2% loss in viscosity. The C1 viscosity was 8.45 times less at 70░ C. then at 25░ C. These results would be even more disparate if the viscosity could be measured at zero shear; however, viscosity must be measured by application of a shearing force. Note that even at 70░ C., the example according to the invention, Example 1, is still more than three times as viscous as compared to Comparative Example 1 at 25░ C.
The ingredients of the B-sides of Examples 1 and C1 were frothed in a kitchen mixer using a wire mesh impeller. To the frothed mixtures were added, respectively, 1.5 parts LC 5615 polyurethane catalyst (Witco), and 65.2 parts Baytuft« 751 (Bayer), and thoroughly mixed. This mixture was then applied to a 6pic woven propylene backing. The coated backing was then lifted and clamped to the rim of a 7ū11 inch rectangular baking pan such that the coated backing was suspended about 0.5″ inch about the bottom of the pan. This assembly was then placed into a curing oven set at 150░ C. for approximately 5 minutes. After curing and cool-down, the parts of the backing that were located above and near the rim of the pan were removed resulting in carpet pieces measuring 9.5 by 4.5 inches. The amount of urethane applied to these samples was determined to be around 27 grams for both the Example and the Comparative Example. The sample processed according to the subject invention displayed a smooth appearance on both sides of the sample. The comparative example showed severe run-off and drip-formation on the underside of the sample.
Polyurethane froth adhesives were prepared by mixing the B-sides of Table 3 with 56 parts of Baytuft« 751. The froths were applied to the reverse side of a 30 oz/yd2 (ca. 1.2 Kg/m2) loop carpet made of 1250 denier, 2-ply nylon fiber tufted through a woven polypropylene primary backing at 8ū10 stitches per inch (3.1ū3.9 stitches/cm) in a straight stitch pattern. In case of examples 4 and 5, a skip-coated secondary backing was applied to the back of the carpet. The skip-coat consisted of 95.6 parts of Acclaims« 2220 (Lyondell Chemical), 2 parts dimethyltin dilaurate catalyst and 2.4 parts of triethylenediamine catalyst. As secondary backing, a 6-pic woven polypropylene backing was used.
Immediately after the application of the froth and the secondary backing in examples 4 and 5, the samples were attached to a wire mesh with clamps. The mesh with the attached carpet sample was then suspended in a curing oven with the carpet facing up. The samples were cured for about 5 minutes at 130░ C.
Atlantis « Q1000
diethylene glycol
LC 5615 catalyst
Calcium carbonate
Aerosil 200
Skip Coated
The applied weights for all the samples ranged from 38 to 40 oz/yd2. Comparative example C3 had an unacceptable appearance. The surface of the backing was uneven with drip lines and noses of urethane extending as much as 1 cm away from the backing, indicating severe leakage of the urethane froth from the greige good. Examples 3, 4 and 5 had good appearance without indications of froth leakage. Example 3 shows the effectiveness of the thickening agent alone. Example 5 shows the effectiveness of the surface viscosifying process alone. Example 4 shows the effectiveness of the combination of thickening agent and the surface viscosifying processes.
Q1000 (Lyondell)
Diethylene Glycol
Calcium Carbonate, WF-70
(Georgia Marble)
Aluminum Trihydrate, CG60-U
(Costum Grinders)
Precipitated Calcium Carbonate, Thixo-
Carb 500 (Specialty Minerals Inc.)
Precipitated Calcium Carbonate, Albacar
5970 (Specialty Minerals Inc.)
The examples were prepared such that the total amount of fillers used in the B-side remained constant at 180. The ingredients of the B-sides of Examples 6,7and C4,C5 were frothed in a kitchen mixer using a wire mesh impeller. To the frothed mixture were added, respectively 1.5 parts LC 5615 polyurethane catalyst (Witco), and 63.6 parts Baytuft 751 (Bayer), and thoroughly mixed. About 44 to 47 g of the mixture was then applied to a 11 pic woven propylene backing which was previously clamped to the rim of a 9ū13 inch rectangular baking pan. The area covered with froth measured slightly above 5ū5 inch. This assembly was then placed into a curing oven set at 150░ C. for approximately 5 minutes. After curing and cool-down, 5ū5 inch areas covered with urethane were cut out and weighted. The amount of urethane, which dripped through the secondary backing and collected in the bottom of the pan, was also measured. Table 5 summarizes the results.
Weight of 5 ū 5 inch secondary
coated with urethane [gr]
Weight of urethane collected in
bottom of pan [gr]
The under side of the backing in Examples 6 and 7 were smooth without any drip through of material. The urethane was completely retained by the secondary backing. Comparative examples C4 and C5 showed significant dripping into the pan with severe nose formation and protrusion through the windows of the secondary. These examples demonstrate the effectiveness of precipitated calcium carbonate as well as the importance of the particle size. The average particle size of the precipitated calcium carbonate used in examples 6 and 7 is approximately 0.15 μm whereas the average particle size of the precipitated calcium carbonate used in C5 is 1.9 μm. Note that the average particle size of the aluminum trihydrate is about 20 μm and the average particle size of the ground marble is about 35 μm.
The carpet adhesive compositions disclosed and claimed herein require one ingredient from each necessary class of ingredients. Necessary ingredients include at least one di- or polyisocyanate, prepolymer, and/or quasi-prepolymer, at least one isocyanate-reactive component: for the first embodiment herein, a non-Newtonian thickener, and for the second embodiment, a viscosity index improving additive. In the third embodiment, the process requires that the surface viscosity of the polyurethane adhesive on the greige good be increased to the extent that flow from the interior of the adhesive past the viscosified surface is minimized or prevented. The invention may be practiced with any combination of classes of ingredients or specific ingredients within those classes to the exclusion of other ingredients or process steps named or unnamed.
By the term "viscosifying" when used describing the surface of the polyurethane precoat or greige good adhesive is meant increasing the viscosity beyond the viscosity of the unaltered adhesive at the surface such that "leaking" or "running" of the adhesive from the interior is reduced or eliminated when cured upside down at elevated temperature. The viscosified surface may be still flowable (liquid) or solid, and may comprise substantially the same composition as the uncured adhesive, or may be a different applied polymer system which cures to form a viscous layer or cured film. By the term "carpet construction adhesive" is meant an adhesive used in the manufacturing of tufted carpet. While the aim of the present invention is to allow the drip-free, face-up curing of carpeting prepared using polyurethane adhesives, the carpeting may be run face-down employing the inventive compositions as well.
Having now fully described the invention, it will be apparent to one of ordinary skill in the art that many changes and modifications can be made thereto without departing from the spirit or scope of the invention as set forth herein.
|Patente citada
|Fecha de presentaci¾n
|Fecha de publicaci¾n
|3 Sep 1974
|23 Dic 1975
|Mitsubishi Petrochemical Co
|Backing agent for carpet
|22 Jul 1974
|18 May 1976
|Fieldcrest Mills, Inc.
|Method of making pile fabric having an adhesive substrate
|22 Nov 1983
|7 May 1985
|Paul Walker
|Method for applying polyurethane backing
|2 May 1986
|10 Mar 1987
|Basf Corporation
|Polyethers modified with alpha olefin oxides
|16 Sep 1985
|29 Sep 1987
|The Dow Chemical Company
|Process for preparing polyurethane-backed textiles
|2 May 1986
|24 Nov 1987
|Basf Corporation
|Polyethers modified with alpha olefin oxides
|29 Sep 1987
|1 Ago 1989
|The Dow Chemical Company
|Process for preparing polyurethane carpet backings based on high equivalent weight polyols
|7 Abr 1989
|3 Sep 1991
|Standard Adhesive & Chemical Co., Inc.
|Nonskid polyurethane coating
|4 Feb 1992
|27 Oct 1992
|Arco Chemical Technology, L.P.
|Process for preparing metal cyanide complex catalyst
|8 Sep 1994
|9 Ene 1996
|Arco Chemical Technology, L.P.
|Highly active double metal cyanide catalysts
|30 Ago 1995
|18 Feb 1997
|Arco Chemical Technology, L.P.
|Process for producing froth polyurethane foam
|14 Jul 1998
|9 Ene 2001
|Bayer Antwerp N.V.
|Polyurethane carpet backings with improved tuft bind
|Patente citante
|Fecha de presentaci¾n
|Fecha de publicaci¾n
|30 Ene 2002
|16 Mar 2004
|Textile Rubber & Chemical Co., Inc.
|Sodium silicate coating process and products incorporating same
|20 Jun 2002
|10 May 2005
|Flexographic ink containing a polymer or copolymer of a 3,4-dialkoxythiophene
|25 Mar 2002
|18 Oct 2005
|Aqueous composition containing a polymer or copolymer of a 3,4-dialkoxythiophene and a non-newtonian binder
|24 Mar 2006
|2 Dic 2008
|Bayer Antwerpen Comm.V.
|Process to laminate polyolefin sheets to urethane
|8 Oct 2004
|29 Dic 2009
|New Spirit Backing Llc
|Polyurethane roller coating process for carpet backing
|15 Jul 2009
|25 Dic 2012
|Davis Jr David M
|Tufted goods manufacturing method and operational apparatus
|6 Nov 2009
|11 Feb 2014
|John H. Bearden
|Method for making artificial turf
|6 May 2011
|16 Dic 2014
|Kusters Zima Corporation
|Polyurethane roller coating device for carpet backing
|1 May 2013
|3 Mar 2015
|John H. Bearden
|Method for coating a tufted athletic turf backing
|25 Mar 2002
|3 Abr 2003
|Aqueous composition containing a polymer or copolymer of a 3,4-dialkoxythiophene and a non-newtonian binder
|20 Jun 2002
|31 Jul 2003
|Flexographic ink containing a polymer or copolymer of a 3, 4-dialkoxythiophene
|30 Ene 2002
|7 Ago 2003
|Doesburg Van I.
|Sodium silicate coating process and products incorporating same
|8 Oct 2004
|1 Dic 2005
|New Spirit Backing, Llc
|Polyurethane roller coating process for carpet backing
|24 Mar 2006
|27 Jul 2006
|Holeschovsky Ulrich B
|Process to laminate polyolefin sheets to urethane
|14 Oct 2003
|22 Feb 2007
|Jenkines Randall C
|Method of preparing carpet backing using recycled carpet scrap
|6 Nov 2009
|27 May 2010
|Precisionjet, Inc.
|Method for making artificial turf
|6 Nov 2009
|27 May 2010
|Precisionjet, Inc.
|Method for making artificial turf
|Clasificaci¾n de EE.UU.
|156/72, 156/275.7, 428/97, 428/96, 156/331.7
|Clasificaci¾n internacional
|Clasificaci¾n cooperativa
|Clasificaci¾n europea
|29 Jun 2005
|Maintenance fee reminder mailed
|12 Dic 2005
|Lapse for failure to pay maintenance fees
|7 Feb 2006
|Expired due to failure to pay maintenance fee
Effective date: 20051211


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Artist: Gourds
Album: Noble Creatures
Genre: Country
Noble Creatures
Moon Gone Down
Me and the coke and cigarettes looking at the crack of dawn
I got a house that's full of lights but I never turn them on
Heater's broken, moon is going down
Living in a house of blue lights, wolf knocking at the door
Chopping down that cedar tree, looking for a couple more
Bells are ringing, moon is going down
Moon gone down on my porch
inhale and exhale this tiny torch
Built me a boat on a rainy day waiting for my ship to sail
Help my thumb up to the moon, look like I lost my fingernail
Cat's are crying, moon is going down
Moon gone down on my porch
Inhale and exhale this tiny torch
Sun comes up in the morning, shines on my sleepy head
One time I woke up and found angels all around my bed
Angels angels moon is going down
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text: Posted November 7, 2012 Perhaps players just thought they had to do just enough and they could get a big paycheck from Hurney..Now that is thrown for a loop they actually have to live up to some sort of expectations. I'm going with this one. Share this post Link to post Share on other sites


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As a part of our healing mission, St. Anthony's is committed to providing quality health care services to patients regardless of their financial situation. We offer payment assistance for those who do not have insurance or who are in financial need.
The Affordable Care Act requires individuals to have health insurance coverage. The Health Insurance Marketplace enables visitors to research plans, apply for coverage and more. For more information about the Marketplace, visit healthcare.gov or call 1-800-318-2596.
A discount from the hospital's regular billed charges will be provided to patients who do not have insurance. The discount for uninsured patients will be 40 percent. Self-pay discounts apply to everyone who does not have health insurance, no matter their ability to pay. The discounts apply to medically necessary hospital services, unless a special discount rate already applies to that service.
The Medical Eligibility Program is a hospital service provided to patients at no cost. Patients may qualify for government programs which pay for all or part of their hospital and medical expenses. Patients may qualify if they are under 21 or over 65 years old, have children in the household, are pregnant, potentially disabled, or have been a victim of crime. Our hospital financial counselors will assist you with the application process.
Financial assistance is available to patients who do not have the means to pay for hospital expenses and do not qualify for any government programs. Financial assistance is based on a sliding scale, taking into consideration the following: Federal Poverty Guidelines, income, assets, family size, medical needs and catastrophic costs. Financial assistance is available to all patients regardless of whether or not they have health insurance. If patients qualify for financial assistance, the amount they will pay is never more than our Medicare cost. To be considered for this assistance program, patients will be required to provide information on their household finances through a confidential Financial Application. Documentation will be requested to verify their circumstances in order to determine eligibility. Download a copy of the Patient Financial Statement form () and Patient Financial Statement instructions ().
Patients are informed about our financial assistance process in a number of ways:
St. Anthony's Medical Center Financial Assistance Policy is reviewed annually and is subject to change without notice.
After appropriate discounts have been applied, arrangements may be made for an interest-free monthly payment plan.
St. Anthony's Medical Center follows the Fair Debt Collection Practices Act and refrains from certain collection practices, including body attachments, excessive phone calls and letters, foreclosures on principal residences, and actions that force bankruptcy.
If you have concerns about your ability to pay for your care or questions about financial assistance or self-pay discounts, please call 314-525-4747 or 800-843-6312, or e-mail us at firstname.lastname@example.com.
If you would like to receive an estimate of your bill prior to care being given, just let us know! See what information we need to provide the fastest response possible.
Request an online billing estimate.


text:
Chocolate Peppermint Shortbread
Total Time
Prep 15 mins
Cook 30 mins
From Betty Crocker. This originally had a chocolate glaze and crushed peppermint candies added to the top but I found they weren't necessary. Tip: Cut the rounds into wedges while they are warm, but do not remove them from the pie plates until they are completely cool so they won't break.
Ingredients Nutrition
- 1 cup butter, softened
- 1⁄2 cup granulated sugar
- 4 ounces bittersweet chocolate, melted & cooled
- 1⁄2 teaspoon peppermint extract
- 2 1⁄4 cups all-purpose flour
- 1⁄3 cup unsweetened baking cocoa
- Heat oven to 325°F Thoroughly grease 2 (9-inch) glass pie plates.
- In large bowl, beat butter, granulated sugar, chocolate and peppermint extract with electric mixer on medium speed until light and fluffy.
- On low speed, beat in flour and 1/3 cup cocoa.
- Divide dough in half. With lightly floured hands, press dough evenly in pie plates. Lightly score (about half-way through) into 12 wedges per plate and poke several holes with a fork into each wedge.
- Bake 22 to 24 minutes or until puffed and edges just begin to pull away from sides of pie plates.
- Cool in pie plates 5 minutes. Carefully cut each round along the previous score lines into 12 wedges. Cool completely in pie plates on cooling rack, about 30 minutes.


text:
École Airdrie Middle School (5-8)
Principal: Cathy Ziegler
Address: 332 1 Ave NE
School Profile
Grade Configuration: French Immersion and English Grade 5 - 8
Attendance Area Maps
Education Plan
2015 - 2019 — School Education Plan (Year 1)
Quote from Parent Advocates
"EAMS never stops thinking of ways to engage the kids. They constantly think 'outside the box' to find new ways for kids to explore and discover their talents."
-CP, parent
"This is a warm and caring school that reaches out to every kid as an individual. The kids, in turn, reach out to the community. They're involved with the community in so many ways."
-JA, parent


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WELCOME, The Chop Shop is the first radio show dedicated to guitar.All aspects of rock music incorporate the guitar to some extent. This show invites the listeners to hear the songs they know and love from different perspectives, while occasionally introducing the audience to some guitar gems they may have missed.
|Scheduled Guest - Chop Shop
|Week Of 5/2/16
|Kim Thayil from Soundgarden/Scott Holiday of Rival Sons
|Week Of 5/9/16
|Mike & Ryan from Red Sun Rising/Kenny Wayne Shepherd
|Week Of 5/16/16
|Zoltan Bathory from Five Finger Death Punch/Mark Tremonti
|Scheduled Guest - Chop Shop Classic
|Week Of 5/2/16
|Steve Vai
|Week Of 5/9/16
|Featured Guitarist Carlos Santana
|Week Of 5/16/16
|Paul Rodgers


text:
Can anyone tell me who are the prefered / lowest priced online Canadian / US shop for mtb bikes & components.
PS. In return I can tell anyone that is interested where the best places are in the UK.
Can anyone tell me who are the prefered / lowest priced online Canadian / US shop for mtb bikes & components.
PS. In return I can tell anyone that is interested where the best places are in the UK.
Originally Posted by spartacus88
I typically shop one of these three:
www.universalcycles.com (does not collect sales tax)
I have yet to find one with the lowest price in all categories. When I shop, I end up with this spreadsheet matrix of parts and prices.
I believe most will match prices, but I've never asked a dealer to meet a competitor's price.
I've used jensonusa.com and had stuff shipped to me in Toronto - they're awesome, and the fedex shipping they use is hassle-free with customs (stay clear of any company that ships UPS if you're shipping from the US to Canada). Bikeroom.com has gotten mixed reviews... they have great prices, but they are hit-or-miss on service. I'd suggest that if the price is 10-15% lower with bikeroom.com to just purchase it from your LBS (which is what I just did for a new M572 crankset - bought it at cycle-solutions for $140 instead of bikeroom.com for $119).
I have been buying from bikeroom for 2 years. Spent well over 3000$ there. And I live in a fairly hard to reach place. No hit or miss here. David the owner is cool and I recently met his son too. Very cool company keeping prices really low for us canadians who have to suffer with Norco as the lead distributor for Canada.
I've been very happy with Bikeroom... until my last order. I orded a set of BLACK Mavic CrossLand wheels, they arbitrarily changed my order to SILVER and credited me back the difference. I would have appreciated an email asking me if I wanted to change my order if there were no black sets available. I've emailed them about my concerns but there has been no reply.
when buying parts for my bike online, i usually check ebay, bikeroom.com and jensonusa.com and compare all the prices and the shipping costs, buying from wherevers cheaper. if the difference between the prices isnt too big, ill go with bikeroom over jenson or ebay just to avoid any extra duty/customs costs.
my experience with jenson has been excellent. my packages always arrive in a short amount of time and they're always packaged well. cant say the same about bikeroom though. my experience with them has been so-so. when i ordered my xt front derrailluer from them, they called me to find out if i wanted a newer model than the one i ordered, which i thought was cool. but when i ordered my 661 full bravo 2 from them i wasnt too pleased with the packaging it came in they sent it in the retail box without any padding or cusioning and the helmet could have been easily damaged en route. luckily, the helmet wasnt damaged (as far as i could tell), so im happy about that.
current ride: 2003 norco vps fluid 3.0 (custom build).
Jenson USA has been my best co. to deal with . they usually have it here in va. from ca. in 3-4 days even though I buy standard shipping. they price match,they have a great cs. dept., its easy to check back on out of stock stuff as they are on time with their guestimate, the people are friendly and knowledable about their products and the sport. my next favorite is Cambria Bicycle outfitters,then performance. id rather pay a couple $ more and know Im getting what I ordered and when its scheduled than save $.it took over 2 weeks for my Panaracer Cinders to arrive from a shop I will not name and they were IN STOCK.
for the creation was subjected to futility,not willingly , but because of Him who subjected it in hope...that he might be the firstborn among many brethren. Romans 8:20-29
the truth may not always be popular but its always true
I've used Pricepoint,com and Performance.com. Never had a prob with Pricepoint. Performance has had prob's with items listed on the website actually being out of stock... but every time this has happened to me Performance has resolved the situation in my favor!
For ANY on-line store: CALL on the PHONE if you have any special instructions/requests!!!!!!
I try to support a local LBS if the price is at all competitive, but some of the on-line close-outs are irresistable.


text:
Boutique Hotel Villa Soy
u Show map
7.6 / 10
Hotel description Boutique Hotel Villa Soy
In the name of our whole staff, we welcome you warmly to the Boutique Hotel Villa Soy.
We provide car parking space at the hotel for your convenience while you stay with us.
On arrival at the hotel you will receive a free bottle of water.
Our café-bistro is an ideal meeting place for family or friends.
Where you will stay
A desk is at your disposal in your room to comfortably write post cards or finish up any work you might have brought back from the office. You will also find satellite TV available in every room. Benefit from your own minibar filled with a large selection of beverages located in all of the rooms. Use the convenient telephone in your room to touch base with your friends or family. Radios are a standard feature in every room.
In your hotel room's bathroom you'll find a shower as well as a hand-held hair-dryer.
For your enjoyment, our hotel has soundproof windows.
Further information on the hotel
If you arrive after 10pm please let us know beforehand. English-speaking staff. Russian-speaking staff. Turkish-speaking staff. Italian speaking staff.
Reception hours
On business days from 6:00 AM to 10:00 PM
On the weekend from 6:00 AM to 10:00 PM
Check-in time:14:00
Check-out time:11:00
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Östliche Stadtmauerstraße 4, 91054 Erlangen, Germany
Distances (km)
|City district (Erlangen)
|Station (Fürth (Bayern) Hauptbahnhof)
|Airport (Nuremberg Airport (NUE))
To reach the hotel
Starting point:Exit 81-Erlangen west direction Erlangen-Dechsendorf/Weisendorf/Heßdorf you drive 270 ms. With St2240 on the left bend (signs to Erlangen) 6.9 kms. Further on Martinsbühler Strasse 270 m.... more
For HOTEL INFO guests
1 bottle of water per stay
Free WI-FI
Hotel features
- Single rooms: 12
- Double rooms: 16
- Triple rooms: 3
- Parking places with security personnel making their rounds
- Wireless LAN in public areas
- Garage
- Hotel foyer with video surveillance
- Fire detector
- No pets allowed
- Shoe-polishing machine
- Laundry service
- Entrances with video surveillance
Room features
- Separate luggage deposit
- Radio
- Mini bar
- Telephone
- Satellite TV
- Noise-protected windows
- Window that can be opened
- Hairdryer
- Wi-Fi
- Shower
- Change of hand towels
- Change of bed linen
- Smoke alarm
- Desk
- Non-smoking room
- Restaurant
- Bar
- Café/Bistro
Accepted credit card payments
- AmericanExpress
- MasterCard
- Visa
Hotel location
|City district
|0.7 km/0.4 mi
|11.65 km/7.2 mi
|1.23 km/0.8 mi
|14.31 km/8.9 mi


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The red open window light on my dash flashes on and off continually. I had to switch the rear trunk light off to keep the light from being on continually. I can unlock the car with my key button but I must lock the car with the key on the driver side to lock the car.
by REC in Houston, TX on June 03, 2010


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We regret that due to the technical limitations of our site, we are unable to offer eBooks or Audio Downloads to customers outside of the UK.
For further details please read our eBooks help.
Uma Aventura Nas Ilhas De Cabo Verbe (Paperback)Ana Maria Magahlaes, Isabel Alcada
Paperback Published: 01/07/2004
- Not in our warehouse
Publisher: Editorial Caminho
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The following is a list of courses that can be counted toward the unit requirement for the statistics minor degree in the Department of Mathematics. The list will be expanded if it is determined that courses not listed below also fit the necessary criteria. See the USC Catalogue for course descriptions. Students should be aware that registration in any course requires that all course prerequisites be satisfied, and that no prerequisite will be waived for the special purpose of the course being a minor elective. We urge students to plan their schedules and elective choices well in advance and have alternatives electives in mind, since courses are sometimes cancelled due to lack of enrollment. Note also that some courses below are less than four units, and students choosing such an elective should be aware that they are still subject to the total unit requirement of the minor degree. Further below are courses that may not be used as electives for the minor.
In addition, any elective approved for the Masters of Science in Statistics can be used for the statistics minor. As with some of the courses below, many of the Masters of Science electives are less than four units and students choosing such an elective should be aware that they are still subject to the total unit requirement of the minor degree. Students in need of one elective unit may want to consider taking a Directed Research course outside their major department.
Biological Sciences
BISC 478 Computational Genome Analysis
Biomedical Engineering
BME 210 Biomedical Computer Simulation Methods
BME 423 Statistical Methods in Biomedical Engineering
Business Administration
BUAD 311 Operations Management
BUAD 425 Data Analysis for Decision Making
Data Sciences and Operations
DSO 424 Business Forecasting
DSO 427 Designing Spreadsheet-Based Business Models
ECON 318 Introduction to Econometrics
ECON 419 Advanced Econometrics
Electrical Engineering
EE 465 Probabilistic Methods in Computer Systems Modeling
Health Promotion and Disease Prevention Studies
HP 350L Health Behavior Research Methods
Industrial Systems Engineering
ISE 426 Statistical Quality Control
Policy, Planning, and Development
PPD 502X Statistical Foundations for Public Management and Policy [2 units]
Preventative Medicine
PM 522AB Introduction to the Theory of Statistics
PSYC 421L Applied Multivariate Statistical Methods
The following courses may not be used as electives for the minor:


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Hello, I'm fairly new to mountain biking. I started a few years ago after my brother took me out for a ride. I'd had an very early Raleigh Mountain bike I purchased used about 15 years which mostly saw use in the campground or riding around the block with the kids. All that has changed, I know ride every Thursday night at Dash Point State Park in WA state. The ride is organized by Phil's South Side Cyclery here in Federal Way. We put some lights on the helmets and go year around. If your not from the Seattle/ Tacoma area, let me emphasize it is cold, rainy and dark.
I work in Finance and am a do it yourself mechanic type. Yes, a strange mix indeed. So, the first thing I did was look over my old mountain bike and thought I could use it. My brother looked at the 1.5" wide tires I was running and said you need wider tires. So, I purchased some 2.1" wide knobby tires for about $20 each. They were hung from the garage rafters for future use (that new bike someday). So, I searched and found a new 1.95" tire for $15 and a similar used one for $3. I took them home and they still rubbed on the frame (emphasis: a very early mountain bike). purchased those only to see the tread still rubbed. Four tires and no success yet, I'm thinking my wife is going to notice a dent in the family budget soon. I look around the garage and spot the tires on my daughters big box store bike. They were 26" and 1.95" wide but not as knobby but had some tread. So, I put those one the bike and they just fit. I started rideing with the Thursday night group again. It was January with lots of mud and rain. The tires were not working well. I needed a wider frame. About 2 months later I spotted a beat up Specialized Rockhopper frame at Recycled Cycles in Seattle for $15. I also purchase a used fork for $40 and have them press in the new headset into the frame. I'm out the door for $75. I located a seat post that fit at another bike shop (it was an odd size that year frame) for $15. I proceed to insert the seat post into the frame only to discover a broken off end seat post deep in the frame. I'm thinking great, all that money is wasted. Nope, not going to let this stop me. After a hour with a pin punch through a very small hole in the bottom bracket I drove out the seat post with minor cosmetic damage to the already questionable old frame. Onward, only to discover there are different bottom bracket widths and widths for bikes. You'll find the park tools repair book quite helpful at this point ($25). I found a used shimano square drive bottom bracket for $10 at the local bike shop that was the right size. I tossed on the old SunTour cranks and we were close to a completed bike. Within a week or two I was back out riding with the Thursdays night group with those big knobby tires purchased months ago installled. The bike worked well. But as time wore on, I found there were some shifting problems and and some of it was due to some compatability problems with the old SunTour equipment and mix of a few newer items. These were top of the line Suntour components , but I was tired of poor shifting. Off with the rear Sun Tour Deraileur on with something better. Being the cheap guy I was I started to add up the cost of the componets need and it didn't make sense. Well, that was until I opted to salvage shimano parts off my wifes 10 year old bike and just purchase her a Women's mountain bike I saw on clearance at Toy's R Us store closing its doors near by. More on this later, but never by a cheap bike even for your wife if your getting into riding. Now, I had a good mix of semi modern components along with a better set of wheels from my wifes old bike. I rode the Specialized about 3 times a week for the next year. It was nice and I continued to add a new part to improve it along the way. I upgraded some more components. I over $300 into the bike. I'm sure your all laughing by now along the local bike shop owner, because for about $300 I could have purchased an entry level mountain bike and save myself a lot of labor hours. But, the components were now better than a $300 bike would have. The components surrounded an old nicked up and rusty silver specialized frame. Still, not a bad ride.
I found I was really into this sport and I was keeping my eyes and ears open for the opporunity for a good deal on a new bike. I ended up with a Jamis Dakar Full Suspension Comp year end clearance for $1,300. It was great, but was a bit of a dent to the family budget. I kept the old specialized rockhopper as a back up bike, but recently was tempted when I saw a Jamis Dragon frame on clearance. I swapped out the $300 of components purchased above and added some Avid Juicy 7's along with a better suspension fork onto the Dragon frame. Within three short years I've radically changed my bikes and engage in the whole mountain bike activities. The enefit of doing what I did is it allowed me to get into the sport and learn all about the bikes. I was also purchasing all the necessary riding gear and such along the way as well (light, helmet, mountian bike shoes, clothing, etc.)
This summer, I entered a couple of local mountain bike races. My wife has also joined me in this sport as well. Remember the department store bike ... not a good idea. She went riding with my sister in law. Tried out her bike and commented how much lighter and easier to ride the Cannondale than the cheap Schwiin she had. I had a Jamis Dakota Comp Hard Tail comp under the Christmas tree for her that year. We're totally engaged in the mountian bike part of the sport. We went on a road ride, but really enjoy our local trails which have less car traffic. Our next step may be entering a cyclocross race with our mountain bikes this fall. Cyndi entered a Mountain bike race this summer as well. She took 2nd place at once race in remote Eastern Washington. I have to 40 lbs to pass her going up the hills. I'll fly by her going downhill in a technical section, but if the climb is long she'll catch and pass me up. I better get back in the saddle and shed those excess pounds.
I'm sure this forum will be a good place to share riding experiences.


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What does MBCB stand for?
MBCB stands for Medecine Buccale Chirurgie Buccale (French: Buccal Medicine Buccal Surgery)
This definition appears rarely and is found in the following Acronym Finder categories:
- Science, medicine, engineering, etc.
See other definitions of MBCB
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A new image from the Atacama Pathfinder Experiment (APEX) telescope in Chile shows a beautiful view of clouds of cosmic dust in the region of Orion.
"While these dense interstellar clouds seem dark and obscured in visible-light observations, APEX's LABOCA camera can detect the heat glow of the dust and reveal the hiding places where new stars are being formed.But one of these dark clouds is not what it seems".
In space, dense clouds of cosmic gas and dust are the birthplaces of new stars. In visible light, this dust is dark and obscuring, hiding the stars behind it. In order to better understand star formation, astronomers need telescopes that can observe at longer wavelengths. APEX, on the Chajnantor Plateau in the Chilean Andes, is the largest single-dish submillimetre-wavelength telescope operating in the southern hemisphere, and is ideal for ESO astronomers studying the birth of stars in this way reaching New Heights in Astronomy.
Located in the constellation of Orion (The Hunter), 1500 light-years away from Earth, the Orion Molecular Cloud Complex is the closest region of massive star formation to Earth, a treasury of bright nebulae, dark clouds and young stars.
"The new image shows just part of this vast complex in visible light. The bright patch below of the centre of the image is the nebula NGC 1999. This region when seen in visible light is what astronomers call a reflection nebula, where the pale blue glow of background starlight is reflected from clouds of dust. The nebula is mainly illuminated by the energetic radiation from the young star V380 Orionis lurking at its heart".
Astronomers using the Atacama Large Millimeter/submillimeter Array (ALMA) telescope have also seen a key stage in the birth of giant planets and vast streams of gas flowing across a gap in the disc of material around a young star. These are the first direct observations of such streams, which are expected to be created by giant planets guzzling gas as they grow. According to theory, the giant planets grow by capturing gas from the outer disc, in streams that form bridges across the gap in the disc. Read more…
Source: ESOAt blooms – SCIENCE, POLICY & DEVELOPMENTS