Patterned self-warming wipe substrates

Information

  • Patent Grant
  • 7924142
  • Patent Number
    7,924,142
  • Date Filed
    Monday, June 30, 2008
    15 years ago
  • Date Issued
    Tuesday, April 12, 2011
    13 years ago
Abstract
Generally stated, the present disclosure relates to wiping substrates such as wet wipes and dry wipes that include a thermal grill utilized to deliver a warming sensation. In an exemplary aspect, disposed on at least one structural layer of the wipe substrate is a thermal grill. The thermal grill includes an alternating pattern of thermally active areas and secondary areas that provide a feeling of warmth to a user of the wipe across the entire surface of the wipe. The thermally active portions of the wipe include a temperature change substance that when in liquid communication with an activation agent is adapted to provide a temperature change of at least 5° C. from the temperature of the secondary portion. By providing a thermal grill with thermally active portions, the entire wipe gives the user of the wipe a warming sensation.
Description
FIELD

The present disclosure generally relates to wipes that are self-warming or become warm quickly after dispensing. More particularly, wipes having alternating patterned thermally active areas that provide a warming sensation for the entire wipe is disclosed.


BACKGROUND

Wet wipes and dry wipes and related products have been commonly used by consumers for various cleaning and wiping tasks. For example, many parents have utilized wet wipes to clean the skin of infants and toddlers before and after urination and/or defecation. Many types of wipes both wet and dry are currently commercially available for this purpose.


Today, many consumers are demanding that personal health care products, such as wet wipes, have the ability to not only provide their intended cleaning function, but also to deliver a comfort benefit to the user. In recent studies, it has been shown that baby wet wipes currently on the market are sometimes perceived to be uncomfortably cold upon application to the skin, particularly for newborns. To mitigate this problem, there have been many attempts to produce warming products to warm the wipes to comfort the wet wipe users from the inherent cool sensation given off by the contact of the moistened wipes with the skin.


Warming wipes have been developed utilizing different chemistries, including use of reduction/oxidation reactions or providing crystallization enthalpy of a supersaturated solution capable of imparting a temperature change on the wipes that will provide heat. However, one drawback of utilizing these certain chemistries is the amount needed to warm the wipe.


Additionally, it is known that a sensation of heat is elicited within an individual when the individual touches interlaced warm and cool bars with their skin. The sensations of discomfort and temperature and even pain have been analogized to the burning sensation that accompanies touching extremely cold objects.


One of the prevailing explanations of this warming sensation is that the perception of “heat” is a fusion of sensations resulting from simultaneous activation of warm and cool sensors within the body. Modern physiological findings have confirmed the existence of separate cutaneous receptors for warm and cool. It is interesting to note that the cutaneous receptors that are associated with a cold sensation appear to be activated by low and high temperatures.


A thermal grill is a device that includes interlaced or alternating warm and cool portions that are able to provide a warming sensation to an individual when the individual touches the interlaced warm and cool portions. The relative size, shape, design, configuration, temperature, and orientation of the interlaced warm and cool portions may be varied to adjust the level of discomfort that can be generated within an individual that touches the thermal grill with their skin. However, there is a need to provide a thermal grill that does not provide a feeling of discomfort, but a pleasant feeling of warmth.


Based on the foregoing, there is a need in the art for wipes that can produce a warming sensation just prior to, or at the point of use, without using external heating products by providing the minimum amount of heating chemistries necessary to provide a warming sensation for the entire wipe substrate. It would be desirable if the wipes would produce a warming sensation within less than about 10 seconds after activation and raise the temperature of the wet wipe solution and the wipe substrate at least 5° C. or more for at least 20 seconds.


SUMMARY

Generally stated, the present disclosure relates to wiping substrates such as wet wipes and dry wipes including a thermal grill that is used to deliver a warming sensation. In an exemplary aspect, disposed on at least one structural layer of the wipe substrate is a thermal grill. The thermal grill includes an alternating pattern of thermally active areas and secondary areas that provide a feeling of warmth to a user of the wipe across the entire surface of the wipe. The thermally active portions of the wipe include a temperature change substance adapted to provide a temperature change of at least 5° C. from the temperature of the secondary portion when placed in communication with an activation agent.


In an exemplary aspect, the thermally active portions of the wipe include a temperature change substance adapted to provide a temperature change of at least 5° C. from the temperature of the secondary portion. In another aspect, the thermally active portions of the wipe include an amount of the temperature change substance in communication with an activation agent to provide a temperature change of between about 5° C. and about 30° C. from the temperature of the secondary portion, and more particularly between 10° C. and about 15° C. from the temperature of the secondary portion.


In another aspect, the secondary portions of the wipe are at room temperature. Correspondingly, temperatures in the thermally active areas would range from about 30° C. and about 55° C., and more particularly range from about 35° C. and about 40° C.


In another aspect, the thermally active portions and secondary portions form a pattern of bars extending substantially the entire length of the wipe. In an exemplary aspect, each thermally active portion has a width of about 0.05 centimeters to about 2 centimeters. In an exemplary embodiment, the width of the thermally active portion is substantially the same as the width of the secondary portion. In another embodiment, the width of the thermally active portions is between 50% to about 200% of the width of the secondary portions. For example, if each thermally active portion forms a bar pattern extending the length of the wipe having a width of about 1.0 centimeters then each secondary portion forms a bar pattern extending the length of the wipe having a width of about 1.0 centimeters.


In another aspect, the thermal grill contains at least two thermally active portions with at least one secondary portion between the at least two thermally active portions.


In an exemplary aspect, thermally active areas comprise a temperature change substance in liquid communication with an activation agent capable of imparting a temperature change to the products through an exothermic reaction. In one example, the temperature change substance and activation agent are topically applied to the thermally active area. In another aspect, the thermally active portions include an encapsulated composition containing the activation agent, and wherein upon rupture of the encapsulated portion, a reaction occurs between the activation agent and the temperature change substance.


In exemplary aspects, the temperature change substance is a supersaturated solution prepared from an aqueous solution of a salt, the salt being selected from the group consisting of sodium acetate, sodium sulfate, sodium thiosulfate, potash alum, calcium nitrate, potassium acetate, ammonium nitrate, potassium nitrate, lithium acetate, magnesium acetate, chromium alum, sodium carbonate, magnesium sulfate, sodium borate, sodium bromide, sodium chromate, calcium chloride, magnesium chloride, magnesium nitrate, disodium phosphate, urea nitrate, and hydrates thereof. To initiate the reaction an activation agent may be selected from the group consisting of sodium acetate, sodium sulfate, sodium sulfate decahydrate, sodium thiosulfate, potash alum, calcium nitrate, potassium acetate, ammonium nitrate, potassium nitrate, lithium acetate, magnesium acetate, chromium alum, sodium carbonate, magnesium sulfate, sodium borate, sodium bromide, sodium chromate, calcium chloride, magnesium chloride, magnesium nitrate, disodium phosphate, urea nitrate, and hydrates thereof. For example, a supersaturated solution may be encapsulated in the thermally active portions of an interior layer of the wipe, and wherein upon rupture of the encapsulated portion, an activation agent initiates a phase change in the supersaturated salt solution, causing it to crystallize, and imparts a temperature change to the thermally active potions.


In another exemplary aspect, the temperature change substance could be an aqueous solution having an oxidizing agent in liquid communication with a reducing agent, wherein a reaction occurs between the oxidizing agent and the reducing agent imparting a temperature change to the thermally active portions.


The oxidizing agent may be selected from hydrogen peroxide, sodium percarbonate, carbamide peroxide, ammonium persulfate, calcium peroxide, ferric chloride, magnesium peroxide, melamine peroxide, phthalimidoperoxycaproic acid, potassium bromate, potassium caroate, potassium chlorate, potassium persulfate, potassium superoxide, PVP-hydrogen peroxide, sodium bromate, sodium chlorate, sodium chlorite, sodium hypochlorite, sodium iodate, sodium perborate, sodium persulfate, strontium peroxide, urea peroxide, zinc peroxide, benzoyl peroxide, sodium peroxide, sodium carbonate, and barium peroxide. The reducing agent is selected from the group consisting of sodium ascorbate, sodium erythrobate, sodium sulfite, sodium bisulfite, thiourea, ammonium bisulfite, ammonium sulfite, ammonium thioglycolate, ammonium thiolactate, cysteamine hydrochloride, cysteine, cysteine hydrochloride, dithiothreitol, ethanolamine thioglycolate, glutathione, glyceryl thiopropionate, hydroquinone, p-hydroxyanisole, isooctyl thioglycolate, mercaptopropionic acid, potassium metabisulfite, potassium sulfite, potassium thioglycolate, sodium hydrosulfite, sodium hydroxymethane sulfonate, sodium metabisulfite, sodium thioglycolate, sodium tocopheryl phosphate, strontium thioglycolate, superoxide dismutase, thioglycerin, thioglycolic acid, thiolactic acid, thiosalicylic acid, thiosulfate salts, borohydride salts, hypophosphite salts, ascorbic acid and salts, tocopherol salts, esters, aluminum powder, and magnesium powder.


In a further exemplary aspect, the temperature change substance may be an ionic salt in liquid communication with an active metal wherein a metal ion replacement reaction occurs between an ionic salt and the active metal imparting a temperature change to the thermally active portions. The ionic salt may be selected from the group consisting of, but not limited to, copper chloride, copper oxide, and copper acetate. The active metal may be selected from the group consisting of aluminum and magnesium.





BRIEF DESCRIPTION


FIG. 1 illustrates a plan view of an exemplary wipe substrate of the present disclosure; and



FIG. 2 illustrates a cross sectional view of the wipe substrate shown in FIG. 1.





DETAILED DESCRIPTION

It is to be understood by one of ordinary skill in the art that the present discussion is a description of exemplary embodiments only, and is not intended as limiting the broader aspects of the present disclosure.


The present disclosure relates to wiping substrates such as wet wipes and dry wipes including a thermal grill that is used to deliver a warming sensation. Disposed on at least one structural layer of the wipe substrate is a thermal grill. The thermal grill includes an alternating pattern of thermally active areas and secondary areas that provide a feeling of warmth to a user of the wipe across the entire surface of the wipe. The thermally active portions of the wipe include a temperature change substance adapted to provide a temperature change of at least 5° C. from the temperature of the secondary portion. Surprisingly, it has been found that when incorporating a thermal grill into a wipe and then allowing a user to come into contact upon wipe use, the entire wipe provides a warming sensation to allow for a comforting feel to the skin.


Referring to FIGS. 1 and 2, an exemplary wipe substrate 10 of the present disclosure is illustrated. As used herein a wipe substrate is a flexible sheet or web material, which is useful for household chores, personal care, health care, food wrapping, and cosmetic application or removal. Non-limiting examples of suitable substrates of the present invention include nonwoven substrates, woven substrates, hydro-entangled substrates, air-entangled substrates, paper substrates such as tissue, toilet paper, or paper towels, waxed paper substrates, coform substrates, wet wipes, film or plastic substrates such as those used to wrap food, and metal substrates such as aluminum foil. Furthermore, laminated or plied together multi-layer substrates of two or more layers of any of the preceding substrates are suitable.


In an exemplary aspect, the wipe substrate of the pending disclosure is a nonwoven substrate. Nonwoven substrates can be formed by a variety of known forming processes, including airlaying, meltblowing, spunbonding, or bonded carded web formation processes. “Airlaid” refers to a porous web formed by dispersing fibers in a moving air stream prior to collecting the fibers on a forming surface. The collected fibers are then typically bonded to one another using, for example, hot air or a spray adhesive. Suitable examples of airlaid webs can be found in U.S. Pat. No. 5,486,166 issued to Bishop et al., U.S. Pat. No. 6,960,349 issued to Shantz et al., and U.S. Publication No. 2006/0008621 to Gusky et al., all incorporated by reference to the extent that they are consistent herewith.


The fibrous nonwoven substrate material may also comprise meltblown materials. “Meltblown” refers to fibers formed by extruding a molten thermoplastic material through a plurality of fine, usually circular, die capillaries as molten threads or filaments into converging high velocity gas (e.g., air) streams, generally heated, which attenuate the filaments of molten thermoplastic material to reduce their diameters. Thereafter, the meltblown fibers are carried by the high velocity gas stream and are deposited on a collecting surface or support to form a web of randomly dispersed meltblown fibers. Such a process is disclosed, for example, in U.S. Pat. No. 3,849,241 to Butin et al. Meltblowing processes can be used to make fibers of various dimensions, including macrofibers (with average diameters from about 40 to about 100 microns), textile-type fibers (with average diameters between about 10 and 40 microns), and microfibers (with average diameters of less than about 10 microns). Meltblowing processes are particularly suited to making microfibers, including ultra-fine microfibers (with an average diameter of about 3 microns or less). A description of an exemplary process of making ultra-fine microfibers may be found in, for example, U.S. Pat. No. 5,213,881 to Timmons et al. Meltblown fibers may be continuous or discontinuous and are generally self bonding when deposited onto a collecting surface.


“Spunbonded fibers” refers to small diameter fibers which are formed by extruding molten thermoplastic material as filaments from a plurality of fine, usually circular capillaries of a spinneret with the diameter of the extruded filaments then being rapidly reduced to fibers as by, for example, in U.S. Pat. No. 4,340,563 to Appel et al., and U.S. Pat. No. 3,692,618 to Dorschner et al., U.S. Pat. No. 3,802,817 to Matsuki et al., U.S. Pat. Nos. 3,338,992 and 3,341,394 to Kinney, U.S. Pat. No. 3,502,763 to Hartman, and U.S. Pat. No. 3,542,615 to Dobo et al., the contents of which are incorporated herein by reference in their entirety. Spunbond fibers are generally continuous and have diameters generally greater than about 7 microns, more particularly, between about 10 and about 20 microns.


“Bonded-carded web” refers to a web made from staple fibers sent through a combing or carding unit, which separates or breaks apart and aligns the fibers to form a nonwoven web. For example, the web may be a powder bonded carded web, an infrared bonded carded web, or a through-air bonded carded web. Examples of such materials may be found in U.S. Pat. No. 5,490,846 to Ellis et al.; U.S. Pat. No. 5,364,382 to Latimer; and U.S. Pat. No. 6,958,103 to Anderson et al.


Disposed on at least one structural layer of the wipe substrate 10 is a thermal grill. The thermal grill 12 is a device that has one or more thermally active portions 16 that are interlaced or alternated with one or more secondary portions 18. When the thermally active portions 116 are activated and an individual contacts the thermal grill 12, the temperature differences between thermally active portions 16 and secondary portions 18 of the thermal grill 12 cause the individual to feel a warm sensation across the entire width of the wipe substrate 10. The relative size, shape, design, configuration, temperature, and orientation of the interlaced thermally active portions 16 and secondary portions 18 may be varied in order to adjust the level of warmth that can be generated within an individual that touches the thermal grill 12 with their skin. In addition, thermally active portions 16 and secondary portions 18 may be positioned in a generally horizontal orientation as shown in FIG. 1, in a generally vertical orientation, or in any other suitable orientation. Additionally, the thermally active portions 16 may be applied in alternating stripes, a checkerboard pattern, a concentric pattern of aligned circles or other shapes, or any other suitable geometric or non-geometric pattern.


As used herein, the term thermally active portion and its plural refer to the portion of the thermal grill that is exothermic or potentially exothermic. The thermally active portions 16 may actually feel warm as it does upon activation, or the thermally active portions 16 may be potentially warm or warmable as it is before activation in that it includes material that will give off heat upon activation. Likewise, as used herein, the term secondary portion 18 and its plural refer to the portion of the thermal grill 12 that is unaltered, is endothermic or potentially endothermic. The secondary portions 18 may actually be at room temperature, feel cool as it does upon activation, or the secondary portions 18 may be potentially cool or coolable as it is before activation in that it includes material that will absorb heat upon activation.


It is generally the case that the greater the temperature differences between the thermally active portions 16 and secondary portions 18, the greater the probability that the user or the child will experience consequential discomfort. A temperature difference in the range of between about 5 to 10° C. is where a warming sensation typically begins to be experienced. At higher temperature differences, the intensity of the discomfort response and the percent of users who will have an uncomfortably warm feeling increases (see Bouhassira et al., “Investigation of the Paradoxical Painful Sensation (‘Illusion of Pain’) Produced by a Thermal Grill”—Pain 114 (2005) 160-167). As a result, the configuration and amount of temperature change substance on the thermally active portions 16 and secondary portions 18 may be varied in order to adjust the level of warmth that can be generated within an individual that touches the thermal grill 12 with their skin.


In another aspect, an amount of heating chemistry is added to the thermally active portions of the thermal grill 12 to provide warmer areas of the wipe. In an exemplary aspect, the thermally active portions 16 include a temperature change substance and an activation agent in liquid communication to provide a temperature change of at least 5° C. from the temperature of the secondary portion. More particularly, an amount of the temperature change substance is included to provide a temperature change of between about 5° C. and about 30° C. from the temperature of the secondary portion, and more particularly, an amount of the temperature change substance is added to provide a temperature change of between about 15° C. and about 20° C. from the temperature of the secondary portion. In an exemplary embodiment, the secondary portions of the wipe substrate will be at room temperature, typically about 20 to 22° C. Therefore, temperatures in the thermally active areas would range from about 30° C. and about 45° C., and more particularly range from about 35° C. and about 40° C.


Similarly, the width and spacing of the thermally active portions 16 and secondary portions 18 in the wipe substrate 10 may be varied to give the correct warming sensation to the user. In an exemplary aspect, the thermally active portions form a pattern of bars extending the length of the wipe having a width of between about 0.05 centimeters to 2 centimeters. In an exemplary embodiment, the width of the thermally active portion is substantially the same as the width of the secondary portion. In another embodiment, the width of the thermally active portions is between 50% to about 200% of the width of the secondary portions. For example, if each thermally active portion forms a bar pattern extending the length of the wipe having a width of about 1.0 centimeters and each secondary portion forms a bar pattern extending the length of the wipe having a width of about 1.0 centimeters.


Generally, the wipe substrates have one or more structural layers comprising similar or different materials. In one aspect, the thermal grill 12 is positioned on the structural layer in a location most likely to be in contact with the user, or an exterior surface of the wipe substrate 10. In another aspect, the thermal grill 12 may be placed on both sides of the wipe substrate. In still other aspects, the thermal grill 12 may be placed on an inner structural layer. The positioning of the thermal grill 12 can be on any structural layer as the heat provided by the thermal grill 12 applied to one exterior surface of the wipe effectively transfers through the wipe to the opposing side. The amount of temperature change substance that is provided depends on the chemistries involved and the amount of heat necessary to raise the temperature the specified amounts.


In one aspect of the present invention, the thermally active portions 16 of the thermal grill 12 are formed by applying alternating stripes of a temperature change substance to one of the structural layers of the wipe substrate 10. In various aspects, the temperature change substance may be applied to a thermally active area 16 by blending into a lotion which is then applied to one of the structural layers, such as the exterior surface of the wipe substrate. In another aspect, the temperature change substance may also be combined into a liquid concentrated solution and sprayed onto the structural layer. In still another aspect, the temperature change substance may be produced in crystalline form and sprinkled or otherwise applied to the structural layer, using a suitable adhesive if desired. In any of these aspects, the thermally active portions 16 may be applied in alternating stripes, a checkerboard pattern, a concentric pattern of aligned circles or other shapes, or any other suitable geometric or non-geometric pattern. Similarly, the thermally active portions may be colored using inks, dyes, or any other suitable substance to illustrate the thermal grill.


In terms of the temperature change aspect of the thermally active areas 16 of the wipe substrate 10, the temperature change substance provides a surface temperature change of from between about 5 and about 30° C. More desirably, the temperature change substance provides a surface temperature change when wet of from between about 10° C. to about 20° C., and particularly between about 15° C. for improved performance. Also, the warm sensation produced by the thermally active areas 16 should last from about 1 to about 120 seconds, and particularly from about 10 to about 60 seconds, such as about 30 seconds.


A suitable procedure for determining the surface temperature change of the wipe substrate containing thermally active areas with a temperature change substance is as follows. The test should be conducted in an environment having a stable temperature of 21 to 22° C. and a stable humidity of about 50 percent. The surface temperature of the wipe substrate at the location of the temperature change substance and at the location of the secondary portions is measured by utilizing a standard infrared video imaging camera. Video images are taken of the wipe substrate to illustrate the surface temperature at 20 second intervals during the first 120 second after the temperature change substance is activated and the peak temperature values of each thermally active portion and each secondary portion are recorded.


In one exemplary aspect, encapsulation, or any suitable means for delaying of the activating agent being in communication with the temperature change substance, may be used to delay the temperature change until desired by a user. Specifically, the activation agent can be included in an encapsulated composition and the temperature change substance can be included in an aqueous solution, or vice versa. A consumer would rupture the encapsulated activation agent by applying pressure to produce a reaction or initiate a phase change. Once ruptured, the contents of the encapsulated activation agent react with a temperature change substance in the aqueous solution, causing a reaction that results in the heating of the thermally active areas of the wipe substrate.


The encapsulated composition may include an encapsulation layer that substantially completely surrounds the activation agent or temperature change substance. The encapsulation layer allows the activation agent to be separate from the temperature change substance until activation by the user.


Generally, the encapsulation layer may include a crosslinked polymeric material. For example, the encapsulation layer may be comprised of a polymeric material, a crosslinked polymeric material, a metal, a ceramic or a combination thereof, that results in a shell material that may be formed during manufacturing. Specifically, the encapsulation layer may be comprised of superabsorbent materials, crosslinked sodium alginate, anionic dispersed latex emulsions, crosslinked polyacrylic acid, crosslinked polyvinyl alcohol, crosslinked polyvinyl acetate, silicates, carbonates, sulfates, phosphates, borates, polyvinyl pyrolidone, PLA/PGA, thermoionic gels, urea formaldehyde, melamine formaldehyde, polymelamine, crosslinked starch, nylon, ureas, hydrocolloids, and combinations thereof.


In another exemplary aspect, a lotion including the encapsulated activation agents is held in the dispenser separately from the wet wipe until the wet wipe is dispensed from the system. When the lotion including the activation agents is held separately from the wet wipe (and the aqueous wet wipe solution present on the wet wipe) until the wet wipe is dispensed, one advantage realized is that there is a significantly reduced chance of heating the wipe substrate before the desired time; that is, because the activation agents are held in a container separate from the aqueous solution of the wet wipe, the heating agent cannot contact the aqueous solution prior to mixing and lose potency prior to use. In an exemplary aspect, a wet wipe container including a cartridge configured to further define a lotion container formed integrally therewith and having an internal compartment for containing a lotion may be utilized. A lotion may be disposed within the internal compartment such that the lotion is out of contact with the wipes in the wipe container.


In another aspect, the lotion including the activation agent is held separately from the wipe, and therefore separately from the aqueous solution held on the wipe, until just prior to use, so that the activation agent could be introduced into the wipe substrate. Because the lotions are generally non-aqueous based, the heating agent can survive over time in the lotions without losing potency as there is no available water for the activation agent to react with. Once dispensed onto the wipe including the aqueous wet wipe solution, the activation agent can react with the water to produce heat without any need for rupturing of an encapsulated shell.


The cartridge on the dispenser generally may comprise an applicator that communicates with the internal compartment of the lotion container and is operable to apply lotion from the container onto a wipe as the wipe is dispensed from a slot in the cartridge. For example, rollers provided for generally free rotation relative to the lotion container may be configured to sealingly seat the roller in the lotion container so that a portion of the roller surface is disposed within the internal compartment of the lotion container, in contact with the lotion in the container, and the remaining portion of the roller surface is disposed exterior of the lotion container to double as part of the activating member as well.


Upon rotation of the roller, lotion coats the surface of the portion of the roller within the internal compartment and the coated portion is rotated exterior of the roller for transferring the lotion from the coated portion of the roller onto a wipe in a pattern creating a thermal grill as described above as the wet wipe passes through the nip formed between the rollers.


Suitable temperature change substances provide heat through a chemical reaction or phase change when put in communication with an activation agent. One exemplary temperature change substance for use with the present disclosure is a supersaturated solution. The supersaturated solution, upon activation and contact with an activation agent, is capable of evolving heat and causing a warming sensation on the skin of a user of the wipe. In one aspect, the activation agent is included in a core layer that may optionally include one or more encapsulating layers.


As noted above, the wipes may contain a composition comprising a supersaturated solution. Supersaturated solutions can be formed by heating aqueous solutions to a temperature of suitably from about 30° C. to about 100° C., and more suitably, from about 32° C. to about 90° C., and dissolving particles (e.g., salts or sugars) in the heated aqueous solutions. Typically, the aqueous solutions are made up of water. Under these heated conditions, more particles are capable of dissolving in the solutions, and upon cooling, a supersaturated solution is formed. These supersaturated solutions are unstable and will completely crystallize if exposed to an activation means such as a nucleation site (e.g., a seed crystal) as described more fully below. As the solute from the supersaturated solution crystallizes, heat is produced through crystallization enthalpy or latent heat of fusion.


Suitable supersaturated solutions, therefore, are capable of producing a high crystallization enthalpy and a high crystallization rate. Generally, the supersaturated solutions are capable of generating a crystallization enthalpy of at least about 70 Joules/gram, and more suitably at least about 125 Joules/gram. In one embodiment, the supersaturated solutions are capable of generating a crystallization enthalpy of from about 70 Joules/gram to about 500 Joules/gram. Additionally, the supersaturated solutions suitably produce a crystallized solid product having a crystallization rate, that is the rate at which the solution crystallizes, of at least about 0.01 centimeters/second, more suitably at least about 0.03 centimeters/second, even more suitably, at least about 0.05 centimeters/second, and even more suitably at least about 0.10 centimeters/second.


Additionally, the supersaturated solution for use in the wet wipes according to one embodiment suitably has a crystallization temperature of from about 25° C. to about 90° C. More suitably, the supersaturated solution has a crystallization temperature of from about 30° C. to about 60° C. supersaturated solutions with these crystallization temperatures are capable of warming the wipe to a level of giving the perception of warmth without overheating the wipe to risk skin burns.


One particularly suitable example is a supersaturated solution of sodium acetate. Specifically, to produce a supersaturated solution of sodium acetate, a solution of sodium acetate and water is heated to a temperature of greater than about 58° C. and allowed to slowly cool to room temperature. The resulting supersaturated solution of sodium acetate will crystallize once it comes into contact with an activation means such as a sodium acetate seed crystal. The supersaturated sodium acetate solution is capable of generating a crystallization enthalpy of 264 Joules/gram, and thus, will produce a temperature to heat the thermally active areas of the wipe substrate from about 50° C. to about 60° C. The generation of this amount of heat will generally lead to an increase in wet wipe temperature of approximately 15° C. to 20° C. Additionally, the supersaturated solution will produce a crystallized product, sodium acetate trihydrate, having a crystallization rate of as high as about 0.68 centimeters/second.


Other suitable supersaturated solutions for use in the wipes of the present disclosure include, for example, supersaturated solutions prepared from aqueous solutions of salts or sugars, the salt or sugar being selected from the group consisting of sodium sulfate, sodium thiosulfate, potash alum, calcium nitrate, potassium acetate, ammonium nitrate, potassium nitrate, lithium acetate, magnesium acetate, chromium alum, sodium carbonate, magnesium sulfate, sodium borate, sodium bromide, sodium chromate, calcium chloride, magnesium chloride, magnesium nitrate, disodium phosphate, urea nitrate, and hydrates thereof.


Typically, the activation means is comprised of one or more seed crystals having a similar chemistry as compared to the supersaturated solution. More particularly, a suitable activation means will have crystallographic data being within about 15% of that of the material to be crystallized in the supersaturated solution. As such, in the embodiment wherein the supersaturated solution is a supersaturated salt solution, the activation means is suitably a salt selected from the group consisting of sodium acetate, sodium sulfate, sodium sulfate decahydrate, sodium thiosulfate, potash alum, calcium nitrate, potassium acetate, ammonium nitrate, potassium nitrate, lithium acetate, magnesium acetate, chromium alum, sodium carbonate, magnesium sulfate, sodium borate, sodium bromide, sodium chromate, calcium chloride, magnesium chloride, magnesium nitrate, disodium phosphate, urea nitrate, and hydrates thereof.


For example, a supersaturated solution may be encapsulated in the thermally active portions of an interior layer of the wipe, and wherein upon rupture of the encapsulated portion, an activation agent initiates a phase change in the supersaturated salt solution, causing it to crystallize, and imparts a temperature change to the thermally active potions.


In another aspect, the reaction is caused by an oxidizing agent and a reducing agent coming into contact within the wipe substrate. As noted above, in one particularly suitable embodiment, the reactive chemistry is a reduction/oxidation reaction, involving an oxidizing agent and a reducing agent. When the oxidizing agent contacts the reducing agent, a reduction/oxidation reaction occurs that can generate heat, gas, or a combination thereof.


An oxidizing agent is the chemical reactant of the reduction/oxidation reaction that readily gains electrons. Suitable oxidizing agents include, for example, hydrogen peroxide, sodium percarbonate, carbamide peroxide, ammonium persulfate, calcium peroxide, ferric chloride, magnesium peroxide, melamine peroxide, phthalimidoperoxycaproic acid, potassium bromate, potassium caroate, potassium chlorate, potassium persulfate, potassium superoxide, PVP-hydrogen peroxide, sodium bromate, sodium chlorate, sodium chlorite, sodium hypochlorite, sodium iodate, sodium perborate, sodium persulfate, sodium perborate monohydrate, strontium peroxide, urea peroxide, zinc peroxide, benzoyl peroxide, sodium peroxide, sodium carbonate, barium peroxide, alkyl metal salts of perborates, and carbonate-peroxides.


In addition to the oxidizing agent, the reduction/oxidation reaction requires a reducing agent. The reducing agent is the reactant that reduces the oxidizing agent; that is the reactant of the reduction/oxidation reaction that donates electrons to the oxidizing agent. Typically, the reducing agent can be incorporated either into a microencapsulated composition or included in an aqueous solution, as long as the oxidizing agents described above do not contact the reducing agents until the desired point of use.


As noted above, the reactive chemistries can be incorporated into an aqueous solution or into a microencapsulated composition. In determining whether to incorporate specific reactants into the microencapsulated composition or into the aqueous solution, the primary factor to consider is whether or not the specific reactant is stable in the aqueous solution. Specifically, when the reactive chemistry is a reduction/oxidation reaction using hydrogen peroxide as the oxidizing agent and sodium sulfite as the reducing agent, hydrogen peroxide is included in an aqueous solution and sodium sulfite is incorporated into a microencapsulated composition as sodium sulfite has been found to be unstable when in an aqueous solution and further when in contact with the pulp fibers within the basesheet of a wipe substrate such as a wet wipe.


Suitable reducing agents for use in the wipe substrates of the present disclosure include, for example, sodium ascorbate, sodium erythrobate, sodium sulfite, sodium bisulfite, thiourea, ammonium bisulfite, ammonium sulfite, ammonium thioglycolate, ammonium thiolactate, cysteamine hydrochloride, cysteine, cysteine hydrochloride, dithiothreitol, ethanolamine thioglycolate, glutathione, glyceryl thiopropionate, hydroquinone, p-hydroxyanisole, isooctyl thioglycolate, mercaptopropionic acid, potassium metabisulfite, potassium sulfite, potassium thioglycolate, sodium hydrosulfite, sodium hydroxymethane sulfonate, sodium metabisulfite, sodium thioglycolate, sodium tocopheryl phosphate, strontium thioglycolate, superoxide dismutase, thioglycerin, thioglycolic acid, thiolactic acid, thiosalicylic acid, thiosulfate salts, borohydride salts, hypophosphite salts, ascorbic acid, ascorbic salts, ascorbic esters, and ascorbic derivatives (e.g., ascorbyl palmitate and ascorbyl polypeptide), tocopherol salts, tocopherol esters, and tocopherol derivatives (e.g., tocopherol acetate), aluminum powder, and magnesium powder.


Alternatively, the reactive chemistry is a metal ion replacement reaction. During a metal ion replacement reaction, a more active metal replaces a less active metal ion from the solution, generating heat as a byproduct. A suitable example is contacting an aluminum powder with a copper(II) chloride salt solution. The aluminum replaces the copper ion in the salt solution.


Suitable metals for use as the active metal in the metal ion replacement reaction include aluminum and magnesium. Suitable ionic salts that are capable of undergoing metal ion replacement include copper chloride, copper oxide, and copper acetate.


The present disclosure is illustrated by the following examples which are merely for the purpose of illustration and are not to be regarded as limiting the scope of the disclosure or manner in which it may be practiced.


EXAMPLE 1

A multiple layer wipe having an area of approximately 290 centimeters2 was prepared comprising about 70% pulp fiber and 30% melt-blown fibers and an aqueous wet wipe solution was added to the sheet. A strip of plastic film was placed over the wipe and a warming lotion was applied to the wipe substrate with a roller creating a patterned thermal grill on the wipe. The warming lotion comprises a magnesium chlorides temperature change substance and mineral oil applied to the surface of the wipe. In this example, heat is generated when the water in the wipe combines with the magnesium chloride in the warming lotion.


Approximately 1.2 grams of the warming lotion was applied to the wipe substrate covering approximately 35% of the wipe. Therefore, approximately 9.5 mg/centimeters2 of the warming lotion was added to the wipe. Images were taken utilizing an infrared camera and illustrated localized maximum temperatures of between 39 and 49° C. There was little heat distribution away from the area of application. However, due to the effect of the thermal grill, the entire wipe substrate gave the sensation of warmth upon touching of the wipe.


EXAMPLE 2

A multiple layer wipe having an area of approximately 290 centimeters2 was prepared comprising about 70% pulp fiber and 30% melt-blown fibers and an aqueous wet wipe solution was added to the sheet. A strip of plastic film was placed over the wipe and a warming lotion was applied to the wipe substrate with a roller creating a patterned thermal grill on the wipe. The warming lotion comprises a magnesium chlorides temperature change substance and mineral oil applied to the surface of the wipe. In this example, heat is generated when the water in the wipe combines with the magnesium chloride in the warming lotion.


Approximately 2.4 grams of the warming lotion was applied to approximately 35% of the wipe. Therefore, approximately 18 mg/centimeters2 of the warming lotion was added to the wipe. Images were taken utilizing an infrared camera and illustrated localized maximum temperatures of between 51 and 57° C. The temperature provided by this example is extremely warm and illustrates how the concentration of the warming lotion affects the temperature of the thermally active portions. Similar to example 1, there was little heat distribution away from the area of application. However, due to the effect of the thermal grill, the entire wipe substrate gave the sensation of warmth upon touching of the wipe.


In a preferred embodiment illustrated by the two examples, the amount of add-on lotion including temperature change substance provided for the thermally active areas of the wipe substrate may be between about 8 mg/centimeters2 and 15 mg/centimeters2 of an anhydrous magnesium chloride warming lotion and mineral oil.


When introducing elements of the present disclosure, the articles “a”, “an”, “the” and “said” are intended to mean that there are one or more of the elements. The terms “comprising”, “including” and “having” are intended to be inclusive and mean that there may be additional elements other than the listed elements.


As various changes could be made in the above formulations and products without departing from the scope of the disclosure, it is intended that all matter contained in the above description shall be interpreted as illustrative and not in a limiting sense.

Claims
  • 1. A wipe substrate comprising a thermal grill disposed on at least one structural layer of the wipe substrate, wherein the wipe substrate is selected from nonwoven substrates, woven substrates, hydro-entangled substrates, air-entangled substrates, and coform substrates; the wipe substrate having an external surface, the thermal grill comprising an alternating pattern of a thermally active portions and secondary portions, the thermally active portions comprising a temperature change substance and an activation agent in liquid communication to provide a temperature change of at least 5° C. from the temperature of the secondary portion; wherein the secondary portions are at room temperature.
  • 2. The wipe substrate of claim 1 wherein the thermally active portions include an amount of the temperature change substance to provide a temperature change of between about 5° C. and about 30° C. from the temperature of the secondary portion.
  • 3. The wipe substrate of claim 1 wherein the thermally active portions include an amount of the temperature change substance to provide a temperature change of between about 10° C. and about 15° C. from the temperature of the secondary portion.
  • 4. The wipe substrate of claim 1 wherein the thermally active portions and secondary portions form a pattern of bars extending substantially the entire length of the wipe.
  • 5. The wipe substrate of claim 4 wherein each thermally active portion has a width of about 0.05 centimeters to about 2 centimeters.
  • 6. The wipe substrate of claim 1 wherein each thermally active portion forms a bar extending the length of the wipe having a width of between about 50% and 200% of the width of a bar formed by each secondary portion.
  • 7. The wipe substrate of claim 1 wherein the thermal grill contains at least two thermally active portions with at least one secondary portion between the at least two thermally active portions.
  • 8. The wipe substrate of claim 1 wherein the temperature change substance comprises a supersaturated solution in liquid communication with an activation agent capable of imparting a temperature change to the products through crystallization enthalpy.
  • 9. The wipe substrate of claim 1, wherein the temperature change substance and the activation agent are topically applied to the thermally active area.
  • 10. The wipe substrate of claim 1, wherein the thermally active portions further comprise an encapsulated composition containing the activation agent, and wherein upon rupture of the encapsulated portion, a reaction occurs between the activation agent and the temperature change substance.
  • 11. The wipe substrate of claim 9, wherein the supersaturated solution is a supersaturated salt solution prepared from an aqueous solution of a salt, the salt being selected from the group consisting of sodium acetate, sodium sulfate, sodium thiosulfate, potash alum, calcium nitrate, potassium acetate, ammonium nitrate, potassium nitrate, lithium acetate, magnesium acetate, chromium alum, sodium carbonate, magnesium sulfate, sodium borate, sodium bromide, sodium chromate, calcium chloride, magnesium chloride, magnesium nitrate, disodium phosphate, urea nitrate, and hydrates thereof.
  • 12. The wipe substrate of claim 9, wherein the activation agent is selected from the group consisting of sodium acetate, sodium sulfate, sodium sulfate decahydrate, sodium thiosulfate, potash alum, calcium nitrate, potassium acetate, ammonium nitrate, potassium nitrate, lithium acetate, magnesium acetate, chromium alum, sodium carbonate, magnesium sulfate, sodium borate, sodium bromide, sodium chromate, calcium chloride, magnesium chloride, magnesium nitrate, disodium phosphate, urea nitrate, and hydrates thereof.
  • 13. A wipe substrate of claim 1 wherein the temperature change substance comprises an aqueous solution having an oxidizing agent in liquid communication with a reducing agent.
  • 14. The wipe substrate of claim 13 wherein the oxidizing agent is selected from the group consisting of hydrogen peroxide, sodium percarbonate, carbamide peroxide, ammonium persulfate, calcium peroxide, ferric chloride, magnesium peroxide, melamine peroxide, phthalimidoperoxycaproic acid, potassium bromate, potassium caroate, potassium chlorate, potassium persulfate, potassium superoxide, PVP-hydrogen peroxide, sodium bromate, sodium chlorate, sodium chlorite, sodium hypochlorite, sodium iodate, sodium perborate, sodium persulfate, strontium peroxide, urea peroxide, zinc peroxide, benzoyl peroxide, sodium peroxide, sodium carbonate, and barium peroxide.
  • 15. The wipe substrate of claim 14 wherein the reducing agent is selected from the group consisting of sodium ascorbate, sodium erythrobate, sodium sulfite, sodium bisulfite, thiourea, ammonium bisulfite, ammonium sulfite, ammonium thioglycolate, ammonium thiolactate, cysteamine hydrochloride, cysteine, cysteine hydrochloride, dithiothreitol, ethanolamine thioglycolate, glutathione, glyceryl thiopropionate, hydroquinone, p-hydroxyanisole, isooctyl thioglycolate, mercaptopropionic acid, potassium metabisulfite, potassium sulfite, potassium thioglycolate, sodium hydrosulfite, sodium hydroxymethane sulfonate, sodium metabisulfite, sodium thioglycolate, sodium tocopheryl phosphate, strontium thioglycolate, superoxide dismutase, thioglycerin, thioglycolic acid, thiolactic acid, thiosalicylic acid, thiosulfate salts, borohydride salts, hypophosphite salts, ascorbic acid and salts, tocopherol salts, esters, aluminum powder, and magnesium powder.
  • 16. The wipe substrate of claim 1 wherein the temperature change substance comprises an ionic salt in liquid communication with an active metal.
  • 17. The wipe substrate of claim 16 wherein the ionic salt is selected from the group consisting of copper chloride, copper oxide, and copper acetate.
  • 18. The wipe substrate of claim 16 wherein the active metal is selected from the group consisting of aluminum and magnesium.
US Referenced Citations (262)
Number Name Date Kind
2602302 Poux Jul 1952 A
2766478 Raley, Jr. et al. Oct 1956 A
3084664 Perlman et al. Apr 1963 A
3132688 Nowak May 1964 A
3141602 Anderson Jul 1964 A
3175558 Caillonette et al. Mar 1965 A
3199490 Karlik Aug 1965 A
3261347 Sherman Jul 1966 A
3338992 Kinney Aug 1967 A
3341394 Kinney Sep 1967 A
3363604 Pschibul Jan 1968 A
3370630 Haugh et al. Feb 1968 A
3388953 Browning Jun 1968 A
3502763 Hartmann Mar 1970 A
3516941 Matson Jun 1970 A
3542615 Dobo et al. Nov 1970 A
3585982 Hollinshead Jun 1971 A
3638786 Borecki et al. Feb 1972 A
3653585 Kazaros Apr 1972 A
3676190 Landler et al. Jul 1972 A
3691270 Charle et al. Sep 1972 A
3692618 Dorschner et al. Sep 1972 A
3707945 Boone Jan 1973 A
3756483 Schraeder Sep 1973 A
3802817 Matsuki et al. Apr 1974 A
3804061 Cassar et al. Apr 1974 A
3849241 Butin et al. Nov 1974 A
3865271 Gold Feb 1975 A
3900035 Welch et al. Aug 1975 A
3980203 Dearling Sep 1976 A
4041900 Charles Aug 1977 A
4100324 Anderson et al. Jul 1978 A
4106433 Fernando et al. Aug 1978 A
4106616 Boone Aug 1978 A
4132771 Schreiber et al. Jan 1979 A
4159316 Januszewski et al. Jun 1979 A
4340563 Appel et al. Jul 1982 A
4362715 Strianse et al. Dec 1982 A
4375448 Appel et al. Mar 1983 A
4379143 Sherry et al. Apr 1983 A
4381058 Chaussadas et al. Apr 1983 A
4407957 Lim Oct 1983 A
4436224 McInerny Mar 1984 A
4462224 Dunshee et al. Jul 1984 A
4516564 Koiso et al. May 1985 A
4585002 Kissin Apr 1986 A
4596250 Beisang, III et al. Jun 1986 A
4598664 Hamlin Jul 1986 A
4620502 Kimble Nov 1986 A
4626550 Hertzenberg Dec 1986 A
4667846 Marceau May 1987 A
4696050 Sengewald Sep 1987 A
4704116 Enloe Nov 1987 A
4747365 Tusch May 1988 A
4756299 Podella Jul 1988 A
4781193 Pagden Nov 1988 A
4798603 Meyer et al. Jan 1989 A
4798691 Kasai et al. Jan 1989 A
4860748 Chiurco et al. Aug 1989 A
4872442 Manker Oct 1989 A
4878764 Meyer Nov 1989 A
4886063 Crews Dec 1989 A
4904524 Yoh Feb 1990 A
4940464 Van Gompel et al. Jul 1990 A
4964543 Scheiber Oct 1990 A
4966286 Muckenfuhs Oct 1990 A
4981135 Hardy Jan 1991 A
4984530 Dutton Jan 1991 A
4991538 Davids et al. Feb 1991 A
5035321 Denton Jul 1991 A
5036978 Frank et al. Aug 1991 A
5045569 Delgado Sep 1991 A
5048687 Suzuki et al. Sep 1991 A
5067612 Tsuchiya et al. Nov 1991 A
5071706 Soper Dec 1991 A
5163558 Palumbo et al. Nov 1992 A
5167655 McCoy Dec 1992 A
5176672 Bruemmer et al. Jan 1993 A
5180637 Sumii Jan 1993 A
5194356 Sacripante et al. Mar 1993 A
5213881 Timmons et al. May 1993 A
5232118 Samuel Aug 1993 A
5265509 Chen Nov 1993 A
5266592 Grub et al. Nov 1993 A
5282687 Yee Feb 1994 A
5284703 Everhart et al. Feb 1994 A
5348750 Greenberg Sep 1994 A
5350624 Georger et al. Sep 1994 A
5361905 McQueeny et al. Nov 1994 A
5364382 Latimer et al. Nov 1994 A
5366801 Bryant et al. Nov 1994 A
5375616 Chen Dec 1994 A
5392945 Syrek Feb 1995 A
5415222 Colvin et al. May 1995 A
5415624 Williams May 1995 A
5418062 Budd May 1995 A
5425975 Koiso et al. Jun 1995 A
5435465 El Amin Jul 1995 A
5439104 Wolska Klis Aug 1995 A
5443084 Saleur Aug 1995 A
5467894 Altonen et al. Nov 1995 A
5484895 Meister et al. Jan 1996 A
5486166 Bishop et al. Jan 1996 A
5490846 Ellis et al. Feb 1996 A
5509915 Hanson et al. Apr 1996 A
5538531 Hudson et al. Jul 1996 A
5545197 Bowen Aug 1996 A
5598954 Salzano Feb 1997 A
5618008 Dearwester et al. Apr 1997 A
5624025 Hixon Apr 1997 A
5628769 Saringer May 1997 A
5637389 Colvin et al. Jun 1997 A
5649914 Glaug et al. Jul 1997 A
5656708 Meister Aug 1997 A
5677048 Pushaw Oct 1997 A
5681298 Brunner et al. Oct 1997 A
5712212 Scott et al. Jan 1998 A
5722774 Hartz Mar 1998 A
5728454 Inaba et al. Mar 1998 A
5733272 Brunner et al. Mar 1998 A
5738082 Page et al. Apr 1998 A
5747004 Giani et al. May 1998 A
5762710 Ngai et al. Jun 1998 A
5766389 Brandon et al. Jun 1998 A
5780047 Kamiya et al. Jul 1998 A
5785179 Buczwinski et al. Jul 1998 A
5785980 Mathewson Jul 1998 A
5792213 Bowen Aug 1998 A
5819989 Saraceni Oct 1998 A
5820973 Dodge, II et al. Oct 1998 A
5839608 Gillberg LaForce Nov 1998 A
5887759 Ayigbe Mar 1999 A
5944709 Barney et al. Aug 1999 A
5951762 Shangold et al. Sep 1999 A
5967665 MacDonald et al. Oct 1999 A
5975074 Koiso et al. Nov 1999 A
5993433 St. Louis et al. Nov 1999 A
6057372 Nobuhiro et al. May 2000 A
6059882 Steinhardt et al. May 2000 A
6085899 Thorsbakken Jul 2000 A
6096067 Cramer et al. Aug 2000 A
6121165 Mackey et al. Sep 2000 A
6127294 Koiso et al. Oct 2000 A
6171647 Holman Jan 2001 B1
6180124 Ohta et al. Jan 2001 B1
6213645 Beer Apr 2001 B1
6216920 Baggett Apr 2001 B1
6217717 Drummond et al. Apr 2001 B1
6217889 Lorenzi et al. Apr 2001 B1
6248097 Beitz et al. Jun 2001 B1
6248125 Helming Jun 2001 B1
6267975 Smith, III et al. Jul 2001 B1
6287580 Gott et al. Sep 2001 B1
6308341 Shelton Oct 2001 B1
6314971 Schneider Nov 2001 B1
6318555 Kuske et al. Nov 2001 B1
6319318 Pekarek et al. Nov 2001 B1
6321937 DeSimone et al. Nov 2001 B1
6322801 Lorenzi et al. Nov 2001 B1
6333109 Harada et al. Dec 2001 B1
6343491 Jung Feb 2002 B1
6346153 Lake et al. Feb 2002 B1
6387385 Wang May 2002 B1
6397560 Weder Jun 2002 B1
6401968 Huang et al. Jun 2002 B1
6431111 Zhang Aug 2002 B1
6436128 Usui Aug 2002 B1
6457434 Lazar Oct 2002 B1
6484514 Joseph et al. Nov 2002 B1
6503976 Zuckerman et al. Jan 2003 B2
6520942 Putman Feb 2003 B1
6528766 Parks et al. Mar 2003 B1
6547063 Zaveri et al. Apr 2003 B1
6547881 Klöckner Apr 2003 B1
6550633 Huang et al. Apr 2003 B2
6561696 Rusnak et al. May 2003 B1
6567696 Voznesensky et al. May 2003 B2
6592004 Huang et al. Jul 2003 B2
6598103 MacWilliams et al. Jul 2003 B2
6601705 Molina et al. Aug 2003 B2
6601737 Sandler Aug 2003 B1
6613144 Loertscher et al. Sep 2003 B1
6626570 Fox et al. Sep 2003 B2
6642427 Roe et al. Nov 2003 B2
6645190 Olson et al. Nov 2003 B1
6658432 Alavi et al. Dec 2003 B1
6663686 Geiger et al. Dec 2003 B1
6673358 Cole et al. Jan 2004 B1
6680084 Chtourou Jan 2004 B1
6708823 Cottingham et al. Mar 2004 B2
6708845 Weng Mar 2004 B2
6749148 Helfer Grand Jun 2004 B2
6752998 Verdrel Lahaxe et al. Jun 2004 B2
6770064 Ruscher Aug 2004 B1
6791004 Sprengard Eichel et al. Sep 2004 B2
6827080 Fish et al. Dec 2004 B2
6831051 Sommerville Roberts et al. Dec 2004 B2
6838154 Varona et al. Jan 2005 B1
6847011 McConnell et al. Jan 2005 B2
6866145 Richards et al. Mar 2005 B2
6868666 Frank et al. Mar 2005 B2
6869441 Agarwal et al. Mar 2005 B2
6881219 Agarwal et al. Apr 2005 B1
6881792 Harada et al. Apr 2005 B2
6890553 Sun et al. May 2005 B1
6890592 Seehafer et al. May 2005 B2
6903307 McConnell et al. Jun 2005 B1
6918513 Downey Jul 2005 B1
6946413 Lange et al. Sep 2005 B2
6952849 Pacella Oct 2005 B2
6958103 Anderson et al. Oct 2005 B2
6960349 Shantz et al. Nov 2005 B2
7008620 Sun et al. Mar 2006 B2
7021848 Gruenbacher et al. Apr 2006 B1
7083839 Fish et al. Aug 2006 B2
7321309 Cohen Jan 2008 B2
7517582 Amundson et al. Apr 2009 B2
7597954 Amundson et al. Oct 2009 B2
20020050659 Toreki et al. May 2002 A1
20020192268 Alwattari et al. Dec 2002 A1
20030082217 Afriat et al. May 2003 A1
20030084914 Simon May 2003 A1
20030105192 Li et al. Jun 2003 A1
20030175517 Voigt et al. Sep 2003 A1
20030232090 Ahmad et al. Dec 2003 A1
20040062732 Friscia et al. Apr 2004 A1
20040063603 Dave et al. Apr 2004 A1
20040069298 Minami Apr 2004 A1
20040084791 Han et al. May 2004 A1
20040116017 Smith, III et al. Jun 2004 A1
20040118862 Amundson Jun 2004 A1
20040121072 Xing et al. Jun 2004 A1
20040127880 Weber Jul 2004 A1
20040164085 Kitching et al. Aug 2004 A1
20040169299 Davis et al. Sep 2004 A1
20040254550 Huang et al. Dec 2004 A1
20040265589 Yamada et al. Dec 2004 A1
20050033251 Toreki et al. Feb 2005 A1
20050048090 Rau Mar 2005 A1
20050053647 Matusch et al. Mar 2005 A1
20050067423 Cho Mar 2005 A1
20050067726 Yan et al. Mar 2005 A1
20050113771 MacDonald et al. May 2005 A1
20050136765 Shannon Jun 2005 A1
20050169868 Mohammadi et al. Aug 2005 A1
20050226834 Lambino et al. Oct 2005 A1
20050250169 Gonzalez et al. Nov 2005 A1
20060003649 Runge et al. Jan 2006 A1
20060008621 Gusky et al. Jan 2006 A1
20060018953 Guillon et al. Jan 2006 A1
20060141882 Quincy et al. Jun 2006 A1
20060236998 Cohen Oct 2006 A1
20060252899 Himori et al. Nov 2006 A1
20060270585 Jordan et al. Nov 2006 A1
20060270586 Jordan et al. Nov 2006 A1
20060276356 Panandiker et al. Dec 2006 A1
20070049881 Ales et al. Mar 2007 A1
20070142797 Long et al. Jun 2007 A1
20070252712 Allen et al. Nov 2007 A1
20080045913 Johnson et al. Feb 2008 A1
20080140165 Cohen et al. Jun 2008 A1
20080145437 Amundson et al. Jun 2008 A1
Foreign Referenced Citations (84)
Number Date Country
2 346 223 Aug 2001 CA
29 12 972 Aug 1982 DE
31 01 474 Aug 1982 DE
34 47 833 Jul 1986 DE
35 35 330 Apr 1987 DE
39 22 159 Jan 1991 DE
197 16 254 Jan 1999 DE
199 20 685 Nov 2000 DE
199 37 884 Feb 2001 DE
100 02 590 Aug 2001 DE
201 08 351 Oct 2001 DE
100 26 453 Nov 2001 DE
102 34 257 Feb 2004 DE
0 077 005 Apr 1983 EP
0 288 909 Nov 1988 EP
0 351 907 Jan 1990 EP
0 370 600 May 1990 EP
0 252 553 Mar 1991 EP
0 863 240 Sep 1998 EP
0 865 755 Sep 1998 EP
0 897 719 Feb 1999 EP
0 953 312 Nov 1999 EP
1 038 793 Sep 2000 EP
1 166 866 Jan 2002 EP
1 181 911 Feb 2002 EP
1 186 286 Mar 2002 EP
1 191 092 Mar 2002 EP
1 229 097 Aug 2002 EP
1 247 568 Oct 2002 EP
1 334 921 Aug 2003 EP
0 994 650 Feb 2004 EP
1 051 478 Nov 2004 EP
1 479 432 Nov 2004 EP
1 495 704 Jan 2005 EP
2 669 205 May 1992 FR
2 823 137 Oct 2002 FR
1 370 633 Oct 1974 GB
2 168 031 Jun 1986 GB
2 192 171 Jan 1988 GB
2 297 490 Aug 1996 GB
08-112303 May 1996 JP
08-173471 Jul 1996 JP
2002-020739 Jan 2002 JP
WO 9304622 Mar 1993 WO
WO 9924159 May 1999 WO
WO 0037009 Jun 2000 WO
WO 0043286 Jul 2000 WO
WO 0106903 Feb 2001 WO
WO 0108658 Feb 2001 WO
WO 0110366 Feb 2001 WO
WO 0112147 Feb 2001 WO
WO 0112148 Feb 2001 WO
WO 0112149 Feb 2001 WO
WO 0135906 May 2001 WO
WO 0139704 Jun 2001 WO
WO 0142117 Jun 2001 WO
WO 0154661 Aug 2001 WO
WO 0164525 Sep 2001 WO
WO 0176439 Oct 2001 WO
WO 0189353 Nov 2001 WO
WO 0201129 Jan 2002 WO
WO 0206421 Jan 2002 WO
WO 02064069 Aug 2002 WO
WO 03000487 Jan 2003 WO
WO 03005876 Jan 2003 WO
WO 03018186 Mar 2003 WO
WO 03028515 Apr 2003 WO
WO 03048654 Jun 2003 WO
WO 03049939 Jun 2003 WO
WO 03059139 Jul 2003 WO
WO 03094644 Nov 2003 WO
WO 03099427 Dec 2003 WO
WO 2004014540 Feb 2004 WO
WO 2004016234 Feb 2004 WO
WO 2004043311 May 2004 WO
WO 2004047977 Jun 2004 WO
WO 2004084782 Oct 2004 WO
WO 2004108075 Dec 2004 WO
WO 2005011855 Feb 2005 WO
WO 2005011856 Feb 2005 WO
WO 2005018514 Mar 2005 WO
WO 2005018795 Mar 2005 WO
WO 2005055790 Jun 2005 WO
WO 2005087068 Sep 2005 WO
Related Publications (1)
Number Date Country
20090325838 A1 Dec 2009 US