Patent Grant
6949168
Consumers use paper-wiping products, such as facial tissues and bath tissues, for a wide variety of applications. Facial tissues are not only used for nose care but, in addition to other uses, may also be used as a general wiping product. Consequently, there are many different types of tissue products currently commercially available.
In some applications, tissue products are treated with polysiloxane lotions in order to increase the softness of the tissue. Adding silicone compositions to a tissue may impart improved softness to the tissue while maintaining the tissue's strength and while reducing the amount of lint produced by the tissue during use.
In some applications, tissue products may be treated with other beneficial agents as well. For example, in addition to softening agents such as polysiloxane lotions, other desirable agents may be added to a tissue in order to provide a benefit to the user. For example, vitamins, plant extracts, medications, antimicrobial compounds, and the like may also be added to the web in order to transfer the desired agent to the consumer upon use.
In the papermaking industry, various manufacturing techniques have been specifically designed to produce paper products which consumers find appealing. Manufacturers have employed various methods to apply chemical additives, such as silicone compositions and other beneficial agents, to the surface of a tissue web. Currently, one method of applying chemicals to the surface of a tissue web is the rotogravure printing process. A rotogravure printing process utilizes printing rollers to transfer chemicals onto a substrate. Chemicals that are applied to webs using the rotogravure printing process typically require the addition of water, surfactants, and/or solvents in order to prepare an emulsion to be printed onto the substrate. Such additions are not only costly but also increase wet-out time, drying time, and add process complexity.
Another method of applying chemical additives to the surface of a tissue web is spray atomization. Spray atomization is the process of combining a chemical with a pressurized gas to form small droplets that are directed onto a substrate, such as paper. One problem posed with atomization processes is that manufacturers often find it difficult to control the amount of chemical that is applied to a paper ply. Thus, a frequent problem with spray atomization techniques is that a large amount of over-spray is generated, which undesirably builds upon machinery as well as the surfaces of equipment and products in the vicinity of the spray atomizer. Furthermore, over-spray wastes the chemical being applied, and comprises a generally inefficient method of applying additives to a tissue web. Additionally, lack of control over the spray atomization technique also affects the uniformity of application to the tissue web.
In view of the above, a need exists in the industry for improving the method for application of chemical additives to the surface of a paper web.
Further, besides the above-mentioned difficulties in applying chemical additives to the surface of a paper web, some additives, such as softening agents, may also have a tendency to impart hydrophobicity to the treated paper web. Although hydrophobicity may be desirable in some applications, in other applications, increased hydrophobicity may adversely affect the product. For instance, increased hydrophobicity in a bath tissue may prevent the bath tissue from being wetted in a sufficient amount of time and prevent disintegration and dispersing when disposed in a commode or toilet. Hence, in some applications, it is difficult to find a proper balance between softness and absorbency, both of which are desirable attributes for tissues, particularly bath tissues.
Thus, a need also exists for a process of applying hydrophobic compositions to tissues for providing benefits to the tissue without increasing the hydrophibicity of the tissue beyond desirable limits.
In general, the present invention is directed to an improved process for applying compositions to paper webs, such as tissue webs, paper towels and wipers. The present invention is also directed to improved paper products made from the process.
The process of the present invention includes extruding a composition onto the surface of a paper web through a meltblown die. For instance, a paper web having a basis weight of less than about 60 gsm may be suitable for the present invention. The extruded composition is highly viscous and may form fibers as it is extruded, either continuous or discontinuous fibers, as desired. In one embodiment, the fibers may be attenuated fibers. In one embodiment, the composition may comprise between about 0.01% to about 30% of a beneficial agent and from about 70% to about 99% of a polysiloxane softener. In one embodiment, the composition may be a neat polysiloxane.
In one embodiment, the fibers may be deposited on the web surface so as to cover a portion of the total surface area. For instance, the fibers may cover between about 20% and about 80% of a surface of the web, more particularly between about 30% and about 50% of a surface of the web. In one embodiment, the fiber distribution can be heterogeneous across the surface of the web, with more fiber coverage in one area of the web and little or no fiber coverage in other areas.
The beneficial agents added to the web may be any beneficial agent, such as, for instance, aloe vera extract, vitamin E, petrolatum, or mixtures of beneficial agents. The polysiloxane softeners added to the web may be hydrophilic or hydrophobic polysiloxanes. In one embodiment, a single composition may be applied to the web consisting essentially of only polysiloxane softeners and beneficial agents. In general, the total add on rate to the web of the combined additives may be between about 0.05% and about 5% by weight of the web.
A composition applied to the web according to one embodiment of the present invention may be quite viscous, with a viscosity of at least about 1,000 cps. In one embodiment, the composition may have a viscosity of between about 1,000 cps and about 100,000 cps.
In one embodiment, loose fibers and lint may be removed from the surface of the web prior to deposition of the composition on the web.
The compositions of the present invention may be deposited onto the web surface with a meltblown die. In one embodiment, the die tips of the meltblown die may be protected from accumulation of dust and lint by the presence of an air boundary blocking device. In one embodiment, the die tips may be between about 0.5 inches and about 3 inches from the web surface as the composition is deposited on the web. In another embodiment, the die tips may be between about one and about two inches from the surface of the web as the composition is extruded onto the web. The meltblown die may generally include between about 2 and about 30 die tips per inch, more specifically between about 3 and about 20 die tips per inch.
In some embodiments, a composition may be deposited on both surfaces of the web. In order to properly align the web in the process, it may be desirous to guide the web by use of guide rolls which may contact the composition containing surface of the web immediately after the deposition process. In such embodiments, it may prove beneficial to clean the surface of the guide roll, such as with an oscillating brush or a vacuum box, to prevent build up of composition on the guide roll.
The paper products of the present invention may include a paper web formed of cellulosic fibers, at least one polysiloxane softener and, at least one beneficial agent, both of which may be applied to a surface of the web in the form of attenuated fibers. For example, the product may contain between about 0.001% and about 2% of the beneficial agent(s) by weight of the product, and between about 0.05% and about 3% of the polysiloxane softener(s) by weight of the product. The additives of the present invention may be applied to the surface of the web together, in a single composition or separately, as desired.
The product may contain a wide variety of combinations of various hydrophilic and/or hydrophobic polysiloxane softeners and beneficial agents.
In one embodiment, the products may have a wet out time of less than about 8 seconds, more specifically between about 4 and about 6 seconds.
The products of the present invention may be quite absorbent. For example, the products may have an absorbent capacity of between about 5 and about 20 times the weight of the dry product. In one embodiment, the product may have an absorbent capacity between about 8 and about 12 times the weight of the dry product.
A full and enabling disclosure of this invention is set forth in this specification. The following Figures illustrate the invention:
Repeated use of reference characters in the present specification and drawings is intended to represent the same or analogous features of the invention.
Reference now will be made to the embodiments of the invention, one or more examples of which are set forth below. Each example is provided by way of explanation of the invention, not as a limitation of the invention. In fact, it will be apparent to those skilled in the art that various modifications and variations may be made in the invention without departing from the scope or spirit of the invention. For instance, features illustrated or described as part of one embodiment may be used in another embodiment to yield a still further embodiment. Thus, it is intended that the present invention cover such modifications and variations as come within the scope of the appended claims and their equivalents. 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 invention, which broader aspects are embodied in the exemplary constructions.
In general, the present invention is directed to applying viscous chemical compositions through a meltblown die tip on to a paper web, such as a tissue web. It has been found by the present inventors that when compared with the rotogravure printing process and the spray atomizing process, the meltblown process is more efficient.
For example, in comparison to the rotogravure printing process, the process of the present invention for applying compositions to paper webs may be simpler and less complex. The process of the present invention also provides more flexibility with respect to operation parameters. For instance, it has been found that the process of the present invention provides better controls over flow rates and add on levels of the compositions being applied to the paper webs. In some applications, the process of the present invention may also allow the compositions to be applied to the paper webs at higher speeds in comparison to many rotogravure printing processes.
In comparison to spray atomization processes, the process of the present invention may provide greater control over application rates and may apply compositions to paper webs more uniformly. The process of the present invention also may better prevent against over application of the composition and may provide better controls over placement of the composition onto the web.
Another advantage to the process of the present invention is that the process is well suited to applying relatively high viscous chemical additives to paper webs. Thus, it has been discovered that additives may be applied to paper webs without first combining the additives with anything which could dilute the additives, e.g., solvents, surfactants, preservatives, antifoamers, and the like. As a result, the process of the present invention may be more economical and less complex than many conventional application systems.
In one embodiment, a composition containing a chemical additive in accordance with the present invention may be applied to a paper web in the form of fibers, such as, for instance, in the form or continuous fibers. Specifically, it has been discovered that under certain circumstances, compositions applied in accordance with the present invention will fiberize when extruded through the meltblown die tip. The ability to fiberize the compositions provides various advantages. For example, when formed into fibers, the composition is easily captured by the paper web. The fibers may also be placed on the web in specific locations. Further, when desired, the fibers will not penetrate through the entire thickness of the web, but instead, will remain on the surface of the web, where the chemical additives are intended to provide benefits to the consumer. For example, more than about 80% of the composition applied to the web in the form of fibers may remain on the surface of the treated web.
Another advantage of the present invention is that for some applications, a lesser amount of the chemical additive may be applied to the web than what was necessary in typical rotogravure processes while still obtaining an equivalent or better result. In particular, it is believed that since the chemical additive may be applied in a relatively viscous form without having to be formed into an emulsion or a solution and because the chemical additive may be applied as fibers uniformly over the surface of a web, it is believed that the same or better results may be obtained without having to apply as much of the chemical additive as was utilized in many prior art processes. For example, a softener may be applied to a web in a lesser amount while still obtaining the same softening effect in comparison to rotogravure processes and spray processes. In addition, the product also may, have better wettability, as may be measured by wet-out time. Further, since less of the chemical additive is needed, additional cost savings are realized.
It has also been discovered that in some applications treating paper webs in accordance with the present invention may significantly increase the wet strength of the webs. For instance, when applying certain compositions such as hydrophobic compositions, it has been discovered that the treated paper web will have an improved cross direction wet:dry ratio. As used herein, the “wet:dry ratio” is the ratio of the wet tensile strength divided by the dry tensile strength. For paper webs treated in accordance with the present invention, the cross direction wet:dry ratio may increase by at least 25% particularly by at least 40%, and more particularly by at least 50%.
For instance, tissue webs treated in accordance with the present invention with a hydrophobic composition, such as a polysiloxane softener, may have a cross direction wet:dry ratio of at least 0.45, particularly at least 0.48, and more particularly at least 0.50. By applying a hydrophobic composition to the surface of a tissue web in the form of continuous filaments, the application of the composition may be heterogeneous across the web surface, such that a network of non-wettable tissue is formed that may provide significant strength when the tissue is wet, but still allow for excellent absorbency due to a large amount of uncoated tissue between the filaments.
In one aspect of the present invention, a composition containing a hydrophobic chemical additive is applied to a tissue, such as a bath tissue. The chemical additive, may be, for instance, a softener. By applying the hydrophobic composition in a heterogeneous manner on the tissue surface, a tissue may be produced not only having a lotiony, soft feel, but also having good wettability, even with the addition of the hydrophobic composition. In this manner, viscous hydrophobic compositions may be applied to bath tissues for improving the properties of the tissue without, adversely affecting the wettability of the tissue.
In one embodiment of the present invention, more than one chemical additive may be combined and applied to a web. For example, a softener, such as a polysiloxane softener may be combined with one or more chemical agents which may provide a desired benefit to the consumer and then the combination may be applied to a paper web according to the present invention.
Possible beneficial agents that may be applied to paper webs in accordance with the present invention include, without limitation, anti-acne actives, antimicrobial actives, antifungal actives, antiseptic actives, antioxidants, cosmetic astringents, drug astringents, aiological additives, deodorants, emollients, external analgesics, film formers, fragrances, humectants, natural moisturizing agents and other skin moisturizing ingredients known in the art such as lanolin, opacifiers, skin conditioning agents, skin exfoliating agents, skin protectants, solvents, sunscreens, and surfactants. More specifically, vitamin E and aloe vera extracts are examples of beneficial agents which may be applied to a surface of a web according to the present inventive process.
The above chemical additives may be applied alone or in combination with other additives in accordance with the present invention. For example, the desired polysiloxane softeners may be mixed with the desired beneficial agents and applied together as a single composition. Alternatively, the softeners and beneficial agents may be applied separately, creating layers of additives on the surface of the paper web.
In one embodiment of the present invention, the process is directed to applying one or more softeners and one or more beneficial agents to a tissue web. The softener may be, for instance, a polysiloxane that makes a tissue product feel softer to the skin of a user. Suitable polysiloxanes that may be used in the present invention include amine, aldehyde, carboxylic acid, hydroxyl, alkoxyl, polyether, polyethylene oxide, and polypropylene oxide derivatized silicones, such as aminopolydialkylsiloxanes. When using an aminopolydialkysiloxane, the two alkyl radicals may be methyl groups, ethyl groups, and/or a straight branched or cyclic carbon chain containing from about 3 to about 8 carbon atoms. Some commercially available examples of polysiloxanes include WETSOFT CTW, AF-21, AF-23 and EXP-2025G of Kelmar Industries, Y-14128, Y-14344, Y-14461 and FTS-226 of the Witco Corporation, and Dow Corning 8620, Dow corning 2-8182 and Dow Corning 2-8194 of the Dow Corning Corporation.
In one embodiment, a polysiloxane softener of the following general chemical structure (hereinafter referred to as Structure 1) may be utilized in the process of the present invention:
wherein,
A is hydrogen; hydroxyl; or straight chain, branched or cyclic, unsubstituted or substituted, C1-C8 alkyl or alkoxy radicals;
R1-R8 are independently, a straight chain, branched or cyclic, unsubstituted or substituted, C1-C6 alkyl radical;
m is from 20 to 100,000;
p is from 1 to 5,000;
q is from 0 to 5,000;
B is the following:
—R9—[(OC2H5)r—(OC3H7)s]t—G—(R10)z—W
D is the following:
—R15—(OC2H5)x—(OC3H7)y—O—R16
Representative amino-functionalized species within the foregoing general Structure 1 include the following (the terms “EO” and “PO” refer to “ethylene oxide” and “propylene oxide” moieties, respectively):
Moreover, in some embodiments, a polysiloxane having the following general structure (hereinafter referred to as Structure 2) may also be utilized in the present invention:
wherein,
X is hydrogen; hydroxyl; or straight chain, branched or cyclic, unsubstituted or substituted, C1-C8 alkyl or C1-C8 alkoxyl radical;
Y is the following:
Representative species within the foregoing general structure (2) include the following (the terms “EO” and “PO” refer to “ethylene oxide” and “propylene oxide” moieties, respectively):
In the past, polysiloxanes were typically combined with water, preservatives, antifoamers, and surfactants, such as nonionic ethoxylated alcohols, to form stable and microbial-free emulsions and applied to tissue webs. Since the process of the present invention may accommodate higher viscosities, however, the polysiloxanes may be added directly to a tissue web or to another paper product without having to be combined with water, a surfactant or any other agent. For example, neat compositions, such as a neat polysiloxane composition or a neat beneficial agent may be applied to the surface of the web separately in any desired order in accordance with the present invention. In an alternative embodiment, a mixed composition including only a polysiloxane and a beneficial agent may be prepared and applied together in a single layer. Since the polysiloxane and the beneficial agents may be applied to a web without having to be combined with any other ingredients, the process of the present invention may be more economical and less complex than many prior processes. Further, as described above, it has also been discovered that lesser amounts of the chemical additives may be applied to the web while still obtaining the same or better results, which may provide additional cost savings.
In the past, polysiloxanes and other additives were also used sparingly in some applications due to their hydrophobicity. For instance, problems have been experienced in applying polysiloxane softeners to bath tissues due to the adverse impact upon the wettability of the tissue. By applying the polysiloxanes as fibers at particular areas on the web, however, it has been discovered that hydrophobic compositions may be applied to tissue webs for improving the properties of the webs while maintaining acceptable wettability properties. In particular, as will be described in more detail below, in one embodiment of the present invention, a hydrophobic composition may be applied in a discrete, discontinuous, or heterogeneous manner to a paper web in order to maintain a proper balance between improving the properties of the web through the use of the composition and maintaining acceptable absorbency and wettability characteristics. For instance, a composition may be applied to a surface of the web in such a fashion so as to apply varying amounts of the composition to the web at different surface locations. For example, the web may have composition in the form of fibers covering sections of the web, and no composition at other areas of the web, such as between the individual fibers which are extruded onto the web surface. In other words, the composition can cover the web in a heterogeneous fashion, with composition coverage varying across the surface of the web.
Referring to
In general, the composition stream 29 is applied to the web 21 after the web has been formed. The composition may be applied to the web, for instance, after the web has been formed and prior to being wound. Alternatively, the composition may be applied in a post treatment process in a rewinder system. As illustrated in
In this embodiment, a single composition containing one or more polysiloxane softeners combined with one or more beneficial agents is extruded to form a composition stream 29 that is directed onto the web 21. In general, any suitable extrusion device may be used in accordance with the present invention. In one embodiment, for instance, the extruder includes a meltblown die 27. A meltblown die is an extruder that includes a plurality of fine, usually circular, square or rectangular die capillaries or nozzles that may be used to form fibers. In one embodiment, a meltblown die may include converging high velocity gas (e.g. air) streams which may be used to attenuate the fibers exiting the nozzles. One example of a meltblown die is disclosed, for instance, in U.S. Pat. No. 3,849,241 to Butin, et al which is incorporated herein by reference.
As shown in
An exhaust fan 31 is located generally below the tissue web 21. The exhaust fan 31 is provided to improve air flow and to employ a pneumatic force to pull the composition stream 29 down on to the first side 45 of the tissue web 21. The exhaust fan 31 serves to remove from the immediate vicinity airborne particles or other debris through an exhaust duct 32. The exhaust fan 31 operates by pulling air using the rotating propeller 33 shown in dotted phantom in FIG. 1.
In
In one specific embodiment of the invention, a pressurized tank (not shown) transfers a gas, such as air, to the meltblown die 27 for forcing the composition through the die tip. Composition 40 is forced through the meltblown die 27 and extruded through, for instance, holes or nozzles spaced along the length of the die tip. In general, the size of the nozzles and the amount of the nozzles located on the meltblown die tip may vary depending upon the particular application.
For example, the nozzles may have a diameter from about 5 mils to about 25 mils, and particularly from about 5 mils to about 10 mils. The nozzles may be spaced along the die tip in an amount from about 3 nozzles per inch to about 50 nozzles per inch, and particularly from about 3 nozzles per inch to about 20 nozzles per inch.
Two streams of pressurized air converge on either side of the composition stream 29 after it exits the meltblown die 27. The resulting air pattern disrupts the laminar flow of the composition stream 29 and attenuates the fibers being formed as they are directed onto the surface of the web. Different sized orifices or nozzles will produce fibers having a different diameter.
In general, the fibers that may be formed according to the present invention include discontinuous fibers and continuous fibers. The fibers may have various diameters depending upon the particular application. For instance, the diameter of the fibers may vary from about 5 microns to about 100 microns. In one embodiment, continuous fibers are formed having a diameter of about 25 microns.
One embodiment of the process of the present invention is illustrated in FIG. 5. In this particular embodiment, the composition may be applied to both surfaces 45, 46 of a web 21 in a post treatment process. For example, the web 21 may be unwound from a roll 22. In this embodiment, the web is calendered using calendar rolls 25 and 26 prior to application of the composition. After being calendered, the web surface 45 which will be accepting the composition may be cleaned of loose fibers and lint by sheet cleaner 1 prior to application of the composition.
The compositions which may be applied to the surface of the web according to the present invention, whether neat compositions or mixtures, tend to be not only viscous, but also very tacky. For example, one embodiment of the present invention contemplates application of a neat polysiloxane composition, which is quite tacky. In addition, paper webs tend to carry a great deal of particulate matter, with a lot of lint and loose fibers associated with the base sheet. The combination of the tacky composition and the particulates associated with the paper web at the meltblown die may cause the die tips to become clogged and block the composition flow to the web. As such, the process and system of the present invention may prevent contact between particulate matter associated with the paper web and the die tips of the meltblown die and may therefore avoid the expense of down time of production due to clogged die tips.
Cleaning the surface of the web prior to application of the composition, such as at sheet cleaner 1, may prevent build up of lint and fibers at the die tips of the meltblown die 27. In the embodiment illustrated in
After the surface 45 of web 21 has been cleaned at sheet cleaner 1, a composition comprising the polysiloxane softener and, in one embodiment, the beneficial agent may be applied to the surface 45 of the web. In the illustrated embodiment, the composition may be applied by use of a meltblown die 27 which may extrude the composition stream and direct it to the surface of web 21. In an alternative embodiment, the different chemical additives may be applied to the surface of the web in separate steps, such as, for instance, with a series of meltblown dies, each extruding a different substance onto the surface of the web such that multiple layers of additive are built onto the web, wherein different layers comprise different additive compositions.
In order to further protect the die tips of the meltblown die 27 from build up of lint and loose fibers, the web 21 may pass through a boundary air blocking device 3 prior to reaching the meltblown die 27. A boundary air blocking device may be, for example, a stationary blocking device or a rotary blocking device which may deflect the flow of boundary air which may travel with the web and may carry lint and fiber which may clog the meltblown die tips.
The composition may be applied to the web 21 by use of meltblown die 27. In the embodiment wherein a meltblown die is used to extrude the composition onto the surface of the web, it has been discovered that the distance between the die tips and the web surface may be important not only for obtaining the desired coating pattern, but also for keeping lint and dust away from the die tips in order to prevent blockage of the composition flow. For instance, the die tips may be between about 0.5 inch and about 3 inches from the web surface 45 as the composition is applied to the web. In one embodiment, the die tips may be between about 1 inch and about 2 inches from the surface of the web during the application process.
The system of the present invention may also include a vacuum box 7. The vacuum box 7 is provided to improve air flow and to employ a pneumatic force to pull the composition stream 29 down on to the first side 45 of the tissue web 21.
In the embodiment illustrated in
Air intakes 28 may have a diameter which may depend, among other things, on the web speed of the system. For example, at a web speed of between about 1,000 and about 3,000 feet/minute air intakes 28 may have a diameter of between about ¼ inch and about 1 inch. In one embodiment, air intakes 28 may have a diameter of between about one-half inch and about two-thirds inch.
Generally, suitable vacuum pressure may be placed on the web when the angled rows of air intakes 28 comprise between about 3 and about 30 individual intakes per row of 10-inch width. In one embodiment, the rows may comprise between about 6 and about 15 individual air intakes per row of 20-inch width. For instance, a single row may include 10 individual air intakes 28.
After the composition has been applied to the surface 45 of the web 21, the web may be guided around a roll 11 to be properly aligned for application of the composition to the second surface 46 of the web 21. In guiding the web 21 around the roll 11, the surface 45 which now carries fibers of the composition 29 will contact the roll 11. Some of the composition may stick to the roll 11 as the web 21 is guided around roll 11. In order to prevent build up of the composition on the surface of the guide roll 11, roll 11 may be cleaned with a roll cleaner 9. For example, a roll cleaner such as an oscillating brush or a vacuum device may be used to prevent build up of composition 29 on guide roll 11.
The second side 46 of web 21 may then be applied with the same or a different polysiloxane composition in a process similar to that used to apply the composition 29 to the first side 45 of the web 21. As shown, the second side of the web 46 may have excess lint and fibers removed at sheet cleaner 1 before having the composition 29 applied to the surface 46 of the web 21 with meltblown die 27. The melt blown die tips may be protected from blockage due to lint and fibers carried in the air boundary with air boundary blocking device 3. Vacuum box 7 may provide desired air flow and help direct the deposit of the composition fibers on the surface 46 of the web 21.
Referring again to
The polysiloxane softeners may be added to the web at a total add on rate of from about 0.05% to about 3% by weight of the paper web. The polysiloxane softeners may include one or more polysiloxane softeners according to Structure 1, described above, one or more polysiloxane softeners according to Structure 2, described above, or a combination of polysiloxanes of both Structure 1 and Structure 2. When more than one polysiloxane softener is applied to the web surface, they may be mixed together and applied at one time, or applied in separate steps, forming separate fibrous layers on the web surface, as desired.
In addition to the polysiloxane softener, the products of the present invention may also include one or more beneficial agents. The beneficial agents may be added to the web at a total add on rate of from about 0.001% to about 1% by weight of the paper web. As with the softeners, the beneficial agents may be mixed together and/or with the softeners for combined application, or applied separately, as desired.
In one embodiment, a single composition may be applied which comprises a combination of one or more polysiloxane softening agents and one or more beneficial agents. For instance, a single composition may be prepared including a polysiloxane softener according to Structure 1, above, Aloe Vera extract and Vitamin E. In one embodiment, the composition may be added to the web at an add on rate for the polysiloxane of between about 0.1% and about 1% by weight of the web, an add on rates for the Aloe of between about 0.01% and about 1% by weight of the web, and an add on rate for the vitamin E of between about 0.01% and about 1% by weight of the web.
In one embodiment, a single composition may be applied which comprises from about 0.01% to about 30% by weight of the beneficial agents and from about 70% to about 99.99% by weight of one or more polysiloxane softeners. In one embodiment, the composition may include only the softeners and the beneficial agents, with no other additives.
The product web may have the polysiloxane softeners and the beneficial agents applied to the surface of the web in a variety of different layered arrangements and combinations. For example, all of the desired topical applications may be premixed and applied to the surface of the web at once, such that all of the fibrous additive on one side of the web is essentially the same and contains both the desired polysiloxanes and the desired beneficial agents. Alternatively, the different agents may be applied in separate steps, creating layers of fibers on the surface of the web, each layer comprising different additives. In addition, some of the additives, for example two different beneficial agents, may be pre-mixed and applied to the web surface together, while the other desired additives may be applied in one or more separate steps and form separate layers of fibers on the web either above or below the others, as desired. Any possible combination of additives is envisioned according to the present invention.
The viscosity of the composition may also vary depending upon the particular circumstances. When it is desired to produce fibers through the meltblown die, the viscosity of the composition should be relatively high. For instance, the viscosity of the composition may be at least 1000 cps, particularly greater than about 2000 cps, and more particularly greater than about 3000 cps. For example, the viscosity of the composition may be from about 1000 to over 100,000 cps, such as from about 1000 cps to about 50,000 cps and particularly from about 2000 to about 10,000 cps.
As stated above, the purpose for air pressure or air curtain 30a-b on either side of the composition stream 29 (in selected embodiments of the invention) is to assist in the formation of fibers, to attenuate the fibers, and to direct the fibers onto the tissue web. Various air pressures may be used.
The temperature of the composition as it is applied to a paper web in accordance with the present invention may vary depending upon the particular application. For instance, in some applications, the composition may be applied at ambient temperatures. In other applications, however, the composition may be heated prior to or during extrusion. The composition may be heated, for instance, in order to adjust the viscosity of the composition. The composition may be heated by a pre-heater prior to entering the meltblown die or, alternatively, may be heated within the meltblown die itself using, for instance, an electrical resistance heater.
In one embodiment, the composition containing the chemical additive may be a solid at ambient temperatures (from about 20° C. to about 23° C.). In this embodiment, the composition may be heated an amount sufficient to create a flowable liquid that may be extruded through the meltblown die. For example, the composition may be heated an amount sufficient to allow the composition to be extruded through the meltblown die and form fibers. Once formed, the fibers are then applied to a web in accordance with the present invention. The composition may resolidify upon cooling.
Examples of additives that may need to be heated prior to being deposited on a paper web include compositions containing behenyl alcohol. Other compositions that may need to be heated include compositions that contain a wax, that contain any type of polymer that is a solid at ambient temperatures, and/or that contain a silicone.
The process of the present invention may be used to apply compositions and chemical additives to numerous and various different types of products. For most applications, however, the present invention is directed to applying chemical additives to paper products, particularly wiping products. Such products include facial tissues and bath tissues that have a basis weight of less than about 60 gsm, particularly from about 20 gsm to about 60 gsm, and more particularly from about 25 gsm to about 45 gsm. The tissue web may be made exclusively of pulp fibers or, alternatively, may contain pulp fibers mixed with other fibers.
In one embodiment, a hydrophobic composition is applied to a tissue web in accordance with the present invention while preserving the wettability and absorbency characteristics of the web. For example, many chemical additives that may be applied to tissue products are hydrophobic and thus when applied to a bath tissue across the surface of the tissue may adversely interfere with the ability of the tissue to become wet and disperse when being disposed of after use. For instance, various aminopolysiloxane softening agents when applied to a tissue may render a tissue unacceptable for use as a bath tissue due to the hydrophobic nature of the polysiloxane, although improving the softness and feel of the tissue.
In accordance with one embodiment of the present invention, however, hydrophobic compositions such as aminopolysiloxanes may be applied to tissue webs and other paper products without adversely interfering with the wettability of the web. In this embodiment of the present invention, the hydrophobic composition is applied to the web in a discontinuous manner, such that the coverage of the composition is heterogeneous across the web surface. For instance, in accordance with the present invention, the hydrophobic composition may be applied across the surface of the web yet be applied to contain various voids in the coverage for permitting the web to become wet when contacted with water. For example, in one embodiment, the hydrophobic composition is applied to the web as fibers that overlap across the surface of the web but yet leave areas on the web that remain untreated. In other applications, however, it should be understood that the viscous composition may be extruded onto the web so as to cover the entire surface area.
Referring to
Geometric mean tensile strength (GMT) is the square root of the product of the machine direction tensile strength and the cross-machine direction tensile strength of the web. Tensile strength may be measured using an Instron tensile tester using a 3-inch jaw width (sample width), a jaw span of 2 inches (gauge length), and a crosshead speed of 25.4 centimeters per minute after maintaining the sample under TAPPI conditions for 4 hours before testing. The product webs of the present invention may have a geometric mean tensile strength of between about 500 g and about 1,000 g. In one embodiment, the webs of the present invention may have a geometric mean tensile strength of between about 650 g and about 800 g.
In the embodiment shown in
As used herein, a material is said to be “absorbent” if it may retain an amount of water equal to at least 100% of its dry weight. Absorbent Capacity refers to the amount of water that a saturated sample may hold relative to the dry weight of the sample and is reported as a dimensionless number (mass divided by mass).
A test for Absorbent Capacity may be performed according to Federal Government Specification UU-T-595b. It is made by cutting a 10.16 cm long by 10.16 cm wide (4 inch long by 4 inch wide) test sample, weighing it, and then saturating it with water for three minutes by soaking. The sample is then removed from the water and hung by one corner for 30 seconds to allow excess water to be drained off. The sample is then re-weighed, and the difference between the wet and dry weights is the water pickup of the sample expressed in grams per 10.16 cm long by 10.16 cm wide sample. The Absorbent Capacity value is obtained by dividing the total water pick-up by the dry weight of the sample. In general, the products of the present invention may have an Absorbent Capacity of between about 5 and about 20 times the weight of the dry paper product.
In one embodiment of the present invention, a hydrophobic softener may be applied to a bath tissue and still permit the bath tissue to disperse in water when disposed of. The softener, for instance, may be an aminopolydialkylsiloxane. In the past, when it has been attempted to apply softeners to bath tissue, typically a hydrophilically modified polysiloxane was used. The hydrophobic polysiloxanes, such as aminopolydialkylsiloxanes, however, not only have better softening properties, but are less expensive. Further, as described above, the process of the present invention allows lesser amounts of the additive to be applied to the tissue product while still obtaining the same or better results than many conventional processes.
One test that measures the wettability of a web is referred to as the “Wet Out Time” test. The Wet Out Time of paper webs treated in accordance with the present invention may be about 10 seconds or less, and more specifically about 8 seconds or less. For instance, paper webs treated in accordance with the present invention may have a Wet Out Time of about 6 seconds or less, still more specifically about 5 seconds or less, still more specifically from about 4 to about 6 seconds.
As used herein, “Wet Out time” is related to absorbency and is the time it takes for a given sample to completely wet out when placed in water. More specifically, the Wet Out Time is determined by cutting 20 sheets of the tissue sample into 2.5-inch squares. The number of sheets used in the test is independent of the number of plies per sheet of product. The 20 square sheets are stacked together and stapled at each corner to form a pad. The pad is held close to the surface of a constant temperature distilled water bath (23+/−2° C.), which is the appropriate size and depth to ensure the saturated specimen does not contact the bottom of the container and the top surface of the water at the same time, and dropped flat onto the water surface, staple points down. The time taken for the pad to become completely saturated, measured in seconds, is the Wet Out Time for the sample and represents the absorbent rate of the tissue. Increases in the Wet Out Time represent a decrease in the absorbent rate.
Any suitable tissue may be treated in accordance with the present invention. Further, a tissue product of the present invention may generally be formed by any of a variety of papermaking processes known in the art. In fact, any process capable of forming a paper web may be utilized in the present invention. For example, a papermaking process of the present invention may utilize adhesive creping, wet creping, double creping, embossing, wet-pressing, air pressing, through-air drying, creped through-air drying, uncreped through-drying, as well as other steps in forming the paper web.
Besides tissue products, however, the process of the present invention may also be applied to paper towels and industrial wipers. Such products may have a basis weight of up to about 200 gsm and particularly up to about 150 gsm. Such products may be made from pulp fibers alone or in combination with other fibers, such as synthetic fibers.
In one embodiment, various additives may be added to the composition in order to adjust the viscosity of the composition. For instance, in one embodiment, a thickener may be applied to the composition in order to increase its viscosity. In general, any suitable thickener may be used in accordance with the present invention. For example, in one embodiment, polyethylene oxide may be combined with the composition to increase the viscosity. For example, polyethylene oxide may be combined with a polysiloxane softener and a beneficial agent to adjust the viscosity of the composition to ensure that the composition will produce fibers when extruded through the meltblown die.
In order to further illustrate the present invention, a conventional polysiloxane formulation was applied to a through-dried tissue web using a rotogravure coater. For purposes of comparison, several different polysiloxane compositions were applied to the same bath tissue according to the present invention. In particular, neat polysiloxane compositions were fiberized using a uniform fiber depositor marketed by ITW Dynatec and applied in a discontinuous fashion to the tissue web.
More specifically, a single-ply, three-layered uncreped throughdried bath tissue was made using eucalyptus fibers for the outer layers and softwood fibers for the inner layer. Prior to pulping, a quaternary ammonium softening agent (C-6027 from Goldschmidt Corp.) was added at a dosage of 4.1 kg/metric ton of active chemical per metric ton of fiber to the eucalyptus furnish. After allowing 20 minutes of mixing time, the slurry was dewatered using a belt press to approximately 32% consistency. The filtrate from the dewatering process was either sewered or used as pulper make-up water for subsequent fiber batches but not sent forward in the stock preparation or tissue making process. The thickened pulp containing the debonder was subsequently re-dispersed in water and used as the outer layer furnishes in the tissue making process.
The softwood fibers were pulped for 30 minutes at 4 percent consistency and diluted to 3.2 percent consistency after pulping, while the debonded eucalyptus fibers were diluted to 2 percent consistency. The overall layered sheet weight was split 30%/40%/30% among the eucalyptus/refined softwood/eucalyptus layers. The center layer was refined to levels required to achieve target strength values, while the outer layers provided the surface softness and bulk. Parez 631NC was added to the center layer at 2-4 kilograms per ton of pulp based on the center layer.
A three layer headbox was used to form the web with the refined northern softwood kraft stock in the two center layers of the headbox to produce a single center layer for the three-layered product described. Turbulence-generating inserts recessed about 3 inches (75 millimeters) from the slice and layer dividers extending about 1 inch (25.4 millimeters) beyond the slice were employed. The net slice opening was about 0.9 inch (23 millimeters) and water flows in all four headbox layers were comparable. The consistency of the stock fed to the headbox was about 0.09 weight percent.
The resulting three-layered sheet was formed on a twin-wire, suction form roll, former with forming fabrics being Lindsay 2164 and Asten 867a fabrics, respectively. The speed of the forming fabrics was 11.9 meters per second. The newly-formed web was then dewatered to a consistency of about 20-27 percent using vacuum suction from below the forming fabric before being transferred to the transfer fabric, which was traveling at 9.1 meters per second (30% rush transfer). The transfer fabric was an Appleton Wire T807-1. A vacuum shoe pulling about 6-15 inches (150-380 millimeters) of mercury vacuum was used to transfer the web to the transfer fabric.
The web was then transferred to a throughdrying fabric (Lindsay wire T1205-1). The throughdrying fabric was traveling at a speed of about 9.1 meters per second. The web was carried over a Honeycomb throughdryer operating at a temperature of about 350° F., (175° C.) and dried to final dryness of about 94-98 percent consistency. The resulting uncreped tissue sheet was then wound into a parent roll.
The parent roll was then unwound and the web was calendered twice. At the first station the web was calendered between a steel roll and a rubber covered roll having a 4 P&J hardness. The calendar loading was about 90 pounds per linear inch (pli). At the second calendaring station, the web was calendered between a steel roll and a rubber covered roll having a 40 P&J hardness. The calender loading was about 140 pli. The thickness of the rubber covers was about 0.725 inch (1.84 centimeters).
A portion of the web was then fed into the rubber-rubber nip of a rotogravure coater to apply the a polydimethylsiloxane emulsion to both sides of the web. The aqueous emulsion contained 25% polydimethylsiloxane (Wetsoft CTW of Kelmar Industries); 8.3% surfactant; 0.75% antifoamer and 0.5% preservative.
The gravure rolls were electronically engraved, chrome over copper rolls supplied by Specialty Systems, Inc., Louisville, Ky. The rolls had a line screen of 200 cells per lineal inch and a volume of 6.0 Billion Cubic Microns (BCM) per square inch of roll surface. Typical cell dimensions for this roll were 140 microns in width and 33 microns in depth using a 130 degree engraving stylus. The rubber backing offset applicator rolls were a 75 shore A durometer cast polyurethane supplied by Amerimay Roller company, Union Grove, Wis. The process was set up to a condition having 0.375 inch interference between the gravure rolls and the rubber backing rolls and 0.003 inch clearance between the facing rubber backing rolls. The simultaneous offset/offset gravure printer was run at a speed of 2000 feet per minute using gravure roll speed adjustment (differential) to meter the polysiloxane emulsion to obtain the desired addition rate. The gravure roll speed differential used for this example was 1000 feet per minute. The process yielded an add-on level of 2.5 weight percent total add-on based on the weight of the tissue (1.25% each side).
Another portion or section of the formed tissue web was then fed through a uniform fiber depositor (UFD—a type of meltblown die) as described above. The uniform fiber depositor had 17 nozzles per inch and operated at an air pressure of 20 psi. The die applied a fiberized neat polysiloxane composition onto the web. The polysiloxanes used in this example included
Wetsoft CTW, a polydimethylsiloxane of Kelmar Industries
AF-23, a reactive aminoethylaminopropyl polysiloxane of Kelmar Industries
EXP-2076, an alkoxy functional poly(dialkyl)siloxane of Kelmar Industries
SWS-5000, a linear non-reactive poly(dialkyl)siloxane of Kelmar Industries. The polysiloxanes were added to the web to yield an add-on level as shown in Table 1, below.
After the webs were formed, each web was tested for Wet Out Time and for geometric mean tensile strength (GMT) as described above. In addition, the webs were tested for softness and stiffness values which were obtained through a Sensory Profile Panel testing method. A group of 12 trained panelists were given a series of tissue prototypes, one sample at a time. For each sample, the panelists rate the tissue for softness and stiffness on a letter grade scale, with A being the highest ranking. Results are reported as an average of panel rankings. The following results were obtained:
As shown above, the tissue samples treated with the uniform fiber deposition method generally had a shorter wet out time with a stronger geometric mean tensile strength and excellent stiffness and softness characteristics.
It is 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 invention, which broader aspects are embodied in the exemplary constructions. The invention is shown by example in the appended claims.
| Number | Name | Date | Kind |
|---|---|---|---|
| 2345543 | Wohnsiedler et al. | Mar 1944 | A |
| 2926116 | Keim | Feb 1960 | A |
| 2926154 | Keim | Feb 1960 | A |
| 3556932 | Coscia et al. | Jan 1971 | A |
| 3556933 | Stamford et al. | Jan 1971 | A |
| 3700623 | Keim | Oct 1972 | A |
| 3722469 | Bartley et al. | Mar 1973 | A |
| 3772076 | Keim | Nov 1973 | A |
| 3849241 | Butin et al. | Nov 1974 | A |
| 3865078 | De Howitt et al. | Feb 1975 | A |
| 3885158 | Flutie et al. | May 1975 | A |
| 3899388 | Petrovich et al. | Aug 1975 | A |
| 3905329 | Cone et al. | Sep 1975 | A |
| 3930465 | Schuierer | Jan 1976 | A |
| 4005028 | Heckert | Jan 1977 | A |
| 4005030 | Heckert | Jan 1977 | A |
| 4016831 | James et al. | Apr 1977 | A |
| 4023526 | Ashmus et al. | May 1977 | A |
| 4061001 | Von Der Eltz et al. | Dec 1977 | A |
| 4081318 | Wietsma | Mar 1978 | A |
| 4089296 | Barchi | May 1978 | A |
| 4099913 | Walter et al. | Jul 1978 | A |
| 4118526 | Gregorian et al. | Oct 1978 | A |
| 4129528 | Petrovich et al. | Dec 1978 | A |
| 4147586 | Petrovich et al. | Apr 1979 | A |
| 4158076 | Wallsten | Jun 1979 | A |
| 4159355 | Kaufman | Jun 1979 | A |
| 4184914 | Jenkins | Jan 1980 | A |
| 4193762 | Namboodri | Mar 1980 | A |
| 4198316 | Nahta | Apr 1980 | A |
| 4222921 | Van Eenam | Sep 1980 | A |
| 4230746 | Nahta | Oct 1980 | A |
| 4237818 | Clifford et al. | Dec 1980 | A |
| 4263344 | Radvan et al. | Apr 1981 | A |
| 4276339 | Stoveken | Jun 1981 | A |
| 4279964 | Heller | Jul 1981 | A |
| 4288475 | Meeker | Sep 1981 | A |
| 4297860 | Pacifici et al. | Nov 1981 | A |
| 4305169 | Vidalis | Dec 1981 | A |
| 4343835 | Jones et al. | Aug 1982 | A |
| 4348251 | Pauls et al. | Sep 1982 | A |
| 4364784 | Van Wersch et al. | Dec 1982 | A |
| 4366682 | Keller | Jan 1983 | A |
| 4384867 | Grüber | May 1983 | A |
| 4385954 | Pauls et al. | May 1983 | A |
| 4387118 | Shelton | Jun 1983 | A |
| 4400953 | Driessen et al. | Aug 1983 | A |
| 4402200 | Clifford et al. | Sep 1983 | A |
| 4408996 | Baldwin | Oct 1983 | A |
| 4426418 | Coleman et al. | Jan 1984 | A |
| 4435965 | Sasseville et al. | Mar 1984 | A |
| 4440808 | Mitter | Apr 1984 | A |
| 4442771 | Mitter | Apr 1984 | A |
| 4444104 | Mitter | Apr 1984 | A |
| 4453462 | Mitter | Jun 1984 | A |
| 4463467 | Grüber et al. | Aug 1984 | A |
| 4463583 | Krüger et al. | Aug 1984 | A |
| 4474110 | Rosner | Oct 1984 | A |
| 4497273 | Mitter | Feb 1985 | A |
| 4498318 | Mitter | Feb 1985 | A |
| 4501038 | Otting | Feb 1985 | A |
| 4502304 | Hopkins | Mar 1985 | A |
| 4529480 | Trokhan | Jul 1985 | A |
| 4534189 | Clifford | Aug 1985 | A |
| 4551199 | Weldon | Nov 1985 | A |
| 4552778 | Zimmer | Nov 1985 | A |
| 4557218 | Sievers | Dec 1985 | A |
| 4559243 | Pässler et al. | Dec 1985 | A |
| 4562097 | Walter et al. | Dec 1985 | A |
| 4571360 | Brown et al. | Feb 1986 | A |
| 4576112 | Funger et al. | Mar 1986 | A |
| 4581254 | Cunningham et al. | Apr 1986 | A |
| 4597831 | Anderson | Jul 1986 | A |
| 4603176 | Bjorkquist et al. | Jul 1986 | A |
| 4605702 | Guerro et al. | Aug 1986 | A |
| 4612874 | Mitter | Sep 1986 | A |
| 4618689 | Traver et al. | Oct 1986 | A |
| 4646675 | Arthur et al. | Mar 1987 | A |
| 4655056 | Zeiffer | Apr 1987 | A |
| 4665723 | Zimmer | May 1987 | A |
| 4667882 | Pacifici | May 1987 | A |
| 4699988 | Traver et al. | Oct 1987 | A |
| 4731092 | Berendt | Mar 1988 | A |
| 4734100 | Berendt et al. | Mar 1988 | A |
| 4741739 | Berendt et al. | May 1988 | A |
| 4762727 | Voswinckel | Aug 1988 | A |
| 4773110 | Hopkins | Sep 1988 | A |
| 4778477 | Lauchenauer | Oct 1988 | A |
| 4792619 | Berendt et al. | Dec 1988 | A |
| 4799278 | Beeh | Jan 1989 | A |
| 4833748 | Zimmer et al. | May 1989 | A |
| 4872325 | Moser et al. | Oct 1989 | A |
| 4894118 | Edwards et al. | Jan 1990 | A |
| 4911956 | Gabryszewski et al. | Mar 1990 | A |
| 4912948 | Brown et al. | Apr 1990 | A |
| 4943350 | Bogart et al. | Jul 1990 | A |
| 4950545 | Walter et al. | Aug 1990 | A |
| 5008131 | Bakhshi | Apr 1991 | A |
| 5009932 | Klett et al. | Apr 1991 | A |
| 5048589 | Cook et al. | Sep 1991 | A |
| 5059282 | Ampulski et al. | Oct 1991 | A |
| 5089296 | Bafford et al. | Feb 1992 | A |
| 5098979 | O'Lenick, Jr. | Mar 1992 | A |
| 5145527 | Clifford et al. | Sep 1992 | A |
| 5164046 | Ampulski et al. | Nov 1992 | A |
| 5165261 | Cho | Nov 1992 | A |
| 5215626 | Ampulski et al. | Jun 1993 | A |
| 5219620 | Potter et al. | Jun 1993 | A |
| 5227023 | Pounder et al. | Jul 1993 | A |
| 5227242 | Walter et al. | Jul 1993 | A |
| 5237035 | O'Lenick, Jr. et al. | Aug 1993 | A |
| 5245545 | Taylor | Sep 1993 | A |
| 5246545 | Ampulski et al. | Sep 1993 | A |
| 5246546 | Ampulski | Sep 1993 | A |
| 5328565 | Rasch et al. | Jul 1994 | A |
| 5328685 | Janchiraponvej et al. | Jul 1994 | A |
| 5340609 | Arthur et al. | Aug 1994 | A |
| 5366161 | Potter et al. | Nov 1994 | A |
| 5385643 | Ampulski | Jan 1995 | A |
| 5389204 | Ampulski | Feb 1995 | A |
| 5399412 | Sudall et al. | Mar 1995 | A |
| 5466337 | Darlington et al. | Nov 1995 | A |
| 5492655 | Morton et al. | Feb 1996 | A |
| 5505997 | Strong et al. | Apr 1996 | A |
| 5510001 | Hermans et al. | Apr 1996 | A |
| 5525345 | Warner et al. | Jun 1996 | A |
| 5529665 | Kaun | Jun 1996 | A |
| 5538595 | Trokhan et al. | Jul 1996 | A |
| 5552020 | Smith et al. | Sep 1996 | A |
| 5558873 | Funk et al. | Sep 1996 | A |
| 5573637 | Ampulski et al. | Nov 1996 | A |
| 5591306 | Kaun | Jan 1997 | A |
| 5591309 | Rugowski et al. | Jan 1997 | A |
| 5601871 | Krzysik et al. | Feb 1997 | A |
| 5605719 | Tench et al. | Feb 1997 | A |
| 5607980 | McAtee et al. | Mar 1997 | A |
| 5614293 | Krzysik et al. | Mar 1997 | A |
| 5623043 | Fost et al. | Apr 1997 | A |
| 5624676 | Mackey et al. | Apr 1997 | A |
| 5635191 | Roe et al. | Jun 1997 | A |
| 5635469 | Fowler et al. | Jun 1997 | A |
| 5637194 | Ampulski et al. | Jun 1997 | A |
| 5643588 | Roe et al. | Jul 1997 | A |
| 5650218 | Krzysik et al. | Jul 1997 | A |
| 5656132 | Farrington, Jr. et al. | Aug 1997 | A |
| 5665426 | Krzysik et al. | Sep 1997 | A |
| 5667636 | Engel et al. | Sep 1997 | A |
| 5688496 | Fost et al. | Nov 1997 | A |
| 5705164 | Mackey et al. | Jan 1998 | A |
| 5707434 | Halloran et al. | Jan 1998 | A |
| 5707435 | Halloran | Jan 1998 | A |
| 5725736 | Schroeder et al. | Mar 1998 | A |
| 5756112 | Mackey | May 1998 | A |
| 5792737 | Grüning et al. | Aug 1998 | A |
| 5807956 | Czech | Sep 1998 | A |
| 5814188 | Vinson et al. | Sep 1998 | A |
| 5830483 | Seidel et al. | Nov 1998 | A |
| 5840403 | Trokhan et al. | Nov 1998 | A |
| 5849313 | Fost et al. | Dec 1998 | A |
| 5856544 | Czech et al. | Jan 1999 | A |
| 5857627 | Horwell et al. | Jan 1999 | A |
| 5861143 | Peterson et al. | Jan 1999 | A |
| 5869075 | Krzysik | Feb 1999 | A |
| 5871763 | Luu et al. | Feb 1999 | A |
| 5882573 | Kwok et al. | Mar 1999 | A |
| 5885697 | Krzysik et al. | Mar 1999 | A |
| 5893965 | Trokhan et al. | Apr 1999 | A |
| 5902540 | Kwok | May 1999 | A |
| 5904298 | Kwok et al. | May 1999 | A |
| 5904809 | Rokman et al. | May 1999 | A |
| 5925469 | Gee | Jul 1999 | A |
| 5932068 | Farrington et al. | Aug 1999 | A |
| 5935383 | Sun et al. | Aug 1999 | A |
| 5981044 | Phan et al. | Nov 1999 | A |
| 5981681 | Czech | Nov 1999 | A |
| 5985434 | Qin et al. | Nov 1999 | A |
| 5990377 | Chen et al. | Nov 1999 | A |
| 6017417 | Wendt et al. | Jan 2000 | A |
| 6030675 | Schroeder et al. | Feb 2000 | A |
| 6033723 | Kistler et al. | Mar 2000 | A |
| 6054020 | Goulet et al. | Apr 2000 | A |
| 6077375 | Kwok | Jun 2000 | A |
| 6080686 | Floyd | Jun 2000 | A |
| 6090885 | Kuo et al. | Jul 2000 | A |
| 6103128 | Koso et al. | Aug 2000 | A |
| 6120784 | Snyder, Jr. | Sep 2000 | A |
| 6126784 | Ficke et al. | Oct 2000 | A |
| 6132803 | Kelly et al. | Oct 2000 | A |
| 6136147 | Edwards et al. | Oct 2000 | A |
| 6179961 | Ficke et al. | Jan 2001 | B1 |
| 6183814 | Nangeroni et al. | Feb 2001 | B1 |
| 6217707 | Garvey et al. | Apr 2001 | B1 |
| 6217940 | Kuni | Apr 2001 | B1 |
| 6224714 | Schroeder et al. | May 2001 | B1 |
| 6231719 | Garvey et al. | May 2001 | B1 |
| 6238518 | Rokman et al. | May 2001 | B1 |
| 6238682 | Klofta et al. | May 2001 | B1 |
| 6261580 | Lehrter et al. | Jul 2001 | B1 |
| 6306408 | Eichhorn et al. | Oct 2001 | B1 |
| 6322604 | Midkiff | Nov 2001 | B1 |
| 6395957 | Chen et al. | May 2002 | B1 |
| 6432268 | Burghardt | Aug 2002 | B1 |
| 6432270 | Liu et al. | Aug 2002 | B1 |
| 6514383 | Liu et al. | Feb 2003 | B1 |
| 6547928 | Barnholtz et al. | Apr 2003 | B2 |
| 6599394 | Liu et al. | Jul 2003 | B1 |
| 6607783 | Vander Heiden et al. | Aug 2003 | B1 |
| 6716309 | Chuang et al. | Apr 2004 | B2 |
| 6761800 | Capizzi | Jul 2004 | B2 |
| 20020028230 | Eichhorn et al. | Mar 2002 | A1 |
| 20020092635 | Capizzi | Jul 2002 | A1 |
| 20020112831 | Barnholtz et al. | Aug 2002 | A1 |
| 20020112835 | Liu et al. | Aug 2002 | A1 |
| 20020139500 | Runge et al. | Oct 2002 | A1 |
| 20030032352 | Chang et al. | Feb 2003 | A1 |
| 20030056917 | Jimenez | Mar 2003 | A1 |
| 20030077314 | Shannon et al. | Apr 2003 | A1 |
| 20030112831 | Williams | Jun 2003 | A1 |
| 20030118847 | Chuang et al. | Jun 2003 | A1 |
| 20030118848 | Liu | Jun 2003 | A1 |
| 20030159796 | Watzinger et al. | Aug 2003 | A1 |
| 20030188839 | Urscheler | Oct 2003 | A1 |
| 20030188841 | Buder et al. | Oct 2003 | A1 |
| 20030221808 | Capizzi | Dec 2003 | A1 |
| 20040079502 | Capizzi | Apr 2004 | A1 |
| 20040084162 | Shannon et al. | May 2004 | A1 |
| 20040084165 | Shannon et al. | May 2004 | A1 |
| 20040086726 | Moline et al. | May 2004 | A1 |
| 20040118532 | Sarbo et al. | Jun 2004 | A1 |
| 20040118533 | Shannon et al. | Jun 2004 | A1 |
| 20040144507 | Shannon et al. | Jul 2004 | A1 |
| Number | Date | Country |
|---|---|---|
| 252208 | Oct 1912 | DE |
| 19711452 | Sep 1998 | DE |
| 0047908 | Mar 1982 | EP |
| 0098362 | Jan 1984 | EP |
| 0120472 | Oct 1984 | EP |
| 0195458 | Sep 1986 | EP |
| 0196576 | Oct 1986 | EP |
| 0333212 | Sep 1989 | EP |
| 0336439 | Oct 1989 | EP |
| 0347153 | Dec 1989 | EP |
| 0347154 | Dec 1989 | EP |
| 0347176 | Dec 1989 | EP |
| 0347177 | Dec 1989 | EP |
| 0643083 | Mar 1995 | EP |
| 1023863 | Feb 2000 | EP |
| 1013823 | Jun 2000 | EP |
| 1059032 | Dec 2000 | EP |
| 1149947 | Oct 2001 | EP |
| 1236827 | Sep 2002 | EP |
| WO 9501478 | Jan 1995 | WO |
| WO 9704171 | Feb 1997 | WO |
| WO 9840207 | Sep 1998 | WO |
| WO 9840425 | Sep 1998 | WO |
| WO 9913158 | Mar 1999 | WO |
| WO 9919081 | Apr 1999 | WO |
| WO 0015907 | Mar 2000 | WO |
| WO 0068503 | Nov 2000 | WO |
| WO 0071177 | Nov 2000 | WO |
| WO 0104416 | Jan 2001 | WO |
| WO 0114631 | Mar 2001 | WO |
| WO 0128337 | Apr 2001 | WO |
| WO 0129315 | Apr 2001 | WO |
| WO 0216689 | Feb 2002 | WO |
| WO 0248458 | Jun 2002 | WO |
| WO 03021037 | Mar 2003 | WO |
| Number | Date | Country | |
|---|---|---|---|
| 20040099392 A1 | May 2004 | US |
