This invention relates to absorbent articles particularly absorbent structures which are useful in personal care products such as disposable diapers, incontinence guards, child care training pants, or sanitary napkins. More particularly, the invention relates to absorbent articles which have a portion designed for rapid intake, temporary liquid control, and subsequent release of repeated liquid surges to the remainder of the article.
Personal care products are absorbent articles including diapers, training pants, feminine hygiene products such as sanitary napkins, incontinence devices and the like. These products are designed to absorb and contain body exudates and are generally single-use or disposable items which are discarded after a relatively short period of use—usually a period of hours—and are not intended to be washed and reused. Such products usually are placed against or in proximity to the wearer's body to absorb and contain various exudates discharged from the body. All of these products typically include a liquid permeable bodyside liner or cover, a liquid impermeable outer cover or backsheet, and an absorbent structure disposed between the bodyside liner and outer cover. The absorbent structure may include a surge layer subjacent to and in liquid communicating contact with the bodyside liner, and an absorbent core often formed of a blend or mixture cellulosic pulp fluff fibers and absorbent gelling particles subjacent to and in liquid communicating contact with the surge layer.
Desirably, personal care absorbent articles exhibit low leakage from the product and a dry feel for the wearer. It has been found that urination can occur at rates as high as 15 to 20 milliliters per second and at velocities as high as 280 centimeters per second and that an absorbent garment, such as a diaper, may fail by leaking from the leg or front or back waist areas. The inability of the absorbent product to rapidly uptake liquid can also result in excessive pooling of liquid on the body-facing surface of the bodyside liner before the liquid is taken up by the absorbent structure. Such pooled liquid can wet the wearer's skin and can leak from leg or waist openings of the absorbent article, causing discomfort, potential skin health problems, as well as soiling of the outer clothing or bedding of the wearer.
Leakage and pooling can result from a variety of performance deficiencies in the design of the product, or individual materials within the product. One cause of such problems is an insufficient rate of liquid intake into the absorbent core, which functions to absorb and retain body exudates. The liquid intake of a given absorbent product, therefore, and particularly the bodyside liner and surge materials used in absorbent product, must attempt to meet or exceed the expected liquid delivery rates into the absorbent product. An insufficient intake rate becomes even more detrimental to product performance on second, third, or fourth liquid surges. In addition, leakage may occur due to poor wet product fit that results when multiple insults are stored in the target location and cause sagging and drooping from the wet, heavy retention material structure.
Various approaches have been taken to reduce or eliminate leakage from personal care absorbent articles. For example, physical barriers, such as elasticized leg openings and elasticized containment flaps, have been incorporated into such absorbent products. The amount and configuration of absorbent material in the zone of the absorbent structure in which liquid surges typically occur (sometimes referred to as a target zone) also have been modified.
Other approaches to improving overall liquid intake of absorbent articles have focused on the bodyside liner and its capacity to rapidly pass liquid to the absorbent structure of the absorbent article. Nonwoven materials, including bonded carded webs and spunbond webs, have been widely used as bodyside liners. Such nonwoven materials generally are intended to be sufficiently open and/or porous to allow liquid to pass through rapidly, while also functioning to keep the wearer's skin separate from the wetted absorbent underlying the liner. Attempts to improve the liquid intake of liner materials have included, for example, aperturing the liner material, treating the fibers forming the liner material with surfactants to enhance the wettability of the liner, and altering the durability of such surfactants.
Yet another approach has been to introduce one or more additional layers of material, typically between the bodyside liner and absorbent core, to enhance the liquid intake performance of the absorbent product and to provide separation between the absorbent core and the bodyside liner adjacent the wearer's skin. One such additional layer, commonly referred to as a surge layer, can suitably be formed of thick, lofty nonwoven materials. Surge layers, particularly high loft, high bulk, compression resistant fibrous structures, provide a temporary retention or absorption function for liquid not yet absorbed into the absorbent core, which tends to reduce fluid flowback or wetback from the absorbent core to the liner.
Despite these improvements, the need exists for further improvement in the liquid intake performance of liner materials employed in absorbent articles. In particular, there is a need for liner materials that can rapidly intake and then control the spreading of a liquid insult to the underlying layers. This improved handling is critical for narrow crotch absorbent product designs that utilize less retention storage material in the target region and incorporate distribution features that remove fluid for storage in remote locations in order to alleviate fit problems as a means to reduce leakage. The present invention provides a heterogeneous surge material that provides for such improved liquid intake and controlled spreading when used in absorbent articles.
The objects of this invention are achieved by a surge material for personal care products which is a layered structure of at least one relatively high permeability layer and at least one relatively low permeability layer where the structure has a capillary tension range between about 1 and 5 cm with a differential of at least about 1 cm from top (wearer side) to bottom. Such a layered structure should provide a first insult run-off value of at most 30 ml from a 100 ml insult delivered at 20 ml/second. Such a surge material is useful in personal care products like diapers, training pants, absorbent underpants, adult incontinence products, feminine hygiene products and the like and should have a thickness of less than 3 cm. The surge material of this invention is particularly well suited for use in narrow crotch (7.6 cm width maximum) diapers.
The FIGURE is a drawing of a side view of a cradle used for the MIST Evaluation test.
“Disposable” includes being disposed of after usually a single use and not intended to be washed and reused.
“Front” and “back” are used throughout this description to designate relationships relative to the garment itself, rather than to suggest any position the garment assumes when it is positioned on a wearer.
“Hydrophilic” describes fibers or the surfaces of fibers which are wetted by the aqueous liquids in contact with the fibers. The degree of wetting of the materials can, in turn, be described in terms of the contact angles and the surface tensions of the liquids and materials involved. Equipment and techniques suitable for measuring the wettability of particular fiber materials can be provided by a Caln SFA-222 Surface Force Analyzer System, or a substantially equivalent system. When measured with this system, fibers having contact angles less than 90° are designated “wettable” or hydrophilic, while fibers having contact angles equal to or greater than 90° are designated “nonwettable” or hydrophobic.
“Inward” and “outward” refer to positions relative to the center of an absorbent garment, and particularly transversely and/or longitudinally closer to or away from the longitudinal and transverse center of the absorbent garment.
“Layer” when used in the singular can have the dual meaning of a single element or a plurality of elements.
“Liquid” means a nongaseous substance and/or material that flows and can assume the interior shape of a container into which it is poured or placed.
“Liquid communication” means that liquid such as urine is able to travel from one location to another location.
“Longitudinal” and “transverse” have their customary meanings. The longitudinal axis lies in the plane of the article when laid flat and fully extended and is generally parallel to a vertical plane that bisects a standing wearer into left and right body halves when the article is worn. The transverse axis lies in the plane of the article generally perpendicular to the longitudinal axis.
“Particles” refers to any geometric form such as, but not limited to, spherical grains, cylindrical fibers or strands, or the like.
“Spray” and variations thereof include forcefully ejecting liquid, either as a stream such as swirl filaments, or atomized particles through an orifice, nozzle, or the like, by means of an applied pressure of air or other gas, by force of gravity, or by centrifugal force. The spray can be continuous or non-continuous.
“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 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. Spunbond fibers are generally not tacky when they are deposited onto a collecting surface. Spunbond fibers are generally continuous and have average diameters (from a sample of at least 10) larger than 7 microns, more particularly, between about 10 and 20 microns. The fibers may also have shapes such as those described in U.S. Pat. No. 5,277,976 to Hogle et al., U.S. Pat. No. 5,466,410 to Hills and U.S. Pat. Nos. 5,069,970 and 5,057,368 to Largman et al., which describe fibers with unconventional shapes.
“Meltblown fibers” means 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, usually hot, gas (e.g. air) streams which attenuate the filaments of molten thermoplastic material to reduce their diameter, which may be to microfiber diameter. Thereafter, the meltblown fibers are carried by the high velocity gas stream and are deposited on a collecting surface to form a web of randomly disbursed meltblown fibers. Such a process is disclosed, for example, in U.S. Pat. No. 3,849,241. Meltblown fibers are microfibers which may be continuous or discontinuous, are generally smaller than 10 microns in average diameter, and are generally tacky when deposited onto a collecting surface.
As used herein, the term “coform” means a process in which at least one meltblown diehead is arranged near a chute through which other materials are added to the web while it is forming. Such other materials may be pulp, superabsorbent particles, cellulose or staple fibers, for example. Coform processes are shown in commonly assigned U.S. Pat. Nos. 4,818,464 to Lau and 4,100,324 to Anderson et al. Webs produced by the coform process are generally referred to as coform materials. “Conjugate fibers” refers to fibers which have been formed from at least two polymer sources extruded from separate extruders but spun together to form one fiber. Conjugate fibers are also sometimes referred to as multicomponent or bicomponent fibers. The polymers are usually different from each other though conjugate fibers may be monocomponent fibers. The polymers are arranged in substantially constantly positioned distinct zones across the cross-section of the conjugate fibers and extend continuously along the length of the conjugate fibers. The configuration of such a conjugate fiber may be, for example, a sheath/core arrangement wherein one polymer is surrounded by another or may be a side by side arrangement, a pie arrangement or an “islands-in-the-sea” arrangement. Conjugate fibers are taught in U.S. Pat. No. 5,108,820 to Kaneko et al., U.S. Pat. No. 5,336,552 to Strack et al., and U.S. Pat. No. 5,382,400 to Pike et al. For two component fibers, the polymers may be present in ratios of 75/25, 50/50, 25/75 or any other desired ratios. The fibers may also have shapes such as those described in U.S. Pat. Nos. 5,277,976 to Hogle et al., and 5,069,970 and 5,057,368 to Largman et al., hereby incorporated by reference in their entirety, which describe fibers with unconventional shapes.
“Biconstituent fibers” refers to fibers which have been formed from at least two polymers extruded from the same extruder as a blend. The term “blend” is defined below. Biconstituent fibers do not have the various polymer components arranged in relatively constantly positioned distinct zones across the cross-sectional area of the fiber and the various polymers are usually not continuous along the entire length of the fiber, instead usually forming fibrils or protofibrils which start and end at random. Biconstituent fibers are sometimes also referred to as multiconstituent fibers. Fibers of this general type are discussed in, for example, U.S. Pat. No. 5,108,827 to Gessner. Bicomponent and biconstituent fibers are also discussed in the textbook Polymer Blends and Composites by John A. Manson and Leslie H. Sperling, copyright 1976 by Plenum Press, a division of Plenum Publishing Corporation of New York, IBSN 0-306-30831-2, at pages 273 through 277.
“Bonded carded web” refers to webs that are made from staple fibers which are sent through a combining or carding unit, which separates or breaks apart and aligns the staple fibers in the machine direction to form a generally machine direction-oriented fibrous nonwoven web. Such fibers are usually purchased in bales which are placed in an opener/blender or picker which separates the fibers prior to the carding unit. Once the web is formed, it then is bonded by one or more of several known bonding methods. One such bonding method is powder bonding, wherein a powdered adhesive is distributed through the web and then activated, usually by heating the web and adhesive with hot air. Another suitable bonding method is pattern bonding, wherein heated calender rolls or ultrasonic bonding equipment are used to bond the fibers together, usually in a localized bond pattern, though the web can be bonded across its entire surface if so desired. Another suitable and well-known bonding method, particularly when using conjugate staple fibers, is through-air bonding.
“Airlaying” is a well known process by which a fibrous nonwoven layer can be formed. In the airlaying process, bundles of small fibers having typical lengths ranging from about 3 to about 19 millimeters (mm) are separated and entrained in an air supply and then deposited onto a forming screen, usually with the assistance of a vacuum supply. The randomly deposited fibers then are bonded to one another using, for example, hot air or a spray adhesive.
“Personal care product” means diapers, training pants, absorbent underpants, adult incontinence products, and feminine hygiene products.
Multiple Insult Test (MIST Evaluation): In this test a fabric, material or structure composed of two or more materials is placed in an acrylic cradle to simulate body curvature of a user such as an infant. Such a cradle is illustrated in FIG. 2. The cradle has a width into the page of the drawing as shown of 33 cm and the ends are blocked off, a height of 19 cm, an inner distance between the upper arms of 30.5 cm and an angle between the upper arms of 60 degrees. The cradle has a 6.5 mm wide slot at the lowest point running the length of the cradle into the page.
The material to be tested is placed on a piece of polyethylene film the same size as the sample and placed in the cradle. The material to be tested is insulted with 100 ml of a saline solution of 8.5 grams of sodium chloride per liter, at a rate of 20 cc/sec with a nozzle normal to the center of the material and ¼ inch (6.4 mm) above the material. The amount of runoff is recorded. The material is immediately removed from the cradle, weighed, and placed on a dry 40/60 pulp/superabsorbent pad having a density of 0.2 g/cc in a horizontal position under 0.01 psi pressure and weighed after 5, 15 and 30 minutes to determine fluid desorption from the material into the superabsorbent pad as well as fluid retention in the material. The pulp fluff and superabsorbent used in this test is Kimberly-Clark's (Dallas Tex.) CR-2054 pulp and Stockhausen Company's (of Greensboro, N.C. 27406) FAVOR 870 superabsorbent through other comparable pulp and superabsorbents could be used provided they yield a desorption pad of 500 gsm and 0.2 g/cc which after immersion into saline solution under free-swell conditions for 5 minutes, retains at least 20 grams of saline solution per gram of desorption pad after being subjected to an air pressure differential, by vacuum suction for example, of about 0.5 psi (about 3.45 kPa) applied across the thickness of the pad for 5 minutes. If the tested piece is made of other components (e.g. is a laminate) the components or layers are separated and weighed to determine liquid partitioning between them and then reassembled after each weighing and placed back onto the fluff/superabsorbent. This test is repeated using fresh desorption pads on each insult so that a total of three insults are introduced and fluid partitioning measured over 1.5 hours with 30 minutes between insults. Five tests of each sample material are recommended.
Permeability: Permeability (k) may be calculated from the Kozeny-Carman equation. This is a widely used method. References include an article by R. W. Hoyland and R. Field in the journal Paper Technology and Industry, December 1976, p. 291-299 and Porous Media Fluid Transport and Pore Structure by F. A. L. Dullien, 1979, Academic Press, Inc. ISBN 0-12-223650-5.
Permeability Example Calculation
For a structure which contains 57% southern softwood pulp, 40% superabsorbent and 3% binder fiber, and has a basis weight of 617.58 g/m2 and a bulk thickness of 5.97 mm at 0.05 psi the example permeability calculation follows. The component properties are as follows (note shape is approximated):
Material Caliper (Thickness)
The caliper of a material is a measure of thickness and is measured at 0.05 psi with a Starret-type bulk tester, in units of millimeters.
Density
The density of the materials is calculated by dividing the weight per unit area of a sample in grams per square meter (gsm) by the bulk of the sample in millimeters (mm) at 68.9 Pascals and multiplying the result by 0.001 to convert the value to grams per cubic centimeter (g/cc). A total of three samples would be evaluated and averaged for the density values.
Wicking Time and Vertical Liquid Flux of an Absorbent Structure
A sample strip of material approximately 2 inches (5 cm) by 15 inches (38 cm) is placed vertically such that when the sample strip is positioned above a liquid reservoir at the beginning of the test, the bottom of the sample strip will just touch the liquid surface. The liquid used was a 8.5 g/l saline solution. The relative humidity should be maintained at about 90 to about 98 percent during the evaluation. The sample strip is placed above the known weight and volume of liquid and a stopwatch started as soon as the bottom edge of the sample strip touches the surface of the solution.
The vertical distance of the liquid front traveling up the sample strip and the liquid weight absorbed by the sample strip at various times is recorded. The time versus liquid front height is plotted to determine the Wicking Time at about 5 centimeters and at about 15 centimeters. The weight of the liquid absorbed by the sample strip from the beginning of the evaluation to about 5 centimeters and to about 15 centimeters height is also determined from the data. The Vertical Liquid Flux value of the sample strip at a particular height was calculated by dividing the grams of liquid absorbed by the sample strip by each of: the basis weight (gsm), of the sample strip; the time, in minutes, needed by the liquid to reach the particular height; and the width, in inches, of the sample strip. Capillary tension in materials not containing superabsorbents (e.g. surge materials) is measured simply by the equilibrium vertical wicking height of a 8.5 g/l saline solution after 30 minutes.
Traditional absorbent systems for personal care products may be generalized as having the functions of surge control and containment (retention) or SC.
Surge control materials, the “S” in SC, are provided to quickly accept the incoming insult and either absorb, hold, channel or otherwise manage the liquid so that it does not leak outside the article. The surge layer may also be referred to as an intake layer, transfer layer, transport layer and the like. A surge material must typically be capable of handling an incoming insult of between about 60 and 100 cc at an insult volumetric flow rate of from about 5 to 20 cc/sec, for infants, for example.
Containment or retention materials, the “C” in SC, must absorb the insult quickly and efficiently. They should be capable of pulling the liquid from the distribution layer and absorbing the liquid without significant “gel blocking” or blocking of penetration of liquid further into the absorbent by the expansion of the outer layers of absorbent. Retention materials are often high rate superabsorbent materials such as blends of polyacrylate superabsorbent and fluff. These materials rapidly absorb and hold liquid.
As mentioned above, traditional absorbent systems having the functions of surge control and containment usually hold the vast majority of any insult in the target area, usually the crotch. This results in personal care products having crotches which are quite wide. Examples of the holding ability and location of containment of various commercial diapers is presented in Table 3 of U.S. patent application Ser. No. 08/755,136, filed The same day and assigned to the same assignee as this application and entitled ABSORBENT ARTICLES WITH CONTROLLABLE FILL PATTERNS.
In contrast with traditional absorbent systems, the patent application ABSORBENT ARTICLES WITH CONTROLLABLE FILL PATTERNS presents an absorbent system which includes components that have been designed, arranged, and assembled so that within a certain time after each insult, liquid will be located in a pre-specified area of the absorbent system, i.e. remote from the target area. Using an absorbent system arbitrarily divided into five zones, these absorbent systems have a “fill ratio” of grams of fluid located in the center target zone, usually in the crotch, to each of the two end zones which is less than 5:1 after three insults of 100 ml separated by 30 minutes. It is preferred that this fill ratio be less than 3:1, and most preferred to be less than 2.5:1. Many currently available commercial diapers have fill ratios of 20:1, 50:1 or even greater, i.e. they hold most insult liquid in the crotch.
In addition to the surge control and containment materials in traditional absorbent systems, recent work has introduced another layer interposed between the S and C layers. This new layer is a distribution layer, producing a system with surge control, distribution and containment or “SDC”.
Distribution materials, the “D” in SDC, must be capable of moving fluid from the point of initial deposition to where storage is desired. Distribution must take place at an acceptable rate such that the target insult area, generally the crotch area, is ready for the next insult. By “ready for the next insult” it is meant that sufficient liquid has been moved out of the target zone so that the next insult results in liquid absorption and runoff within acceptable volumes. The time between insults can range from just a few minutes to hours, generally depending on the age of the wearer.
Absorbent products such as, for example, diapers, generally also have a liner which goes against the wearer, a backsheet which is the most exterior layer. An absorbent product may also contain other layers such as the multifunctional materials described in patent application Ser. No. 08/754,414, filed The same day and assigned to the same assignee as this application and entitled MULTIFUNCTIONAL ABSORBENT MATERIALS AND PRODUCTS MADE THEREFROM. The retention materials in an absorbent product may also be zoned to provide specific fill patterns and to move liquids from the target zone to remote storage areas as described in patent application Ser. No. 08/755,136, filed The same day and assigned to the same assignee as this application and entitled ABSORBENT ARTICLES WITH CONTROLLABLE FILL PATTERNS. While it may appear obvious, it should be noted that in order to function effectively, the materials used in personal care product absorbent systems must have sufficient contact to transfer liquid between them.
The liner is sometimes referred to as a bodyside liner or topsheet and is adjacent the surge material. In the thickness direction of the article, the liner material is the layer against the wearer's skin and so the first layer in contact with liquid or other exudate from the wearer. The liner further serves to isolate the wearer's skin from the liquids held in an absorbent structure and should be compliant, soft feeling and non-irritating.
Various materials can be used in forming the bodyside liner of the present invention, including apertured plastic films, woven fabrics, nonwoven webs, porous foams, reticulated foams and the like. Nonwoven materials have been found particularly suitable for use in forming the bodyside liner, including spunbond or meltblown webs of polyolefin, polyester, polyamide (or other like fiber forming polymer) filaments, or bonded carded webs of natural polymers (for example, rayon or cotton fibers) and/or synthetic polymers (for example, polypropylene or polyester) fibers. For example, the bodyside liner can be a nonwoven spunbond web of synthetic polypropylene filaments having an average fiber size (from a sample of at least 10) ranging from about 12 to about 48 microns, and more particularly from about 18 to about 43 microns. The nonwoven web can have a basis weight (for example, ranging from about 10.0 grams per square meter (gsm) to about 68.0 gsm, and more particularly from about 14.0 gsm to about 42.0 gsm, a bulk or thickness ranging from about 0.13 millimeter (mm) to about 1.0 mm, and more particularly from about 0.18 mm to about 0.55 mm, and a density between about 0.025 grams per cubic centimeter (g/cc) and about 0.12 g/cc, and more particularly between about 0.068 g/cc and about 0.083 g/cc. Additionally, the permeability of such nonwoven web can be from about 150 Darcy to about 5000 Darcy. The nonwoven web can be surface treated with a selected amount of surfactant, such as about 0.28% Triton X-102 surfactant, or otherwise processed to impart the desired level of wettability and hydrophilicity. If a surfactant is used, it can be an internal additive or applied to the web by any conventional means, such as spraying, printing, dipping, brush coating and the like.
The surge layer is most typically interposed between and in intimate, liquid communicating contact with the bodyside liner and another layer such as a distribution or retention layer. The surge layer is generally subjacent the inner (unexposed) surface of bodyside liner. To further enhance liquid transfer, it can be desirable to attach the upper and/or lower surfaces of the surge layer to the liner and the distribution layer, respectively. Suitable conventional attachment techniques may be utilized, including without limitation, adhesive bonding (using water-based, solvent-based and thermally activated adhesives), thermal bonding, ultrasonic bonding, needling and pin aperturing, as well as combination of the foregoing or other appropriate attachment methods. If, for example, the surge layer is adhesively bonded to the bodyside liner, the amount of adhesive add-on should be sufficient to provide the desired level(s) of bonding, without excessively restricting the flow of liquid from the liner into the surge layer. The surge material of this invention will be discussed in greater detail below.
As described in the previously cited, co-owned patent application MULTIFUNCTIONAL ABSORBENT MATERIALS AND PRODUCTS MADE THEREFROM, the multifunctional material has been designed to assist the surge material 1) by accepting a portion of the insult volume during forced flow, i.e. during an actual insult, 2) by desorbing the surge material of liquid during and after insults, 3) by allowing a portion of the insult volume to pass through itself (the multifunctional material) to the distribution material and 4) by permanently absorbing a portion of the liquid insult. If such a multifunctional material is used, the multifunctional material and surge should be designed to function together as described in previously cited, co-owned patent application MULTIFUNCTIONAL ABSORBENT MATERIALS AND PRODUCTS MADE THEREFROM. The basic structure of the multifunctional material is a unique blend of superabsorbent material, high bulk wet resilient pulp, and a structure stabilizing component such as a polyolefin binder fiber. The multifunctional material has a permeability of between about 100 and 10000 Darcys, a capillary tension between about 2 and 15 cm, and a runoff rate of less than 25 ml per 100 ml insult, over its life. The “life” of the multifunctional material is considered to be three insults of 100 ml each where each insult is separated by 30 minutes. In order to achieve the required capillary tension and permeability, its preferred that the multifunctional material have between 30 and 75 weight percent of slow rate superabsorbent, between 25 and 70 weight percent of pulp and from a positive amount up to about 10 percent of a binder component. The material should have a density between about 0.05 and 0.5 g/cc. The basis weight of the material will vary depending on the product application but should generally be between about 200 and 700 gsm. The multifunctional material is preferably located between the surge and distribution layers.
The distribution layer must be capable of moving fluid from the point of initial deposition to where storage is desired. Distribution must take place at an acceptable rate such that the target insult area, generally the crotch area, is ready for the next insult. The time between insults can range from just a few minutes to hours, generally depending on the age of the wearer. In order to achieve this transportation function, a distribution layer must have a high capillary tension value. Capillary tension in distribution materials is measured simply by the equilibrium wicking of a 8.5 g/ml saline solution according to the Vertical Liquid Flux rate test, not by the test method given for materials containing superabsorbents. A successful distribution layer must have a capillary tension greater than the adjacent layer (on the side toward the wearer) and preferably a capillary tension of at least about 15 cm. Because of the generally inverse relationship between capillary tension and permeability, such a high capillary tension indicates that the distribution layer will usually have a low permeability.
Another liquid transport property desired of a suitable distribution material is that it exhibit a Vertical Liquid Flux rate, at a height of about 15 centimeters, suitably of at least about 0.002 grams of liquid per minute per square meter (gsm) of distribution material per inch of cross-sectional width of the distribution material g/(min*gsm*inch), up to about 0.1 g/(min*gsm*inch). As used herein, the Vertical Liquid Flux rate value of a distribution material is meant to represent the amount of liquid transported across a boundary a specified vertical distance away from a centralized liquid insult location per minute per normalized quantity of the distribution material. The Vertical Liquid Flux rate, at a height of about 15 centimeters, of a distribution may be measured according to the test method described herein.
Another liquid transport property desired of a distribution material is that it exhibit a Vertical Liquid Flux rate, at a height of about 5 centimeters, suitably of at least about 0.01 g/(min*gsm*inch) up to about 0.5 g/(min*gsm*inch). The Vertical Liquid Flux rate, at a height of about 5 centimeters, of an absorbent structure may be measured according to the test method described herein.
Materials from which the distribution layer may be made include woven fabrics and nonwoven webs. For example, the distribution layer may be a nonwoven fabric layer composed of a meltblown or spunbond web of polyolefin, polyester, polyamide (or other web forming polymer) filaments. Such nonwoven fabric layers may include conjugate, biconstituent and homopolymer fibers of staple or other lengths and mixtures of such fibers with other types of fibers. The distribution layer also can be a bonded carded web, an airlaid web or a wetlaid pulp structure composed of natural and/or synthetic fibers, or a combination thereof. The distribution layer may have a basis weight of from 35 to 300 gsm, or more preferably from 80 to 200 gsm, a density of between about 0.1 and 0.5 g/cc and a permeability between about 50 and 1000 Darcys.
Retention materials are typically cellulosic materials or superabsorbents or mixtures thereof. Such materials are usually designed to quickly absorb liquids and hold them without, usually without release. Superabsorbents are commercially available from a number of manufactures including Dow Chemical Company of Midland, Mich. and Stockhausen Corporation of Greensboro, N.C. As described in the previously cited, co-owned patent application entitled ABSORBENT ARTICLES WITH CONTROLLABLE FILL PATTERNS, retention materials may be zoned and their composition chosen to move liquids away from the target zone to more remote storage locations. Such a design more efficiently uses the entire absorbent article, and in the case of a diaper, for example, helps allows for the production of a more narrow crotch item where “narrow crotch” means diapers having a width of at most 7.6 cm. The fill patterns and materials taught in ABSORBENT ARTICLES WITH CONTROLLABLE FILL PATTERNS result in liquid by weight in the target zone of less than 5 times that in the remote storage locations, a significant improvement over prior designs.
The backsheet is sometimes referred to as the outer cover and is the farthest layer from the wearer. The outer cover is typically formed of a thin thermoplastic film, such as polyethylene film, which is substantially impermeable to liquid. The outer cover functions to prevent body exudates contained in an absorbent structure from wetting or soiling the wearer's clothing, bedding, or other materials contacting the diaper. The outer cover may be, for example, a polyethylene film having an initial thickness of from about 0.5 mil (0.012 millimeter) to about 5.0 mil (0.12 millimeter). The polymer film outer cover may be embossed and/or matte finished to provide a more aesthetically pleasing appearance. Other alternative constructions for outer cover include woven or nonwoven fibrous webs that have been constructed or treated to impart the desired level of liquid impermeability, or laminates formed of a woven or nonwoven fabric and thermoplastic film. The outer cover may optionally be composed of a vapor or gas permeable, microporous “breathable” material, that is permeable to vapors or gas yet substantially impermeable to liquid. Breathability can be imparted in polymer films by, for example, using fillers in the film polymer formulation, extruding the filler/polymer formulation into a film and then stretching the film sufficiently to create voids around the filler particles, thereby making the film breathable. Generally, the more filler used and the higher the degree of stretching, the greater the degree of breathability. Backings may also serve the function of a mating member for mechanical fasteners, in the case, for example, where a nonwoven fabric is the outer surface.
In regard to surge materials, various woven fabrics and nonwoven webs can be used to construct a surge layer. For example, the surge layer may be a nonwoven fabric layer composed of a meltblown or spunbond web of polyolefin filaments. Such nonwoven fabric layers may include conjugate, biconstituent and homopolymer fibers of staple or other lengths and mixtures of such fibers with other types of fibers. The surge layer also can be a bonded carded web or an airlaid web composed of natural and/or synthetic fibers. The bonded carded web may, for example, be a powder bonded carded web, an infrared bonded carded web, or a through-air bonded carded web. The bonded carded webs can optionally include a mixture or blend of different fibers, and the fiber lengths within a selected web may range from about 3 mm to about 60 mm. Previous surge layers have had have a basis weight of at least about 0.50 ounce per square yard (about 17 grams per square meter), a density of at least about 0.010 gram per cubic centimeter at a pressure of 68.9 Pascals, a bulk of at least about 1.0 mm at a pressure of 68.9 Pascals, a bulk recovery of at least about 75 percent, a permeability of about 500 to about 5000 Darcy, and a surface area per void volume of at least about 20 square centimeters per cubic centimeter. Examples of surge materials may be found in U.S. Pat. No. 5,490,846 to Ellis et al. And in U.S. Pat. No. 5,364,382 to Latimer. A homogeneous surge material is disclosed in patent application Ser. No. 08/755,514, filed The same day and assigned to the same assignee as this application and entitled HIGHLY EFFICIENT SURGE MATERIAL FOR ABSORBENT ARTICLES. Surge layers may be composed of a substantially hydrophobic material, and the hydrophobic material may optionally be treated with a surfactant or otherwise processed to impart a desired level of wettability and hydrophilicity. Surge layers can have a generally uniform thickness and cross-sectional area.
Surge control materials must take insult liquids in at the rate and volume of delivery to avoid top surface pooling or runoff and keep the liquid within the material structure once it is taken in to prevent runoff. Traditional surge control materials are low density, high permeability structures with low capillary tension that facilitate intake and spreading, especially during an insult. However, these high permeability, low capillary structures exert a low level of control on the liquid and the spreading liquid can rapidly approach the perimeter of the surge control material and run out. This is a source of leakage in the crotch area of personal care products where the product width is generally less than the product length and is of special concern in narrow crotch, (less than 7.6 cm) personal care products.
If the void volume of the surge control material is maintained, the thickness of a narrow crotch surge control material must be greater than wider crotch examples or more surge control material must be made available in the length dimension of the product. Additional thickness and/or length will not be beneficial unless this extra void volume is filled with liquid prior to runout. Lower permeabilities are required to cause thicker surge control materials to fill to higher height during an insult and higher capillary tensions are required to control the liquid, keeping it in the structure as well as wicking liquid so that more void volume along the length of the product can be used. The lower permeability acts to increase liquid height and slow the planar spread from reaching the material edges while the higher capillary tension acts to hold the liquid in the material so that it will not come out at the edges during and after filling.
The benefits of lower permeability high capillary tension surge control materials is demonstrated in the patent application entitled HIGHLY EFFICIENT SURGE MATERIAL FOR ABSORBENT ARTICLES. However, as permeability is reduced, the potential for surface pooling or runoff of liquid from the top surface of the material increases, especially at high insult rates or when an insult impinges the surface of the surge control material at an acute angle, limiting liquid penetration of the surge control structure. These effects can be very dependent on user habits and use conditions. It has been found that a surge control material with a decreasing permeability gradient in the z-direction, where a capillary tension gradient can also be imparted, provides improved intake and control performance especially for high rate and volume insult conditions with narrow crotch products over many use conditions.
The surge material of this invention is designed to address a number of the important aspects of liquid intake and controlled spreading.
Liquid intake is important since it has been found that urination can occur at volumetric rates as high as 15 to 20 milliliters per second and at velocities as high as 280 centimeters per second. Failure to rapidly intake this liquid may result in leakage from the leg or front or back waist areas. The inability of an absorbent product to rapidly uptake liquid can also result in excessive pooling of liquid on the body-facing surface of the bodyside liner before the liquid is taken up by the absorbent structure. Such pooled liquid can wet the wearer's skin and can leak from leg or waist openings of the absorbent article, causing discomfort, potential skin health problems, as well as soiling of the outer clothing or bedding of the wearer.
Controlled spreading of the liquid from an insult is important, particularly in narrow crotch absorbent articles, since it increases the contact area of the layer subjacent the surge layer with the incoming liquid insult. This larger contact area more efficiently uses all of the mass of the subjacent layers.
The intake and controlled spreading objectives of this invention are achieved by using a surge material having a permeability gradient in the z direction combined with an increasing level of capillary control in the z-direction. More particularly, the inventive surge has a relatively high permeability on the side of the material towards the wearer and a relatively lower permeability on the side away from the wearer and towards the subjacent layers. Sill more particularly, the inventive surge has a permeability on the side toward the wearer of greater than 1000 Darcys and on the side away from the wearer of less than 1000 Darcys. Even more particularly, the inventive surge should have a permeability differential between the layers of at least about 250 Darcys and more particularly at least 500 Darcys.
In addition to the permeability requirements of the inventive surge material, such a surge material must also have a capillary tension gradient in the z-direction where the surge has a relatively low capillary tension on the side of the material towards the wearer and a relatively higher capillary tension on the side away from the wearer and towards the subjacent layers. More particularly, the inventive surge has a capillary tension range between about 1 and 5 cm with a differential of at least about 1 cm from top to bottom.
The exact permeabilities of a finished surge material will be dependent on the width of the absorbent article as well as the thickness of the surge material's layers. As the thickness of the surge material's high permeability upper layer is reduced, for example, the permeability of the lower layer must be reduced. As the overall width of the surge material is reduced the permeability of the lower surge layer must be reduced also. For example, if the width of the surge material is 7.6 cm and the upper layer has a permeability of 1000 Darcys and a thickness of 1.1 cm, the thickness and permeability of the lower layer should be 1.1 cm and 980 Darcys. If the width of the surge material is reduced to 5.1 cm with the same upper layer permeability and thickness, the thickness and permeability of the bottom layer should be 4 cm and 74 Darcys. If the width of the surge material is 7.6 cm and the upper layer permeability is 2000 Darcys and the thickness 0.77 cm, the thickness and permeability of the lower layer should be 1.4 cm and 590 Darcys.
The layers of the surge material may also be oriented, as determined by tensile testing, in the machine direction (MD) or cross-machine direction (CD). They may be oriented at least 3:1, MD:CD or more. Such a surge is given in Example 6.
The permeability and thickness of the upper and lower surge layers can be controlled by selecting the proper combination of fiber size and web density. Further, the materials from which the surge layers are constructed may be selected to ensure that the targeted permeability levels are maintained through numerous liquid insults. In addition, though for purposes of discussion the surge has been referred to as having two layers, the surge may have any number of layers provided the permeability and capillary tension of the overall layered structure are within the claimed invention.
A number of surge layers were tested according to the Mist Evaluation Test to determine run-off. The width of the surge material was 5.1 cm and the length 17.4 cm in Examples 1-6 to result in an available void volume of about 100 cc. The insult was delivered at a rate of 20 ml/sec in a total amount of 100 ml of 8.5 g/l saline solution at room temperature. The data is shown in the Table where the density (Den.) is in grams/cc, the number of layers in the sample is given in the “No. of Layer” column, the permeability (Perm.) is given in Darcys, the capillary tension (C.T.) is given in centimeters according to equilibrium vertical wicking, the overall sample thickness (Thick.) is in centimeters (cm), the runoff after each insult (1st R, etc.) is given in milliliters (ml) and the fluid retained after each insult (1st F, etc.) in the three right-hand columns in grams. Note that Examples 4 and 5 are multilayer surge materials as indicated in the permeability and cap. Tension columns which give the data for each component layer.
In the examples that follow the component properties used in the calculations herein were as follows:
Note that the relationship between denier and diameter is as follows: diameter (microns)=(denier/pi×fiber density×9×105)1/2×104.
For the surge material of this invention, the first insult run-off value should be equal to or less than 30 ml from a 100 ml insult delivered at 20 ml/second, with the remaining two insult runoffs being equal to or less than 30 ml each. In the most preferred embodiments, all three insults have run-off values less than or equal to 25 ml.
The materials described in Examples 1-4 are through air bonded carded web structures produced on a dual 40 inch (102 cm) card pilot line. The bonded carded web structures were produced at a basis weight of approximately 100 gsm. The test samples for Examples 1-4 had length and width dimensions of 6 inches (15 cm) by 2 inches (5.1 cm) respectively. Layers of 100 gsm material were plied as indicated in the Table to give the required thickness also indicated in the Table. The resulting test samples contained approximately 150 cc of total volume calculated by multiplying length times width times thickness. The test configuration, however, resulted in less than 10.2 cm of the 15.2 length accessible and usable to the insults resulting in approximately 100 cc of accessible void volume. It has been empirically found that samples in the MIST test cradle use about 2 inches of length on either side of the point of insult, or 4 inches (10.2 cm), not the entire sample length, which results in the calculated 100 cc of void volume.
Example 1 is a through-air bonded carded web that contains 90 weight percent of a 1.8 denier, 1.5 inch (3.8 cm) conjugate sheath/core polyethylene/polyethylene terephthalate (PE/PET) fibers and 10 weight percent of a 1.5 denier, 1.5 inch rayon fiber. The PE/PET fibers are available from BASF Fibers, 6805 Morrison Boulevard, Charlotte, N.C. 28211-3577 and were conjugate sheath/core polyethylene/polyethylene terephthalate (PE/PET) fibers with a polyethylene glycol based C S-2 finish. The rayon fibers were 1.5 denier Merge 18453 fibers from Courtaulds Fibers Incorporated of Axis, Ala.
Examples 2 is a through-air bonded carded web that contains 90 weight percent of a 3.0 denier, 1.5 inch conjugate sheath/core PE/PET fibers and 10 weight percent of 1.5 denier, 1.5 inch rayon fiber. The PE/PET fibers are available from BASF Fibers, 6805 Morrison Boulevard, Charlotte, N.C. 28211-3577 and were conjugate sheath/core polyethylene/polyethylene terephthalate (PE/PET) fibers with a polyethylene glycol based C S-2 finish.
Examples 3 is a through-air bonded carded web that contains 90 weight percent of a 10.0 denier, 1.5 inch conjugate sheath/core PE/PET fibers and 10 weight percent of 1.5 denier, 1.5 inch rayon fiber. The PE/PET fibers are available from BASF Fibers, 6805 Morrison Boulevard, Charlotte, N.C. 28211-3577 and were conjugate sheath/core polyethylene/polyethylene terephthalate (PE/PET) fibers with a polyethylene glycol based C S-2 finish.
Examples 4 is a two component gradient structure meeting the criteria of the invention. The top component is as given in Example 3 and the bottom as given in Example 1.
Examples 5 is a two component gradient structure meeting the criteria of the invention. The top component is as given in Example 2 and the bottom as given in Example 1.
Example 6 is a two component gradient structure meeting the criteria of the invention. The top component is a homogeneous blend of 60 weight percent 3.0 denier, 1.5 inch conjugate PE/PET fiber and 40 weight percent 6 denier, 1.5 inch PET fiber. Nine layers of each component were plied together to produce material for testing.
The top component fibers were from the Hoechst Celanese Corporation, Charlotte, N.C. under the codes T256 and T295 respectively. The top component had a basis weight of about 1.5 osy (50 gsm) and a density of about 0.014 g/cc. The top component blend was carded using a Master Card with a Web-Master® take off roll from John D. Hollingworth of Wheels, Inc., Greenville, N.C. The top component had about a 3 to 5:1 MD:CD fiber orientation ratio as determined by tensile strength ratios in the MD and CD.
The bottom component was 100 weight percent 2.2 denier, 1.5 inch polypropylene fiber available from the Hercules Chemical Co., Wilmington, Del. under the code T186 and had a basis weight of about 1.0 osy (35 gsm). After through air bonding this layer had a density of about 0.067 g/cc. This layer was carded using a Master Card with a Dof-Master® take off roll from John D. Hollingsworth on Wheels, Inc. The bottom component had about a 12 to 15:1 MC:CD fiber orientation ratio as determined by tensile strength ratios.
The top component had a capillary tension of about 0.6 and the bottom about 2.7 cm.
Example 7 is a two component gradient structure similar to Example 6 meeting the criteria of the invention. The top component is a homogeneous blend of 30 weight percent 3.0 denier, 1.5 inch conjugate PE/PET fiber and 70 weight percent 6 denier, 1.5 inch PET fiber. The bottom component was 100 weight percent 2.2 denier, 1.5 inch polypropylene fiber. The suppliers and basis weights of each layer were the same as in Example 6. Neither layer was carded to increase orientation.
!
It is quite striking from examining the data in the Table that a multilayer surge material of about the same thickness as a single layer surge material can have better (lower) runoff results. This may be seen by comparing Example 3 to Examples 4 and 5, which, while slightly thinner overall, have lower runoff values than homogeneous, high permeability Example 3. Such a result is counterintuitive.
Although only a few exemplary embodiments of this invention have been described in detail above, those skilled in the art will readily appreciate that many modifications are possible in the exemplary embodiments without materially departing from the novel teachings and advantages of this invention. Accordingly, all such modifications are intended to be included within the scope of this invention as defined in the following claims. In the claims, means plus function claims are intended to cover the structures described herein as performing the recited function and not only structural equivalents but also equivalent structures. Thus although a nail and a screw may not be structural equivalents in that a nail employs a cylindrical surface to secure wooden parts together, whereas a screw employs a helical surface, in the environment of fastening wooden parts, a nail and a screw may be equivalent structures.
Number | Name | Date | Kind |
---|---|---|---|
3338992 | Kinney | Aug 1967 | A |
3341394 | Kinney | Sep 1967 | A |
3502763 | Hartmann | Mar 1970 | A |
3542615 | Dobo et al. | Nov 1970 | A |
3692618 | Dorschner et al. | Sep 1972 | A |
3802817 | Matsuki et al. | Apr 1974 | A |
3849241 | Butin et al. | Nov 1974 | A |
4100324 | Anderson et al. | Jul 1978 | A |
4340563 | Appel et al. | Jul 1982 | A |
4397644 | Matthews et al. | Aug 1983 | A |
4413032 | Hartmann et al. | Nov 1983 | A |
4480000 | Watanabe et al. | Oct 1984 | A |
4500315 | Pieniak et al. | Feb 1985 | A |
4531945 | Allison | Jul 1985 | A |
4537590 | Pieniak et al. | Aug 1985 | A |
4540414 | Wishman | Sep 1985 | A |
4573988 | Pieniak et al. | Mar 1986 | A |
4578070 | Holtman | Mar 1986 | A |
4636209 | Lassen | Jan 1987 | A |
4637819 | Ouellette et al. | Jan 1987 | A |
4650479 | Insley | Mar 1987 | A |
4670011 | Mesek | Jun 1987 | A |
4673402 | Weisman et al. | Jun 1987 | A |
4681577 | Stern et al. | Jul 1987 | A |
4685914 | Holtman | Aug 1987 | A |
4699619 | Bernardin | Oct 1987 | A |
4723953 | Rosenbaum et al. | Feb 1988 | A |
4755178 | Insley et al. | Jul 1988 | A |
4798603 | Meyer et al. | Jan 1989 | A |
4818464 | Lau | Apr 1989 | A |
4834735 | Alemany et al. | May 1989 | A |
4842594 | Ness | Jun 1989 | A |
4880419 | Ness | Nov 1989 | A |
4883707 | Newkirk | Nov 1989 | A |
4892534 | Datta et al. | Jan 1990 | A |
4904249 | Miller et al. | Feb 1990 | A |
4908026 | Sukiennik et al. | Mar 1990 | A |
4935022 | Lash et al. | Jun 1990 | A |
4938756 | Salek | Jul 1990 | A |
4950264 | Osborn, III | Aug 1990 | A |
4988344 | Reising et al. | Jan 1991 | A |
4988345 | Reising | Jan 1991 | A |
4994037 | Bernardin | Feb 1991 | A |
5009653 | Osborn, III | Apr 1991 | A |
5030229 | Yang | Jul 1991 | A |
5037409 | Chen et al. | Aug 1991 | A |
5043206 | Ternstrom | Aug 1991 | A |
5047023 | Berg | Sep 1991 | A |
5057368 | Largman et al. | Oct 1991 | A |
5062839 | Anderson | Nov 1991 | A |
5069970 | Largman et al. | Dec 1991 | A |
5108820 | Kaneko et al. | Apr 1992 | A |
5108827 | Gessner | Apr 1992 | A |
5124197 | Bernardin et al. | Jun 1992 | A |
5134007 | Reising et al. | Jul 1992 | A |
5147345 | Young et al. | Sep 1992 | A |
5171391 | Chmielewski et al. | Dec 1992 | A |
5176668 | Bernardin | Jan 1993 | A |
5188624 | Young, Sr. et al. | Feb 1993 | A |
5192606 | Proxmire et al. | Mar 1993 | A |
5200248 | Thompson et al. | Apr 1993 | A |
5217445 | Young et al. | Jun 1993 | A |
5236427 | Hamajima et al. | Aug 1993 | A |
5242435 | Murji et al. | Sep 1993 | A |
5248309 | Serbiak et al. | Sep 1993 | A |
5257982 | Cohen et al. | Nov 1993 | A |
5277976 | Hogle et al. | Jan 1994 | A |
5281207 | Chmielewski et al. | Jan 1994 | A |
5281208 | Thompson et al. | Jan 1994 | A |
5294478 | Wanek et al. | Mar 1994 | A |
5300054 | Feist et al. | Apr 1994 | A |
5304161 | Noel et al. | Apr 1994 | A |
5318554 | Young et al. | Jun 1994 | A |
5330457 | Cohen | Jul 1994 | A |
5334176 | Buenger et al. | Aug 1994 | A |
5334177 | Cohen | Aug 1994 | A |
5336552 | Strack et al. | Aug 1994 | A |
5342334 | Thompson et al. | Aug 1994 | A |
5342336 | Meirowitz et al. | Aug 1994 | A |
5348547 | Payne et al. | Sep 1994 | A |
5350370 | Jackson et al. | Sep 1994 | A |
5356405 | Thompson et al. | Oct 1994 | A |
H001377 | Perry | Nov 1994 | H |
5360420 | Cook et al. | Nov 1994 | A |
5364382 | Latimer et al. | Nov 1994 | A |
5366451 | Levesque | Nov 1994 | A |
5368926 | Thompson et al. | Nov 1994 | A |
5382245 | Thompson et al. | Jan 1995 | A |
5382400 | Pike et al. | Jan 1995 | A |
5401267 | Couture-Dorschner | Mar 1995 | A |
5418045 | Pike et al. | May 1995 | A |
5423787 | Kjellberg | Jun 1995 | A |
5429629 | Latimer et al. | Jul 1995 | A |
5439458 | Noel et al. | Aug 1995 | A |
5456982 | Hansen et al. | Oct 1995 | A |
5460622 | Dragoo et al. | Oct 1995 | A |
5466410 | Hills | Nov 1995 | A |
5466513 | Wanek et al. | Nov 1995 | A |
H001511 | Chappell et al. | Dec 1995 | H |
5486166 | Bishop et al. | Jan 1996 | A |
5486167 | Dragoo et al. | Jan 1996 | A |
5487736 | Van Phan | Jan 1996 | A |
5490846 | Ellis et al. | Feb 1996 | A |
5505719 | Cohen et al. | Apr 1996 | A |
5509915 | Hanson et al. | Apr 1996 | A |
5514105 | Goodman, Jr. et al. | May 1996 | A |
5514120 | Johnston et al. | May 1996 | A |
5525407 | Yang | Jun 1996 | A |
5527300 | Sauer | Jun 1996 | A |
5531727 | Cohen et al. | Jul 1996 | A |
5531728 | Lash | Jul 1996 | A |
5536264 | Hsueh et al. | Jul 1996 | A |
5540979 | Yahiaoui et al. | Jul 1996 | A |
5549589 | Horney et al. | Aug 1996 | A |
5556392 | Koczab | Sep 1996 | A |
5562646 | Goldman et al. | Oct 1996 | A |
5562650 | Everett et al. | Oct 1996 | A |
5569226 | Cohen et al. | Oct 1996 | A |
5599335 | Goldman et al. | Feb 1997 | A |
5601545 | Glaug et al. | Feb 1997 | A |
5607414 | Richards et al. | Mar 1997 | A |
5609947 | Kamei et al. | Mar 1997 | A |
5611981 | Phillips et al. | Mar 1997 | A |
5628736 | Thompson | May 1997 | A |
5641441 | Yang | Jun 1997 | A |
5643238 | Baker | Jul 1997 | A |
5643240 | Jackson et al. | Jul 1997 | A |
5647862 | Osborn, III et al. | Jul 1997 | A |
5649916 | DiPalma et al. | Jul 1997 | A |
5658268 | Johns et al. | Aug 1997 | A |
5665082 | Boulanger | Sep 1997 | A |
5728081 | Baer et al. | Mar 1998 | A |
5733635 | Terakawa et al. | Mar 1998 | A |
5752945 | Mosley et al. | May 1998 | A |
5820973 | Dodge, II et al. | Oct 1998 | A |
5843063 | Anderson et al. | Dec 1998 | A |
5843064 | Koczab | Dec 1998 | A |
5843852 | Dutkiewicz et al. | Dec 1998 | A |
5879343 | Dodge, II et al. | Mar 1999 | A |
5931823 | Stokes et al. | Aug 1999 | A |
5964743 | Abuto et al. | Oct 1999 | A |
5994615 | Dodge, II et al. | Nov 1999 | A |
Number | Date | Country |
---|---|---|
1996002147685 | Feb 1996 | CA |
0 235 309 | Sep 1987 | EP |
1993000539703 | May 1993 | EP |
1995000640330 | Mar 1995 | EP |
1996000719530 | Jul 1996 | EP |
0 742 305 | Nov 1996 | EP |
0 669 995 | Jan 1997 | EP |
2 698 384 | May 1994 | FR |
1994002269109 | Feb 1994 | GB |
2 272 859 | Jun 1994 | GB |
1996002295321 | May 1996 | GB |
1996008164160 | Jun 1996 | JP |
1996008164163 | Jun 1996 | JP |
1996008299385 | Nov 1996 | JP |
1996008317939 | Dec 1996 | JP |
1997009000562 | Jan 1997 | JP |
1997009117471 | May 1997 | JP |
WO9012130 | Oct 1990 | WO |
WO9111978 | Aug 1991 | WO |
WO9315702 | Aug 1993 | WO |
WO9429506 | Dec 1994 | WO |
WO9500183 | Jan 1995 | WO |
WO9501147 | Jan 1995 | WO |
WO9516422 | Jun 1995 | WO |
WO9525495 | Sep 1995 | WO |
WO9535081 | Dec 1995 | WO |
WO9601608 | Jan 1996 | WO |
WO9603947 | Feb 1996 | WO |
WO 9611107 | Apr 1996 | WO |
WO9612460 | May 1996 | WO |
WO9620667 | Jul 1996 | WO |
WO9641045 | Dec 1996 | WO |
WO9711660 | Apr 1997 | WO |
WO9713909 | Apr 1997 | WO |
WO9723182 | Jul 1997 | WO |
Number | Date | Country | |
---|---|---|---|
Parent | 08754417 | Nov 1996 | US |
Child | 09314492 | US |