# Patent

## Title
Method of making a wiper/towel product with cellulosic microfibers

## Abstract

A method of making a multi-ply wiper/towel product with cellulosic microfibers. The method includes compactively dewatering a nascent web that includes at least about 10% fibrillated cellulosic microfibers and has an apparently random distribution of fibers. The dewatered web having the apparently random distribution of fibers is applied to a transfer surface. The web is belt-creped from the transfer surface utilizing a creping belt. The belt-creping step occurs under pressure in a belt creping nip defined between the transfer surface and the creping belt. The web is dried to form a dried web having a plurality of fiber-enriched hollow domed regions protruding from an upper side of the dried web. The hollow domed regions have a sidewall of a relatively high local basis weight formed along at least a leading edge thereof. The web also has connecting regions of a relatively lower local basis weight forming a network interconnecting the hollow domed regions of the dried web, and transition areas provided with upwardly and inwardly inflected consolidated fibrous regions that transition from the connecting regions into the sidewalls of the hollow domed regions formed along at least the leading edge thereof.

## Background
CROSS-REFERENCE TO RELATED APPLICATIONS AND INCORPORATION BY REFERENCE
This application is a continuation application of U.S. patent application Ser. No. 13/137,216, filed on Jul. 28, 2011, published on Jan. 26, 2012, as U.S. Patent Application Publication No. 2012/0021178, now U.S. Pat. No. 8,540,846, which is a continuation in part of U.S. patent application Ser. No. 12/694,650, filed Jan. 27, 2010, U.S. Patent Application Publication No. 2010/0186913, entitled “Belt-Creped, Variable Local Basis Weight Absorbent Sheet Prepared With Perforated Polymeric Belt”, published Jul. 29, 2010, now U.S. Pat. No. 8,293,072, which was based upon U.S. Provisional Patent Application No. 61/206,146, filed Jan. 28, 2009, the right of priority of the foregoing being hereby claimed. All of the foregoing applications are incorporated herein by reference.
This application relates to the subject matter of U.S. Patent Application Publication No. 2009/0020139, published Jan. 22, 2009, based on U.S. patent application Ser. No. 12/284,148, filed Sep. 17, 2008, now U.S. Pat. No. 8,187,422, entitled “High Efficiency Disposable Cellulosic Wiper”. This application also relates to the subject matter of U.S. Patent Application Publication No. 2009/0020248, published Jan. 22, 2009, based on U.S. patent application Ser. No. 12/284,147, also filed Sep. 17, 2008, now U.S. Pat. No. 8,187,421, entitled “Absorbent Sheet Incorporating Regenerated Cellulose Microfiber”. Both U.S. patent application Ser. Nos. 12/284,148 and 12/284,147 were based, in part, on U.S. patent application Ser. No. 11/725,253, filed Mar. 19, 2007, entitled “Absorbent Sheet Having Regenerated Cellulose Microfiber Network”, now U.S. Pat. No. 7,718,036. This application also relates, in part, to the subject matter of the following U.S. Provisional Patent Applications:
(1) Provisional Application No. 60/784,228, filed Mar. 21, 2006;
(2) Provisional Application No. 60/850,467, filed Oct. 10, 2006;
(3) Provisional Application No. 60/850,681, filed Oct. 10, 2006; and
(4) Provisional Application No. 60/881,310, filed on Jan. 19, 2007;
(5) Provisional Application No. 60/994,344, filed Sep. 19, 2007; and
(6) Provisional Application No. 60/994,483, filed Sep. 19, 2007.


The disclosures of the foregoing applications are incorporated herein by reference in their entireties.
BACKGROUND
Lyocell fibers are typically used in textiles or filter media. See, for example, U.S. Patent Application Publication No. 2003/0177909, now U.S. Pat. No. 6,872,311, and No. 2003/0168401, now U.S. Pat. No. 6,835,311, both to Koslow, as well as to U.S. Pat. No. 6,511,746 to Collier et al. On the other hand, high efficiency wipers for cleaning glass and other substrates are typically made from thermoplastic fibers.
U.S. Pat. No. 6,890,649 to Hobbs et al. (3M) discloses polyester microfibers for use in a wiper product. According to the '649 patent, the microfibers have an average effective diameter of less than 20 microns and, generally, from 0.01 microns to 10 microns. See column 2, lines 38 to 40. These microfibers are prepared by fibrillating a film surface and then harvesting the fibers.
U.S. Pat. No. 6,849,329 to Perez et al. discloses microfibers for use in cleaning wipes. These fibers are similar to those described in the '649 patent discussed above. U.S. Pat. No. 6,645,618 to Hobbs et al. also discloses microfibers in fibrous mats such as those used for removal of oil from water or those used as wipers.
U.S. Patent Application Publication No. 2005/0148264 to Varona et al., discloses a wiper with a bimodal pore size distribution. The wipe is made from melt blown fibers, as well as coarser fibers, and papermaking fibers. See page 2, paragraph 16.
U.S. Patent Application Publication No. 2004/0203306 to Grafe et al., discloses a flexible wipe including a non-woven layer and at least one adhered nanofiber layer. The nanofiber layer is illustrated in numerous photographs. It is noted on page 1, paragraph 9, that the microfibers have a fiber diameter of from about 0.05 microns to about 2 microns. In this patent application, the nanofiber webs were evaluated for cleaning automotive dashboards, automotive windows, and so forth. For example, see page 8, paragraphs 55 and 56.
U.S. Pat. No. 4,931,201 to Julemoni discloses a non-woven wiper incorporating melt-blown fiber. U.S. Pat. No. 4,906,513 to Kebbell et al. also discloses a wiper having melt-blown fiber. Here, polypropylene microfibers are used, and the wipers are reported to provide streak-free wiping properties. This patent is of general interest, as is U.S. Pat. No. 4,436,780 to Hotchkiss et al., which discloses a wiper having a layer of melt-blown polypropylene fibers and, on either side, a spun bonded polypropylene filament layer. See also U.S. Pat. No. 4,426,417 to Meitner et al., which discloses a non-woven wiper having a matrix of non-woven fibers including microfiber and staple fiber. U.S. Pat. No. 4,307,143 to Meitner discloses a low cost wiper for industrial applications, which includes thermoplastic, melt-blown fibers.
U.S. Pat. No. 4,100,324 to Anderson et al. discloses a non-woven fabric useful as a wiper that incorporates wood pulp fibers.
U.S. Patent Application Publication No. 2006/0141881, now U.S. Pat. No. 7,691,760, to Bergsten et al., discloses a wipe with melt-blown fibers. This publication also describes a drag test, at pages 7 and 9. Note, for example, page 7, paragraph 59. According to the test results on page 9, microfiber increases the drag of the wipes on a surface.
U.S. Patent Application Publication No. 2003/0200991 to Keck et al., discloses a dual texture absorbent web. Note pages 12 and 13, which describe cleaning tests and a Gardner wet abrasion scrub test.
U.S. Pat. No. 6,573,204 to Philipp et al. discloses a cleaning cloth having a non-woven structure made from micro staple fibers of at least two different polymers, and secondary staple fibers bound into the micro staple fibers. The split fiber is reported to have a titer of 0.17 to 3.0 dtex prior to being split. See column 2, lines 7 through 9. Note also, U.S. Pat. No. 6,624,100 to Pike, which discloses splittable fiber for use in microfiber webs.
TECHNICAL FIELD
This application relates to multi-ply wipers comprising at least one variable local basis weight absorbent sheet including a significant proportion of fibrillated cellulose microfiber having a plurality of arched or domed regions interconnected by a generally planar, densified fibrous network including at least some areas of consolidated fiber bordering the domed areas. The domed regions have a leading edge with a relatively high local basis weight and, at their lower portions, transition sections that include upwardly and inwardly inflected sidewall areas of consolidated fiber.
While there have been advances in the art as to high efficiency wipers, existing products tend to be relatively difficult and expensive to produce. Many do not have the absorbent capacity of premium paper towels and are not readily re-pulped or recycled. Moreover, the wipers of the invention are capable of removing micro-particles and, if not substantially all of the residue from a surface, then, at least almost all, reducing the need for biocides and cleaning solutions in typical cleaning or sanitizing operations.
SUMMARY OF THE INVENTION
The present invention is directed, in part, to multi-ply absorbent sheets incorporating cellulose microfiber that are suitable for paper towels and wipers. The sheets exhibit high absorbency (SAT) values as well as low-residue, “wipe-dry” characteristics. The sheets can accordingly be used as high efficiency wipers, or as ordinary paper towels, eliminating the need for multiple products.
In one embodiment, the present invention is a multi-ply absorbent sheet exhibiting a wipe-dry time of less than 20 seconds, preferably, 10 seconds or less, and an SAT capacity in the range of 9.5 to 11 g/g. In a further embodiment, the absorbent sheet exhibits an SAT rate in the range of 0.05 to 0.25 g/s0.5.
A preferred variable basis weight ply is prepared by a belt-creping process including compactively dewatering a nascent web containing from about 10% to about 60% of fibrillated cellulosic microfiber, applying the dewatered web to a transfer surface with an apparently random distribution of fibers, and belt-creping the web under pressure with nip parameters selected so as to rearrange the fiber orientation and, optionally, providing local basis weight variation. The plies of this invention will exhibit a repeating structure of raised arched portions that define hollow areas on their opposite side. The raised arched portions or domes have a relatively high local basis weight interconnected with a network of densified fiber. Transition areas bridging the connecting regions and the domes include upwardly and optionally inwardly inflected consolidated fiber. Generally speaking, the furnish is selected and the steps of belt creping, applying vacuum and drying are controlled such that a dried web is formed having a plurality of fiber-enriched hollow domed regions protruding from the upper surface of the sheet, the hollow domed regions having a sidewall of a relatively high local basis weight formed along at least a leading edge thereof, and connecting regions forming a network interconnecting the fiber-enriched hollow domed regions of the sheet, wherein consolidated groupings of fibers extend upwardly from the connecting regions into the sidewalls of the fiber-enriched hollow domed regions along at least the leading edge thereof. Fibrillated cellulosic microfiber present at the surface of such consolidated groupings forms venation over the surface of the consolidated grouping, while fibrillated cellulosic microfiber present within the consolidated groupings appears to enhance the bonding and consolidation therein, both apparently contributing to an increase in very small pores in the sheet structure. Preferably, such consolidated groupings of fibers are present at least at the leading and trailing edges of the domed areas. In many cases, the consolidated groupings of fibers form saddle shaped regions extending at least partially around the domed areas, wherein a venation of cellulosic microfibers extends over the surface of the consolidated regions. In other less consolidated regions of the ply, the fibrillated cellulosic microfibers are present as intermittently bonded fibers distributed through less consolidated regions of the ply, and intermingled with conventional papermaking fibers therein, and bonded thereto largely at crossover regions where the fibers contact.
The superior wipe-dry characteristics of the inventive products are surprising in view of the very low SAT rates observed. FIGS. 1A to 1H, 1J to 1N, and 1P to 1T are photomicrographs illustrating the microstructure at a surface of multi-ply products of the invention (FIGS. 1G, 1J, and 1L), along with a variety of somewhat similar products. It is considered to be quite surprising that such greatly improved wipe dry characteristics can be observed when apparent porosity is suppressed to the extreme shown here. Without intending to be bound by theory, it is believed that the microfiber venation seen on the surfaces of the consolidated regions in the inventive products FIGS. 1G, 1J, and 1L (formed by creping from a transfer drum using a perforated polymeric belt) provides a very slow observed SAT rate and a high capillary pressure due to a large percentage of very small, easily accessible pores, as described hereafter, as well as the large number of very small pores distributed throughout the consolidated groupings. The inventive products are remarkably efficient wipers for cleaning surfaces, leaving little, if any, residue, thus, providing streak-free cleaning that is especially desirable for glass and glossy surfaces, and much preferred for sanitation purposes. Briefly, “Wipe Dry” is the time it takes for residual Windex® original glass cleaner to evaporate from a plate after a wiper substrate is dragged across a wetted surface. Low values indicate less residual liquid that results in less streaking. Without being bound by theory, it is hypothesized that Campbell's forces draw the fibrillated cellulosic microfibers into rather intimate adhesion to the consolidated fibrous regions, so that rather than bonds being formed only at crossover points between fibers, in areas of venation, line-surface adhesion can be observed between the fibrillated cellulosic microfibers and the underlying consolidated fibrous region, creating numerous highly accessible micropores therebetween, contributing to the excellent wipe dry properties. In any event, the sheets of the present invention formed by creping from a transfer surface using perforated polymeric belts exhibit both remarkable microporosity and remarkably quick wipe dry times, while maintaining satisfactory SAT capacity. Overall, sheets that are more highly consolidated exhibit shorter wipe dry times than more open sheets.
The products of the invention also exhibit wet tensiles significantly above those of commercial towel products, but have similar SAT capacity, so that the wipe-dry characteristics endure as the product absorbs liquid. FIG. 2 shows the combined attributes of wipe-dry, absorbency, and wet strength achieved in a two-ply product of the invention. Wipe-dry times approach 10 seconds or less with a cellulosic microfiber (CMF) content of 40% as compared to 25 to 30 seconds for a conventional towel.
While exhibiting very high strength, the products of the invention also exhibit an unexpectedly high level of softness, as is appreciated from FIG. 3, which illustrates softness as a function of wet tensile and cellulosic microfiber (CMF) content. It is seen in FIG. 3 that elevated softness levels are achieved even at wet tensiles, more than twice that of conventional towel. Preferred products of the present invention will exhibit a differential pore volume for pores under 5 microns in a diameter of at least about 75 mm3/g/micron.
Further details and advantages will become apparent from the discussion provided hereafter.



BRIEF DESCRIPTION OF THE DRAWINGS
The invention is described with reference to the drawings, wherein:
FIGS. 1A, 1C, and 1E illustrate cellulose microfiber (CMF) containing wipers formed by creping a nascent web from a transfer cylinder using a creping fabric and are placed for easy comparison of these to similarly formed wipers without CMF, in FIGS. 1B, 1D and IF.
FIGS. 1G, 1J, and 1L illustrate venation on CMF containing wipers formed by creping a nascent web from a transfer cylinder using a perforated polymeric creping belt and are placed for easy comparison of those to through-air dried (TAD) formed wipers, without CMF, in FIGS. 1H, 1K, and 1M.
FIGS. 1N, 1Q, and 1S illustrate CMF containing wipers formed by conventional wet press technology and are placed for easy comparison of these to similarly formed wipers, without CMF, in FIGS. 1P, 1R and 1T.
FIG. 2 illustrates the wipe dry times of three commercially available kitchen roll towel products as compared to two ply wipers containing varying amounts of CMF formed by belt creping from a transfer cylinder using an exemplary perforated belt as described herein and illustrated in FIG. 7.
FIG. 3 illustrates the relationship among softness, wet tensile strength, and fibrillated cellulosic microfiber content in wipers.
FIG. 4 illustrates the distribution of fiber lengths in a cellulosic microfiber, which is preferred for the practice of the present invention.
FIG. 5 illustrates the extraordinarily high percentage of very long cellulosic fibers attainable with fibrillated cellulosic microfiber.
FIG. 6 illustrates the emboss pattern known as “Fantale” mentioned in Example 2.
FIG. 7 illustrates the sheet contact surface of a perforated polymeric belt mentioned in Example 1.
FIG. 8 illustrates the extrusion/intrusion porosimetry system used for measuring pore volume and pore size distribution.
FIG. 9 is a schematic diagram illustrating the interaction between the pressure plate and the sample in the apparatus for measurement of pore volume distribution.
FIG. 10 illustrates the extraordinarily high percentage of very small pores attainable in wipers comprising various amounts of fibrillated cellulosic microfibers.
FIG. 11 illustrates the relationship between wipe dry times and capillary pressure in wipers.
FIG. 12 illustrates the relationship between capillary pressure and fibrillated cellulosic microfiber content in wipers.
FIG. 13 illustrates the inter-relationship among wet tensile strength, wipe dry time, and content of fibrillated cellulosic microfiber content in a wiper.
FIG. 14 illustrates the softness of a variety of wipers as a function of GM tensile strength with fibrillated cellulosic microfiber content being indicated as a parameter.
FIG. 15 illustrates the softness of a variety of wipers as a function of cross machine direction (CD) wet tensile strength with fibrillated cellulosic microfiber content being indicated as a parameter.
FIG. 16 illustrates wipe dry times as a function of SAT capacity with fibrillated cellulosic microfiber content being indicated as a parameter.
FIG. 17 illustrates wipe dry times as a function of water holding capacity with fibrillated cellulosic microfiber content being indicated as a parameter.
FIG. 18 illustrates wipe dry times as a function of SAT rate with fibrillated cellulosic microfiber content being indicated as a parameter.
FIG. 19 illustrates wipe dry times as a function of fibrillated cellulosic microfiber content with wet strength resin content being indicated as a parameter.
FIG. 20 illustrates variation in wet extracted lint for a variety of wipers with fibrillated cellulosic microfiber content, wet strength agent content, and debonder content being indicated.
FIG. 21 illustrates the response of caliper and SAT capacity in wipers to calendering.
FIG. 22 illustrates variation in the cross machine direction (CD) wet tensile strength for a variety of towels as a function of basis weight.
FIG. 23 illustrates the response of basesheet caliper to shoe press load in a variety of wipers.
FIG. 24 illustrates basesheet caliper as a function of fibrillated cellulosic microfiber content at a constant shoe press load.
FIGS. 25A and 25B illustrate an emboss pattern known as “Little Circles” mentioned in Example 2.
FIG. 26 illustrates an emboss pattern known as “Patchwork” mentioned in Example 2.
FIG. 27 illustrates the CD wet tensile strength of a variety of towels as a function of basis weight.
FIG. 28 is a schematic scale drawing of a preferred belt usable in the practice of the present invention.
FIG. 29 illustrates the CD wet tensile strength of a variety of towels as a function of caliper.
FIG. 30 illustrates the SAT capacity of a variety of towels as a function of caliper.
FIG. 31 illustrates variation in SAT capacity for a variety of towels as a function of basis weight.
FIG. 32 illustrates the relationship between CD wet tensile strength and Sensory Softness for a variety of towels.
FIG. 33 presents SAT capacity and wipe dry times for both black glass and stainless steel surfaces for the wipers of Example 2.
FIG. 34 is a sectional scanning electron micrograph (SEM) illustrating a consolidated region in a sheet formed by belt creping using a perforated polymeric belt.
FIG. 35 is an enlarged view of a portion of FIG. 34 illustrating a domed region and a consolidated region in more detail.
FIG. 36 is a sectional scanning electron micrograph (SEM) illustrating another consolidated region in a sheet formed by belt creping using a perforated polymeric belt.
FIG. 37 compares the relative improvements in wipe dry of wipers made by creping with a woven fabric as compared to wipers made by belt creping using a perforated polymeric belt.
FIG. 38 compares wipe dry of wipers made by creping with a woven fabric as compared to wipers made by belt creping using a perforated polymeric belt.
FIG. 39 illustrates the effect of excessive quaternary ammonium salt release agent on wipers made by belt creping using a perforated polymeric belt.
FIG. 40 is an isometric schematic illustrating a device to measure roll compression of tissue products.
FIG. 41 is a sectional view taken along line 41-41 of FIG. 40.
FIG. 42 illustrates the dimensions of a marked microscope slide used in evaluating the resistance of the products of the present invention to wet linting.



DETAILED DESCRIPTION OF THE INVENTION
The invention is described in detail below with reference to several embodiments and numerous examples. Such a discussion is for purposes of illustration only. Modifications to particular examples within the spirit and scope of the present invention, set forth in the appended claims, will be readily apparent to one of skill in the art.
Terminology used herein is given its ordinary meaning, for example, mils refers to thousandths of an inch, mg refers to milligrams and m2 refers to square meters, percent means weight percent (dry basis), “ton” means short ton (2000 pounds), unless otherwise indicated “ream” means 3000 ft2, and so forth. A “ton” is 2000 pounds while a “tonne” is a metric ton of 100 kg or 2204.62 pounds Unless otherwise specified, in an abbreviation “t” stands for “ton”. Unless otherwise specified, the version of a test method applied is that in effect as of Jan. 1, 2010, and test specimens are prepared under standard TAPPI conditions, that is, preconditioned for 24 hours, then conditioned in an atmosphere of 23°±1.0° C. (73.4°±1.8° F.) at 50% relative humidity for at least about 2 hours.
Test methods, materials, equipment, manufacturing techniques, and terminology are those enumerated in the applications referred to above as supplemented herein.
Throughout this specification and claims, when we refer to a nascent web having an apparently random distribution of fiber orientation or use like terminology), we are referring to the distribution of fiber orientation that results when known forming techniques are used for depositing a furnish on the forming fabric. When examined microscopically, the fibers give the appearance of being randomly oriented, even though, depending on the jet to wire speed ratio, there may be a significant bias toward machine direction orientation making the machine direction tensile strength of the web exceed the cross machine direction tensile strength.
In many applications related to U.S. Patent Application Publication No. 2004/0238135, entitled “Fabric Crepe Process for Making Absorbent Sheet”, now U.S. Pat. No. 7,399,378, the importance of the distinction between creping using a woven fabric and a creping belt formed by perforating a solid belt was of minor importance, so the term “belt” could apply to either creping medium. In this application, however, as well as in U.S. Patent Application Publication No. 2010/0186913, entitled “Belt-Creped. Variable Local Basis Weight Absorbent Sheet Prepared With Perforated Polymeric Belt”, now U.S. Pat. No. 8,293,072, the distinction between the use of a creping fabric and a perforated polymeric belt is of considerable importance, as it has been found that the use of a perforated polymeric belt makes it possible to obtain consolidated regions, particularly, consolidated saddle shaped regions, in the web giving, it improved physical properties over the webs previously formed using the technique of creping from a transfer drum. For convenience, we refer to this method of forming a sheet as Fiber Reorienting Belt Creping or FRBC. Further, in this application, it is demonstrated that CMF containing wipers made using a perforated polymeric belt have substantial performance advantages over wipers made using a woven creping fabric, which we term Fiber Reorienting Fabric Creping or FRFC. Throughout this application, we have endeavored to make this distinction explicit, but, definitional language in applications incorporated by reference notwithstanding, in this application, belts and creping fabrics should not be considered to be synonymous.
Unless otherwise specified, “basis weight”, BWT, bwt, BW, and so forth, refers to the weight of a 3000 square-foot (278.7 m2) ream of product (basis weight is also expressed in g/m2 or gsm). Likewise, “ream” means a 3000 square-foot (278.7 m2) ream unless otherwise specified. Local basis weights and differences therebetween are calculated by measuring the local basis weight at two or more representative low basis weight areas within the low basis weight regions and comparing the average basis weight to the average basis weight at two or more representative areas within the relatively high local basis weight regions. For example, if the representative areas within the low basis weight regions have an average basis weight of 15 lbs/3000 ft2 (24.5 g/m2) ream and the average measured local basis weight for the representative areas within the relatively high local basis regions is 20 lbs/3000 ft2 ream (32.6 g/m2), the representative areas within the high local basis weight regions have a characteristic basis weight of ((20−15)/15)×100% or 33% higher than the representative areas within the low basis weight regions. Preferably, the local basis weight is measured using a beta particle attenuation technique as referenced herein. In some cases, X-ray techniques can be suitable, provided that the X-rays are sufficiently “soft” —that the energy of the photons is sufficiently low and the basis weight differences between the various regions of the sheet are sufficiently high that significant differences in attenuation are attained.
Calipers and/or bulk reported herein may be measured at 8 or 16 sheet calipers as specified. The sheets are stacked and the caliper measurement taken about the central portion of the stack. Preferably, the test samples are conditioned in an atmosphere of 23°+1.0° C. (73.4°±1.8° F.) at 50% relative humidity for at least about 2 hours and then measured with a Thwing-Albert Model 89-11-JR or Progage Electronic Thickness Tester with 2 in. (50.8-mm) diameter anvils, 539±10 grams dead weight load, and 0.231 in/sec (5.87 mm/sec) descent rate. For finished product testing, each sheet of product to be tested must have the same number of plies as the product as sold. For testing in general, eight sheets are selected and stacked together. For napkin testing, napkins are unfolded prior to stacking. For base sheet testing off of winders, each sheet to be tested must have the same number of plies as produced oil of the winder. For base sheet testing off of the papermachine reel, single plies must be used. Sheets are stacked together aligned in the machine direction (MD). Bulk may also be expressed in units of volume/weight by dividing caliper by basis weight.
Consolidated fibrous structures are those that have been so highly densified that the fibers therein have been compressed to ribbon-like structures and the void volume is reduced to levels approaching or perhaps even less than those found in flat papers, such as are used for communications purposes. In preferred structures, the fibers are so densely packed and closely matted that the distance between adjacent fibers is typically less than the fiber width, often less than half or even less than a quarter of the fiber width. In the most preferred structures, the fibers are largely collinear and strongly biased in the MD. The presence of consolidated fiber or consolidated fibrous structures can be confirmed by examining thin sections that have been embedded in resin, then microtomed in accordance with known techniques. Alternatively, if SEM's of both faces of a region are so heavily matted as to resemble flat paper, then that region can be considered to be consolidated. Sections prepared by focused ion beam cross section polishers, such as those offered by JEOL®. 11 Dearborn Road, Peabody, Mass., 01960, are especially suitable for observing densification throughout the thickness of the sheet, to determine whether regions in the tissue products of the present invention have been so highly densified as to become consolidated.
Creping belt, and like terminology, refers to a belt that bears a perforated pattern suitable for practicing the process of the present invention. In addition to perforations, the belt may have features, such as raised portions and/or recesses between perforations, if so desired. Preferably, the perforations are tapered, which appears to facilitate transfer of the web, especially, from the creping belt to a dryer, for example. Typically, the face of the sheet contacting the web during the fabric creping step will have a greater open area than the face away from the web. In some embodiments, the creping belt may include decorative features, such as geometric designs, floral designs, and so forth, formed by rearrangement, deletion, and/or a combination of perforations having varying sizes and shapes.
“Dome”, “domed”, “dome-like,” and so forth, as used in the description and claims, refers generally to hollow, arched protuberances in the sheet of the class seen in the various Figures, and is not limited to a specific type of dome structure as is illustrated in FIGS. 34 to 36. The terminology refers to vaulted configurations, generally, whether symmetric or asymmetric about a plane bisecting the domed area. Thus, “dome” generally refers to spherical domes, spheroidal domes, elliptical domes, ellipsoidal domes, oval domes, domes with polygonal bases, and related structures, generally including a cap and sidewalls, preferably inwardly and upwardly inclined, that is, the sidewalls being inclined toward the cap along at least a portion of their length.
Extractable Lint Test
To quantify the amount of lint removed from towel, tissue, and related products when used dry (“Extractable Lint”), a Sutherland Rub Tester with a 4.0-lb sled is used. This apparatus is available from: Danilee Company, 27223 Starry Mountain Street, San Antonio, Tex. 78260, 830-438-7737, 800-438-7738 (FAX). The 4.0-lb rub block for the Rub Tester has dimensions of 2′′ by 4′′, so that the pressure exerted during testing is 0.5 psi.
After the samples to be evaluated are preconditioned at 10 to 35% RH at 22° to 40° C. for 24 hours, then conditioned at 50.0%±2.0% RH and 23.0±1.0° C. for 2 hours, all of the subsequent procedures are performed within the confines of a room maintained at between 48 to 53% RH and a temperature of between 22° C. and 24° C.
Two stacks of four 2.25 in.×4.5 in. test strips with a 4.5 in. length in the machine direction are cut from the sample with the top (exterior of roll) side up.
Two 2.5 in.×6 in. strips of black felt are cut with the 6 in. length in the machine direction, and the top side labeled with sample ID numbers.
A baseline reading for the felt is determined by taking one L* lightness color reading on the labeled side of each black felt strip used for testing in the middle of what will be the rubbed area using a GretagMacbeth® Ci5 spectrophotometer using the following settings on the spectrophotometer: Large area view, Specular component excluded, UV Source C, 2 degree observer, and Illuminant C. (In this connection, the asterisk “*” is not a reference mark directing the reader to some other location in this document, but a portion of the commonly used symbol for CIF 1976 lightness “L*”. “L*” as used in this connection relates to CIE 1976, also known as CIELAB measurement of lightness, and should not be confused with Hunger lightness typically denominated “L”.) The GretagMacbeth® spectrophotometer Model Ci5 is available from: GretagMacbeth®, 617 Little Britain Road, New Windsor, N.Y. 12553, 914-565-7660, 914-565-0390 (FAX); www.gretagmacbeth.com. The “before testing” reading is later compared to the “after testing” reading in the same area of the black felt strip on the same side, so particular care is taken to be sure that a comparison is made only between the same felt strips.
To evaluate a specimen, the specimen is taped to the galvanized plate on the Sutherland Rub Tester with the top side up, so that rubbing will be in the machine direction with care being observed to ensure that each specimen is taped in the same rub area each time the test is performed. The first black felt specimen is taped, labeled side out, to the bottom of the 4.0-lb rub block of the Sutherland Rub Tester, the number of strokes on the rub tester is set to four, and the slow speed selected (#2 setting for 4 speed model or #1 setting for 2 speed model), the rub block is placed on the Sutherland Rub Tester carriage arm and the “Start” button pressed to start testing. After the four strokes are completed, the rub block is removed from the tester and the black felt is removed from the bottom of the rub block with the black felt being preserved for L* “after testing” color reading. The specimen is removed from the galvanized plate and discarded.
One L* color reading is taken on the labeled side of each black felt strip, reading the same spot used to obtain the “before testing” value, in the middle of the rubbed area. The “after testing” reading is paired up with the appropriate “before testing” reading to calculate difference between the readings—“ΔL*”.
For each sample, the average, standard deviation, minimum and maximum test results are recorded as measured to the nearest 0.01 L* unit for both the before testing and after testing values. The difference value of the after reading minus the before reading is indicative of the lint removal by the standardized dry rubbing procedure.
Wet Abrasion Lint Test
Two tests are used herein to evaluate wet linting of tissue samples: in one approach, fiber is rubbed against a wetted pigskin under controlled conditions, the resulting fiber is washed off of the pigskin and the number of fibers removed is measured using an OpTest® Fiber Quality Analyzer. In the second, tissue is rubbed against wetted black felt under controlled conditions and the area of the lint left behind is measured using a flat bed scanner as described below.
Area Test
To evaluate a tissue sample for lint removal by wet abrasion, the sample is first subjected to simulated wet use against a sample of standard black felt with a Crockmeter Rub Tester, modified as described herein, then, the area in mm2 of the lint left on the felt is measured with an Epson Perfection 4490 flat bed scanner and Apogee, SpecScan Software, version 2.3.6.
The Crockmetcr Rub is available from: SDL Atlas, LLC, 3934 Airway Drive, Rock Hill, S.C. 29732, (803) 329-2110. To be used to measure wet lint as described herein, the Crockmeter is modified to accept a 360 gram arm and a 1′′×2′′ foot that exerts a pressure on the specimen of 0.435 psi. The weight of the rub block is 355 g for the weighted arm supported on one end, and 36 g for the rub foot. These weights are exerted on a 1′′×2′′ area, for a pressure of 391 g/12.9 cm2−30.3 g/cm2. In contrast, the method of evaluating wet abrasion in U.S. Pat. No. 5,958,187 to Bhat et et al., and U.S. Pat. No. 6,059,928 to Luu et al., used a 135 g sled placed on a 2×3′′ sample for a pressure of 135 g/38.7 cm2=3.5 g/cm2.
Research Dimensions, at 1720 Oakridge Road, Neenah, Wis. 54956, 920-722-2289, will modify Crockmeter Rub Testers to conform hereto.
Suitable black felt is 3/16-inch thick, part number 113308F-24 available from Aetna Felt Corporation, 2401 W. Emaus Avenue, Allentown, Pa. 18103, 800-526-4451.
To test a sample, the outer three layers of tissue are removed from the roll. Three sheets of tissue are cut at the perforations and placed in a stack using a paper cutter ensuring that the tissue sheets are placed in the same orientation relative to the direction and the side of the roll. From the stack, samples that are 2 inches by 2.5 inches are cut with the long dimension being the machine direction. Enough samples are cut for 4 replicates. The short (2′) side of the tissue is marked with a small dot to indicate the surface of the tissue that was outwardly facing when on the roll. The foot is mounted to the arm of the Crockmeter with the short dimension parallel to the stroke of the Crockmeter and the stroke distance set at 4′′±1⁄8 inch, and the stroke speed is set to ten strokes per minute. The black felt is cut into 3 inch by 6 inch pieces with the inside surface being marked along the short edge. In this test, the tissue sample to be tested will be rubbed against the inside of the felt starting at the mark. A 12 inch by 12 inch sheet of Black Acrylic, a 2 inch by 3 inch glass microscope slide marked as shown in FIG. 42, a tape, a pipette, and a beaker of distilled water are located on any nearby convenient flat surface. The Crockmeter is turned on, then turned off, to position the arm at its furthest back position. The spacer is placed under the arm to hold it above the rubbing surface. A clean piece of black felt is taped to the base of the Crockmeter over the rubbing surface with the marked surface oriented upward with the marked end up adjacent to the beginning point of the stroke of the foot. A sample is taped along one shorter edge to the foot with the top side of the tissue facing up, and the length of the tissue is wrapped around the foot and attached to the arm of the Crockmeter with the taped side and the marked location on the tissue sample facing the operator at the forward portion of the Crockmeter. The type of tape used is not critical. Office tape commonly referred to as cellophane tape or sold wider the trademark “Scotch® Tape” is suitable. The spacer is removed from under the arm and the arm with the attached foot is set down on the black felt with the long dimension of the foot perpendicular to the rub direction, and the foot is fixed in place. The glass microscope slide is placed on the felt forward of the foot and 3 volumes of 200 μL of distilled water each are dispensed from the pipette onto the cross-marks on the glass slide. The sample, foot and arm are gently lifted, the glass slide is placed under the sample, and the sample is lowered to allow the water to wet the sample for 5 seconds, after which time the arm is lifted, the glass slide removed and the Crockmeter activated to allow the sample to make three forward strokes on the felt with the arm being lifted manually at the beginning of each return stroke to prevent the sample from contacting the felt during the return strokes. After three forward strokes, the Crockmeter is inactivated and the spacer placed under the arm so that the black felt can be removed without disturbing the abraded lint thereupon. Three minutes after the felt is removed from the rubbing surface, the felt is scanned in an Epson, Perfection 4490 flat bed scanner using Apogee SpecScan Software version 2.3.36 with the software being set for “lint” in the “Scanner Settings” window, with “5” being set in the “Process Groups of:” window on the “Defaults panel”, the “Resolution” being set at “600 dots/inch”, the “Scanner Mode” being set to “256-Grayscale”, the “Area Setting” being set to “Special”, the “Scan Image” being set to “Reverse Image”, the “Upper Limit” window on the “Dirt Histogram” panel being set to “>=5.000” the “Lower Limit” window of that panel being set to “0.013-0.020” and the “X Scale:” window being set to “25”; and the “PPM” window of the “Bad Handsheet” panel set to “2500.0”. On the “Printout Settings:” panel, the “Gray-Summary”, “Sheet Summary” and “Gray Histogram” boxes are checked, the “Copies” window is set to “1”, while the “Dirt Histogram”, “Categories” and “XY Location boxes on that panel are unchecked. Both the “Enable Display” and “Enable Zoom” boxes are checked on the Display Mode panel. On the “Scanner Setup” panel, the “White” box is set for “255” while the “Black” box is set for “0”, the “Contrast Filter” box is set for “0.000”, the upper “Threshold=” box is set for 80.0 [% percent of background plus] while the lower “Threshold=” box is set for “0.0” [grayscale value]. The “Percent of Background, plus offset” box on the “Scanner Setup” panel is checked while the “Manual Threshold Setting” and “Function of StdDev of Background” boxes are unchecked. If desired, the “Grade Identification:” and “Reel/Load Number:” boxes may be used to record indicia related to the identification of the samples being tested. On the “Special Area Definition” panel, “Inches” is checked in the “Dimensions:” region while “Rectangular” is checked in the “Shape:” region. In the “Border at top and left:” region, “0.15” [in.] is entered in the “At the left side: (X)” box and “0.625” [in.] is entered in the “At the top: (Y)” box. In the “Area to scan:” regions “2.7” [in.] is entered in the “Width (X)” box and “5.2” [in.] is entered in the “Height (Y)” box. After scanning, the area in mm2 of the abraded lint left on the black felt is output in the “SHEETS” Table in the “Total Area” column under the “Sample Sheet(s)” heading on the “Sheet & Category Summary” screen. This result is sometimes referred to herein as “WALA” for Wet Abraded Lint Area, which is reported in mm2.
Fiber Count Test
In other cases, rather than using black felt, a pigskin comparable to human skin is substituted therefor, the fiber removed will be washed off and the solution subjected to testing in an Optest® Fiber Quality Analyzer to determine the number of fibers removed having a length in excess of 40 μm. The Optest® Fiber Quality Analyzer has become a standard in the paper industry for determining fiber length distributions and fiber counts (above a certain minimal length, which keeps decreasing periodically, as Optest® continually upgrades their technique). The Optest® Fiber Quality Analyzer is available from:

    
    
        OpTest Equipment Inc.
        900 Tupper St. —Hawkesbury—ON—K6A 3S3—Canada
        Phone: 613-632-5169 Fax: 613-632-3744.
    
    


Fpm refers to feet per minute, while fps refers to feet per second.
MD means machine direction and CD means cross-machine direction.
“Predominantly” means more than 50% of the specified component, by weight unless otherwise indicated.
Roll Compression Test
Roll compression is measured by compressing roll 285 under a 1500 g flat platen 281 of a test apparatus 283 similar to that shown in FIGS. 40 and 41, then measuring the difference in height between the uncompressed roll and the compressed roll while in the fixture. Sample rolls 285 are conditioned and tested in an atmosphere of 23.0°±1.0° C. (73.4°±1.8° F.). A suitable test apparatus 283 with a movable 1500 g platen 281 (referred to as a Height Gauge) is available from:

    
    
        Research Dimensions
        1720 Oakridge Road
        Neenah, Wis. 54956
        920-722-2289
        920-725-6874 (FAX).
    
    


The test procedure is generally as follows:
(a) Raise the platen 281 and position the roll 285 to be tested on its side, centered under the platen 281, with the tail seal 287 to the front of the gauge and the core 289 parallel to the back of the gauge 291.
(b) Slowly lower the platen 281 until it rests on the roll 285.
(c) Read the compressed roll diameter height fiom the gauge pointer 293 to the nearest 0.01 inch (0.254 mm).
(d) Raise the platen 281 and remove the roll 285.
(e) Repeat for each roll to be tested.
To calculate roll compression in percent, the following formula is used:




  
    RC
    ⁡
    
      (
      %
      )
    
  
  =
  
    100
    ×
    
      
        
          (
          
            
              initial
              ⁢
              
                
              
              ⁢
              roll
              ⁢
              
                
              
              ⁢
              diameter
            
            -
            
              composed
              ⁢
              
                
              
              ⁢
              roll
              ⁢
              
                
              
              ⁢
              diameter
            
          
          )
        
        
          initial
          ⁢
          
            
          
          ⁢
          roll
          ⁢
          
            
          
          ⁢
          diameter
        
      
      .
    
  




Dry tensile strengths (MD and CD), stretch, ratios thereof, modulus, break modulus, stress and strain are measured with a standard Instron® test device or other suitable elongation tensile tester, which may be configured in various ways, typically, using 3 inch (76.2 mm) or 1 inch (25.4 mm) wide strips of tissue or towel, conditioned in an atmosphere of 23°±1° C. (73.4°±1° F.) at 50% relative humidity for 2 hours. The tensile test is run at a crosshead speed of 2 in/min (50.8 mm/min). Break modulus is expressed in grams/3 inches/% strain or its SI equivalent of g/mm/% strain. % strain is dimensionless and need not be specified. Unless otherwise indicated, values are break values. GM refers to the square root of the product of the MD and CD) values for a particular product. Tensile energy absorption (TEA), which is defined as the area under the load/elongation (stress/strain) curve, is also measured during the procedure for measuring tensile strength. Tensile energy absorption is related to the perceived strength of the product in use. Products having a higher TEA may be perceived by users as being stronger than similar products that have lower TEA values, even if the actual tensile strength of the two products are the same. In fact, having a higher tensile energy absorption may allow a product to be perceived as being stronger than one with a lower TEA, even if the tensile strength of the high-TEA product is less than that of the product having the lower tensile energy absorption. When the term “normalized” is used in connection with a tensile strength, it simply refers to the appropriate tensile strength from which the effect of basis weight has been removed by dividing that tensile strength by the basis weight. In many cases, similar information is provided by the term “breaking length”.
Tensile ratios are simply ratios of the values determined by way of the foregoing methods. Unless otherwise specified, a tensile property is a dry sheet property.
“Upper”, “upwardly” and like terminology is used purely for convenience and does not require that the sheet be placed in a specified orientation, but rather, refers to position or direction toward the caps of the dome structures, that is, the belt side of the web, which is generally opposite to the Yankee side, unless the context clearly indicates otherwise.
“Venation” means a structure presenting a generally smooth surface having raised, generally continuous ridges defined thereacross, similar to the venation observable on the lower surface of many common leaves.
The void volume and/or void volume ratio, as referred to hereafter, are determined by saturating a sheet with a nonpolar POROFILTM liquid, available from Coulter Electronics Ltd. (Beckman Coulter, Inc. 250 S. Kraemer Boulevard, P.O. Box 8000, Brea, Calif. 92822-8000 USA, Part No. 9902458), and measuring the amount of liquid absorbed. The volume of liquid absorbed is equivalent to the void volume within the sheet structure. The % weight increase (PWI) is expressed as grams of liquid absorbed per grain of fiber in the sheet structure times one hundred, as noted hereafter. More specifically, for each single-ply sheet sample to be tested, select 8 sheets and cut out a 1 inch by 1 inch (25.4 mm by 25.4 mm) square (1 inch (25.4 mm) in the machine direction and 1 inch (25.4 mm) in the cross machine direction). For multi-ply product samples, each ply is measured as a separate entity. Multiple samples should be separated into individual single plies and 8 sheets from each ply position used for testing. Weigh and record the dry weight of each test specimen to the nearest 0.0001 gram. Place the specimen in a dish containing POROFILTM liquid having a specific gravity of about 1.93 grams per cubic centimeter. After 10 seconds, grasp the specimen at the very edge (1 to 2 millimeters in) of one corner with tweezers and remove from the liquid. Hold the specimen with that corner uppermost and allow excess liquid to drip for 30 seconds. Lightly dab (less than 1⁄2 second contact) the lower corner of the specimen on #4 filter paper (Whatman Ltd., Maidstone, England) in order to remove any excess of the last partial drop. Immediately weigh the specimen, within 10 seconds, recording the weight to the nearest 0.0001 gram. The PWI for each specimen, expressed as grams of POROFILTM liquid per gram of fiber, is calculated as follows:

PWI=[(W2−W1)/W1]×100,

wherein
“W1” is the dry weight of the specimen, in grains; and
“W2” is the wet weight of the specimen, in grams.
The PWI for all eight individual specimens is determined as described above and the average of the eight specimens is the PWI for the sample.
The void volume ratio is calculated by dividing the PWI by 1.9 (density of fluid) to express the ratio as a percentage, whereas the void volume (gms/gm) is simply the weight increase ratio, that is, PWI divided by 100.
Water absorbency rate is related to the time it takes for a sample to absorb a 0.1 gram droplet of water disposed on its surface by way of an automated syringe. The test specimens are preferably conditioned at 23° C.±1° C. (73.4° F.±1.8° F.) at 50% relative humidity. For each sample, four 3×3 inch test specimens are prepared. Each specimen is placed in a sample holder such that a high intensity lamp is directed toward the specimen. 0.1 ml of water is deposited on the specimen surface and a stop watch is started. When the water is absorbed, as indicated by lack of further reflection for light from the drop, the stopwatch is stopped and the time is recorded to the nearest 0.1 seconds. The procedure is repeated for each specimen and the results averaged for the sample. SAT rate is determined by graphing the weight of water absorbed by the sample (in grams) against the square root of time (in seconds). The SAT rate is the best fit slope between 10 and 60 percent of the end point (grams of water absorbed), and is expressed in g/s0.5.
The wet tensile of a wiper of the present invention is measured generally following TAPPI Method T 576 pm-07 using a three-inch (76.2 mm) wide strip of tissue that is folded into a loop, clamped in a special fixture termed a Finch Cup, then immersed in water. A suitable Finch cup, 3 inch (76.2 mm), with base to fit a 3 inch (76.2 mm) grip, is available from:

    
    
        High-Tech Manufacturing Services, Inc.
        3105-B NE 65th Street
        Vancouver, Wash. 98663
        360-696-1611
        360-696-9887 (FAX).
    
    


For fresh basesheet and finished product (aged 30 days or less for towel product, aged 24 hours or less for tissue product) containing wet strength additive, the test specimens are placed in a forced air oven heated to 105° C. (221° F.) for five minutes. No oven aging is needed for other samples. The Finch cup is mounted onto a tensile tester equipped with a 2.0 pound (8.9 Newton) load cell with the flange of the Finch cup clamped by the tester's lower jaw and the ends of tissue loop clamped into the upper jaw of the tensile tester, The sample is immersed in water that has been adjusted to a pH of 7.01±0.1 and the tensile is tested after a 5 second immersion time using a crosshead speed of 2 inches/minute (50.8 mm/minute). The results are expressed in g/3 in. or (g/mm), dividing the readout by two to account for the loop as appropriate.
Wipe dry times are evaluated using a turntable wipe dry instrument with a spray fluid dispensing instrument, each being as described below. For purposes of this application, two standard test surfaces are used: stainless steel and black glass. To evaluate a sample, the paper is first pre-conditioned and conditioned as described below, the test surface cleaned with Windex® original glass cleaner from S.C. Johnson and Son, Racine, Wis., and then wiped dry with a lint-free wipe.
The test sample is folded so that the fold extends in the cross machine direction and centered on the black foam side of the sample head, so that the machine direction runs perpendicular to the shaft (i.e., the machine direction is parallel to the directions of motion) and taped in position at its corners so that the sample's leading edge is the folded edge and the towel sample is flush with the right hand edge of the sample head. The sample head is placed on the test surface and the slack in the sample removed. Windex® original glass cleaner is sprayed on the test surface in an amount of 0.75±0.1 grains in the center of the area not occupied by the test head. The table is rotated for 3 revolutions at 30 to 32 rpm with the head in engagement with the test surface at a load of 1065 g spread over bearing surface dimensions of 23 cm×9.5 cm. After the turntable has made three revolutions, the area on the test surface to which the Windex® original glass cleaner was applied is observed and the elapsed time recorded until all of the Windex® original glass cleaner has evaporated. This time is recorded in seconds as the Wipe Dry Time.
To quantify the amount of lint removed from towel, tissue, and related products (Extractable Lint), a Sutherland Rub Tester with 4.0-lb rub block is used. This is discussed above.
After the samples to be evaluated are preconditioned at 10 to 35% RH at 22° to 40° C. for 24 hours, then conditioned at 50.0%±2.0% RH and 23.0±1.0° C. for 2 hours, all of the subsequent procedures are performed within the confines of a room maintained at between 48 to 53% RH and a temperature of between 22° C. and 24° C.
Two stacks of four 2.25 in.×4.5 in. test strips with 4.5 in. length in the machine direction are cut from the sample with the top (exterior of roll) side up.
Two 2.5 in.×6 in. strips of black felt are cut with the 6 in. length in the machine direction, and the top side labeled with sample ID numbers.
A baseline reading for the felt is determined by taking one L* color reading on the labeled side of each black felt strip used for testing in the middle of what will be the rubbed area using a GretagMacbeth Spectrophotometer Model Ci5 as discussed above. The “before testing” reading is later compared to the “after testing” reading in the same area of the black felt strip on the same side, so particular care is taken to be sure that comparison are made only between the same felt strips.
One L* color reading is taken on the labeled side of each black felt strip, reading the same spot used to obtain the “before testing” value, in the middle of the rubbed area. The “after testing” reading is paired up with the appropriate “before testing” reading to calculate the difference between the two readings—“ΔL*”.
For each sample, the average, standard deviation, minimum and maximum test results are recorded as measured to the nearest 0.01 L* unit for both the before testing and after testing values. The difference value of the after reading minus the before reading is indicative of the lint removal by the standardized rubbing procedure.
Liquid Porosimetry
Liquid porosimetry is a procedure for determining the pore volume distribution (PVD) within a porous solid matrix. Each pore is sized according to its effective radius, and the contribution of each size to the total free volume is the principal objective of the analysis. The data reveals useful information about the structure of a porous network, including absorption and retention characteristics of a material.
The procedure generally requires quantitative monitoring of the movement of liquid either into or out of a porous structure. The effective radius R of a pore is operationally defined by the Laplace equation:




  R
  =
  
    
      2
      ⁢
      γ
      ⁢
      
        
      
      ⁢
      cos
      ⁢
      
        
      
      ⁢
      θ
    
    
      Δ
      ⁢
      
        
      
      ⁢
      P
    
  




where γ is liquid surface tension, θ is advancing or receding contact angle of the liquid, and ΔP is pressure difference across the liquid/air meniscus. For liquid to enter or to drain from a pore, an external pressure must be applied that is just enough to overcome the Laplace ΔP. Cos θ is negative when liquid must be forced in, cos θ is positive when it must be forced out. If the external pressure on a matrix having a range of pore sizes is changed, either continuously or in steps, filling or emptying will start with the largest pore and proceed in turn down to the smallest size that corresponds to the maximum applied pressure difference. Porosimetry involves recording the increment of liquid that enters or leaves with each pressure change and can be carried out in the extrusion mode, that is, liquid is forced out of the porous network rather than into it. The receding contact angle is the appropriate term in the Laplace relationship, and any stable liquid that has a known cos θr>0 can be used. If necessary, initial saturation with liquid can be accomplished by preevacuation of the dry material. The basic arrangement used for extrusion porosimetry measurements is illustrated in FIG. 8. The presaturated specimen is placed on a microporous membrane which is itself supported by a rigid porous plate. The gas pressure within the chamber is increased in steps, causing liquid to flow out of some of the pores, the largest ones first. The amount of liquid removed is monitored by the top-loading recording balance. In this way, each level of applied pressure (which determines the largest effective pore size that remains tilled) is related to an increment of liquid mass. The chamber is pressurized by means of a computer-controlled, reversible, motor-driven piston/cylinder arrangement that can produce the required changes in pressure to cover a pore radius range from 1 to 1000 μm.
Eight finished product samples were analyzed for pore volume distribution testing. Measurements were performed on the TRI/Autoporosimeter®. The instrument and the PVD methodology are described in the paper “Liquid Porosimetry: New Methodology and Applications” by Dr. B. Miller and Dr. I. Tyomkin, published in the Journal of Colloid and Interface Science, 162, 163-170, (1994), the disclosure of which is incorporated herein by reference.
The test liquid was 0.1% TX-100 solution in water, surface tension 30 mN/m. TX-100 is a surfactant. For reference, water at room temperature has a sum lace tension of 72 dyne/cm. Sample size was 30 cm2. The test started in an advancing mode and finished in a receding mode. The advancing mode requires good contact with fine porous membrane in the test chamber. Therefore, samples were covered with a multi-pin plate as shown in FIG. 9. The pin plate area is 30 cm2. It has 196 0.9×0.9 mm square pins, the height of each pin is 4 mm, the distance between pins is 3.2 mm, and the total area of pins is 159 mm2. The pin plate locally compressed the sample. The total area of the pins is 5% of sample.
Data from 1 micron to 500 microns represent the advancing part of the curve, and data from 500 microns to 1 micron represent the receding part of the curve. At the end of the test at 1 micron, there was some liquid left in the sample. This liquid is a sum of liquid in swollen fibers, liquid in pores below 1 micron, and liquid trapped in the larger pores. The amount of liquid in a sample at the end of experiment was usually below 0.5 mm3/mg.
Water Holding Capacity is determined pursuant to withdrawn ASTM Standard Method D-4250-92, Standard Method for Water-Holding Capacity of Bibulous Fibrous Products. It is considered to be generally very comparable to SAT.
Regenerated Cellulose Microfiber
In accordance with the invention, regenerated cellulose fiber is prepared from a cellulosic dope comprising cellulose dissolved in a solvent comprising tertiary amine N-oxides or ionic liquids. The solvent composition for dissolving cellulose and preparing underivatized cellulose dopes suitably includes tertiary amine oxides, such as N-methylmorpholine-N-oxide (NMMO), and similar compounds enumerated in U.S. Pat. No. 4,246,221 to McCorsley, the disclosure of which is incorporated herein by reference. Cellulose dopes may contain non-solvents for cellulose such as water, alkanols or other solvents, as will be appreciated from the discussion that follows.
Suitable cellulosic dopes are enumerated in Table 1, below.







TABLE 1







EXAMPLES OF TERTIARY AMINE N-OXIDE SOLVENTS









Tertiary Amine N-oxide
% water
% cellulose





N-methylmorpholine N-oxide
up to 22
up to 38


N,N-dimethyl-ethanol-amine N-oxide
up to 12.5
up to 31


N,N-dimethylcyclohexylamine N-oxide
up to 21
up to 44


N-methylhomopiperidine N-oxide
5.5-20
1-22


N,N,N-triethylamine N-oxide
  7-29
5-15


2(2-hydroxypropoxy)-N-ethyl-N,N,-dimethyl-
  5-10
2-7.5


amide N-oxide


N-methylpiperidine N-oxide
up to 17.5
5-17.5


N,N-dimethylbenzylamine N-oxide
5.5-17
1-20









See, also, U.S. Pat. No. 3,508,941 to Johnson, the disclosure of which is incorporated herein by reference.

Details with respect to preparation of cellulosic dopes including cellulose dissolved in suitable ionic liquids and cellulose regeneration therefrom are found in U.S. Patent Application Publication No. 2003/0157351, now U.S. Pat. No. 6,824,599, of Swatloski et al., entitled “Dissolution and Processing of Cellulose Using Ionic liquids”, the disclosure of which is incorporated herein by reference. Here again, suitable levels of non-solvents for cellulose may be included. This patent generally describes a process of dissolving cellulose in an ionic liquid without derivatization and regenerating the cellulose in a range of structural forms. It is reported that the cellulose solubility and the solution properties can be controlled by the selection of ionic liquid constituents with small cations and halide or pseudohalide anions favoring solution. Preferred ionic liquids for dissolving cellulose include those with cyclic cations, such as the following cations: imidazolium; pyridinum; pyridazinium; pyrimidinium; pyrazinium; pyrazolium; oxazolium; 1,2,3-triazolium; 1,2,4-triazolium; thiazolium; piperidinium; pyrrolidinium; quinolinium; and isoquinolinium.
Processing techniques for ionic liquids/cellulose dopes are also discussed in U.S. Pat. No. 6,808,557 to Holbrey et al., entitled “Cellulose Matrix Encapsulation and Method”, the disclosure of which is incorporated herein by reference. Note also, U.S. Patent Application Publication No. 2005/0288484, now U.S. Pat. No. 7,888,412, of Holbrey et al., entitled “Polymer Dissolution and Blend Formation in Ionic Liquids”, as well as U.S. Patent Application Publication No. 2004/0038031, now U.S. Pat. No. 6,808,557, of Holbrey et al., entitled “Cellulose Matrix Encapsulation and Method”, the disclosures of which are incorporated herein by reference. With respect to ionic fluids, in general, the following documents provide further detail: U.S. Patent Application Publication No. 2006/0241287, now U.S. Pat. No. 7,763,715, of Hecht et al., entitled “Extracting Biopolymers From a Biomass Using Ionic Liquids”; U.S. Patent Application Publication No. 2006/0240727 of Price eC al., entitled “Ionic Liquid Based Products and Method of Using The Same”; U.S. Patent Application Publication No. 2006/0240728 of Price et al., entitled “Ionic Liquid Based Products and Method of Using the Same”; U.S. Patent Application Publication No. 2006/0090271 of Price et al., entitled “Processes For Modifying Textiles Using Ionic Liquids”; and U.S. Patent Application Publication No. 2006/0207722 of Amano et al., entitled “Pressure Sensitive Adhesive Compositions, Pressure Sensitive Adhesive Sheets and Surface Protecting Films,” now U.S. Pat. No. 8,318,859, the disclosures of which are incorporated herein by reference. Some ionic liquids and quasi-ionic liquids that may be suitable are disclosed by Imperato et al., Chemical Communications 2005, pages 1170 to 1172, the disclosure of which is incorporated herein by reference.
“Ionic liquid”, refers to a molten composition including an ionic compound that is preferably a stable liquid at temperatures of less than 100° C. at ambient pressure. Typically, such liquids have a very low vapor pressure at 100° C., less than 75 mBar or so, and preferably, less than 50 mBar or less than 25 mBar at 100° C. Most suitable liquids will have a vapor pressure of less than 10 mBar at 100° C., and often, the vapor pressure is so low that it is negligible, and is not easily measurable, since it is less than 1 mBar at 100° C.
Suitable commercially available ionic liquids are BasionicTM ionic liquid products available from BASF (Florham Park, N.J.) and are listed in Table 2 below.







TABLE 2







Exemplary Ionic Liquids










IL
Basionic TM




Abbreviation
Grade
Product name
CAS Number










STANDARD










EMIM Cl
ST 80
1-Ethyl-3-methylimidazolium chloride
65039-09-0


EMIM
ST 35
1-Ethyl-3-methylimidazolium
145022-45-3


CH3SO3

methanesulfonate


BMIM Cl
ST 70
1-Butyl-3-methylimidazolium chloride
79917-90-1


BMIM
ST 78
1-Butyl-3-methylimidazolium
342789-81-5


CH3SO3

methanesulfonate


MTBS
ST 62
Methyl-tri-n-butylammonium
13106-24-6




methylsulfate


MMMPZ
ST 33
1,2,4-Trimethylpyrazolium methylsulfate


MeOSO3


EMMIM
ST 67
1-Ethyl-2,3-di-methylimidazolium
516474-08-01


EtOSO3

ethylsulfate


MMMIM
ST 99
1,2,3-Trimethyl-imidazolium
65086-12-6


MeOSO3

methylsulfate







ACIDIC










HMIM Cl
AC 75
Methylimidazolium chloride
35487-17-3


HMIM HSO4
AC 39
Methylimidazolium hydrogensulfate
681281-87-8


EMIM HSO4
AC 25
1-Ethyl-3-methylimidazolium
412009-61-1




hydrogensulfate


EMIM AlCl4
AC 09
1-Ethyl-3-methylimidazolium
80432-05-9




tetrachloroaluminate


BMIM HSO4</
AC 28
1-Butyl-3-methylimidazolium
262297-13-2




hydrogensulfate


BMIM AlCl4
AC 01
1-Butyl-3-methylimidazolium
80432-09-3




tetrachloroaluminate







BASIC










EMIM Acetat
BC 01
1-Ethyl-3-methylimidazolium acetate
143314-17-4


BMIM Acetat
BC 02
1-Butyl-3-methylimidazolium acetate
284049-75-8







LIQUID AT RT










EMIM EtOSO3
LQ 01
1-Ethyl-3-methylimidazolium
342573-75-5




ethylsulfate


BMIM
LQ 02
1-Butyl-3-methylimidazolium
401788-98-5


MeOSO3

methylsulfate







LOW VISCOSITY










EMIM SCN
VS 01
1-Ethyl-3-methylimidazolium thiocyanate
331717-63-6


BMIM SCN
VS 02
1-Butyl-3-methylimidazolium thiocyanate
344790-87-0







FUNCTIONALIZED










COL Acetate
FS 85
Choline acetate
14586-35-7


COL Salicylate
FS 65
Choline salicylate
2016-36-6


MTEOA
FS 01
Tris-(2-hydroxyethyl)-
29463-06-7


MeOSO3

methylammonium methylsulfate









Cellulose dopes, including ionic liquids having dissolved therein about 5% by weight underivatized cellulose, are commercially available from Aldrich. These compositions utilize alkyl-methylimidazolium acetate as the solvent. It has been found that choline-based ionic liquids are not particularly suitable for dissolving cellulose.
After the cellulosic dope is prepared, it is spun into fiber, fibrillated and incorporated into absorbent sheet, as described later.
A synthetic cellulose, such as lyocell, is split into micro- and nano-fibers, and added to conventional wood pulp. The fiber may be fibrillated in an unloaded disk refiner, for example, or any other suitable technique including using a PFI beater mill. Preferably, relatively short fiber is used, and the consistency kept low during fibrillation. The beneficial features of fibrillated lyocell include biodegradability, hydrogen bonding, dispersibility, repulpability, and smaller microfibers than obtainable with meltspun fibers, for example.
Fibrillated lyocell or its equivalent has advantages over splittable meltspun fibers. Synthetic microdenier fibers come in a variety of forms. For example, a 3 denier nylon/PET fiber in a so-called pie wedge configuration can be split into 16 or 32 segments, typically, in a hydroentangling process. Each segment of a 16-segment fiber would have a coarseness of about 2 mg/100 m versus eucalyptus pulp at about 7 mg/100 m. Unfortunately, a number of deficiencies has been identified with this approach for conventional wet laid applications. Dispersibility is less than optimal. Melt spun fibers must be split before sheet formation, and an efficient method is lacking. Most available polymers for these fibers are not biodegradable. The coarseness is lower than that of wood pulp, but still high enough that they must be used in substantial amounts and form a costly part of the furnish. Finally, the lack of hydrogen bonding requires other methods of retaining the fibers in the sheet.
Fibrillated lyocell has fibrils that can be as small as 0.1 to 0.25 microns (μm) in diameter, translating to a coarseness of 0.0013 to 0.0079 mg/100 m. Assuming these fibrils are available as individual strands—separate from the parent fiber—the furnish fiber population can be dramatically increased at various addition rates. Even fibrils not separated from the parent fiber may provide benefit. Dispersibility, repulpability, hydrogen bonding, and biodegradability remain product attributes since the fibrils are cellulose.
Fibrils from lyocell fiber have important distinctions from wood pulp fibrils. The most important distinction is the length of the lyocell fibrils. Wood pulp fibrils are only perhaps microns long, and, therefore, act in the immediate area of a fiber-fiber bond. Wood pulp fibrillation from refining leads to stronger, denser sheets. Lyocell fibrils, however, are potentially as long as the parent fibers. These fibrils can act as independent fibers and improve the bulk, while maintaining or improving strength. Southern pine and mixed southern hardwood (MSHW) are two examples of fibers that are disadvantaged relative to premium pulps with respect to softness. The term “premium pulps” used herein refers to northern softwoods and eucalyptus kraft pulps commonly used in the tissue industry for producing the softest bath, facial, and towel grades. Southern pine is coarser than northern softwood kraft, and mixed southern hardwood is both coarser and higher in fines than market eucalyptus. The lower coarseness and lower lines content of premium market pulp leads to a higher fiber population, expressed as fibers per gram (N or Ni>0.2) in Table 3. The coarseness and length values in Table 3 were obtained with an OpTest Fiber Quality Analyzer. Definitions are as follows:



  
    
      L
      n
    
    =
    
      
        
          ∑
          
            all
            ⁢
            
              
            
            ⁢
            fibers
          
        
        ⁢
        
          
            n
            i
          
          ⁢
          
            L
            i
          
        
      
      
        
          ∑
          
            all
            ⁢
            
              
            
            ⁢
            fibers
          
        
        ⁢
        
          n
          i
        
      
    
  




  
    
      L
      
        n
        ,
        
          i
          >
          0.2
        
      
    
    =
    
      
        
          ∑
          
            i
            >
            0.2
          
        
        ⁢
        
          
            n
            i
          
          ⁢
          
            L
            i
          
        
      
      
        
          ∑
          
            i
            >
            0.2
          
        
        ⁢
        
          n
          i
        
      
    
  




  
    C
    =
    
      
        10
        5
      
      ×
      
        sampleweight
        
          
            ∑
            
              all
              ⁢
              
                
              
              ⁢
              fibers
            
          
          ⁢
          
            
              n
              i
            
            ⁢
            
              L
              i
            
          
        
      
    
  




  
    N
    =
    
      
        
          100
          CL
        
        ⁡
        
          [
          =
          ]
        
      
      ⁢
      
        millionfibers
        /
        gram
      
    
  



Northern bleached softwood kraft (NBSK) and eucalyptus have more fibers per gram than do southern pine and hardwood. Lower coarseness leads to higher fiber populations and smoother sheets.








TABLE 3







Fiber Properties














Sample
Type
C, mg/100 m
Fines, %
Ln,mm
N, MM/g
Ln,i>0.2,mm
Ni>0.2, MM/g

















Southern HW
Pulp
10.1
21
0.28
35
0.91
11


Southern HW - low
Pulp
10.1
7
0.54
18
0.94
11


fines









Aracruz Eucalyptus
Pulp
6.9
5
0.50
29
0.72
20


Southern SW
Pulp
18.7
9
0.60
9
1.57
3


Northern SW
Pulp
14.2
3
1.24
6
1.74
4


Southern
Base sheet
11.0
18
0.31
29
0.93
10


(30 SW/70 HV)









30 Southern SW/70
Base sheet
8.3
7
0.47
26
0.77
16


Eucalyptus









For comparison, the “parent” or “stock” fibers of unfibrillated lyocell have a coarseness 16.6 mg/100 m before fibrillation and a diameter of about 11 to 12 μm.
The fibrils of fibrillated lyocell have a coarseness on the order of 0.001 to 0.008 mg/100 m. Thus, the fiber population can be dramatically increased at relatively low addition rates. FIG. 4 illustrates the distribution of fiber lengths found in a regenerated cellulosic microfiber, which is preferred for the practice of the present invention. Fiber length of the parent fiber is selectable, and fiber length of the fibrils can depend on the starting length and the degree of cutting during the fibrillation process, as can be seen in FIG. 5.
The dimensions of the fibers passing the 200 mesh screen are on the order of 0.2 micron by 100 micron long. Using these dimensions, one calculates a fiber population of 200 billion fibers per gram. For perspective, southern pine might be three million fibers per gram and eucalyptus might be twenty million fibers per gram (Table 3). It appears that these fibers are the fibrils that are broken away from the original unrefined fibers. Different fiber shapes with lyocell intended to readily fibrillate could result in 0.2 micron diameter fibers that are perhaps 1000 microns or more long, instead of 100. As noted above, fibrillated fibers of regenerated cellulose may be made by producing “stock” fibers having a diameter of 10 to 12 microns, or so, followed by fibrillating the parent fibers. Alternatively, fibrillated lyocell microfibers have recently become available from Engineered Fibers Technology (Shelton, Conn.) having suitable properties.
Particularly preferred materials contain more than 40% fiber that is finer than 14 mesh and exhibit a very low coarseness (low freeness). For ready reference, mesh sizes appear in Table 4, below.







TABLE 4







Mesh Size









Sieve Mesh #
Inches
Microns












14
.0555
1400


28
.028
700


60
.0098
250


100
.0059
150


200
.0029
74









Details as to fractionation using the Bauer-McNett Classifier appear in Gooding et al., “Fractionation in a Bauer-McNett Classifier”, Journal of Pulp and Paper Science. Vol. 27. No. 12, December 2001, the disclosure of which is incorporated herein by reference. A particularly preferred microfiber is shown in Table 4A.








TABLE 4A







Fiber Length Distribution of Preferred


Regenerated Cellulosic Microfiber










Fiber Length
Weight %














+14 mesh
2.3%



 28 mesh
20.5%



 48 mesh
10.6%



100 mesh
15.6%



200 mesh
17.2%



<200 mesh 
33.8%










FIG. 5 is a plot showing fiber length as measured by a Fiber Quality Analyzer (FQA) for various samples of regenerated cellulosic microfiber. From this data, it is appreciated that much of the fine fiber is excluded by the FQA and length prior to fibrillation has an effect on fineness. The Optest Fiber Quality Analyzer has become a standard in the paper industry for determining fiber length distributions and fiber counts (above a certain minimum length that keeps decreasing steadily as Optest continually upgrades their technology). The OpTest Fiber Quality Analyzer is available from:

    
    
        OpTest Equipment Inc.
        900 Tupper St. —Hawkesbury—ON—K6A 3S3—Canada
        Phone: 613-632-5169 Fax: 613-632-3744.
    
    


EXAMPLE 1
Perforated Polymeric Belt Creping
A series of belt-creped base-sheets was prepared with the materials and layering described in Table 5, with the CMF having the approximate fiber length distribution shown in FIG. 4.







TABLE 5







Base-sheet Cells

















BW
CMC
Amres




Cell
NBSK %
CMF %
lb/R
lb/t
lb/t
Layered
Comments

















1
100
0
14
0
12
No
Control, balanced charge


2
80
20
14
0
12
No
20% CMF, two-ply towel


3
60
40
14
0
12
No
40% CMF, two-ply towel


4
40
60
14
0
12
No
60% CMF, two-ply towel


5
100
0
14
12
40
No
Control, high resin


6
80
20
14
12
40
No
20% CMF, two-ply towel, high wet


7
60
40
14
12
40
No
40% CMF, two-ply towel, high wet


8
40
60
14
12
40
No
60% CMF, two-ply towel, high wet


9
60
40
14
12
40
Yes
100% CMF on surface


10
60
40
14
12
40
Yes
100% CMF on surface, calender


11
40
60
14
12
40
No
High wet/dry 3 lb/t GP-C in MC 1









and MC 2


12
40
60
14
12
40
No
High wet/dry 3 lb/t GP-C, calender


13
60
40
14
12
40
No
High wet/dry 3 lb/t GP-C in MC 1









and MC 2









100% NBSK was delivered from a first machine chest. 100% CMF was supplied from a second machine chest. The softwood fiber was refined an average of 2.2 HPD/ton based on total flow, requiring less refined horsepower as softwood fiber content decreased. The average freeness of the softwood fiber across the trial was 541 ml CSF.
Amres® HP 100, from Georgia-Pacific Resins, Inc., was split proportionally to the suction of each machine chest pump. Amtex Gelycel® carboxymethylcellulose (CMC) was split proportionally to the static mixer or stuff box. Titratable charge averaged 0.02 ml/10 ml for cells with no CMC and 12 lb/ton Amres®. Titratable charge averaged −0.17 ml/10 ml for cells with 12 lb/ton CMC and 40 lb/ton Amres®.
Trial speed averages appear in Table 6:







TABLE 6





Trial Speed Averages


















Jet Speed, fpm
2450



Form Roll Speed, fpm
1574



Small Dryer Speed, fpm
1559



Yankee Speed, fpm
1251



Reel Speed, fpm
1190



Jet/Wire Ratio
1.56



Fabric Crepe Ratio
1.25



Reel Crepe Ratio
1.05



Total Crepe Ratio
1.31










A perforated polymer creping belt was used as described in U.S. Patent Application Publication No. 2010/0186013, entitled “Belt-Creped, Variable Local Basis Weight Absorbent Sheet Prepared With Perforated Polymeric Belt”, the disclosure of which is incorporated herein by reference. The sheet contact surface of the perforated polymeric belt is illustrated in FIG. 7.
The basesheets produced had the properties set forth in Table 7. Base-sheets were converted to two-ply sheet using Fantale emboss pattern, FIG. 6, with a THVS configuration, that is, the pattern is embossed into only one of the two plies, which is joined to the non-embossed ply by glue lamination in points to the inside configuration, such that the outer surface of the embossed ply is debossed, and the asperities created by embossing bear against and are shielded by the unembossed ply.
Softness panel, wet lint, and wipe dry tests were completed in addition to conventional strength and absorbency tests described above. Porosity of the sheets is discussed in some detail below. The results of these tests are set forth in Table 8.







TABLE 7







Basesheet (perforated polymeric belt creped)





























CD Wet



CD











Tens



Tensile





Caliper
Basis
MD
MD
CD
CD
Finch
SAT
GM
GM Break
Wet/



CMF
Amres ®,
8 Sheet
Weight
Tensile
Stretch
Tensile
Stretch
Cured
Capacity
Tensile
Modulus
Dry


Roll
Percent
lb/t
mils/8 sht
lb/3000 ft2
g/3 in.
%
g/3 in.
%
g/3 in.
g/m2
g/3 in.
gms/%
Unitless























22989
0
12
77.7
14.0
1891
31.7
1556
6.5
345
364
1714
121
0.22


22988
0
12
77.5
14.5
1928
33.7
1539
6.4
317
354
1722
119
0.21


22990
20
12
74.6
14.1
1939
37.3
2068
7.6
554
336
2002
119
0.27


22992
20
12
73.4
14.3
2177
36.1
1886
6.4
561
332
2026
135
0.30


22996
40
12
86.9
14.0
1802
40.3
1931
9.1
486
377
1865
99
0.25


22997
40
12
83.9
14.5
1837
39.1
1766
8.6
544
373
1799
101
0.31


22998
60
12
94.8
13.8
1419
39.2
1324
9.1
445
392
1369
73
0.34


22999
60
12
94.6
14.8
1756
42.2
1340
9.9
520
404
1534
74
0.39


23010
0
40
88.2
14.3
1881
25.3
2490
6.6
924
403
2162
170
0.37


23012
0
40
84.2
14.9
2877
32.7
2086
6.4
696
435
2449
168
0.33


23015
20
40
87.0
14.0
2535
32.3
2701
8.0
1,155
410
2615
165
0.43


23017
20
40
88.2
14.6
2307
31.1
2235
6.3
1,078
410
2266
162
0.48


23019
40
40
89.1
14.5
2833
38.0
2393
8.6
968
399
2602
146
0.40


23020
40
40
93.8
14.6
2640
39.5
2468
9.2
1,147
400
2552
134
0.46


23024
60
40
99.4
14.1
2342
37.6
2216
9.8
1,077
431
2278
117
0.49


23025
60
40
92.0
14.5
2412
36.7
1868
8.6
993
403
2123
119
0.53


23027
40
40
97.1
14.0
2148
38.0
1950
9.3
810
432
2043
112
0.42


23028
40
40
93.4
14.4
2315
37.4
2075
9.2
845
416
2192
118
0.41


23032
60
40
104.1
13.8
2761
36.7
2453
9.3
1,325
473
2602
143
0.54


23034
60
40
70.6
14.4
3286
38.1
3058
9.5
1,378
395
3169
169
0.45


23036
40 strat Y*
40
96.8
14.1
2811
38.2
2973
8.4
1,393
447
2891
159
0.47


23037
40 strat Y*
40
95.9
13.9
3080
37.1
3047
7.8
1,432
446
3063
177
0.47


23038
40 strat Y*
40
66.0
12.9
2895
37.7
2999
8.8
1,444
391
2946
163
0.48


23040
40 strat Y*
40
62.4
13.0
2172
37.9
2315
8.0
1,050
356
2242
129
0.45





*The overall composition of the Yankee side ply is 40% CMF by weight with the Yankee side layer of the headbox issuing substantially 100% CMF.













TABLE 8





Finished Product Data (perforate polymeric belt creped)































Caliper











Basis
8 Sheet
MD









Softness
Weight
mils/
Tensile
MD
CD Tensile
CD



Description
Basesheet
CMF
Panel
lb/3000 ft2
8 sht
g/3 in.
Stretch %
g/3 in.
Stretch %





1
P3424.1
22989 22988
0
6.26
28.6
184
3,321
29
2,949
7.4


2
P3425.1
23010 23012
0
4.88
29.6
204
4,057
28
4,547
8.3


3
P3426.1
23033 23032
60
4.73
27.9
227
5,156
31
4,379
9.7


4
P3427.1
23034 23032
60
4.62
28.4
215
5,191
30
4,382
9.6


5
P3428.1
23036 23037
40
5.37
28.0
221
5,007
31
5,082
9.1


6
P3429.1
23038 23040
40
5.75
25.8
185
4,315
30
4,499
8.9


7
P3430.1
23024 23025
60
5.77
28.5
203
4,773
34
3,958
10.4


8
P3431.1
23028 23027
40
7.29
27.7
205
3,791
31
3,624
10.2


9
P3432.053
23020 23019
40

29.2
182
5,696
35
4,999
9.9


10
P3432.083
23020 23019
40

29.2
240
4,487
31
4,032
9.6


11
P3531.053
23028 23027
40

27.8
183
4,413
32
3,970
10.0


12
P3531.083
23028 23027
40

27.7
225
3,825
31
3,143
10.2


13
P3432.1
23020 23019
40
5.14
29.2
205
5,377
35
4,672
11.1


14
P3433.1
22999 22998
60
8.02
28.3
193
3,584
38
3,142
12.4


15
P3434.1
23015 23017
20
4.67
28.8
204
4,761
32
4,895
9.6


16
P3435.1
22997 22996
40
6.75
28.7
186
3,579
36
3,535
11.0


17
P3436.1
22990 22992
20
6.33
29.3
182
3,554
32
3,536
8.3
























Wet













Tens
CD



Break







GM
Finch
Tensile
SAT
SAT

Modulus
Wet
Wipe
Wipe




Tensile
Cured-CD
Wet/Dry
Capacity
Rate
SAT
GM
Extracted
Dry
Dry




g/3 in.
g/3 in.
Unitless
g/m2
g/s0.5
Times
g/%
Lint %
Tops
Bottems






1
3,128
730
0.25
395
0.27
20
212
0.25
19
32



2
4,293
1,380
0.30
440
0.33
17
283
0.22
23
34



3
4,747
2,263
0.52
438
0.09
105
280
0.09
9
9



4
4,764
2,185
0.50
446
0.11
74
278
0.11
12
10



5
5,042
2,262
0.45
468
0.12
69
300
0.19
12
11



6
4,404
1,934
0.43
418
0.14
42
267
0.17
10
9



7
4,345
1,856
0.47
439
0.10
104
230
0.21
11
9



8
3,705
1,494
0.41
415
0.10
79
210
0.10
9
8



9
5,333
1,924
0.39
409
0.11
79
288
0.28
13
13



10
4,252
1,669
0.41
459
0.16
42
245
0.28
23
11



11
4,184
1,677
0.42
393
0.10
78
235
0.09
9
7



12
3,466
1,395
0.44
451
0.12
69
194
0.10
9
10



13
5,011
1,903
0.41
411
0.10
79
251
0.25
10
13



14
3,356
937
0.30
395
0.07
133
154
0.14
5
5



15
4,825
1,745
0.36
430
0.21
25
276
0.21
25
17



16
3,556
1,077
0.30
391
0.09
77
178
0.13
9
9



17
3,545
1,007
0.29
353
0.14
37
216
0.39
15
18









Details as to base-sheet properties and converted two-ply wiper properties appear in Tables 7 and 8. From Table 8, it can be appreciated that the addition of even 20% CMF significantly improves the wipe dry characteristics of the sheets. See lines 15 and 17 in comparison to lines 1 and 2, while improvement in wipe dry starts leveling out with the addition of 40% CMF. Compare line 16 with lines 3, 4 and 7. As is shown in line 14, however, the best overall results for wipe dry and softness were obtained with 60% CMF.
Referring to FIG. 2, it is seen that the two-ply products of the invention exhibit wipe dry and wet tensile that is far superior to that achieved with the conventional towel. As illustrated in FIGS. 10, 11, and 12, it appears that faster wipe dry times may be at least partially attributable to the micropore structure of the sheets formed. In FIG. 10, it can be seen that as CMF is increased, the number of pores less than 5 microns also increases, while the curves for products with 40 or 60% CMF are essentially similar, again, suggesting that only diminishing benefit is obtained beyond 40% CMF. This hypothesis is consistent with that shown in FIG. 10, showing that 20% CMF significantly improves wipe dry, but the effect levels off above 40% CMF. Preferred wiper towel products exhibit a differential pore volume for pores under 5 microns having a diameter of at least about 75 mm3/g/micron, more preferably, above about 100 mm3/g/micron, still more preferably, above about 150 mm3/g/micron for pores under 2.5 microns.
FIG. 11 suggests that there is a correlation between wipe dry and capillary pressure at 10% saturation, both in advancing and receding mode. FIG. 12 shows increasing capillary pressure at 10% saturation as CMF is increased.
FIG. 13 shows wipe dry as a function of CMF and wet strength. Cellulose microfiber (CMF) was varied between 0 and 60%, and Amres® wet strength resin was either 12 lb/ton or 40 lb/ton. Carboxymethycellulose (CMC) was added at the higher wet strength dosage to balance charge. The non-CMF portion of the furnish was NBSWK refined at a constant net specific horsepower, so that strength changes can be primarily attributed to CMF and resin rather than NBSK refining level. The two curves at roughly constant wet tensile define three planes comprising a 3-D surface on which wipe dry time beneficially decreases as the amount of CMF in the sheet is increased, indicating that wipe dry times of under 10 seconds can be obtained with 40% CMF in the sheet. The surface in FIG. 13 can be described by Equation 1:

Wipe Dry=22.1−0.662·CMF+0.00495·CMF2+0.00493·Wet Tensile R2=0.99  Equation (1)

FIG. 3 shows the impact of CMF and wet tensile on softness. CMF has a positive impact, while increasing wet tensile strength reduces softness. The surface in FIG. 3 can be described by Equation 2:

Softness=7.90+0.0348 CMF−0.00223 Wet Tensile R2=0.99  Equation (2)

FIGS. 2, 14, and 15 illustrate the results of analyses of towels and wipers produced in Example 1, and include retail towel data for comparison. Surprisingly, the inventive product has higher wet tensile at a given softness level than Brawny® towels or Sparkle® towels.
FIGS. 16 and 17 show that wipers with 40% or 60% CMF have very fast wipe dry times, while also having good capacity. FIG. 16 used SAT data, while FIG. 17 used the old water holding capacity test (withdrawn ASTM Standard Method D-4250-92, Standard Method for Water-Holding Capacity of Bibulous Fibrous Products). The general pattern of performance is similar with either test.
FIG. 18 illustrates the counter-intuitive and surprising result that, as CMF is increased, we have found that, even though SAT Rate decreases, wipe dry times decrease.
FIG. 19 illustrates the effect that CMF has upon the wipe dry times at various levels of the wet strength resins Amres® and CMC. It appears that increasing the amount of resin in the outer layers increases the wipe dry times.
FIG. 20 shows wet extracted lint for finished product. CMF typically reduces lint at a variety of levels of CMF and wet strength resins. It can be appreciated that linting generally decreases as the amount of CMF is increased, except that the wet extracted lint generally hovered between 0.20 and 0.25 with the Amres® containing sheets for all levels of CMF.
FIG. 21 shows that any softness benefit from calendering is obtained at a significant cost with respect to lost caliper and absorbency. In one case, a calendered, embossed ply was matched with an unembossed ply for no softness benefit and 12 mil drop in caliper. In another case, a product with two calendered plies had a 0.4 point softness increase, while dropping 35 mils of caliper (see FIG. 21) and 50 gsm SAT. In our experience with softness panels for towel products, a gain of 0.32 points of softness is enough that one product, having a softness panel score 0.32 units greater than another, would be perceived as being noticeably softer, consistently, at the 90% confidence level.
FIG. 22 illustrates the dependence of CD Wet Tensile Strength on both resin addition and CMF. The ratio is higher with CMF at a given resin dose, but the highest ratios are achieved at high CMF and high resin levels.
CMF makes the sheet more difficult to dewater compactively, as the tendency of the sheet to extrude itself out of the pressing nip increases as the CMF content is increased. Oftentimes, this is referred to as sheet crushing. When attempting to dewater a nascent web containing increasing amounts of CMF, the Visconip pressure had to be progressively reduced to prevent sheet crushing at the nip as the level of CMF in the sheet was increased (See FIG. 23). Even though increasing the proportion of CMF in a sheet increases the bulk attainable with a given basis weight (FIG. 24), the reduction in the pressing load that the sheet will sustain results in a wetter sheet going forward, which normally entails much higher expenses for drying energy.
FIG. 33 presents SAT Capacity and wipe dry times for both black glass and stainless steel surfaces for the wipers as shown in Example 2.
FIG. 34 is an SEM section (75×) along the machine direction (MD) of perforated polymeric belt creped basesheet 600, showing a domed area corresponding to a belt perforation as well as the densified pileated structure of the sheet. It is seen in FIG. 34 that the domed regions, such as region 640, have a “hollow” or domed structure with inclined and at least partially densified sidewall areas, while surround areas 618, 620 are densified, but less so than transition areas. Sidewall areas 658, 660 are inflected upwardly and inwardly, and are so highly densified as to become consolidated, especially, about the base of the dome. It is believed that these regions contribute to the very high caliper and roll firmness observed. The consolidated sidewall areas form transition areas from the densified fibrous, planar network between the domes to the domed features of the sheet and form distinct regions that may extend completely around and circumscribe the domes at their bases, or may be densified in a horseshoe or bowed shape only around part of the bases of the domes. At least portions of the transition areas are consolidated and also inflected upwardly and inwardly.
FIG. 35 is another SEM (120×) along the MD of basesheet 600 showing region 640, as well as consolidated sidewall areas 658 and 660. It is seen in this SEM that the cap 662 is fiber-enriched, of a relatively high basis weight as compared with areas 618. 620, 658, 660. CD fiber orientation bias is also apparent in the sidewalls and dome.
FIG. 36 is an SEM section (120×) along the machine direction (MD) of basesheet 700, in which consolidated sidewall areas 758, 760 are densified and are inflected inwardly and upwardly.
EXAMPLE 2
Fabric Creping
Basesheets having the properties set forth in Table 9 were made using fabric creping technology in which the nascent webs were creped from a creping cylinder using a woven creping fabric. These basesheets were converted to finished product towels by embossing one ply with the emboss pattern shown in FIG. 26 (Patches) and glue laminating it to an unembossed ply, as set forth in Tables 9 and 10.







TABLE 9







FRFC/CMF Basesheet Data, (fabric creped) Basesheet Properties



































CD Wet



















Ten

GM

CD









8 Sheet
Basis


CD

Finch
GM
Break
Tensile
Tensile
CD Wet
Specific




TI


Caliper
Weight
MD Tensile
MD
Tensile
CD
Cured-
Tensile
Tensile
Ratio
Wet/Dry
Breaking
Bulk,


Cell
Emboss ply
2008-1905
Description
Furnish
mils/8 sht
lb/3000 ft2
g/3 in.
Stretch %
g/3 in.
Stretch %
g/3 in.
g/3 in.
gms/%
Dry %
Unitless
length, m
cc/g



























1
x
14-1
19721 229
50/50 M/A
85.1
15.3
1754
26.4
1638
5.5
587
1693
142
1.07
0.36
310
10.9




15-1
19723 239
50/50 M/A
83.2
15.3
1695
23.3
1527
5.8
521
1607
140
1.11
0.34
274
10.6




















15 lb/ream Control Average (Calendered)
84.1
15.3
1,724
24.9
1,582
5.6
554
1,650
141
1.09
0.35
292
10.7
























2

22-1
19731 1008 
50/50 M/A
82.1
11.7
1745
19.8
1454
5.5
504
1590
157
1.21
0.35
346
13.7



x
24-1
19733 1030 
50/50 M/A
77.1
11.6
2054
20.8
1338
5.1
520
1657
164
1.54
0.39
361
13.0




















12 lb/ream Control Average (Uncalendered)
79.6
11.7
1,899
20.3
1,396
5.3
512
1,434
160
1.37
0.37
354
13.3
























3
x
29-1
197381140 
50/50
95.5
12.6
2059
30.9
1604
6.7
831
1816
126
1.29
0.52
530
14.7






M/MCF

















30-1
19739 1154 
50/50
94.8
12.6
1972
30.6
1526
7.4
699
1734
116
1.30
0.46
446
14.6






M/CMF

































12 lb/ream Microfiber Average (Uncalendered)
95.1
12.6
2,016
30.8
1,375
7.0
765
1,775
121
1.29
0.49
488
14.7
























4

36-1
19755 155
50/50
110.4
14.5
2791
33.6
2298
7.2
1,075
2532
14.6
1.21
0.47
599
14.9






M/CMF
















x
37-1
19756 205
50/50
114.6
13.6
2429
37.4
2160
7.2
1,129
2290
14.7
1.13
0.52
670
16.5






M/CMF

































12 lb/ream Microfiber Average (Uncal, higher FC)
112.5
14.0
2,610
36.7
1,437
8.8
621
1,442
81
1.01
0.43
507
20.9
























5
x
37-1
19756 205
50/50
114.6
13.6
2429
37.4
2160
7.2
1,129
2290
141
1.13
0.52
670
16.5






M/CMF

















38-1
19757 216
50/50
105.7
9.9
1,449
36.7
1,437
8.8
621
1,442
81
1.01
0.43
507
20.9






M/CMF





















10 lb/ream Microfiber (Uncal, higher FC)

























6

38-1
19757 216
50/50
105.7
9.9
1,449
36.7
1,437
8.8
621
1,442
81
1.01
0.43
507
20.9






M/CMF
















x
43-1
19762 310
50/50 M/
59.4
9.9
1,612
27.1
1,362
8.0
768
1,482
102
1.18
0.56
623
11.7






CMF





















10 lb/ream Microfiber (Calendered)

























7
x
41-1
19760 248
50/50 M/
94.8
10.2
1796
31.2
1550
8.1
791
1668
105.2
1.16
0.51
625
18.2






CMF

















42-1
19761 300
50/50
93.2
10.3
1921
29.3
1451
7.8
802
1669
111.1
1.32
0.55
628
17.6






M/CMF

































10 lb/ream Microfiber Average (Uncalendered)
940
10.2
1859
30.2
1501
7.9
797
1669
108
1.24
0.53
626
17.9





M = Northern SW Kraft;


A = Aracruz Eucalyptus Kraft













TABLE 10







Base Sheet Assignment and Estimated Finished Product Physical Properties















Emboss
Basesheet
Sheet
Caliper
Roll Diameter
CD Wet Tensile
Emboss


cell
Ply
Roll #
Count
(mils/8 sheets)
(inches)
(“Finch Cup”) (g/3 in.)
Penetration

















1
x
19721
48
248 ± 5
5.0 ± 0.1
500
65




19723







2

19731
48
float
float
500




x
19733




65


3
x
19738
48
float
float
750
65




19739







4A

19755
48
float
float
1100




x
19756




65


4B

19755
48
max
>5.0
>1100




x
19756




60


5A
x
19756
48
float
float
850
65




19757







5B
x
19756
48
max
>5.0
>850
60




19757







6A

19757
48
float
float
700
65



x
19762







6B

19757
48
float
float
700
60



x
19762







7A
x
19760
48
float
float
800
65




19761







7B
x
19760
48
float
float
800
60




19761







7C
x
19760
48
float
float
800
55




19761









When tested for physical properties, the results set forth in Table 11 were obtained. Subsequently, other rolls of basesheet were converted using the emboss design shown in FIG. 25A (Little Circles) in a point to point mode, i.e., registered debosses were formed in the outer surface of each ply with the depths of the debossed regions in each ply being pressed so forcefully against the debossed regions in the other, that the plies are thereby bonded to each other. In some cases, the contact regions between the plies may be glassined. When Little Circles is used in point to point mode both surfaces show the pattern of FIG. 25A. In cases when a nested mode is used, one surface bears the pattern of FIG. 25A, while the other bears the pattern of FIG. 25B. The physicals of the rolls thereby formed are set forth in Table 11 and the preliminary evaluation of performance is set forth in Table 12.







TABLE 11





Appendix 1







Properties of Rolls Converted with THVS Emboss in THVS Mode












Cell ID














1
2
3
4A
4B
5A












Furnish
50/50
50/50



M/Aracruz
M/CMF













Basis Weight (lb/3000 ft2)
29.0
23.0
24.4
27.2
26.2
22.0


Caliper (mils/8 sheet)
200
180
199
230
214
207


MD Tensile (g/3 in.)
2539
2487
3599
5713
6007
3638


MD Stretch (%)
19.2
15.6
21.1
25.1
26.3
24.1


CD Tensile (g/3 in.)
2317
1974
2473
3739
3738
2828


CD Stretch (%)
5.4
5.4
7.3
6.9
7.6
8.3


GM Tensile (g/3 in.)
2423
2215
2982
4620
4736
3206


CD Wet Tensile-Finch (g/3 in.)
670
676
1048
1749
1683
1278


CD Tensile Wet/Dry (Unitless)
0.29
0.34
0.42
0.47
0.45
0.45


SAT Capacity (g/m2)
469
399
447
497
476
460


GM Break Modulus (g/%)
242.4
241.9
239.7
346.3
330.3
223.9


GM Modulus (g/% Stretch)
42.0
46.3
37.3
44.8
40.6
34.2


Roll Diameter (in)
4.98
4.78
4.82
5.25
4.89
4.81


Roll Compress Value (%)
19.7
20.4
16.5
20.9
16.4
15.7


Sensory Softness
8.19
6.76
6.19
4.30
4.52
5.54


Wet Extracted Lint (%)
0.069
0.050
0.063
0.076
0.080
0.062














Wipe Dry
Top
17
26
14
13
415
15


(Black Glass) (s)
Bottom
16
28
12
15
13
17



Average
16
27
13
14
14
16


Wipe Dry
Top
18
26
14
16
16
22


(Stainless Steel) (s)
Bottom
20
22
15
13
15
14



Average
20
22
15
13
15
14













Wet Lint (Pigskin)-FQA Fiber
1601
808
786
884
814
631


Count (Number)












Cell ID
















5B
6A
6B
7A
7B
7C











Furnish
50/50



M/CMF













Basis Weight (lb/3000 ft2)
22.1
19.5
19.4
19.5
19.6
19.6


Caliper (mils/8 sheet)
200
175
165
176
173
169


MD Tensile (g/3 in.)
3856
2554
3051
3539
3680
3971


MD Stretch (%)
24.6
20.9
21.1
21.1
21.1
21.2


CD Tensile (g/3 in.)
3113
2332
2619
2598
2702
2983


CD Stretch (%)
8.3
8.3
8.3
8.0
7.9
8.2


GM Tensile (g/3 in.)
3464
2438
2824
3031
3152
3441


CD Wet Tensile-Finch (g/3 in.)
1418
1095
1141
1162
1263
1343


CD Tensile Wet/Dry (Unitless)
0.46
0.47
0.44
0.45
0.47
0.45


SAT Capacity (g/m2)
456
408
413
424
411
416


GM Break Modulus (g/%)
246.4
187.2
211.4
235.2
246.0
263.1


GM Modulus (g/% Stretch)
33.8
34.3
34.7
34.9
35.9
36.1


Roll Diameter (in)
4.77
4.55
4.35
4.67
4.63
4.34


Roll Compress Value (%)
14.5
14.6
14.3
16.5
17.2
13.5


Sensory Softness
5.26
7.35
6.94
5.75
5.47
5.12


Wet Extracted Lint (%)
0.069
0.055
0.063
0.048
0.048
0.050














Wipe Dry
Top
14
15
13
14
17
18


(Black Glass) (s)
Bottom
20
19
18
16
20
20



Average
17
17
15
15
18
19


Wipe Dry
Top
20
24
21
25
28
21


(Stainless Steel) (s)
Bottom
18
18
19
21
27
23



Average
18
18
19
21
27
23













Wet Lint (Pigskin)-FQA Fiber
829
676
577
572
616
594


Count (Number)










Properties of Rolls Converted with Little Circles Emboss in Point to Point Mode









Cell ID














4C
4D
4E
7D
7E
7F











Furnish
50/50 M/CMF













Basis Weight (lb/3000 ft2)
24.8
25.9
25.9
18.2
18.3
18.6


Caliper (mils/8 sheet)
278
234
211
234
224
168


MD Tensile (g/3 in.)
5188
5555
6413
2749
3308
4242


MD Stretch (%)
18.0
17.9
20.3
13.2
14.3
15.7


CD Tensile (g/3 in.)
2952
3589
4203
1725
2065
2934


CD Stretch (%)
10.0
9.4
8.3
10.0
9.7
8.7


GM Tensile (g/3 in.)
3913
4460
5191
2174
2612
3527


CD Wet Tensile-Finch (g/3 in.)
1389
1591
1865
780
974
1349


CD Tensile Wet/Dry (Unitless)
0.47
0.44
0.44
0.45
0.47
0.46


SAT Capacity (g/m2)
406
379
405
349
345
342


GM Break Modulus (g/%)
289.6
341.4
401.6
188.5
224.5
300.1


GM Modulus (g/% Stretch)
39.1
46.0
48.8
31.2
33.8
44.2


Roll Diameter (in)
5.52
5.10
4.88
5.32
5.17
4.52


Roll Compress Value (%)
14.2
13.3
15.2
16.4
16.1
15.1


Sensory Softness
5.17
4.51
3.92
7.48
6.85
5.83


Wet Extracted Lint (%)
0.057
0.082
0.075
0.050
0.052
0.056














Wipe Dry
Top
12
12
14
10
16
16


(Black Glass) (s)
Bottom
17
11
10
17
17
17



Average
14
11
12
14
16
17


Wipe Dry
Top
15
12
10
17
17
17


(Stainless Steel) (s)
Bottom
12
12
14
10
16
16



Average
12
12
14
10
16
16













Wet Lint (Pigskin)-FQA Fiber
561
902
726
679
600
689


Count (Number)
















TABLE 12







Wipe Dry Data using Wiper Test Method (Single Sheet) (Preliminary Results)









Cell ID


























1
2
3
4A
4B
5A
5B
6A
6B
7A
4C
4D
4E
7D
7E
7F
4C
4D












Furnish
50/50
50/50



M/Aracruz
M/CMF

























Basis Weight
29.0
23.0
24.4
27.2
26.2
22.0
22.1
19.5
19.4
19.5
24.8
25.9
25.9
18.2
18.3
18.6
24.8
25.9


(lb/3000 ft2)




















Caliper
200
180
199
230
214
207
200
175
165
176
278
234
211
234
224
168
278
234


(mils/8 sheet)




















SAT Capacity
469
399
447
497
476
460
456
408
413
424
406
379
405
349
345
342
406
379


(g/m2)




















Wipe Dry
Top

92
64
95
133
134
131
123
110
231
115
155
137
165
114
231
115


(Black Glass) (s)
Bottom
59
109
73
113
101
113
133
95
87
222
139
109
129
140
114
222
139



Average
59
101
68
104
117
123
132
109
99
227
127
132
133
152
114
227
127


Wipe Dry
Top
41
64
50
71
59
76
79
69
68
104
69
58
120
78
61
104
69


(Stainless Steel)
Bottom
43
63
56
49
71
88
81
67
76
78
70
82
134
80
66
78
70


(s)
Average
43
63
56
49
71
88
81
67
76
78
70
82
134
80
66
78
70









By comparing FIGS. 1G, 1J, and 1L, of structures formed by creping from a transfer surface with a perforated polymeric belt, with micrographs of CMF containing structures formed by a variety of other methods, including creping from a transfer surface with a woven fabric, conventional wet pressing, and through-air drying (TAD), it can be appreciated that structures formed by creping from a transfer surface with a perforated polymeric belt exhibit “venation” in some regions in which the CMF fibrils are tightly adhered to an underlying consolidated structure with line contact between the CMF and the underlying consolidated structure. This venation resembles the vein that can be seen in the undersurface of a leaf, and contrasts strongly with the structure formed by the other methods, in which the CMF is part of an open structure more closely resembling ivy growing on a wall than the veins on a leaf. As mentioned previously, without being bound by theory, it is hypothesized that this line surface contact may create micropores that are responsible for the remarkable wipe dry properties of these structures as discussed above. In any event, the superior wipe dry proertlies of the sheets formed using the perforated polymeric belt and exhibiting venation are undeniable—no matter what the explanation.
FIG. 37 compares the results of Examples 1 and 2 on a normalized basis obtained by dividing the wipe dry time for each cell by the best wipe dry time obtained with a 0% CMF in each of Examples 1 and 2, then plotting these against the CD wet tensile of the wiper in that cell with the fabric creped sheets being indicated by solid symbols, and the samples obtained by creping with a perforated polymeric belt being indicated by hollow symbols in accordance with the legend. It can be appreciated that there is quite a substantial difference between the wipers obtained using the fabric and those using the perforated polymeric belt, particularly, when it is considered that the fabric creped samples indicated by the solid circle contain 50% CMF, while many of the belt creped samples contain far less CMF, the hollow diamonds indicating the presence of 40% CMF and the hollow squares indicating only 20%.
FIG. 38 compares the results of Examples 1 and 2 without normalization of the wipe dry times so that the wipe dry times are compared directly. Again, it can be appreciated that the wipers produced with the perforated polymeric belt are far superior to those produced with a fabric, particularly, when differences in CMF content are considered.
FIG. 39 shows the wipe dry times from Example 1 plotted against the ratio of PAE adhesive to quaternary ammonia salt based release agent in the creping package. It can be appreciated that wipe dry times suffer at low values of this ratio (high levels of quaternary ammonia salt release agent). Therefore, in those cases when, as is common, the outer surface of the wiper is the Yankee side, care should be exercised to ensure that the level of quaternary ammonium salt retained on the surface of the web is sufficiently low that the wipe dry time is not increased unduly. In the present case, this point is primarily important as being the most likely reason why a few of the wipers with 40% CMF exhibited anomalously high wipe dry times as shown in FIGS. 37 and 38.
While the invention has been described in detail, modifications within the spirit and scope of the invention will be readily apparent to those of skill in the art. In view of the foregoing discussion, relevant knowledge in the art and references including the copending applications discussed above in connection with the Background and Detailed Description, the disclosures of which are all incorporated herein by reference, further description is deemed unnecessary. In addition, it should be understood that aspects of the invention and portions of various embodiments may be combined or interchanged either in whole or in part. Furthermore, those of ordinary skill in the art will appreciate that the foregoing description is by way of example only, and is not intended to limit the invention.

## Claims

1. A method of making multi-ply a wiper/towel product, the method comprising:
(a) compactively dewatering a nascent web comprising at least about 10% fibrillated regenerated cellulosic microfibers and having an apparently random distribution of fibers;
(b) applying the dewatered web having the apparently random distribution of fibers to a transfer surface;
(c) belt-creping the web from the transfer surface utilizing a creping belt, the belt-creping step occurring under pressure in a belt creping nip defined between the transfer surface and the creping belt;
(d) drying the web to form a dried web having:
(i) a plurality of fiber-enriched hollow domed regions protruding from an upper side of the dried web, the hollow domed regions having a sidewalls of a relatively high local basis weight formed along at least a leading edge thereof;
(ii) connecting regions of a relatively lower local basis weight forming a network interconnecting the hollow domed regions of the dried web; and
(iii) transition areas with consolidated fibrous regions that transition from the connecting regions into the hollow domed regions, by extending upwardly and inwardly from the connecting regions into the respective sidewalls of the hollow domed regions; and

(e) converting said dried web into a multi-ply wiper/towel.

2. The method according to claim 1, wherein the nascent web comprises at least about 40% wood pulp derived papermaking fibers.

3. The method according to claim 1, wherein fibrillated regenerated cellulosic microfibers present in the dried web form venation on the surface of the consolidated fibrous regions such that the surface has raised, generally continuous ridges defined thereacross.

4. The method according to claim 1, wherein the consolidated fibrous regions are saddle shaped.

5. The method according to claim 1, wherein the fiber-enriched hollow domed regions exhibit a local basis weight of at least 5% higher than the mean basis weight of a sheet of the product.

6. The method according to claim 1, wherein the fiber-enriched hollow domed regions exhibit a local basis weight of at least 10% higher than the mean basis weight of a sheet of the product.

7. The method according to claim 1, wherein one of at least a portion of the fiber-enriched hollow domed regions and transition areas in the dried web exhibits a cross machine direction (CD) fiber orientation bias.

8. The method according to claim 1, wherein at least a portion of the connecting regions in the dried web exhibits a cross machine direction (CD) fiber orientation bias.

9. The method according to claim 1, wherein at least a portion of the consolidated fibrous regions of the domed region sidewalls in the dried web exhibits a matted structure on both their outer and inner surfaces, and the fibrillated regenerated cellulosic microfibers form venation thereupon, such that the surface has raised, generally continuous ridges defined thereacross.

10. The method according to claim 1, wherein the fibrillated regenerated cellulosic microfibers have a characteristic Canadian Standard Freeness (CSF) value of less than 175 ml.

11. The method according to claim 1, wherein the fibrillated regenerated cellulosic microfibers exhibit a cross machine direction (CD) wet breaking length in the range of about 300 to about 800 m.

12. The method according to claim 11, wherein the fibrillated regenerated cellulosic microfibers exhibit a CD wet breaking length in the range of about 350to about 800 m.

13. The method according to claim 11, wherein the fibrillated regenerated cellulosic microfibers exhibit a CD wet breaking length in the range of about 400 to about 800 m.

14. The method according to claim 1, wherein the fibrillated regenerated cellulosic microfibers have a number average diameter of less than about 2 microns.

15. The method according to claim 1, wherein the fibrillated regenerated cellulosic microfibers have a number average diameter of from about 0.1 to about 2 microns.

16. The method according to claim 1, wherein the fibrillated regenerated cellulosic microfibers have a fiber count of greater than about 400 million fibers/gram.

17. The method according to claim 1, wherein the fibrillated regenerated cellulosic microfibers have a fiber count of greater than about 50 billion fibers/gram.

18. The method according to claim 1, wherein the fibrillated regenerated cellulosic microfibers have a fiber count greater than about 200 billion fibers/gram.

19. The method according to claim 1, wherein the nascent web comprises from about 10% to about 60% fibrillated cellulosic microfibers.

20. The method according to claim 19, wherein the nascent web comprises at least about 40% wood pulp derived papermaking fibers.

21. A method of making multi-ply a wiper/towel product, the method comprising:
(a) compactively dewatering a nascent web comprising at least about 10% fibrillated regenerated cellulosic microfibers and having an apparently random distribution of fibers;
(b) applying the dewatered web having the apparently random distribution of fibers to a transfer surface;
(c) belt-creping the web from the transfer surface utilizing a creping belt, the belt-creping step occurring under pressure in a belt creping nip defined between the transfer surface and the creping belt;
(d) drying the web to form a dried web having:
(i) a plurality of fiber-enriched regions including (A) hollow domed portions having respective sidewalls of a relatively high local basis weight formed along at least a leading edge thereof and (B) pileated fiber-enriched portions with a cross machine direction (CD) fiber orientation bias adjacent to the hollow domed portions, the fiber-enriched portions being interconnected with:
(ii) connecting regions of a relatively lower local basis weight,
wherein the hollow domed portions having upwardly projecting densified sidewalls, at least a portion of the upwardly projecting densified sidewalls comprising a densified region that extends inwardly; and

(e) converting said dried web into a multi-ply wiper/towel.

22. The method according to claim 21, wherein the nascent web comprises at least about 40% wood pulp derived papermaking fibers.

23. The method according to claim 21, wherein the fibrillated regenerated cellulosic microfibers exhibit a cross machine direction (CD) wet breaking length in the range of about 300 to about 800 m.

24. The method according to claim 23, wherein the fibrillated regenerated cellulosic microfibers exhibit a CD wet breaking length in the range of about 350 to about 800 m.

25. The method according to claim 23, wherein the fibrillated regenerated cellulosic microfibers exhibit a CD wet breaking length in the range of about 400 to about 800 m.

26. The method according to claim 21, wherein the nascent web comprises from about 10% to about 60% fibrillated regenerated cellulosic microfibers.

27. The method according to claim 26, wherein the nascent web comprises at least about 40% wood pulp derived papermaking fibers.

28. A method of making multi-ply a wiper/towel product, the method comprising:
(a) compactively dewatering a nascent web comprising at least about 10% fibrillated regenerated cellulosic microfibers and having an apparently random distribution of fibers:
(b) applying the dewatered web having the apparently random distribution of fibers to a transfer surface;
(c) belt-creping the web from the transfer surface utilizing a creping belt, the belt-creping step occurring under pressure in a belt creping nip defined between the transfer surface and the creping belt;
(d) drying the web to form a dried web having upper and lower surfaces and comprising:
(i) a plurality of fiber-enriched hollow domed regions protruding from the upper surface of the dried web, the hollow domed regions having respective sidewalls of a relatively high local basis weight formed along at least a leading edge thereof; and
(ii) connecting regions of a relatively lower local basis weight forming a network interconnecting the fiber-enriched hollow domed regions of the dried web; and
(iii) consolidated groupings of fibers extending upwardly from the connecting regions into the respective sidewalls of the fiber-enriched hollow domed regions,

(e) converting said dried web into a multi-ply wiper/towel.

29. The method according to claim 28, wherein the nascent web comprises at least about 40% wood pulp derived papermaking fibers.

30. The method according to claim 28, wherein the consolidated groupings of fibers extend inwardly and deflect upwardly from the connecting regions into the respective sidewalls of the fiber-enriched hollow domed regions.

31. The method according to claim 28, wherein:
(i) the fiber-enriched hollow domed regions include an inclined sidewall; and
(ii) the fibrillated regenerated cellulosic microfibers form venation on the surface of the consolidated groupings of fibers, such that the surface has raised, generally continuous ridges defined thereacross.

32. The method according to claim 28, wherein the fiber-enriched hollow domed regions exhibit a local basis weight of at least 5% higher than the mean basis weight of a sheet of the product.

33. The method according to claim 28, wherein the fiber-enriched hollow domed regions exhibit a local basis weight of at least 10% higher than the mean basis weight of a sheet of the product.

34. The method according to claim 28, wherein the respective sidewalls of the fiber-enriched hollow domed regions comprise regions of consolidated fibers that extend upwardly.

35. The method according to claim 28, wherein consolidated groupings of fibers are saddle shaped and extend upwardly from the connecting regions into the respective sidewalls of the fiber-enriched hollow domed regions.

36. The method according to claim 28, wherein the respective sidewalls of the fiber-enriched hollow domed regions comprise consolidated groupings of fibers that are saddle shaped and extend at least partially around the domed regions.

37. The method according to claim 28, wherein the respective sidewalls extend upwardly and form highly densified consolidated fibrous regions that are saddle shaped about the base of a dome of the domed regions.

38. The method according to claim 28, wherein saddle shaped transition areas with consolidated fibrous regions extend upwardly and inwardly from the connecting regions into the respective sidewalls of the hollow domed regions.

39. The method according to claim 28, wherein the fibrillated regenerated cellulosic microfibers have a fiber count of greater than about 2 billion fibers/gram.

40. The method according to claim 28, wherein the fibrillated regenerated cellulosic microfibers exhibit a cross machine direction (CD) wet breaking length in the range of about 300 to about 800 m.

41. The method according to claim 40, wherein the fibrillated cellulosic microfibers exhibit a CD wet breaking length in the range of about 350 to about 800 m.

42. The method according to claim 40, wherein the fibrillated regenerated cellulosic microfibers exhibit a CD wet breaking length in the range of about 400 to about 800 m.

43. The method according to claim 28, wherein the dried web has transition areas with consolidated fibers that extend upwardly and inwardly from the connecting regions into the respective sidewalls of the hollow domed regions, the transitions areas at least partially circumscribe domes of the domed regions at their respective bases.

44. The method according to claim 28, wherein the dried web has transition areas with consolidated fibers that extend upwardly and inwardly from the connecting regions into the sidewalls of the hollow domed regions, the transition areas being densified in a bowed shape around a portion of respective bases of domes of the domed regions.

45. The method according to claim 28, wherein the nascent web comprises from about 10% to about 60% of the fibrillated regenerated cellulosic microfibers.

46. The method according to claim 45, wherein the nascent web comprises at least about 40% wood pulp derived papermaking fibers.

47. A method of making multi-ply a wiper/towel product, the method comprising:
(a) compactively dewatering a nascent web comprising at least about 10% fibrillated regenerated cellulosic microfibers and having an apparently random distribution of fibers;
(b) applying the dewatered web having the apparently random distribution of fibers to a transfer surface;
(c) belt-creping the web from the transfer surface utilizing a creping belt, the belt-creping step occurring under pressure in a belt creping nip defined between the transfer surface and the creping belt;
(d) drying the web to form a dried web comprising:
(i) a plurality of fiber-enriched regions including (A) hollow domed portions having respective sidewalls of a relatively high local basis weight formed along at least a leading edge thereof, the hollow domed portions having upwardly projecting densified sidewalls, at least a portion of each of the upwardly projecting densified sidewalls comprising a densified region that extends inwardly, and (B) pileated fiber-enriched portions with a cross machine direction (CD) fiber orientation bias adjacent to the hollow domed portions, the fiber-enriched portions being interconnected with; and
(ii) connecting regions of a relatively lower local basis weight

(e) converting said dried web into a multi-ply wiper/towel.

48. The method according to claim 47, wherein the nascent web comprises at least about 40% wood pulp derived papermaking fibers.

49. The method according to claim 47, wherein the fibrillated regenerated cellulosic microfibers have a Canadian Standard Freeness (CSF) value of less than 175 mL.

50. The method according to claim 47, wherein 40% by weight of the fibrillated regenerated cellulosic microfibers is finer than 14 mesh.

51. The method according to claim 47, wherein at least a portion of each of the upwardly projecting densified sidewalls comprises a densified region that is saddle shaped and extends inwardly.

52. The method according to claim 47, wherein the dried web includes transition areas with consolidated fibrous regions that transition from the connecting regions to the fiber-enriched regions.

53. The method according to claim 47, wherein the fibrillated regenerated cellulosic microfibers have a fiber count of greater than about 400 million fibers/gram.

54. The method according to claim 47, wherein the fibrillated regenerated cellulosic microfibers exhibit a CD wet breaking length in the range of about 300 to about 800 m.

55. The method according to claim 54, wherein the fibrillated regenerated cellulosic microfibers exhibit a CD wet breaking length in the range of about 350 to about 800 m.

56. The method according to claim 54, wherein the fibrillated regenerated cellulosic microfibers exhibit a CD wet breaking length in the range of about 400 to about 800 m.

57. The method according to claim 47, wherein the fibrillated regenerated cellulosic microfibers have a fiber count of greater than about 50 billion fibers/gram.

58. The method according to claim 47, wherein the fibrillated regenerated cellulosic microfibers have a fiber count of greater than about 10 billion fibers/gram.

59. The method according to claim 47, wherein the nascent web comprises from about 10% to about 60% fibrillated regenerated cellulosic microfibers.

60. The method according to claim 59, wherein the nascent web comprises at least about 40% wood pulp derived papermaking fibers.

61. A method of making multi-ply a wiper/towel product, the method comprising:
(a) compactively dewatering a nascent web comprising at least about 10% fibrillated regenerated cellulosic microfibers and having an apparently random distribution of fibers;
(b) applying the dewatered web having the apparently random distribution of fibers to a transfer surface;
(c) belt-creping the web from the transfer surface utilizing a creping belt, the belt-creping step occurring under pressure in a belt creping nip defined between the transfer surface and the creping belt;
(d) drying the web to form a dried web having upper and lower surfaces and comprising:
(i) a plurality of fiber-enriched hollow domed regions protruding from the upper surface of the dried web, the hollow domed regions having respective sidewalls of a relatively high local basis weight formed along at least a leading edge thereof; and
(ii) connecting regions of a relatively lower local basis weight forming a network interconnecting the fiber-enriched hollow domed regions of the dried web; and

(e) converting said dried web into a multi-ply wiper/towel.

62. The method according to claim 61, wherein the nascent web comprises at least about 40% wood pulp derived papermaking fibers.

63. The method according to claim 61, wherein the fibrous composition of the web, the geometry of the fibrillated cellulosic microfibers, and the number average count are chosen such that the wiper/towel product exhibits a wipe-dry time of less than about 20 seconds.

64. The method according to claim 63, wherein the wiper/towel product exhibits a wipe-dry time of at most 10 seconds.

65. The method according to claim 61, wherein the fibrillated regenerated cellulosic microfibers exhibit a CD wet breaking length in the range of about 300 to about 800 m.

66. The method according to claim 65, wherein the fibrillated regenerated cellulosic microfibers exhibit a CD wet breaking length in the range of about 350 to about 800 m.

67. The method according to claim 65, wherein the fibrillated regenerated cellulosic microfibers exhibit a CD wet breaking length in the range of about 400 to about 800 m.

68. The method according to claim 61, wherein the fibrous composition of the web, the geometry of the fibrillated regenerated cellulosic microfibers, and the number average count are chosen such that the wiper/towel product exhibits an SAT capacity in the range of about 9.5 to about 11.0 g/g.

69. The method according to claim 68, wherein the sheet exhibits an SAT rate in the range of about 0.05 to about 0.25 g/s0.5.

70. The method according to claim 61, wherein consolidated groupings of fibers extend upwardly from the connecting regions into the sidewalls of the fiber-enriched hollow domed regions, and the wiper/towel product exhibits a relative wipe dry time that is less than 50% of the wipe dry time exhibited by a wipe of the same fibrous composition, but without fibrillated regenerated cellulosic microfibers.

71. The method according to claim 70, wherein the product exhibits a relative wipe dry time that is less than about 40% of the wipe dry time exhibited by a wipe of the same fibrous composition, but without fibrillated regenerated cellulosic microfibers.

72. The method according to claim 61, wherein the nascent web comprises from about 10% to about 60% fibrillated regenerated cellulosic microfibers.

73. The method according to claim 72, wherein the nascent web comprises at least about 40% wood pulp derived papermaking fibers.