Patent Grant
9017517
This application relates to methods of making a belt-creped absorbent cellulosic sheet prepared with a perforated polymeric belt. Typical products for tissue and towel include 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.
Methods of making paper tissue, towel, and the like, are well known, including various features such as Yankee drying, through-air drying (TAD), fabric creping, dry creping, wet creping, and so forth. Wet pressing processes have certain advantages over through-air drying (TAD) processes including: (1) lower energy costs associated with the mechanical removal of water rather than transpiration drying with hot air, and (2) higher production speeds, which are more readily achieved with processes that utilize wet pressing to form a web. See, Klerelid et al., Advantage™ NTT™: low energy, high quality, pages 49-52, Tissue World, October/November, 2008. On the other hand, through-air drying processes have become the method of choice for new capital investment, particularly, for the production of soft, bulky, premium quality towel products.
U.S. Pat. No. 7,435,312 to Lindsay et al. suggests a method of making a through-air dried product including rush-transferring the web followed by structuring the web on a deflection member and applying a latex binder. The patent also suggests a variation in basis weight between dome and network areas in the sheet. See col. 28, lines 55+. U.S. Pat. No. 5,098,522 to Smurkoski et al. describes a deflection member or belt with holes therethrough for making a textured web structure. The backside, or machine side of the belt has an irregular, textured surface that is reported to reduce fiber accumulation on equipment during manufacturing. U.S. Pat. No. 4,528,239 to Trokhan discusses a through-air dry process using a deflection fabric with deflection conduits to produce an absorbent sheet with a domed structure. The deflection member is made using photopolymer lithography. U.S. Patent Application Publication No. 2006/0088696 suggests a fibrous sheet that includes domed areas and cross machine direction (CD) knuckles having a product of caliper and a CD modulus of at least 10,000. The sheet is prepared by forming the sheet on a wire, transferring the sheet to a deflection member, throughdrying the sheet and imprinting the sheet on a Yankee dryer. The nascent web is dewatered by noncompressive means; See ¶156, page 10. U.S. Patent Application Publication No. 2007/0137814 of Gao describes a throughdrying process for making an absorbent sheet that includes rush-transferring a web to a transfer fabric and transferring the web to a through drying fabric with raised portions. The throughdrying fabric may be travelling at the same or a different speed than that of the transfer fabric. See ¶39. Note also U.S. Patent Application Publication No. 2006/0088696 of Manifold et al.
Fabric creping has also been referred to in connection with papermaking processes that include mechanical or compactive dewatering of the paper web as a means to influence product properties. See, U.S. Pat. No. 5,314,584 to Grinnell et al.; U.S. Pat. No. 4,689,119 and U.S. Pat. No. 4,551,199 to Weldon; U.S. Pat. No. 4,849,054 to Klowak; and U.S. Pat. No. 6,287,426 to Edwards et al. In many cases, operation of fabric creping processes has been hampered by the difficulty of effectively transferring a web of high or intermediate consistency to a dryer. Further patents relating to fabric creping include the following: U.S. Pat. No. 4,834,838; U.S. Pat. No. 4,482,429 as well as U.S. Pat. No. 4,448,638. Note also, U.S. Pat. No. 6,350,349 to Hermans et al. which discloses wet transfer of a web from a rotating transfer surface to a fabric. See also U.S. Patent Application Publication No. 2008/0135195 of Hermans et al., now U.S. Pat. No. 7,785,443, which discloses an additive resin composition that can be used in a fabric crepe process to increase strength. Note
In connection with papermaking processes, fabric molding as a means to provide texture and bulk is reported in the literature. U.S. Pat. No. 5,073,235 to Trokhan discloses a process for making absorbent sheet using a photopolymer belt which is stabilized by application of anti-oxidants to the belt. The web is reported to have a networked, domed structure that may have a variation in basis weight. See Col. 17, lines 48+ and
U.S. Pat. No. 6,660,362 to Lindsay et al. enumerates various constructions of deflection members for imprinting tissue. In a typical construction, a patterned photopolymer is utilized. See Col. 19, line 39 through Col. 31, line 27. With respect to wet-molding of a web using textured fabrics, see also, the following U.S. Pat. Nos. 6,017,417 and 5,672,248 both to Wendt et al.; U.S. Pat. No. 5,505,818 to Hermans et al. and U.S. Pat. No. 4,637,859 to Trokhan. U.S. Pat. No. 7,320,743 to Freidbauer et al. discloses a wet-press process using a patterned absorbent papermaking felt with raised projections for imparting texture to a web while pressing the web onto a Yankee dryer. The process is reported to decrease tensiles. See Col. 7. With respect to the use of fabrics used to impart texture to a mostly dry sheet, see U.S. Pat. No. 6,585,855 to Drew et al., as well as U.S. Patent Application Publication No. 2003/0000664, now U.S. Pat. No. 6,607,638.
U.S. Pat. No. 5,503,715 to Trokhan et al. refers to a cellulosic fibrous structure having multiple regions distinguished from one another by basis weight. The structure is reported as having an essentially continuous higher basis weight network, and discrete regions of lower basis weight that circumscribe discrete regions of intermediate basis weight. The cellulosic fibers forming the low basis weight regions may be radially oriented relative to the centers of the regions. The paper is described as being formed by using a forming belt having zones with different flow resistances. The basis weight of a region of the paper is said to be generally inversely proportional to the flow resistance of the zone of the forming belt, upon which such a region was formed. See also, U.S. Pat. No. 7,387,706 to Herman et al. A similar structure is reported in U.S. Pat. No. 5,935,381, also to Trokhan et al., where the use of different fiber types is described. See also U.S. Pat. No. 6,136,146 to Phan et al. Also noteworthy in this regard is U.S. Pat. No. 5,211,815 to Ramasubramanian et al. which discloses a wet-press process for making absorbent sheet using a layered forming fabric with pockets. The product is reported to have high bulk and fiber alignment where many fiber segments or fiber ends are “on end” and substantially parallel to one another within the pockets forming on the sheet, which are interconnected with a network region substantially in the plane of the sheet. See also, U.S. Pat. No. 5,098,519 to Ramasubramanian et al.
Through-air dried (TAD), creped products are also disclosed in the following patents: U.S. Pat. No. 3,994,771 to Morgan, Jr. et al.; U.S. Pat. No. 4,102,737 to Morton; U.S. Pat. No. 4,440,597 to Wells et al. and U.S. Pat. No. 4,529,480 to Trokhan. The processes described in these patents comprise, very generally, forming a web on a foraminous support, thermally pre-drying the web, applying the web to a Yankee dryer with a nip defined, in part, by an impression fabric, and creping the product from the Yankee dryer. Transfer to the Yankee typically takes place at web consistencies of from about 60% to about 70%. A relatively uniformly permeable web is typically required.
Through-air dried products tend to provide desirable product attributes such as enhanced bulk and softness; however, thermal dewatering with hot air tends to be energy intensive and requires a relatively uniformly permeable substrate, necessitating the use of virgin fiber or virgin equivalent recycle fiber. More cost effective, environmentally preferred and readily available recycle furnishes with elevated fines content, for example, tend to be far less suitable for throughdry processes. Thus, wet-press operations wherein the webs are mechanically dewatered are preferable from an energy perspective and are more readily applied to furnishes containing recycle fiber which tends to form webs with permeability which is usually lower and less uniform than webs formed with virgin fiber. A Yankee dryer can be more easily employed because a web is transferred thereto at consistencies of 30% or so which enables the web to be firmly adhered for drying. In one proposed method of improving wet-pressed products, U.S. Patent Application Publication No. 2005/0268274 of Beuther et al. discloses an air-laid web combined with a wet-laid web. This layering is reported to increase softness, but would no doubt be expensive and difficult to operate efficiently.
Despite the many advances in the art, improvements in absorbent sheet qualities such as bulk, softness and tensile strength generally involve compromising one property in order to gain advantage in another or involve prohibitive expense and/or operating difficulty. Moreover, existing premium products generally use limited amounts of recycle fiber or none at all, despite the fact that the use of recycle fiber is beneficial to the environment and is much less expensive as compared with virgin kraft fiber.
In accordance with this invention, an improved variable basis weight product exhibits, among other preferred properties, surprising caliper or bulk. A typical product has a repeating structure of arched raised 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 a 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 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. 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. These regions appear to be especially effective in imparting bulk accompanied by high roll firmness to the absorbent sheet.
In other preferred aspects of the invention, the network regions form a densified (but not so highly densified as to be consolidated) reticulum imparting enhanced strength to the web.
This invention is directed, in part, to absorbent products produced by way of belt-creping a web from a transfer surface with a perforated creping belt formed from a polymer material, such as polyester. In various aspects, the products are characterized by a fiber matrix that is rearranged by belt creping from an apparently random wet-pressed structure to a shaped structure with fiber-enriched regions and/or a structure with fiber orientation and shape that defines a hollow dome-like repeating pattern in the web. In still further aspects of the invention, non-random CD orientation bias in a regular pattern is imparted to the fiber in the web.
Belt creping occurs under pressure in a creping nip while the web is at a consistency between about 30 and 60 percent. Without intending to be bound by theory, it is believed that the velocity delta in the belt-creping nip, the pressure employed and the belt and nip geometry cooperate with the nascent web of 30 to 60 percent consistency to rearrange the fiber, while the web is still labile enough to undergo structural change and re-form hydrogen bonds between rearranged fibers in the web due to Campbell's interactions when the web is dried. At consistencies above about 60 percent, it is believed there is insufficient water present to provide for sufficient reformation of hydrogen bonds between fibers as the web dries to impart the desired structural integrity to the microstructure of the web, while below about 30 percent, the web has too little cohesion to retain the features of the high solids fabric-creped structure provided by way of the belt-creping operation.
The products are unique in numerous aspects, including smoothness, absorbency, bulk and appearance.
The process can be more efficient than TAD processes using conventional fabrics, especially with respect to the use of energy and vacuum, which is employed in production to enhance caliper and other properties. A generally planar belt can more effectively seal off a vacuum box with respect to the solid areas of the belt, such that the airflow due to the vacuum is efficiently directed through the perforations in the belt and through the web. So also, the solid portions of the belt, or “lands” between perforations, are much smoother than a woven fabric, providing a better “hand” or smoothness on one side of the sheet and texture in the form of domes when suction is applied on the other side of the sheet, which increases caliper, bulk, and absorbency. Without suction or vacuum applied, “slubbed” regions include arched or domed structures adjacent to pileated regions that are fiber-enriched as compared with other areas of the sheet.
In yarn production, fiber-enriched texture or “slubs” are produced by including uneven lengths of fiber in spinning, providing a pleasing, bulky texture with fiber-enriched areas in the yarn. In accordance with the invention, “slubs” or fiber-enriched regions are introduced onto the web by redistributing fiber into perforations of the belt to form local fiber-enriched regions defining a pileated, hollow dome repeating structure that provides surprising caliper, especially, when a vacuum is applied to the web while the web is held in the creping belt. The domed regions in the sheet appear to have fiber with an inclined, partially erect orientation that is upwardly inflected and consolidated or very highly densified in wall areas, which is believed to contribute substantially to the surprising caliper and roll firmness observed. Fiber orientation on the sidewalls of the arched or domed regions is biased in the cross-machine direction (CD) in some regions, while fiber orientation is biased toward the cap in some regions as is seen in the photomicrographs, the scanning electron micrographs (SEM's) and the β-radiograph images attached. Also provided is a densified, but not necessarily, consolidated, generally planar, network interconnecting the domed or arched regions, also of variable local basis weight.
The belt-creping operation may be effective to tessellate the sheet into distinct adjacent areas of like and/or interfitting repeating shapes, if so desired, as will be appreciated from the following description and appended Figures.
In one aspect, our invention provides a method of making a belt creped absorbent cellulosic sheet that has an upper surface and a lower surface. The method includes compactively dewatering a papermaking furnish to form a dewatered web having an apparently random distribution of papermaking fiber orientation, applying the dewatered web having the apparently random distribution of papermaking fiber orientation to a translating transfer surface that is moving at a transfer surface speed, and belt-creping the web from the transfer surface utilizing a generally planar polymeric creping belt provided with a plurality of perforations through the belt, the belt-creping step occurring under pressure in a belt creping nip defined between the transfer surface and the creping belt, wherein the belt is traveling at a belt speed that is slower than the transfer surface speed, and the web is creped from the transfer surface and redistributed on the creping belt to form a web. The web includes a plurality of fiber-enriched hollow domed regions protruding from the upper surface of the sheet, the hollow domed regions having sidewalls being formed along at least a leading edge of the sheet, connecting regions forming a network interconnecting the fiber-enriched hollow domed regions of the sheet, and transition areas comprising consolidated groupings of fibers that extend upwardly from the connecting regions into the sidewalls of the fiber-enriched hollow domed regions. The method further includes (d) drying the web to produce the belt-creped absorbent cellulosic sheet.
In another aspect, our invention provides a method of making a belt-creped absorbent cellulosic sheet. The method includes compactively dewatering a papermaking furnish to form a dewatered web having an apparently random distribution of papermaking fiber orientation, applying the dewatered web having the apparently random distribution of papermaking fiber orientation to a translating transfer surface that is moving at a transfer surface speed, belt-creping the web from the transfer surface utilizing a generally planar polymeric creping belt provided with a plurality of perforations through the belt, the belt-creping step occurring under pressure in a belt creping nip defined between the transfer surface and the creping belt, wherein the belt is traveling at a belt speed that is slower than the transfer surface speed, and the web is creped from the transfer surface and redistributed on the creping belt to form a web having a plurality of interconnected regions of different local basis weights. The web includes at least a plurality of fiber-enriched hollow domed regions having densified caps, the fiber-enriched hollow domed regions projecting from an upper side of the sheet and having sidewalls, connecting regions forming a network interconnecting the fiber-enriched hollow domed regions of the sheet, the connecting regions having a local basis weight that is lower than a local basis weight of the hollow domed regions, and transition areas that transition from the connecting regions into the fiber-enriched hollow domed regions by extending upwardly and inwardly from the connecting regions into the sidewalls of the hollow domed regions. The method further includes drying the web to produce the belt-creped absorbent cellulosic sheet.
In yet another aspect, our invention provides a method of making a belt-creped absorbent cellulosic sheet. The method includes compactively dewatering a papermaking furnish to form a dewatered web having an apparently random distribution of papermaking fiber orientation, applying the dewatered web having the apparently random distribution of papermaking fiber orientation to a translating transfer surface that is moving at a transfer surface speed, and belt-creping the web from the transfer surface utilizing a generally planar polymeric creping belt provided with a plurality of tapered perforations through the creping belt, the belt-creping step occurring under pressure in a belt creping nip defined between the transfer surface and the creping belt, wherein the creping belt is traveling at a belt speed that is slower than the transfer surface speed, and the web is creped from the transfer surface and redistributed on the creping belt to form a wet web on the creping belt having a plurality of fiber-enriched, slubbed regions of a local basis weight that is higher than a mean basis weight of the sheet and including hollow domed portions, the hollow domed portions having upwardly projecting densified sidewalls, and (ii) pileated fiber-enriched regions with a cross-machine direction fiber orientation bias adjacent to the hollow domed portions, the fiber-enriched regions being interconnected with (b) connecting regions having a local basis weight that is lower than the local basis weight of the fiber-enriched regions. The method further includes applying a vacuum to the creping belt while the wet web is held on the creping belt, in order to expand the wet web and to merge the domed and pileated fiber-enriched regions, and drying the web to produce the belt-creped absorbent cellulosic sheet.
The unique aspects of our invention are better understood with reference to
Referring to
Referring to
The elevated local basis weight at the leading edge of the domed areas is perhaps seen best in
Still another noteworthy feature of the sheet is the upward or “on end” fiber orientation at the leading and trailing edges of the domed areas, especially at the leading areas as is seen, for example at 29. This orientation does not appear on the “CD” edges of the domes where the orientation appears more random.
It is seen in
Domed region 12 has a somewhat asymmetric, hollow dome shape with a cap 32, which is fiber-enriched with a relatively high local basis weight, particularly, at the “leading” edge toward right hand side 35 of
Without intending to be bound by any theory, it is believed this unique, hollow dome structure contributes substantially to the surprising caliper values seen with the sheet, as well as the roll compression values seen with the products of the invention.
In other cases, the fiber-enriched hollow domed regions project from the upper side of the sheet and have both relatively high local basis weight and consolidated caps, the consolidated caps having the general shape of a portion of a spheroidal shell, more preferably, having the general shape of an apical portion of a spheroidal shell.
Further details and attributes of the inventive products and process for making them are discussed below.
The invention is described in detail below with reference to the various Figures, wherein like numerals designate similar parts. The file of this patent contains at least one drawing executed in color. Copies of this patent or patent application publication with color drawings will be provided in the U.S. Patent and Trademark Office upon request and payment of the necessary fee. In the Figures:
In connection with photomicrographs, magnifications reported herein are approximate except when presented as part of a scanning electron micrograph where an absolute scale is shown. In many cases, where sheets were sectioned, artifacts may be present along this cut edge, but we have only referenced and described structures that we have observed away from the cut edge or were not altered by the cutting process.
The invention is described below with reference to numerous embodiments. Such 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 consistent with the exemplary definitions set forth immediately below; mg refers to milligrams and m2 refers to square meters, and so forth.
The creping adhesive “add-on” rate is calculated by dividing the rate of application of adhesive (mg/min) by surface area of the drying cylinder passing under a spray applicator boom (m2/min). The resinous adhesive composition most preferably consists essentially of a polyvinyl alcohol resin and a polyamide-epichlorohydrin resin wherein the weight ratio of polyvinyl alcohol resin to polyamide-epichlorohydrin resin is from about 2 to about 4. The creping adhesive may also include a modifier sufficient to maintain good transfer between the creping belt and the Yankee cylinder, generally, less than 5% by weight modifier and, more preferably, less than about 2% by weight modifier, for peeled products. For blade creped products, from about 5%-25% modifier or more may be used.
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 a machine direction orientation, making the machine direction tensile strength of the web exceed the cross-direction tensile strength.
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 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 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 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.
“Belt crepe ratio” is an expression of the speed differential between the creping belt and the forming wire and, typically, is calculated as the ratio of the web speed immediately before belt creping and the web speed immediately following belt creping, the forming wire and transfer surface being typically, but not necessarily, operated at the same speed:
Belt crepe ratio=transfer cylinder speed÷creping belt speed
Belt crepe can also be expressed as a percentage calculated as:
Belt crepe=[Belt crepe ratio−1]×100.
A web creped from a transfer cylinder with a surface speed of 750 fpm (3.81 m/s) to a belt with a velocity of 500 fpm (2.54 m/s) has a belt crepe ratio of 1.5 and a belt crepe of 50%.
For reel crepe, the reel crepe ratio is typically calculated as the Yankee speed divided by reel speed. To express reel crepe as a percentage, 1 is subtracted from the reel crepe ratio and the result multiplied by 100%.
The belt crepe/reel crepe ratio is calculated by dividing the belt crepe by the reel crepe.
The line or overall crepe ratio is calculated as the ratio of the forming wire speed to the reel speed and a % total crepe is:
Line Crepe=[Line Crepe Ratio−1]×100.
A process with a forming wire speed of 2000 fpm (10.2 m/s) and a reel speed of 1000 fpm (5.08 m/s) has a line or total crepe ratio of 2 and a total crepe of 100%.
“Belt side” and like terminology refers to the side of the web that is in contact with the creping belt. “Dryer-side” or “Yankee-side” is the side of the web in contact with the drying cylinder, typically, opposite to the belt-side of the web.
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-II-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 off of the winder. For base sheet testing off of the papermachine reel, single plies must be used. Sheets are stacked together and aligned in the MD. Bulk may also be expressed in units of volume/weight by dividing caliper by basis weight.
The term “cellulosic”, “cellulosic sheet,” and the like, is meant to include any wet-laid product incorporating papermaking fiber having cellulose as a major constituent. “Papermaking fibers” include virgin pulps or recycle (secondary) cellulosic fibers or fiber mixes comprising cellulosic fibers. Fibers suitable for making the webs of this invention include: nonwood fibers, such as cotton fibers or cotton derivatives, abaca, kenaf, sabai grass, flax, esparto grass, straw, jute hemp, bagasse, milkweed floss fibers, and pineapple leaf fibers; and wood fibers such as those obtained from deciduous and coniferous trees, including softwood fibers, such as northern and southern softwood kraft fibers; hardwood fibers, such as eucalyptus, maple, birch, aspen, or the like. Papermaking fibers can be liberated from their source material by any one of a number of chemical pulping processes familiar to one experienced in the art including sulfate, sulfite, polysulfide, soda pulping, etc. The pulp can be bleached if desired by chemical means including the use of chlorine, chlorine dioxide, oxygen, alkaline peroxide, and so forth. The products of the present invention may comprise a blend of conventional fibers (whether derived from virgin pulp or recycle sources) and high coarseness lignin-rich tubular fibers, and mechanical pulps such as bleached chemical thermomechanical pulp (BCTMP). “Furnishes” and like terminology refers to aqueous compositions including papermaking fibers, optionally, wet strength resins, debonders, and the like, for making paper products. Recycle fiber is typically more than 50% by weight hardwood fiber and may be 75% to 80% or more hardwood fiber.
As used herein, the term compactively dewatering the web or furnish refers to mechanical dewatering by overall wet pressing such as on a dewatering felt, for example, in some embodiments, by use of mechanical pressure applied continuously over the web surface as in a nip between a press roll and a press shoe, wherein the web is in contact with a papermaking felt. The terminology “compactively dewatering” is used to distinguish from processes wherein the initial dewatering of the web is carried out largely by thermal means as is the case, for example, in U.S. Pat. No. 4,529,480 to Trokhan and U.S. Pat. No. 5,607,551 to Farrington et al. Compactively dewatering a web thus refers, for example, to removing water from a nascent web having a consistency of less than 30% or so by application of pressure thereto and/or increasing the consistency of the web by about 15% or more by application of pressure thereto; that is, increasing the consistency, for example, from 30% to 45%.
Consistency refers to % solids of a nascent web, for example, calculated on a bone dry basis. “Air dry” means including residual moisture, by convention, up to about 10% moisture for pulp and up to about 6% for paper. A nascent web having 50% water and 50% bone dry pulp has a consistency of 50%.
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 exceeding 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 direction. The presence of consolidated fiber or consolidated fibrous structures can be confirmed by examining thin sections which 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 consolidated. Sections prepared by focused ion beam cross-section polishers, such as those offered by JEOL, are especially suitable for observing densification 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. 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.
“Domed”, “dome-like,” and so forth, as used in the description and claims, refer 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. The terminology refers to vaulted configurations, generally, whether symmetric or asymmetric about a plane bisecting the domed area. Thus, “domed” refers generally to spherical domes, spheroidal domes, elliptical 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.
Fpm refers to feet per minute; while fps refers to feet per second.
MD means machine direction and CD means cross-machine direction.
When applicable, MD bending length (cm) of a product is determined in accordance with ASTM test method D 1388-96, cantilever option. Reported bending lengths refer to MD bending lengths unless a CD bending length is expressly specified. The MD bending length test was performed with a Cantilever Bending Tester available from Research Dimensions, 1720 Oakridge Road, Neenah, Wis., 54956, which is substantially the apparatus shown in the ASTM test method, item 6. The instrument is placed on a level stable surface, horizontal position being confirmed by a built in leveling bubble. The bend angle indicator is set at 41.5° below the level of the sample table. This is accomplished by setting the knife edge appropriately. The sample is cut with a one inch (25.4 mm) JD strip cutter available from Thwing-Albert Instrument Company, 14 Collins Avenue, W. Berlin, N.J. 08091. Six (6) samples are cut into 1 inch×8 inch (25.4 mm×203 mm) machine direction specimens. Samples are conditioned at 23° C.±1° C. (73.4° F.±1.8° F.) at 50% relative humidity for at least two hours. For machine direction specimens, the longer dimension is parallel to the machine direction. The specimens should be flat, free of wrinkles, bends or tears. The Yankee-side of the specimens is also labeled. The specimen is placed on the horizontal platform of the tester aligning the edge of the specimen with the right hand edge. The movable slide is placed on the specimen, being careful not to change its initial position. The right edge of the sample and the movable slide should be set at the right edge of the horizontal platform. The movable slide is displaced to the right in a smooth, slow manner at approximately 5 inches/minute (127 mm/minute) until the specimen touches the knife edge. The overhang length is recorded to the nearest 0.1 cm. This is done by reading the left edge of the movable slide. Three specimens are preferably run with the Yankee-side up and three specimens are preferably run with the Yankee-side down on the horizontal platform. The MD bending length is reported as the average overhang length in centimeters divided by two to account for bending axis location.
Nip parameters include, without limitation, nip pressure, nip width, backing roll hardness, creping roll hardness, belt approach angle, belt takeaway angle, uniformity, nip penetration and velocity delta between surfaces of the nip.
Nip width (or length as the context indicates) means the MD length over which the nip surfaces are in contact.
PLI or pli means pounds of force per linear inch. The process employed is distinguished from other processes, in part, because belt creping is carried out under pressure in a creping nip. Typically, rush transfers are carried out using suction to assist in detaching the web from the donor fabric and, thereafter, attaching it to the receiving or receptor fabric. In contrast, suction is not required in a belt creping step, so accordingly, when we refer to belt creping as being “under pressure” we are referring to loading of the receptor belt against the transfer surface, although suction assist can be employed at the expense of further complication of the system, so long as the amount of suction is not sufficient to undesirably interfere with rearrangement or redistribution of the fiber.
Pusey and Jones (P&J) hardness (indentation) is measured in accordance with ASTM D 531, and refers to the indentation number (standard specimen and conditions).
“Predominantly” means more than 50% of the specified component, by weight unless otherwise indicated.
Roll compression is measured by compressing the roll under a 1500 g flat platen. Sample rolls are conditioned and tested in an atmosphere of 23.0°±1.0° C. (73.4°±1.8° F.). A suitable test apparatus with a movable 1500 g platen (referred to as a Height Gauge) is available from:
The test procedure is generally as follows:
(a) Raise the platen and position the roll or sleeve to be tested on its side, centered under the platen, with the tail seal to the front of the gauge and the core parallel to the back of the gauge.
(b) Slowly lower the platen until it rests on the roll or sleeve.
(c) Read the compressed roll diameter or sleeve height from the gauge pointer to the nearest 0.01 inch (0.254 mm).
(d) Raise the platen and remove the roll or sleeve.
(e) Repeat for each roll or sleeve to be tested.
To calculate roll compression in percent, the following formula is used:
100×[(initial roll diameter−compressed 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 (TEA) 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 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.
The wet tensile of the tissue of the present invention is measured 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-in. (76.2 mm), with base to fit a 3-in. (76.2 mm) grip, is available from:
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 7.0±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″ or (g/mm), dividing the readout by two to account for the loop as appropriate.
A translating transfer surface refers to the surface from which the web is creped onto the creping belt. The translating transfer surface may be the surface of a rotating drum as described hereafter, or may be the surface of a continuous smooth moving belt or another moving fabric that may have surface texture, and so forth. The translating transfer surface needs to support the web and facilitate the high solids creping, as will be appreciated from the discussion which follows.
Velocity delta means a difference in linear speed.
The void volume and/or void volume ratio, as referred to hereafter, are determined by saturating a sheet with a nonpolar POROFIL™ liquid and measuring the amount of liquid absorbed. The volume of liquid absorbed is equivalent to the void volume within the sheet structure. The percent weight increase (PWI) is expressed as grams of liquid absorbed per gram of fiber in the sheet structure one hundred times, 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 POROFIL™ liquid having a specific gravity of about 1.93 grams per cubic centimeter, available from Coulter Electronics Ltd., Northwell Drive, Luton, Beds, England, Part No. 9902458. After 10 seconds, grasp the specimen at the very edge (1-2 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 ½ second contact) the lower corner of the specimen on #4 filter paper (Whatman Lt., 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 POROFIL™ liquid per gram of fiber, is calculated as follows:
PWI=[(W2−W1)/W1]×100
wherein
“W1” is the dry weight of the specimen, in grams; 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, or WAR, is measured in seconds and is 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±1.8° F.) at 50% relative humidity for 2 hours. For each sample, 4 3×3 inch (76.2×76.2 mm) 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 stopwatch is started. When the water is absorbed, as indicated by lack of further reflection of light from the drop, the stopwatch is stopped and the time recorded to the nearest 0.1 seconds. The procedure is repeated for each specimen and the results averaged for the sample. WAR is measured in accordance with TAPPI method T 432 cm-99.
The creping adhesive composition used to secure the web to the Yankee drying cylinder is preferably a hygroscopic, re-wettable, substantially non-crosslinking adhesive. Examples of preferred adhesives are those that include poly(vinyl alcohol) of the general class described in U.S. Pat. No. 4,528,316 to Soerens et al. Other suitable adhesives are disclosed in copending U.S. patent application Ser. No. 10/409,042, filed Apr. 9, 2003, entitled “Creping Adhesive Modifier and Process for Producing Paper Products”, Publication No. 2005/0006040, now U.S. Pat. No. 7,959,761. The disclosures of the '316 patent and the '042 application are incorporated herein by reference. Suitable adhesives are optionally provided with crosslinkers, modifiers, and so forth, depending upon the particular process selected.
Creping adhesives may comprise a thermosetting or non-thermosetting resin, a film-forming semi-crystalline polymer and, optionally, an inorganic cross-linking agent, as well as modifiers. Optionally, the creping adhesive of the present invention may also include other components, including, but not limited to, hydrocarbons oils, surfactants, or plasticizers. Further details as to creping adhesives useful in connection with the present invention are found in copending U.S. patent application Ser. No. 11/678,669, entitled “Method of Controlling Adhesive Build-Up on a Yankee Dryer”, filed Feb. 26, 2007, Publication No. 2007/0204966, now U.S. Pat. No. 7,850,823, the disclosure of which is incorporated herein by reference.
The creping adhesive may be applied as a single composition or may be applied in its component parts. More particularly, the polyamide resin may be applied separately from the polyvinyl alcohol (PVOH) and the modifier.
In connection with the present invention, an absorbent paper web is made by dispersing papermaking fibers into aqueous furnish (slurry) and depositing the aqueous furnish onto the forming wire of a papermaking machine. Any suitable forming scheme might be used. For example, an extensive, but non-exhaustive, list in addition to Fourdrinier formers includes a crescent former, a C-wrap twin wire former, an S-wrap twin wire former, or a suction breast roll former. The forming fabric can be any suitable foraminous member including single layer fabrics, double layer fabrics, triple layer fabrics, photopolymer fabrics, and the like. Non-exhaustive background art in the forming fabric area includes U.S. Pat. Nos. 4,157,276; 4,605,585; 4,161,195; 3,545,705; 3,549,742; 3,858,623; 4,041,989; 4,071,050; 4,112,982; 4,149,571; 4,182,381; 4,184,519; 4,314,589; 4,359,069; 4,376,455; 4,379,735; 4,453,573; 4,564,052; 4,592,395; 4,611,639; 4,640,741; 4,709,732; 4,759,391; 4,759,976; 4,942,077; 4,967,085; 4,998,568; 5,016,678; 5,054,525; 5,066,532; 5,098,519; 5,103,874; 5,114,777; 5,167,261; 5,199,261; 5,199,467; 5,211,815; 5,219,004; 5,245,025; 5,277,761; 5,328,565; and 5,379,808, all of which are incorporated herein by reference in their entirety. One forming fabric particularly useful with the present invention is Voith Fabrics Forming Fabric 2164 made by Voith Fabrics Corporation, Shreveport, La.
Foam-forming of the aqueous furnish on a forming wire or fabric may be employed as a means for controlling the permeability or void volume of the sheet upon belt-creping. Foam-forming techniques are disclosed in U.S. Pat. Nos. 6,500,302; 6,413,368; 4,543,156 and Canadian Patent No. 2053505, the disclosures of which are incorporated herein by reference. The foamed fiber furnish is made up from an aqueous slurry of fibers mixed with a foamed liquid carrier just prior to its introduction to the headbox. The pulp slurry supplied to the system has a consistency in the range of from about 0.5 to about 7 weight % fibers, preferably, in the range of from about 2.5 to about 4.5 weight %. The pulp slurry is added to a foamed liquid comprising water, air and surfactant containing 50 to 80% air by volume forming a foamed fiber furnish having a consistency in the range of from about 0.1 to about 3 weight % fiber by simple mixing from natural turbulence and mixing inherent in the process elements. The addition of the pulp as a low consistency slurry results in excess foamed liquid recovered from the forming wires. The excess foamed liquid is discharged from the system and may be used elsewhere or treated for recovery of surfactant therefrom.
The furnish may contain chemical additives to alter the physical properties of the paper produced. These chemistries are well understood by the skilled artisan and may be used in any known combination. Such additives may be surface modifiers, softeners, debonders, strength aids, latexes, opacifiers, optical brighteners, dyes, pigments, sizing agents, barrier chemicals, retention aids, insolubilizers, organic or inorganic crosslinkers, or combinations thereof, said chemicals optionally comprising polyols, starches, PPG esters, PEG esters, phospholipids, surfactants, polyamines, HMCP (Hydrophobically Modified Cationic Polymers), HMAP (Hydrophobically Modified Anionic Polymers), or the like.
The pulp can be mixed with strength adjusting agents such as wet strength agents, dry strength agents and debonders/softeners, and so forth. Suitable wet strength agents are known to the skilled artisan. A comprehensive, but non-exhaustive, list of useful strength aids include urea-formaldehyde resins, melamine formaldehyde resins, glyoxylated polyacrylamide resins, polyamide-epichlorohydrin resins, and the like. Thermosetting polyacrylamides are produced by reacting acrylamide with diallyl dimethyl ammonium chloride (DADMAC) to produce a cationic polyacrylamide copolymer, which is ultimately reacted with glyoxal to produce a cationic cross-linking wet strength resin, glyoxylated polyacrylamide. These materials are generally described in U.S. Pat. No. 3,556,932 to Coscia et al. and U.S. Pat. No. 3,556,933 to Williams et al., both of which are incorporated herein by reference in their entirety. Resins of this type are commercially available under the trade name of PAREZ 631NC by Bayer Corporation. Different mole ratios of acrylamide/-DADMAC/glyoxal can be used to produce cross-linking resins, which are useful as wet strength agents. Furthermore, other dialdehydes can be substituted for glyoxal to produce thermosetting wet strength characteristics. Of particular utility are the polyamide-epichlorohydrin wet strength resins, an example of which is sold under the trade names Kymene 557LX and Kymene 557H by Hercules Incorporated of Wilmington, Del. and Amres® from Georgia-Pacific Resins, Inc. These resins and the processes for making the resins are described in U.S. Pat. No. 3,700,623 and U.S. Pat. No. 3,772,076, each of which is incorporated herein by reference in its entirety. An extensive description of polymeric-epihalohydrin resins is given in Chapter 2: Alkaline-Curing Polymeric Amine-Epichlorohydrin by Espy in Wet Strength Resins and Their Application (L. Chan, Editor, 1994), herein incorporated by reference in its entirety. A reasonably comprehensive list of wet strength resins is described by Westfelt in Cellulose Chemistry and Technology Volume 13, page 813, 1979, which is also incorporated herein by reference.
Suitable temporary wet strength agents may likewise be included, particularly, in applications where disposable towel, or more typically, tissue with permanent wet strength resin is to be avoided. A comprehensive, but non-exhaustive, list of useful temporary wet strength agents includes aliphatic and aromatic aldehydes including glyoxal, malonic dialdehyde, succinic dialdehyde, glutaraldehyde and dialdehyde starches, as well as substituted or reacted starches, disaccharides, polysaccharides, chitosan, or other reacted polymeric reaction products of monomers or polymers having aldehyde groups, and optionally, nitrogen groups. Representative nitrogen containing polymers, which can suitably be reacted with the aldehyde containing monomers or polymers, includes vinyl-amides, acrylamides and related nitrogen containing polymers. These polymers impart a positive charge to the aldehyde containing reaction product. In addition, other commercially available temporary wet strength agents, such as, PAREZ FJ98, manufactured by Kemira can be used, along with those disclosed, for example, in U.S. Pat. No. 4,605,702.
The temporary wet strength resin may be any one of a variety of water-soluble organic polymers comprising aldehydic units and cationic units used to increase dry and wet tensile strength of a paper product. Such resins are described in U.S. Pat. Nos. 4,675,394; 5,240,562; 5,138,002; 5,085,736; 4,981,557; 5,008,344; 4,603,176; 4,983,748; 4,866,151; 4,804,769 and 5,217,576. Modified starches sold under the trademarks CO-BOND® 1000 and CO-BOND® 1000 Plus, by National Starch and Chemical Company of Bridgewater, N.J. may be used. Prior to use, the cationic aldehydic water soluble polymer can be prepared by preheating an aqueous slurry of approximately 5% solids maintained at a temperature of approximately 240° F. (116° C.) and a pH of about 2.7 for approximately 3.5 minutes. Finally, the slurry can be quenched and diluted by adding water to produce a mixture of approximately 1.0% solids at less than about 130° F. (54.4° C.).
Other temporary wet strength agents, also available from National Starch and Chemical Company are sold under the trademarks CO-BOND® 1600 and CO-BOND® 2300. These starches are supplied as aqueous colloidal dispersions and do not require preheating prior to use.
Suitable dry strength agents include starch, guar gum, polyacrylamides, carboxymethyl cellulose, and the like. Of particular utility is carboxymethyl cellulose, an example of which is sold under the trade name Hercules CMC, by Hercules Incorporated of Wilmington, Del. According to one embodiment, the pulp may contain from about 0 to about 15 lb/ton (0.0075%) of dry strength agent. According to another embodiment, the pulp may contain from about 1 (0.0005%) to about 5 lbs/ton (0.0025%) of dry strength agent.
Suitable debonders are likewise known to the skilled artisan. Debonders or softeners may also be incorporated into the pulp or sprayed upon the web after its formation. The present invention may also be used with softener materials including, but not limited to, the class of amido amine salts derived from partially neutralized amines. Such materials are disclosed in U.S. Pat. No. 4,720,383. Evans, Chemistry and Industry, 5 Jul. 1969, pages 893-903; Egan, J. Am. Oil Chemist's Soc., Vol. 55 (1978), pages 118 to 121; and Trivedi et al., J. Am. Oil Chemist's Soc., June 1981, pages 754 to 756, incorporated by reference in their entireties, indicate that softeners are often available commercially only as complex mixtures rather than as single compounds. While the following discussion will focus on the predominant species, it should be understood that commercially available mixtures would generally be used in practice.
Hercules TQ 218 or equivalent is a suitable softener material, which may be derived by alkylating a condensation product of oleic acid and diethylenetriamine. Synthesis conditions using a deficiency of alkylation agent (e.g., diethyl sulfate) and only one alkylating step, followed by pH adjustment to protonate the non-ethylated species, result in a mixture consisting of cationic ethylated and cationic non-ethylated species. A minor proportion (e.g., about 10%) of the resulting amido amine cyclize to imidazoline compounds. Since only the imidazoline portions of these materials are quaternary ammonium compounds, the compositions as a whole are pH-sensitive. Therefore, in the practice of the present invention with this class of chemicals, the pH in the head box should be approximately 6 to 8, more preferably, from about 6 to about 7, and most preferably, from about 6.5 to about 7.
Quaternary ammonium compounds, such as dialkyl dimethyl quaternary ammonium salts are also suitable, particularly when the alkyl groups contain from about 10 to 24 carbon atoms. These compounds have the advantage of being relatively insensitive to pH.
Biodegradable softeners can be utilized. Representative biodegradable cationic softeners/debonders are disclosed in U.S. Pat. Nos. 5,312,522; 5,415,737; 5,262,007; 5,264,082; and 5,223,096, all of which are incorporated herein by reference in their entireties. The compounds are biodegradable diesters of quaternary ammonia compounds, quaternized amine-esters, and biodegradable vegetable oil based esters functional with quaternary ammonium chloride and diester dierucyldimethyl ammonium chloride and are representative biodegradable softeners.
In some embodiments, a particularly preferred debonder composition includes a quaternary amine component, as well as a nonionic surfactant.
The nascent web may be compactively dewatered on a papermaking felt. Any suitable felt may be used. For example, felts can have double-layer base weaves, triple-layer base weaves, or laminated base weaves. Preferred felts are those having the laminated base weave design. A wet-press-felt, which may be particularly useful with the present invention, is Vector 3 made by Voith Fabric. Background art in the press felt area includes U.S. Pat. Nos. 5,657,797; 5,368,696; 4,973,512; 5,023,132; 5,225,269; 5,182,164; 5,372,876; and 5,618,612. A differential pressing felt as is disclosed in U.S. Pat. No. 4,533,437 to Curran et al. may likewise be utilized.
The products of this invention are advantageously produced in accordance with a wet-press or compactively dewatering process wherein the web is belt creped after dewatering at a consistency of from 30-60%, as described hereafter. The creping belt employed is a perforated polymer belt of the class shown in
In the process of the invention, upper surface 52 of belt 50 is normally the “creping” side of this belt; that is, the side of the belt contacting the web, while the opposite or lower surface 76 shown in
It will be appreciated from
Shapes of the tapered perforations through the belt may be varied to achieve particular structures in the product. Exemplary shapes are shown in
Belts 50 or 100 may be made by any suitable technique, including photopolymer techniques, molding, hot pressing or perforation by any means. Use of belts having a significant ability to stretch in the machine direction without buckling, puckering or tearing can be particularly beneficial; as, if the path length around all of the rolls defining the path of a translating fabric or belt in a paper machine is measured with precision, in many cases, that path length varies significantly across the width of the machine. For example, on a paper machine having a trim width of 280 inches (7.11 meters), a typical fabric or belt run might be approximately 200 feet (60.96 meters). However, while the rolls defining the belt or fabric run are close to cylindrical in shape, they often vary significantly from cylindrical, having slight crowns, warps, tapers or bows, either induced deliberately or resulting from any of a variety of other causes. Further, as many of these rolls are to some extent cantilevered as supports on the tending side of the machine are often removable, even if the rolls could be considered to be perfectly cylindrical, the axes of these cylinders would not in general be precisely parallel to each other. Thus, the path length around all of these rolls might be 200 feet (60.96 meters) precisely along the center line of the trim width but 199′ 6″ (60.8 meters) on the machine side trim line and 201′ 4″ (61.4 meters) on the tending side trim line with a rather non-linear variation in length occurring in-between the trim lines. Accordingly, we have found that it is desirable for the belts to be able to give slightly to accommodate this variation. In conventional paper-making, as well as in fabric creping, woven fabrics have the ability to contract transversely to the machine direction to accommodate strains or to stretch in the machine direction, so that non-uniformities in the path length are almost automatically adjusted. We have found that many polymeric belts formed by joining a large number of monolithically formed belt sections are unable to adapt easily to the variations in path length across the width of the machine without tearing, buckling or puckering. However, such a variation can often be accommodated by a belt that can stretch significantly in the machine direction by contracting in the cross direction without tearing, buckling or puckering. One particular advantage of belts formed by encapsulating a woven conventional fabric in a polymer is that such belts can have a significant capacity to resolve the variance in path length by contracting slightly in the cross-machine direction where the path length is longer, particularly, if polymer regions are free to follow the fabric. In general, we prefer that the belts have the capacity to adapt to variations of between about 0.01% and 0.2% in length without tearing, puckering or buckling.
To form the perforations through the belt, we particularly prefer to use laser engraving or drilling a polymer sheet. The sheet may be a layered, monolithic solid or optionally, a filled or reinforced polymer sheet material with suitable microstructure and strength. Suitable polymeric materials for forming the belt include polyesters, copolyesters, polyamides, copolyamides and other polymers suitable for sheet, film or fiber forming. The polyesters that may be used are generally obtained by known polymerization techniques from aliphatic or aromatic dicarboxylic acids with saturated aliphatic and/or aromatic diols. Aromatic diacid monomers include the lower alkyl esters, such as the dimethyl esters of terephthalic acid or isophthalic acid. Typical aliphatic dicarboxylic acids include adipic, sebacic, azelaic, dodecanedioic acid or 1,4-cyclohexanedicarboxylic acid. The preferred aromatic dicarboxylic acid or its ester or anhydride is esterified or trans-esterified and polycondensed with the saturated aliphatic or aromatic diol. Typical saturated aliphatic diols preferably include the lower alkane-diols such as ethylene glycol. Typical cycloaliphatic diols include 1,4-cyclohexane diol and 1,4-cyclohexane dimethanol. Typical aromatic diols include aromatic diols such as hydroquinone, resorcinol and the isomers of naphthalene diol (1,5-; 2,6-; and 2,7-). Various mixtures of aliphatic and aromatic dicarboxylic acids and saturated aliphatic and aromatic diols may also be used. Most typically, aromatic dicarboxylic acids are polymerized with aliphatic diols to produce polyesters, such as polyethylene terephthalate (terephthalic acid+ethylene glycol, optionally including some cycloaliphatic diol). Additionally, aromatic dicarboxylic acids can be polymerized with aromatic diols to produce wholly aromatic polyesters, such as polyphenylene terephthalate (terephthalic acid+hydroquinone). Some of these wholly aromatic polyesters form liquid crystalline phases in the melt and thus, are referred to as “liquid crystal polyesters” or LCPs.
Examples of polyesters include polyethylene terephthalate; poly(1,4-butylene) terephthalate; and 1,4-cyclohexylene dimethylene terephthalate/isophthalate copolymer and other linear homopolymer esters derived from aromatic dicarboxylic acids, including isophthalic acid, bibenzoic acid, naphthalene-dicarboxylic acid including the 1,5-; 2,6-; and 2,7-naphthalene-dicarboxylic acids; 4,4,-diphenylene-dicarboxylic acid; bis(p-carboxyphenyl) methane acid; ethylene-bis-p-benzoic acid; 1,4-tetramethylene bis(p-oxybenzoic) acid; ethylene bis(p-oxybenzoic) acid; 1,3-trimethylene bis(p-oxybenzoic) acid; and diols selected from the group consisting of 2,2-dimethyl-1,3-propane diol; cyclohexane dimethanol and aliphatic glycols of the general formula HO(CH2)nOH where n is an integer from 2 to 10, e.g., ethylene glycol; 1,4-tetramethylene glycol; 1,6-hexamethylene glycol; 1,8-octamethylene glycol; 1,10-decamethylene glycol; and 1,3-propylene glycol; and polyethylene glycols of the general formula HO(CH2CH2O)nH where n is an integer from 2 to 10,000, and aromatic diols such as hydroquinone, resorcinol and the isomers of naphthalene diol (1,5-; 2,6-; and 2,7). There can also be present one or more aliphatic dicarboxylic acids, such as adipic, sebacic, azelaic, dodecanedioic acid or 1,4-cyclohexanedicarboxylic acid.
Also included are polyester containing copolymers such as polyesteramides, polyesterimides, polyesteranhydrides, polyesterethers, polyesterketones, and the like.
Polyamide resins, which may be useful in the practice of the invention, are well-known in the art and include semi-crystalline and amorphous resins, which may be produced, for example, by condensation polymerization of equimolar amounts of saturated dicarboxylic acids containing from 4 to 12 carbon atoms with diamines, by ring opening polymerization of lactams, or by copolymerization of polyamides with other components, e.g., to form polyether polyamide block copolymers. Examples of polyamides include polyhexamethylene adipamide (nylon 66), polyhexamethylene azelaamide (nylon 69), polyhexamethylene sebacamide (nylon 610), polyhexamethylene dodecanoamide (nylon 612), polydodecamethylene dodecanoamide (nylon 1212), polycaprolactam (nylon 6), polylauric lactam, poly-11-aminoundecanoic acid, and copolymers of adipic acid, isophthalic acid, and hexamethylene diamine.
If a Fourdrinier former or other gap former is used, the nascent web may be conditioned with suction boxes and a steam shroud until it reaches a solids content suitable for transferring to a dewatering felt. The nascent web may be transferred with suction assistance to the felt. In a crescent former, use of suction assist is generally unnecessary, as the nascent web is formed between the forming fabric and the felt.
A preferred mode of making the inventive products involves compactively dewatering a papermaking furnish having an apparently random distribution of fiber orientation and belt creping the web so as to redistribute the furnish in order to achieve the desired properties. Salient features of a typical apparatus for producing the inventive products are shown in
In operation, felt 152 conveys a nascent web 154 around a suction roll 156 into a press nip 158. In press nip 158, the web is compactively dewatered and transferred to a backing roll 162 (sometimes referred to as a transfer roll hereafter) where the web is conveyed to the creping belt. In a creping nip 174, web 154 is transferred into belt 50 (top side) as discussed in more detail hereafter. The creping nip is defined between backing roll 162 and creping belt 50, which is pressed against backing roll 162 by creping roll 172, which may be a soft covered roll as is also discussed hereafter. After the web is transferred onto belt 50, a suction box 176 may optionally be used to apply suction to the sheet in order to at least partially draw out minute folds, as will be seen in the vacuum-drawn products described hereafter. That is, in order to provide additional bulk, a wet web is creped onto a perforated belt and expanded within the perforated belt by suction, for example.
A papermachine suitable for making the product of the invention may have various configurations as is seen in
There is shown in
Referring to
Press section 150 includes a papermaking felt 152 supported on rollers 344, 346, 348, 350 and shoe press roll 352. Shoe press roll 352 includes a shoe 354 for pressing the web against transfer drum or backing roll 162. Transfer drum or backing roll 162 may be heated if so desired. In one preferred embodiment, the temperature is controlled so as to maintain a moisture profile in the web so a sided sheet is prepared, having a local variation in sheet moisture which does not extend to the surface of the web in contact with backing roll 162. Typically, steam is used to heat backing roll 162, as is noted in U.S. Pat. No. 6,379,496 to Edwards et al. Backing roll 162 includes a transfer surface 358, upon which the web is deposited during manufacture. Crepe roll 172 supports, in part, a creping belt 50, which is also supported on a plurality of rolls 362, 364 and 366.
Dryer section 328 also includes a plurality of can dryers 368, 370, 372, 374, 376, 378, and 380, as shown in the diagram, wherein cans 376, 378, and 380 are in a first tier, and cans 368, 370, 372, and 374 are in a second tier. Cans 376, 378, and 380 directly contact the web, whereas cans in the other tier contact the belt. In this two tier arrangement where the web is separated from cans 370 and 372 by the belt, it is sometimes advantageous to provide impingement air dryers at cans 370 and 372, which may be drilled cans, such that air flow is indicated schematically at 371 and 373.
There is further provided a reel section 382, which includes a guide roll 384 and a take up reel 386, shown schematically in the diagram.
Paper machine 320 is operated such that the web travels in the machine direction indicated by arrows 388, 392, 394, 396, and 398, as is seen in
Belt 50 travels in the direction indicated by arrow 396 and picks up web 154 in the creping nip indicated at 174 on the top, or more open side of the belt. Belt 50 is traveling at a second speed slower than the first speed of the transfer surface 358 of backing roll 162. Thus, the web is provided with a Belt Crepe, typically, in an amount of from about 10 to about 100% in the machine direction.
The creping belt defines a creping nip over the distance in which creping belt 50 is adapted to contact surface 358 of backing roll 162, that is, applies significant pressure to the web against the transfer cylinder. To this end, creping roll 172 may be provided with a soft deformable surface, which will increase the width of the creping nip and increase the belt creping angle between the belt and the sheet at the point of contact, or a shoe press roll or similar device could be used as backing roll 162 or 172, to increase effective contact with the web in high impact belt creping nip 174 where web 154 is transferred to belt 50 and advanced in the machine-direction. By using known configurations of existing equipment, it is possible to adjust the belt creping angle or the takeaway angle from the creping nip. A cover on creping roll 172 having a Pusey and Jones hardness of from about 25 to about 90 may be used. Thus, it is possible to influence the nature and amount of redistribution of fiber, delamination/debonding which may occur at belt creping nip 174 by adjusting these nip parameters. In some embodiments, it may by desirable to restructure the z-direction interfiber characteristics, while in other cases, it may be desired to influence properties only in the plane of the web. The creping nip parameters can influence the distribution of fiber in the web in a variety of directions, including inducing changes in the z-direction, as well as the MD and CD. In any case, the transfer from the transfer cylinder to the creping belt is high impact in that the belt is traveling slower than the web, and a significant velocity change occurs. Typically, the web is creped anywhere from 5 to 60% and even higher during transfer from the transfer cylinder to the belt. One of the advantages of the invention is that high degrees of crepe can be employed, approaching or even exceeding 100%.
Creping nip 174 generally extends over a belt creping nip distance or width of anywhere from about ⅛″ to about 2″ (3.18 mm to 50.8 mm), typically, ½″ to 2″ (12.7 mm to 50.8 mm).
The nip pressure in nip 174, that is, the loading between creping roll 172 and transfer drum 162 is suitably 20 to 100 (3.5 to 17.5 kN/meter), preferably, 40 to 70 pounds per linear inch (PLI) (7 to 12.25 kN/meter). A minimum pressure in the nip of 10 PLI (1.75 kN/meter) or 20 PLI (3.5 kN/meter) is necessary; however, one of skill in the art will appreciate in a commercial machine, the maximum pressure may be as high as possible, limited only by the particular machinery employed. Thus, pressures in excess of 100 PLI (17.5 kN/meter), 500 PLI (87.5 kN/meter), 1000 PLI (175 kN/meter) or more may be used, if practical, and provided a velocity delta can be maintained.
Following the belt crepe, web 154 is retained on belt 50 and fed to dryer section 328. In dryer section 328, the web is dried to a consistency of from about 92 to 98% before being wound up on reel 386. Note that there is provided in the drying section a plurality of heated drying rolls 376, 378, and 380, which are in direct contact with the web on belt 50. The drying cans or rolls 376, 378, and 380 are steam heated to an elevated temperature operative to dry the web. Rolls 368, 370, 372, and 374 are likewise heated, although these rolls contact the belt directly and not the web directly. Optionally provided is a suction box 176, which can be used to expand the web within the belt perforations to increase caliper, as noted above.
In some embodiments of the invention, it is desirable to eliminate open draws in the process, such as the open draw between the creping and drying belt and reel 386. This is readily accomplished by extending the creping belt to the reel drum and transferring the web directly from the belt to the reel, as is disclosed generally in U.S. Pat. No. 5,593,545 to Rugowski et al.
The products and processes of the present invention are thus likewise suitable for use in connection with touchless automated towel dispensers of the class described in co-pending U.S. patent application Ser. No. 11/678,770, entitled “Method of Controlling Adhesive Build-Up on a Yankee Dryer”, filed Feb. 26, 2007, Publication No. 2007/0204966, now U.S. Pat. No. 7,850,823, and U.S. patent application Ser. No. 11/451,111, entitled “Method of Making Fabric-Creped Sheet for Dispensers”, filed Jun. 12, 2006, Publication No. 2006/0289134, now U.S. Pat. No. 7,585,389, the disclosures of which are incorporated herein by reference. In this connection, the base sheet is suitably produced on a paper machine of the class shown in
The nascent web is advanced to a papermaking felt 152, which is supported by a plurality of rolls 450, 452, 454, 455, and the felt is in contact with a shoe press roll 456. The web is of a low consistency as it is transferred to the felt. Transfer may be assisted by suction, for example, roll 450 may be a suction roll if so desired, or a pickup or suction shoe as is known in the art. As the web reaches the shoe press roll, it may have a consistency of 10-25%, preferably, 20 to 25% or so as it enters nip 458 between shoe press roll 456 and transfer drum 162. Transfer drum 162 may be a heated roll if so desired. It has been found that increasing steam pressure to transfer drum 162 helps lengthen the time between required stripping of excess adhesive from the cylinder of Yankee dryer 420. Suitable steam pressure may be about 95 psig or so, bearing in mind that backing roll 162 is a crowned roll and creping roll 172 has a negative crown to match such that the contact area between the rolls is influenced by the pressure in backing roll 162. Thus, care must be exercised to maintain matching contact between rolls 162, 172 when elevated pressure is employed.
Instead of a shoe press roll, roll 456 could be a conventional suction pressure roll. If a shoe press is employed, it is desirable and preferred that roll 454 is a suction roll effective to remove water from the felt prior to the felt entering the shoe press nip, since water from the furnish will be pressed into the felt in the shoe press nip. In any case, using a suction roll at 454 is typically desirable to ensure the web remains in contact with the felt during the direction change as one of skill in the art will appreciate from the diagram.
Web 444 is wet-pressed on the felt in nip 458 with the assistance of press shoe 160. The web is thus compactively dewatered at nip 458, typically, by increasing the consistency by fifteen or more points at this stage of the process. The configuration shown at nip 458 is generally termed a shoe press. In connection with the present invention, backing roll 162 is operative as a transfer cylinder, which operates to convey web 444 at high speed, typically, 1000 fpm to 6000 fpm (5.08 m/s to 30.5 m/s), to the creping belt. Nip 458 may be configured as a wide or extended nip shoe press as is detailed, for example, in U.S. Pat. No. 6,036,820 to Schiel et al., the disclosure of which is incorporated herein by reference.
Backing roll 162 has a smooth surface 464, which may be provided with adhesive (the same as the creping adhesive used on the Yankee cylinder) and/or release agents if needed. Web 444 is adhered to transfer surface 464 of backing roll 162, which is rotating at a high angular velocity as the web continues to advance in the machine-direction indicated by arrows 466. On the cylinder, web 444 has a generally random apparent distribution of fiber orientation.
Direction 466 is referred to as the machine-direction (MD) of the web as well as that of papermachine 410; whereas the cross-machine-direction (CD) is the direction in the plane of the web perpendicular to the MD.
Web 444 enters nip 458, typically, at consistencies of 10-25% or so, and is dewatered and dried to consistencies of from about 25 to about 70 by the time it is transferred to the top side of the creping belt 50, as shown in the diagram.
Belt 50 is supported on a plurality of rolls 468, 472 and a press nip roll 474 and forms a belt crepe nip 174 with transfer drum 162 as shown.
The creping belt defines a creping nip over the distance in which creping belt 50 is adapted to contact backing roll 162; that is, applies significant pressure to the web against the transfer cylinder. To this end, creping roll 172 may be provided with a soft deformable surface that will increase the width of the creping nip and increase the belt creping angle between the belt and the sheet at the point of contact, or a shoe press roll could be used as roll 172 to increase effective contact with the web in high impact belt creping nip 174 where web 444 is transferred to belt 50 and advanced in the machine-direction.
The nip pressure in nip 174, that is, the loading between creping roll 172 and backing roll 162 is suitably 20 to 200 (3.5 to 35 kN/meter), preferably, 40 to 70 pounds per linear inch (PLI) (7 to 12.25 kN/meter). A minimum pressure in the nip of 10 PLI (1.75 kN/m) or 20 PLI (3.5 kN/m) is necessary; however, one of skill in the art will appreciate that, in a commercial machine, the maximum pressure may be as high as possible, limited only by the particular machinery employed. Thus, pressures in excess of 100 PLI (17.5 kN/m), 500 PLI (87.5 kN/m), 1000 PLI (175 kN/m) or more may be used, if practical, and provided sufficient velocity delta can be maintained between the transfer roll and creping belt.
After belt creping, the web continues to advance along MD 466 where it is wet-pressed onto Yankee cylinder 480 in transfer nip 482. Optionally, suction is applied to the web by way of a suction box 176, to draw out minute folds as well as to expand the dome structure discussed hereafter.
Transfer at nip 482 occurs at a web consistency of generally from about 25 to about 70%. At these consistencies, it is difficult to adhere the web to surface 484 of Yankee cylinder 480 firmly enough to remove the web from the belt thoroughly. This aspect of the process is important, particularly, when it is desired to use a high velocity drying hood.
The use of particular adhesives cooperate with a moderately moist web (25-70% consistency) to adhere it to the Yankee sufficiently to allow for high velocity operation of the system and high jet velocity impingement air drying, and subsequent peeling of the web from the Yankee. In this connection, a poly(vinyl alcohol)/polyamide adhesive composition as noted above is applied at any convenient location between cleaning doctor D and nip 482, such as at location 486 as needed, preferably, at a rate of less than about 40 mg/m2 of sheet.
The web is dried on Yankee cylinder 480, which is a heated cylinder and by high jet velocity impingement air in Yankee hood 488. Hood 488 is capable of variable temperature. During operation, web temperature may be monitored at wet-end A of the Hood and dry end B of the hood using an infra-red detector or any other suitable means if so desired. As the cylinder rotates, web 444 is peeled from the cylinder at 489 and wound on a take-up reel 490. Reel 490 may be operated 5-30 fpm (preferably 10-20 fpm) (0.025-0.152 meters/second (preferably, 0.051-0.102 m/s)) faster than the Yankee cylinder at steady-state when the line speed is 2100 fpm (10.7 m/s), for example. Instead of peeling the sheet, a creping doctor C may be used to conventionally dry-crepe the sheet. In any event, a cleaning doctor D mounted for intermittent engagement is used to control build up. When adhesive build-up is being stripped from Yankee cylinder 480, the web is typically segregated from the product on reel 490, preferably, being fed to a broke chute at 495 for recycle to the production process.
In many cases, the belt creping techniques revealed in the following applications and patents will be especially suitable for making products: U.S. patent application Ser. No. 11/678,669, entitled “Method of Controlling Adhesive Build-Up on a Yankee Dryer”, filed Feb. 26, 2007, Publication No. 2007/0204966, now U.S. Pat. No. 7,850,823; U.S. patent application Ser. No. 11/451,112, entitled “Fabric-Creped Sheet for Dispensers”, filed Jun. 12, 2006, Publication No. 2006/0289133, now U.S. Pat. No. 7,585,388; U.S. patent application Ser. No. 11/451,111, entitled “Method of Making Fabric-creped Sheet for Dispensers”, filed Jun. 12, 2006, Publication No. 2006/0289134, now U.S. Pat. No. 7,585,389; U.S. patent application Ser. No. 11/402,609, entitled “Multi-Ply Paper Towel With Absorbent Core”, filed Apr. 12, 2006, Publication No. 2006/0237154, now U.S. Pat. No. 7,662,257; U.S. patent application Ser. No. 11/151,761, entitled “High Solids Fabric-crepe Process for Producing Absorbent Sheet with In-Fabric Drying”, filed Jun. 14, 2005, Publication No. 2005/0279471, now U.S. Pat. No. 7,503,998; U.S. patent application Ser. No. 11/108,458, entitled “Fabric-Crepe and In Fabric Drying Process for Producing Absorbent Sheet”, filed Apr. 18, 2005, Publication No. 2005/0241787, now U.S. Pat. No. 7,442,278; U.S. patent application Ser. No. 11/108,375, entitled “Fabric-Crepe/Draw Process for Producing Absorbent Sheet”, filed Apr. 18, 2005, Publication No. 2005/0217814, now U.S. Pat. No. 7,789,995; U.S. patent application Ser. No. 11/104,014, entitled “Wet-Pressed Tissue and Towel Products With Elevated CD Stretch and Low Tensile Ratios Made With a High Solids Fabric-Crepe Process”, filed Apr. 12, 2005, Publication No. 2005/0241786, now U.S. Pat. No. 7,588,660; U.S. patent application Ser. No. 10/679,862, entitled “Fabric-Crepe Process for Making Absorbent Sheet”, filed Oct. 6, 2003, Publication No. 2004/0238135, now U.S. Pat. No. 7,399,378; U.S. patent application Ser. No. 12/033,207, entitled “Fabric Crepe Process With Prolonged Production Cycle”, filed Feb. 19, 2008, Publication No. 2008/0264589, now U.S. Pat. No. 7,608,164; and U.S. patent application Ser. No. 11/804,246, entitled “Fabric-creped Absorbent Sheet with Variable Local Basis Weight”, filed May 16, 2007, now U.S. Pat. No. 7,494,563. The applications and patents referred to immediately above are particularly relevant to the selection of machinery, materials, processing conditions, and so forth, as to fabric creped products of the present invention and the disclosures of these applications patents are incorporated herein by reference. Additional useful information is contained in U.S. Pat. No. 7,399,378, the disclosure of which is also incorporated herein by reference.
The products of the invention are produced with or without application of a vacuum to draw out minute folds to restructure the web and with or without calendering; however, in many cases, it is desirable to use both to promote a more absorbent and uniform product.
The processes of the present invention are especially suitable in cases where it is desired to reduce the carbon footprint of existing operations, while improving tissue quality, as the sheet will typically contact the Yankee at about 50% solids, so the water-removal requirements can be about ⅓ those of the process discussed in U.S. Patent Application Publication No. 2009/0321027 A1, now U.S. Pat. No. 7,871,493, “Environmentally-Friendly Tissue.” Even though the total amount of vacuum may contribute more to the footprint than the so-called air press, the process has the potential to create carbon emissions that are far less than those mentioned above in the Environmentally-Friendly Tissue patent, suitably, in excess of ⅓ less, to even 50% less for equivalent quantities of generally equivalent tissue.
Utilizing an apparatus of the class shown in
In Examples 1-4, belt 50, as shown in
In Examples 5 to 8, a belt similar to belt 100, but with fewer perforations was used and a 20% eucalyptus, 80% northern softwood blended towel furnish was employed.
In Examples 9 and 10, a belt similar to belt 100, but with fewer perforations, was used and an 80% eucalyptus, 20% northern softwood layered tissue furnish was employed.
In Examples 11 and 12, belt 100 was used and a 60% eucalyptus, 40% northern softwood layered tissue furnish was employed.
Hercules D-1145 is an 18% solids creping adhesive that is a high molecular weight polyaminamide-epichlorohydrin having very low thermosetting capability.
Rezosol 6601 is an 11% solids solution of a creping modifier in water; where the creping modifier is a mixture of an 1-(2-alkylenylamidoethyl)-2-alkylenyl-3-ethylimidazolinium ethyl sulfate and a polyethylene glycol.
Varisoft GP-B100 is a 100% actives ion-pair softener based on an imidazolinium quat and an anionic silicone as described in U.S. Pat. No. 6,245,197 B1.
There is shown in
The surround areas 518, 520, and 522 also include relatively elongated minute folds at 530, 532, 534 that also extend in the cross machine direction and provide a pileated or crested structure to the sheet as will be seen from the cross sections discussed below. Note that these minute folds do not extend across the entire width of the web.
The microstructure of basesheet 500 is further appreciated by reference to
There is shown in
The surround areas 618, 620, and 622 still include relatively elongated minute folds that extend in the cross-machine direction (CD) and provide a pileated or crested structure to the sheet as will be seen from the cross sections discussed below.
The microstructure of basesheet 600 is further appreciated by reference to
Note that the minute folds in the previously slubbed regions, now domed, are no longer apparent in the cross-sectional photomicrograph, as compared with the
There is shown in
The surround or network areas 718, 720 and 722 also include relatively elongated minute folds that also extend in the machine direction and provide a pileated or crested structure to the sheet, as will be seen from the cross sections discussed below.
The microstructure of basesheet 700 is further appreciated by reference to
Note that, here again, the minute folds in the slubbed regions are no longer apparent, as compared with the
Friction measurements were taken generally as described generally in U.S. Pat. No. 6,827,819 to Dwiggins et al., using a Lab Master Slip & Friction tester, with special high-sensitivity load measuring option and custom top and sample support block, Model 32-90 available from:
The Friction Tester was equipped with a KES-SE Friction Sensor, available from:
The travel speed of the sled used was 10 mm/minute, and the force required is reported as the Surface Texture Mean Force herein. Prior to testing, the test samples were conditioned in an atmosphere of 23.0°±1° C. (73.4°±1.8° F.) and 50%±2% R.H.
Utilizing a friction tester as described above, Surface Texture Mean Force values and deviation values were generated for the
Mean force,
where x1-xn are the individual sampled data points. The mean deviation of this force data about the mean value was calculated as follows:
Mean deviation,
Results for 5 to 7 scans appear in Table 3 for the Yankee side of the sheet and selected Surface Texture Mean Force values are presented graphically in
It is seen from the data that the calendered products of the invention consistently exhibited lower Surface Texture Mean Force values than the sheet made with the woven fabric, which is consistent with the laser profilometry analyses.
Converted Product
Finished product data for two-ply towel appears in Table 5 and finished product data for two-ply tissue appears in Table 6, along with comparable data on commercial premium products which, are believed to be through-air dried products.
In the towel products, it is seen that the sheet of the invention exhibits comparable properties overall, yet exhibits surprising caliper as compared with the premium commercial product, with more than 10% additional bulk.
Finished tissue product likewise exhibits surprising bulk. There is shown in Table 6 data on two-ply embossed products, two-ply product, with one-ply embossed and two-ply product, where the product is conventionally embossed. The two-ply product with one-ply embossed was prepared in accordance with U.S. Pat. No. 6,827,819 to Dwiggins et al., the disclosure of which is incorporated by reference. The two-ply tissue in Table 6 was prepared from the basesheet of Examples 11 and 12 above.
It is seen from the tissue product data, that the absorbent products of this invention exhibit surprising caliper/basis weight ratios. Premium throughdried tissue products generally exhibit a caliper/basis weight ratio of no more than about 5 (mils/8 sheet)/(lb/ream), while the products of this invention exhibit caliper/basis weight ratios of 6 (mils/8 sheet)/(lb/ream) or 2.48 (mm/8 sheet)/(gsm) and more.
There is shown in Table 7 additional data on both tissue of the invention (prepared from basesheet of Examples 9, 10) and commercial tissue. Here, again, the unexpectedly high bulk is readily apparent. Moreover, it is also seen that the tissue of the invention exhibits surprisingly low roll compression values, especially in view of the high bulk.
β-Radiograph Imaging Analysis
Absorbent sheet of the invention and various commercial products were analyzed using β-radiographic imaging in order to detect basis weight variation. The techniques employed are set forth in Keller et al., β-Radiographic Imaging of Paper Formation Using Storage Phosphor Screens, Journal of Pulp and Paper Science, Vol. 27, No. 4, pages 115-123, April 2001, the disclosure of which is incorporated by reference.
It is seen in
It is seen in
In
Fourier Analysis of β-Radiograph Images
It is appreciated from the foregoing description and the β-radiograph images of the samples, as well as the photomicrographs discussed above, that the variable basis weight of the products of this invention exhibit a two-dimensional pattern in many cases. This aspect of the invention was confirmed using two-dimensional Fast Fourier Transform analysis of a β-radiograph image of a sheet prepared in accordance with the invention.
By subtracting the image content shown in
Towel samples prepared using the techniques described herein were analyzed and compared to prior art and competitive samples using transmission radiography and thickness measurement with a non-contacting Twin Laser Profilometer. Apparent densities were calculated by fusing the maps acquired by these two methods.
In order to quantify the results demonstrated by the photomicrographs and profiles presented supra, a set of more detailed examinations was conducted on several of the previously examined sheets, as set forth along with a prior art fabric creped sheet and a competitive TAD towel as described in Table 8.
More specifically, to quantitatively demonstrate the microstructure of sheets prepared according to the present invention in comparison to the prior art fabric creped sheets, as well as to the commercially available TAD toweling, formation and thickness measurements were conducted on each on a detailed scale, so that density could be calculated for each location in the sheet on a scale commensurate with the scale of the structure being imposed on the sheets by the belt-creping process. These techniques are based on technology described in: (1) Sung Y-J, Ham C H, Kwon O, Lee H L, Keller D S, 2005, Applications of Thickness and Apparent Density Mapping by Laser Profilometry, Trans. 13th Fund. Res. Symp. Cambridge, Frecheville Court (UK), pp 961-1007; (2) Keller D S, Pawlak J J, 2001, β-Radiographic imaging of paper formation using storage phosphor screens J Pulp Pap Sci 27:117 to 123; and (3) Cresson T M, Tomimasu H, Luner P 1990 Characterization Of Paper Formation Part 1: Sensing Paper Formation. Tappi J 73:153 to 159.
Localized thickness measurements were conducted using a twin laser profilometer while formation measurements were conducted using transmission radiography with film, by contacting the top and the bottom surfaces. This provided higher spatial resolution as a function of the distance from the film. Using both the top and bottom formation maps, apparent densities were determined and compared. Fine structure of the caps and bases was observed, and differences between samples were noted. An MD asymmetry of the apparent density across the cap structures and in the base structure could be observed in some samples.
By comparing the apparent density maps generated by the top and bottom radiographs, however, one can see that there are at most subtle, if detectable, differences between the two. Although the top and bottom radiographs show visible differences, once the images have been fused to the thickness maps, density differences are not readily evident between those density maps prepared using the top or bottom radiographs and those prepared using the composite.
The white/blue representation of
In the density maps of
In
Samples of toweling intended for a center-pull application were prepared from furnishes as described in Table 10, which also includes data for TAD towel currently used for that application, as well as the properties thereof along with comparable data for a control towel currently sold for that application produced by fabric creping technology, and an EPA “compliant” towel for the same applications having sufficient post consumer fiber content to meet or to exceed EPA Comprehensive Procurement Guidelines. The TAD towel is a product produced by a TAD technology that is also sold for that application. Of these, the toweling identified as 22624 is considered to be exceptionally suitable for the center-pull application as it exhibits exceptional hand panel softness (as measured by a trained sensory panel) combined with very rapid WAR, and high CD wet tensile.
A set of samples of sheets of the invention intended for bath and/or facial tissue applications (see Table 12A) was also prepared, then analyzed as for Examples 13-18. The results of these analyses are as set forth in
While the invention has been described in connection with a number of examples, modifications to those examples 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 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.
This application is a continuation application of U.S. patent application Ser. No. 13/933,254, filed Jul. 2, 2013, and published as U.S. Patent Application Publication No. 2013/0327489, which is a continuation of U.S. patent application Ser. No. 13/488,597, filed Jun. 5, 2012, now U.S. Pat. No. 8,652,300, which is a divisional application of U.S. patent application Ser. No. 12/694,650, filed Jan. 27, 2010, now U.S. Pat. No. 8,293,072, which was published as U.S. Patent Application Publication No. 2010/0186913 A1 on Jul. 29, 2010, and claims priority of U.S. Provisional Application No. 61/206,146 filed Jan. 28, 2009. This application also relates to the following U.S. patent applications and U.S. patents: U.S. patent application Ser. No. 11/804,246, entitled “Fabric Creped Absorbent Sheet with Variable Local Basis Weight”, filed May 16, 2007, Publication No. 2008/0029235, now U.S. Pat. No. 7,494,563, which was based upon U.S. Provisional Patent Application No. 60/808,863, filed May 26, 2006; U.S. patent application Ser. No. 10/679,862, entitled “Fabric Crepe Process for Making Absorbent Sheet”, filed Oct. 6, 2003, Publication No. 2004/0238135, now U.S. Pat. No. 7,399,378; U.S. patent application Ser. No. 11/108,375, entitled “Fabric Crepe/Draw Process for Producing Absorbent Sheet”, filed Apr. 18, 2005, Publication No. 2005/0217814, now U.S. Pat. No. 7,789,995, which application is a continuation-in-part of U.S. patent application Ser. No. 10/679,862, entitled “Fabric Crepe Process for Making Absorbent Sheet”, filed Oct. 6, 2003, Publication No. 2004/0238135, now U.S. Pat. No. 7,399,378; U.S. patent application Ser. No. 11/108,458, entitled “Fabric Crepe and In Fabric Drying Process for Producing Absorbent Sheet”, filed Apr. 18, 2005, Publication No. 2005/0241787, now U.S. Pat. No. 7,442,278, which application was based upon U.S. Provisional Patent Application No. 60/563,519, filed Apr. 19, 2004; U.S. patent application Ser. No. 11/151,761, entitled “High Solids Fabric Crepe Process for Producing Absorbent Sheet With In-Fabric Drying”, filed Jun. 14, 2005, Publication No. 2005/0279471, now U.S. Pat. No. 7,503,998, which was based upon U.S. Provisional Patent Application No. 60/580,847, filed Jun. 18, 2004; U.S. patent application Ser. No. 11/402,609, entitled “Multi-Ply Paper Towel With Absorbent Core”, filed Apr. 12, 2006, Publication No. 2006/0237154, now U.S. Pat. No. 7,662,257, which application was based upon U.S. Provisional Patent Application No. 60/673,492, filed Apr. 21, 2005; U.S. patent application Ser. No. 11/104,014, entitled “Wet-Pressed Tissue and Towel Products With Elevated CD Stretch and Low Tensile Ratios Made With a High Solids Fabric Crepe Process”, filed Apr. 12, 2005, Publication No. 2005/0241786, now U.S. Pat. No. 7,588,660, which application was based upon U.S. Provisional Patent Application No. 60/562,025, filed Apr. 14, 2004; and U.S. patent application Ser. No. 11/451,111, entitled “Method of Making Fabric-Creped Sheet for Dispensers”, filed Jun. 12, 2006, Publication No. 2006/0289134, now U.S. Pat. No. 7,585,389, which application was based upon U.S. Provisional Patent Application No. 60/693,699, filed Jun. 24, 2005; U.S. patent application Ser. No. 11/678,669, entitled “Method of Controlling Adhesive Build-Up on a Yankee Dryer”, filed Feb. 26, 2007, Publication No. 2007/0204966, now U.S. Pat. No. 7,850,823; U.S. patent application Ser. No. 11/901,599, entitled “Process for Producing Absorbent Sheet”, filed Sep. 18, 2007, Publication No. 2008/0047675, now U.S. Pat. No. 7,651,589, which application is a divisional of the application that matured into U.S. Pat. No. 7,442,278, discussed above; U.S. patent application Ser. No. 11/901,673, entitled “Absorbent Sheet”, filed Sep. 18, 2007, Publication No. 2008/0008860, now U.S. Pat. No. 7,662,255, which application is a divisional of the application that matured into U.S. Pat. No. 7,442,278, discussed above; U.S. patent application Ser. No. 12/156,820, entitled “Fabric Crepe Process for Making Absorbent Sheet”, filed Jun. 5, 2008, Publication No. 2008/0236772, now U.S. Pat. No. 7,588,661, which application is a divisional of the application that matured into U.S. Pat. No. 7,399,378, discussed above; U.S. patent application Ser. No. 12/156,834, entitled “Fabric Crepe Process for Making Absorbent Sheet”, filed Jun. 5, 2008, Publication No. 2008/0245492, now U.S. Pat. No. 7,704,349, which application is a divisional of the application that matured into U.S. Pat. No. 7,399,378, discussed above; and U.S. patent application Ser. No. 12/286,435, entitled “Process for Producing Absorbent Sheet”, filed Sep. 30, 2008, Publication No. 2009/0038768, now U.S. Pat. No. 7,670,457, which application is a divisional of the application that matured into U.S. Pat. No. 7,442,278, discussed above. The disclosures of the foregoing patents and patent applications are incorporated herein by reference in their entireties.
| Number | Name | Date | Kind |
|---|---|---|---|
| 2926116 | Keim | Feb 1960 | A |
| 3058873 | Keim et al. | Oct 1962 | A |
| 3432936 | Cole et al. | Mar 1969 | A |
| 3545705 | Hodgson | Dec 1970 | A |
| 3549742 | Benz | Dec 1970 | A |
| 3556932 | Coscia et al. | Jan 1971 | A |
| 3556933 | Williams et al. | Jan 1971 | A |
| 3692622 | Dunning | Sep 1972 | A |
| 3700623 | Keim | Oct 1972 | A |
| 3772076 | Keim | Nov 1973 | A |
| 3858623 | Lefkowitz | Jan 1975 | A |
| 3926716 | Bates | Dec 1975 | A |
| 3974025 | Ayers | Aug 1976 | A |
| 3994771 | Morgan, Jr. et al. | Nov 1976 | A |
| 4041989 | Johansson et al. | Aug 1977 | A |
| 4064213 | Lazorisak et al. | Dec 1977 | A |
| 4071050 | Codorniu | Jan 1978 | A |
| 4102737 | Morton | Jul 1978 | A |
| 4112982 | Bugge et al. | Sep 1978 | A |
| 4149571 | Burroughs | Apr 1979 | A |
| 4157276 | Wandel et al. | Jun 1979 | A |
| 4161195 | Khan | Jul 1979 | A |
| 4182381 | Gisbourne | Jan 1980 | A |
| 4184519 | McDonald et al. | Jan 1980 | A |
| 4225382 | Kearney et al. | Sep 1980 | A |
| 4239065 | Trokhan | Dec 1980 | A |
| 4314589 | Buchanan et al. | Feb 1982 | A |
| 4359069 | Hahn | Nov 1982 | A |
| 4376455 | Hahn | Mar 1983 | A |
| 4379735 | MacBean | Apr 1983 | A |
| 4420372 | Hostetler | Dec 1983 | A |
| 4440597 | Wells et al. | Apr 1984 | A |
| 4448638 | Klowak | May 1984 | A |
| 4453573 | Thompson | Jun 1984 | A |
| 4468254 | Yokoyama et al. | Aug 1984 | A |
| 4482429 | Klowak | Nov 1984 | A |
| 4490925 | Smith | Jan 1985 | A |
| 4528239 | Trokhan | Jul 1985 | A |
| 4528316 | Soerens | Jul 1985 | A |
| 4529480 | Trokhan | Jul 1985 | A |
| 4533437 | Curran et al. | Aug 1985 | A |
| 4543156 | Cheshire et al. | Sep 1985 | A |
| 4546052 | Nicoll | Oct 1985 | A |
| 4551199 | Weldon | Nov 1985 | A |
| 4552709 | Koger, II et al. | Nov 1985 | A |
| 4556450 | Chuang et al. | Dec 1985 | A |
| 4592395 | Borel | Jun 1986 | A |
| 4603176 | Bjorkquist et al. | Jul 1986 | A |
| 4605585 | Johansson | Aug 1986 | A |
| 4605702 | Guerro et al. | Aug 1986 | A |
| 4611639 | Bugge | Sep 1986 | A |
| 4614679 | Farrington, Jr. et al. | Sep 1986 | A |
| 4637859 | Trokhan | Jan 1987 | A |
| 4640741 | Tsuneo | Feb 1987 | A |
| 4675394 | Solarek et al. | Jun 1987 | A |
| 4689119 | Weldon | Aug 1987 | A |
| 4709732 | Kinnunen | Dec 1987 | A |
| 4720383 | Drach et al. | Jan 1988 | A |
| 4759391 | Waldvogel et al. | Jul 1988 | A |
| 4759976 | Dutt | Jul 1988 | A |
| 4795530 | Soerens et al. | Jan 1989 | A |
| 4803032 | Schulz | Feb 1989 | A |
| 4804769 | Solarek et al. | Feb 1989 | A |
| 4834838 | Klowak | May 1989 | A |
| 4849054 | Klowak | Jul 1989 | A |
| 4866151 | Tsai et al. | Sep 1989 | A |
| 4942077 | Wendt et al. | Jul 1990 | A |
| 4967085 | Bryan et al. | Oct 1990 | A |
| 4973512 | Stanley et al. | Nov 1990 | A |
| 4981557 | Bjorkquist | Jan 1991 | A |
| 4983748 | Tsai et al. | Jan 1991 | A |
| 4998568 | Vöhringer | Mar 1991 | A |
| 5008344 | Bjorkquist | Apr 1991 | A |
| 5016678 | Borel et al. | May 1991 | A |
| 5023132 | Stanley et al. | Jun 1991 | A |
| 5048589 | Cook et al. | Sep 1991 | A |
| 5054525 | Vöhringer | Oct 1991 | A |
| 5066532 | Gaisser | Nov 1991 | A |
| 5073235 | Trokhan | Dec 1991 | A |
| 5085736 | Bjorkquist | Feb 1992 | A |
| 5087324 | Awofeso et al. | Feb 1992 | A |
| 5098519 | Ramasubramanian et al. | Mar 1992 | A |
| 5098522 | Smurkoski et al. | Mar 1992 | A |
| 5103874 | Lee | Apr 1992 | A |
| 5114777 | Gaisser | May 1992 | A |
| 5129988 | Farrington, Jr. | Jul 1992 | A |
| 5137600 | Barnes et al. | Aug 1992 | A |
| 5138002 | Bjorkquist | Aug 1992 | A |
| 5167261 | Lee | Dec 1992 | A |
| 5182164 | Eklund et al. | Jan 1993 | A |
| 5199261 | Baker | Apr 1993 | A |
| 5199467 | Lee | Apr 1993 | A |
| 5211815 | Ramasubramanian et al. | May 1993 | A |
| 5215617 | Grupe | Jun 1993 | A |
| 5217756 | Shinzawa | Jun 1993 | A |
| 5219004 | Chiu | Jun 1993 | A |
| 5223096 | Phan et al. | Jun 1993 | A |
| 5225269 | Bohlin | Jul 1993 | A |
| 5240562 | Phan et al. | Aug 1993 | A |
| 5245025 | Trokhan et al. | Sep 1993 | A |
| 5262007 | Phan et al. | Nov 1993 | A |
| 5264082 | Phan et al. | Nov 1993 | A |
| 5277761 | Van Phan et al. | Jan 1994 | A |
| 5312522 | Van Phan et al. | May 1994 | A |
| 5314584 | Grinnell et al. | May 1994 | A |
| 5314585 | Ward | May 1994 | A |
| 5328565 | Rasch et al. | Jul 1994 | A |
| 5336373 | Scattolino et al. | Aug 1994 | A |
| 5338807 | Espy et al. | Aug 1994 | A |
| 5348620 | Hermans et al. | Sep 1994 | A |
| 5366785 | Sawdai | Nov 1994 | A |
| 5368696 | Cunnane, III et al. | Nov 1994 | A |
| 5372876 | Johnson et al. | Dec 1994 | A |
| 5379808 | Chiu | Jan 1995 | A |
| 5411636 | Hermans et al. | May 1995 | A |
| 5415737 | Phan et al. | May 1995 | A |
| 5431840 | Soldanski et al. | Jul 1995 | A |
| 5449026 | Lee | Sep 1995 | A |
| 5451353 | Rezai et al. | Sep 1995 | A |
| 5492598 | Hermans et al. | Feb 1996 | A |
| 5494554 | Edwards et al. | Feb 1996 | A |
| 5501768 | Hermans et al. | Mar 1996 | A |
| 5503715 | Trokhan et al. | Apr 1996 | A |
| 5505818 | Hermans et al. | Apr 1996 | A |
| 5508818 | Hamma | Apr 1996 | A |
| 5510001 | Hermans et al. | Apr 1996 | A |
| 5510002 | Hermans et al. | Apr 1996 | A |
| 5549790 | Van Phan | Aug 1996 | A |
| 5556509 | Trokhan et al. | Sep 1996 | A |
| 5593545 | Rugowski et al. | Jan 1997 | A |
| 5601871 | Krzysik et al. | Feb 1997 | A |
| 5607551 | Farrington, Jr. et al. | Mar 1997 | A |
| 5609725 | Van Phan | Mar 1997 | A |
| 5614293 | Krzysik et al. | Mar 1997 | A |
| 5618612 | Gstrein | Apr 1997 | A |
| H001672 | Hermans et al. | Aug 1997 | H |
| 5656132 | Farrington, Jr. et al. | Aug 1997 | A |
| 5657797 | Townley et al. | Aug 1997 | A |
| 5667636 | Engel et al. | Sep 1997 | A |
| 5672248 | Wendt et al. | Sep 1997 | A |
| 5674590 | Anderson et al. | Oct 1997 | A |
| 5690149 | Lee | Nov 1997 | A |
| 5695607 | Oriaran et al. | Dec 1997 | A |
| 5725734 | Herman et al. | Mar 1998 | A |
| 5746887 | Wendt et al. | May 1998 | A |
| 5772845 | Farrington, Jr. et al. | Jun 1998 | A |
| 5814190 | Van Phan | Sep 1998 | A |
| 5830321 | Lindsay et al. | Nov 1998 | A |
| 5840403 | Trokhan et al. | Nov 1998 | A |
| 5840404 | Graff | Nov 1998 | A |
| 5851353 | Fiscus et al. | Dec 1998 | A |
| 5888347 | Engel et al. | Mar 1999 | A |
| 5932068 | Farrington, Jr. et al. | Aug 1999 | A |
| 5935381 | Trokhan et al. | Aug 1999 | A |
| 5935681 | Paulett | Aug 1999 | A |
| 5961782 | Luu et al. | Oct 1999 | A |
| 6017417 | Wendt et al. | Jan 2000 | A |
| 6027611 | McFarland et al. | Feb 2000 | A |
| 6033736 | Perlman et al. | Mar 2000 | A |
| 6036820 | Schiel et al. | Mar 2000 | A |
| 6036909 | Baum | Mar 2000 | A |
| 6080279 | Hada et al. | Jun 2000 | A |
| 6083346 | Hermans et al. | Jul 2000 | A |
| 6093284 | Hada et al. | Jul 2000 | A |
| 6096169 | Hermans et al. | Aug 2000 | A |
| 6117525 | Trokhan et al. | Sep 2000 | A |
| 6133405 | Allen | Oct 2000 | A |
| 6136146 | Phan et al. | Oct 2000 | A |
| 6139686 | Trokhan et al. | Oct 2000 | A |
| 6143135 | Hada et al. | Nov 2000 | A |
| 6146499 | Lin et al. | Nov 2000 | A |
| 6149769 | Mohammadi et al. | Nov 2000 | A |
| 6161303 | Beck | Dec 2000 | A |
| 6162327 | Batra et al. | Dec 2000 | A |
| 6171442 | Farrington, Jr. et al. | Jan 2001 | B1 |
| 6187137 | Druecke et al. | Feb 2001 | B1 |
| 6190506 | Beck | Feb 2001 | B1 |
| 6197154 | Chen et al. | Mar 2001 | B1 |
| 6207011 | Luu et al. | Mar 2001 | B1 |
| 6210528 | Wolkowicz | Apr 2001 | B1 |
| 6228220 | Hada et al. | May 2001 | B1 |
| 6245197 | Oriaran et al. | Jun 2001 | B1 |
| 6248203 | Beck | Jun 2001 | B1 |
| 6261679 | Chen et al. | Jul 2001 | B1 |
| 6274042 | Beck | Aug 2001 | B1 |
| 6280573 | Lindsay et al. | Aug 2001 | B1 |
| 6287426 | Edwards et al. | Sep 2001 | B1 |
| 6287427 | Beck | Sep 2001 | B1 |
| 6306257 | Hada et al. | Oct 2001 | B1 |
| 6306258 | Lange et al. | Oct 2001 | B1 |
| 6315864 | Anderson et al. | Nov 2001 | B2 |
| 6318727 | Hada | Nov 2001 | B1 |
| 6321963 | Gracyalny et al. | Nov 2001 | B1 |
| 6331230 | Hermans et al. | Dec 2001 | B1 |
| 6350349 | Hermans et al. | Feb 2002 | B1 |
| 6379496 | Edwards et al. | Apr 2002 | B2 |
| 6381868 | Grabscheid et al. | May 2002 | B1 |
| 6412678 | Gracyalny et al. | Jul 2002 | B2 |
| 6413368 | Dwiggins et al. | Jul 2002 | B1 |
| 6416631 | Beck | Jul 2002 | B1 |
| 6419793 | Beck | Jul 2002 | B1 |
| 6420013 | Vinson et al. | Jul 2002 | B1 |
| 6432267 | Watson | Aug 2002 | B1 |
| 6432270 | Liu et al. | Aug 2002 | B1 |
| 6436234 | Chen et al. | Aug 2002 | B1 |
| 6447640 | Watson et al. | Sep 2002 | B1 |
| 6447641 | Wolkowicz et al. | Sep 2002 | B1 |
| 6454904 | Hermans et al. | Sep 2002 | B1 |
| 6461474 | Lindsay et al. | Oct 2002 | B1 |
| 6464829 | Chen et al. | Oct 2002 | B1 |
| 6478927 | Chen et al. | Nov 2002 | B1 |
| 6497789 | Hermans et al. | Dec 2002 | B1 |
| 6500302 | Dwiggins et al. | Dec 2002 | B2 |
| 6534151 | Merker | Mar 2003 | B2 |
| 6540879 | Marinack et al. | Apr 2003 | B2 |
| 6547924 | Klerelid et al. | Apr 2003 | B2 |
| 6551461 | Hermans et al. | Apr 2003 | B2 |
| 6562198 | Beck et al. | May 2003 | B2 |
| 6565707 | Behnke et al. | May 2003 | B2 |
| 6579418 | Lindsay et al. | Jun 2003 | B2 |
| 6585855 | Drew et al. | Jul 2003 | B2 |
| 6589394 | Beck | Jul 2003 | B2 |
| 6592067 | Denen et al. | Jul 2003 | B2 |
| 6607638 | Drew et al. | Aug 2003 | B2 |
| 6610173 | Lindsay et al. | Aug 2003 | B1 |
| 6616812 | Beck | Sep 2003 | B2 |
| 6645420 | Beck | Nov 2003 | B1 |
| 6660362 | Lindsay et al. | Dec 2003 | B1 |
| 6669821 | Edwards et al. | Dec 2003 | B2 |
| 6673210 | Beck | Jan 2004 | B2 |
| 6692008 | Beck | Feb 2004 | B2 |
| 6698681 | Guy et al. | Mar 2004 | B1 |
| 6701637 | Lindsay et al. | Mar 2004 | B2 |
| 6702924 | Beck | Mar 2004 | B2 |
| 6709548 | Marinack et al. | Mar 2004 | B2 |
| 6746558 | Hoeft et al. | Jun 2004 | B2 |
| 6749723 | Lindén | Jun 2004 | B2 |
| 6752907 | Edwards et al. | Jun 2004 | B2 |
| 6766977 | Denen et al. | Jul 2004 | B2 |
| 6793170 | Denen et al. | Sep 2004 | B2 |
| 6797115 | Klerelid et al. | Sep 2004 | B2 |
| 6827819 | Dwiggins et al. | Dec 2004 | B2 |
| 6838887 | Denen et al. | Jan 2005 | B2 |
| 6871815 | Moody et al. | Mar 2005 | B2 |
| 6964117 | Parent | Nov 2005 | B2 |
| 6986932 | Zink et al. | Jan 2006 | B2 |
| 6998017 | Lindsay et al. | Feb 2006 | B2 |
| 6998022 | Hultcrantz | Feb 2006 | B2 |
| 7029620 | Gordon et al. | Apr 2006 | B2 |
| 7070678 | Allen et al. | Jul 2006 | B2 |
| 7122235 | Bourdelais et al. | Oct 2006 | B2 |
| 7160418 | Edwards et al. | Jan 2007 | B2 |
| 7300543 | Mullally et al. | Nov 2007 | B2 |
| 7320743 | Freidbauer et al. | Jan 2008 | B2 |
| 7384588 | Gordon et al. | Jun 2008 | B2 |
| 7387706 | Herman et al. | Jun 2008 | B2 |
| 7399378 | Edwards et al. | Jul 2008 | B2 |
| 7416637 | Murray et al. | Aug 2008 | B2 |
| 7435312 | Lindsay et al. | Oct 2008 | B2 |
| 7442278 | Murray et al. | Oct 2008 | B2 |
| 7468114 | Sato et al. | Dec 2008 | B2 |
| 7476293 | Herman et al. | Jan 2009 | B2 |
| 7494563 | Edwards et al. | Feb 2009 | B2 |
| 7503998 | Murray et al. | Mar 2009 | B2 |
| 7563344 | Beuther et al. | Jul 2009 | B2 |
| 7584017 | Sugano et al. | Sep 2009 | B2 |
| 7585388 | Yeh et al. | Sep 2009 | B2 |
| 7585389 | Yeh et al. | Sep 2009 | B2 |
| 7585392 | Kokko et al. | Sep 2009 | B2 |
| 7588660 | Edwards et al. | Sep 2009 | B2 |
| 7588661 | Edwards et al. | Sep 2009 | B2 |
| 7591925 | Scherb et al. | Sep 2009 | B2 |
| 7608164 | Chou et al. | Oct 2009 | B2 |
| 7651589 | Murray et al. | Jan 2010 | B2 |
| 7662255 | Murray et al. | Feb 2010 | B2 |
| 7662257 | Edwards et al. | Feb 2010 | B2 |
| 7670457 | Murray et al. | Mar 2010 | B2 |
| 7691228 | Edwards et al. | Apr 2010 | B2 |
| 7704349 | Edwards et al. | Apr 2010 | B2 |
| 7726349 | Mullally et al. | Jun 2010 | B2 |
| 7785443 | Hermans et al. | Aug 2010 | B2 |
| 7789995 | Super et al. | Sep 2010 | B2 |
| 7811418 | Klerelid et al. | Oct 2010 | B2 |
| 7820008 | Edwards et al. | Oct 2010 | B2 |
| 7828931 | Edwards et al. | Nov 2010 | B2 |
| 7850823 | Chou et al. | Dec 2010 | B2 |
| 7851047 | Sato et al. | Dec 2010 | B2 |
| 7871493 | Hermans et al. | Jan 2011 | B2 |
| 7918964 | Edwards et al. | Apr 2011 | B2 |
| 7927456 | Murray et al. | Apr 2011 | B2 |
| 7935220 | Edwards et al. | May 2011 | B2 |
| 7959761 | Boettcher et al. | Jun 2011 | B2 |
| 7985319 | Pringle et al. | Jul 2011 | B2 |
| 8142612 | Murray et al. | Mar 2012 | B2 |
| 8152957 | Edwards et al. | Apr 2012 | B2 |
| 8152958 | Super et al. | Apr 2012 | B2 |
| 8177938 | Sumnicht | May 2012 | B2 |
| 8226797 | Murray et al. | Jul 2012 | B2 |
| 8257552 | Edwards et al. | Sep 2012 | B2 |
| 8293072 | Super et al. | Oct 2012 | B2 |
| 8328985 | Edwards et al. | Dec 2012 | B2 |
| 8388803 | Super et al. | Mar 2013 | B2 |
| 8388804 | Super et al. | Mar 2013 | B2 |
| 8393374 | Sato et al. | Mar 2013 | B2 |
| 8394236 | Edwards et al. | Mar 2013 | B2 |
| 8398818 | Edwards et al. | Mar 2013 | B2 |
| 8398820 | Edwards et al. | Mar 2013 | B2 |
| 8435381 | Murray et al. | May 2013 | B2 |
| 8512516 | Murray et al. | Aug 2013 | B2 |
| 8524040 | Edwards et al. | Sep 2013 | B2 |
| 8540846 | Miller et al. | Sep 2013 | B2 |
| 8545676 | Super et al. | Oct 2013 | B2 |
| 8562786 | Murray et al. | Oct 2013 | B2 |
| 8568559 | Murray et al. | Oct 2013 | B2 |
| 8568560 | Murray et al. | Oct 2013 | B2 |
| 8603296 | Edwards et al. | Dec 2013 | B2 |
| 8632658 | Miller et al. | Jan 2014 | B2 |
| 8636874 | Super et al. | Jan 2014 | B2 |
| 8652300 | Super et al. | Feb 2014 | B2 |
| 8673115 | Edwards et al. | Mar 2014 | B2 |
| 20010008180 | Anderson et al. | Jul 2001 | A1 |
| 20020062936 | Klerelid et al. | May 2002 | A1 |
| 20020088577 | Watson et al. | Jul 2002 | A1 |
| 20020134520 | Behnke et al. | Sep 2002 | A1 |
| 20020148584 | Edwards et al. | Oct 2002 | A1 |
| 20020187307 | Tanaka et al. | Dec 2002 | A1 |
| 20020189773 | Marinack et al. | Dec 2002 | A1 |
| 20030000664 | Drew et al. | Jan 2003 | A1 |
| 20030021952 | Zink et al. | Jan 2003 | A1 |
| 20030040574 | Schertz et al. | Feb 2003 | A1 |
| 20030056919 | Beck | Mar 2003 | A1 |
| 20030056921 | Beck et al. | Mar 2003 | A1 |
| 20030056922 | Beck | Mar 2003 | A1 |
| 20030056923 | Beck | Mar 2003 | A1 |
| 20030056925 | Beck | Mar 2003 | A1 |
| 20030059563 | Bourdelais et al. | Mar 2003 | A1 |
| 20030098134 | Scherb et al. | May 2003 | A1 |
| 20030102098 | Allen et al. | Jun 2003 | A1 |
| 20030111195 | Hu | Jun 2003 | A1 |
| 20030121626 | Hultzcrantz | Jul 2003 | A1 |
| 20030131959 | Marinack et al. | Jul 2003 | A1 |
| 20030146581 | Beck | Aug 2003 | A1 |
| 20030153443 | Beck | Aug 2003 | A1 |
| 20030201579 | Gordon et al. | Oct 2003 | A1 |
| 20030203196 | Trokhan et al. | Oct 2003 | A1 |
| 20040050514 | Shannon et al. | Mar 2004 | A1 |
| 20040089168 | Beck | May 2004 | A1 |
| 20040211534 | Clungeon et al. | Oct 2004 | A1 |
| 20040226673 | Edwards et al. | Nov 2004 | A1 |
| 20040238135 | Edwards et al. | Dec 2004 | A1 |
| 20050006040 | Boettcher et al. | Jan 2005 | A1 |
| 20050217814 | Super et al. | Oct 2005 | A1 |
| 20050236122 | Mullally et al. | Oct 2005 | A1 |
| 20050241786 | Edwards et al. | Nov 2005 | A1 |
| 20050241787 | Murray et al. | Nov 2005 | A1 |
| 20050268274 | Beuther et al. | Dec 2005 | A1 |
| 20050279471 | Murray et al. | Dec 2005 | A1 |
| 20060000567 | Murray et al. | Jan 2006 | A1 |
| 20060061016 | Gordon et al. | Mar 2006 | A1 |
| 20060085998 | Herman et al. | Apr 2006 | A1 |
| 20060088696 | Manifold et al. | Apr 2006 | A1 |
| 20060237154 | Edwards et al. | Oct 2006 | A1 |
| 20060289133 | Yeh et al. | Dec 2006 | A1 |
| 20060289134 | Yeh et al. | Dec 2006 | A1 |
| 20070062656 | Murray et al. | Mar 2007 | A1 |
| 20070107863 | Edwards et al. | May 2007 | A1 |
| 20070137807 | Schulz et al. | Jun 2007 | A1 |
| 20070137814 | Gao | Jun 2007 | A1 |
| 20070144694 | Pringle et al. | Jun 2007 | A1 |
| 20070204966 | Chou et al. | Sep 2007 | A1 |
| 20080008860 | Murray et al. | Jan 2008 | A1 |
| 20080008865 | Luu et al. | Jan 2008 | A1 |
| 20080029235 | Edwards et al. | Feb 2008 | A1 |
| 20080035288 | Mullally et al. | Feb 2008 | A1 |
| 20080047675 | Murray et al. | Feb 2008 | A1 |
| 20080083519 | Kokko et al. | Apr 2008 | A1 |
| 20080099169 | Beuther et al. | May 2008 | A1 |
| 20080135195 | Hermans et al. | Jun 2008 | A1 |
| 20080156450 | Klerelid et al. | Jul 2008 | A1 |
| 20080173419 | Sumnicht | Jul 2008 | A1 |
| 20080236772 | Edwards et al. | Oct 2008 | A1 |
| 20080245492 | Edwards et al. | Oct 2008 | A1 |
| 20080264589 | Chou et al. | Oct 2008 | A1 |
| 20090038768 | Murray et al. | Feb 2009 | A1 |
| 20090120598 | Edwards et al. | May 2009 | A1 |
| 20090159223 | Edwards et al. | Jun 2009 | A1 |
| 20090294079 | Edwards et al. | Dec 2009 | A1 |
| 20090301675 | Edwards et al. | Dec 2009 | A1 |
| 20090321027 | Hermans et al. | Dec 2009 | A1 |
| 20100126682 | Murray et al. | May 2010 | A1 |
| 20100170647 | Edwards et al. | Jul 2010 | A1 |
| 20100186913 | Super et al. | Jul 2010 | A1 |
| 20100282423 | Super et al. | Nov 2010 | A1 |
| 20110155337 | Murray et al. | Jun 2011 | A1 |
| 20120021178 | Miller et al. | Jan 2012 | A1 |
| 20120145341 | Super et al. | Jun 2012 | A1 |
| 20120145343 | Edwards et al. | Jun 2012 | A1 |
| 20120152474 | Murray et al. | Jun 2012 | A1 |
| 20120152475 | Edwards et al. | Jun 2012 | A1 |
| 20120160434 | Murray et al. | Jun 2012 | A1 |
| 20120160435 | Edwards et al. | Jun 2012 | A1 |
| 20120164407 | Edwards et al. | Jun 2012 | A1 |
| 20120180965 | Super et al. | Jul 2012 | A1 |
| 20120180966 | Super et al. | Jul 2012 | A1 |
| 20120180967 | Edwards et al. | Jul 2012 | A1 |
| 20120211186 | Murray et al. | Aug 2012 | A1 |
| 20120211187 | Murray et al. | Aug 2012 | A1 |
| 20120216972 | Murray et al. | Aug 2012 | A1 |
| 20120241113 | Super et al. | Sep 2012 | A1 |
| 20120247698 | Murray et al. | Oct 2012 | A1 |
| 20130029105 | Miller et al. | Jan 2013 | A1 |
| 20130153164 | Miller et al. | Jun 2013 | A1 |
| 20130186581 | Super et al. | Jul 2013 | A1 |
| 20130299105 | Miller et al. | Nov 2013 | A1 |
| 20130299106 | Miller et al. | Nov 2013 | A1 |
| 20130327488 | Super et al. | Dec 2013 | A1 |
| 20130327489 | Super et al. | Dec 2013 | A1 |
| Number | Date | Country |
|---|---|---|
| 1002359 | Dec 1976 | CA |
| 2053505 | Apr 1992 | CA |
| 0098683 | Jan 1984 | EP |
| 0399522 | Nov 1990 | EP |
| 0972876 | Jan 2000 | EP |
| 1036880 | Sep 2000 | EP |
| 1201796 | May 2002 | EP |
| 1985754 | Oct 2008 | EP |
| 2319537 | May 1998 | GB |
| 2380977 | Apr 2003 | GB |
| S57-66193 | Apr 1982 | JP |
| H05-506893 | Oct 1993 | JP |
| 8003890 | Jan 1996 | JP |
| 2002-504196 | Feb 2002 | JP |
| 2002-525455 | Aug 2002 | JP |
| 2004-174234 | Jun 2004 | JP |
| 2007-519834 | Jul 2007 | JP |
| 2143508 | Dec 1999 | RU |
| 2226231 | Mar 2004 | RU |
| 8503962 | Sep 1985 | WO |
| 9116492 | Oct 1991 | WO |
| 9606223 | Feb 1996 | WO |
| 9703247 | Jan 1997 | WO |
| 9743484 | Nov 1997 | WO |
| 9949131 | Sep 1999 | WO |
| 0014330 | Mar 2000 | WO |
| 0019014 | Apr 2000 | WO |
| 0036212 | Jun 2000 | WO |
| 0040405 | Jul 2000 | WO |
| 0185109 | Nov 2001 | WO |
| 0240769 | May 2002 | WO |
| 2004033793 | Apr 2004 | WO |
| 2005103375 | Nov 2005 | WO |
| 2005106117 | Nov 2005 | WO |
| 2006009833 | Jan 2006 | WO |
| 2006113025 | Oct 2006 | WO |
| 2006115817 | Nov 2006 | WO |
| 2007001837 | Jan 2007 | WO |
| 2007139726 | Dec 2007 | WO |
| 2008045770 | Apr 2008 | WO |
| 2010088359 | Aug 2010 | WO |
| Entry |
|---|
| Cresson, Thierry M., Hiroshi Tomimasu and Phillip Luner, “Characterization of paper formation Part 1: sensing paper formation,” Tappi Journal, Jul. 1990. pp. 153-159. |
| Egan, R. R., “Cationic Surface Active Agents as Fabric Softeners,” J. Am. Oil Chemists' Soc., Jan. 1978, vol. 55. pp. 118-121. |
| Espy, Herbert H., “Chapter 2 Alkaline-Curing Polymeric Amine-Epichlorohydrin Resins,” Wet Strength Resins and Their Application. L. Chan, Editor (1994). pp. 13-44. |
| Evans, W. P., “Cationic fabric softeners,” Chemistry and Industry, Jul. 5, 1969. pp. 893-903. |
| Keller, D.S., and J. J. Pawlak, “[Beta]-Radiographic Imaging of Paper Formation Using Storage Phosphor Screens,” Journal of Pulp and Paper Science, vol. 27, No. 4, Apr. 2001. pp. 117-123. |
| Klerelid, Ingvar, and Ola Thomasson, “Advantage (TM) NTT (TM): low energy, high quality,” Tissue World, Oct./Nov. 2008. pp. 49-52. |
| Sung, Y.J., C. H. Ham, O. Kwon, H. L. Lee, and D. S. Keller, “Applications of Thickness and Apparent Density Mapping by Laser Profilometry,” 13th Fundamental Research Symposium, Cambridge, Sep. 2005. pp. 961-1007. |
| Trivedi, B. C., et al., “Quaternization of Imidazoline: Unequivocal Structure Proof,” J. Am. Oil Chemists' Soc., Jun. 1981. pp. 754-756. |
| Westfeld, Lars, “Chemistry of Paper West Strength. I. A Survey of Mechanisms of Wet-Strength Development,” Cellulose Chemistry and Technology, vol. 13, 1979. pp. 813-825. |
| Notification of and Transmittal of International Search Report and the Written Opinion of the International Searching Authority, or the Declaration mailed May 6, 2010, in International Application No. PCT/US2010/022369. |
| Written Opinion mailed May 6, 2010 in International Application No. PCT/US2010/022369. |
| International Search Report completed Apr. 22, 2010, and mailed May 6, 2010, in International Application No. PCT/US2010/022369. |
| EPO Communication mailed Jul. 22, 2013, including an Extended European Search Report completed Jul. 12, 2013, issued in European Patent Application No. 13002824.4-1308. |
| Japanese Office Action dated Feb. 4, 2014, issued in corresponding Japanese Patent Application No. 2011-548287. |
| Communication, including an extended European Search Report, dated Jun. 5, 2014, issued in counterpart European Patent Application No. 14001119.8-1308. |
| Egyptian Office Action issued May 14, 2014, in counterpart Egyptian Patent Application No. 2011071262, with an English translation. |
| Eurasian Patent Office Search Report dated Dec. 15, 2014, issued in counterpart Eurasian Patent Application No. 201400619/26. |
| Number | Date | Country | |
|---|---|---|---|
| 20140352901 A1 | Dec 2014 | US |
| Number | Date | Country | |
|---|---|---|---|
| 61206146 | Jan 2009 | US |
| Number | Date | Country | |
|---|---|---|---|
| Parent | 12694650 | Jan 2010 | US |
| Child | 13488597 | US |
| Number | Date | Country | |
|---|---|---|---|
| Parent | 13933254 | Jul 2013 | US |
| Child | 14331429 | US | |
| Parent | 13488597 | Jun 2012 | US |
| Child | 13933254 | US |
