Patent Grant
8361278
1. Field of the Invention
Embodiments of the present disclosure generally relate to paper-containing products and, in particular, to paper suitable for use as a base sheet. More particularly, embodiments of the present disclosure relate to base sheets adapted for use in the production of food wrap products.
2. Description of the Related Art
Paper for producing food-wrap products is well known in the art. Generally speaking, such products are manufactured similarly to tissue type products, except that they are not creped from a Yankee dryer. Instead, they are pulled from the dryer under tension, or may be can-dried on a flat paper machine. Such products include so-called dry-waxing sheets, wet waxing sheets, and sheets adapted for making oil and grease resistant (“OGR”) papers. The base sheet is impregnated or coated with a water-resistant agent such as wax, polyethylene or fluorocarbons to provide water and grease resistance.
While materials for improving water and oil resistance have been improved over the years, numerous desirable attributes in the food-wrap base sheet are currently addressed by additives. Wet strength, for instance, is usually provided by conventional wet strength resins, while opacity is provided by conventional opacifiers such as titanium dioxide and the like. These additives are expensive and can aggravate processing difficulties when the paper is impregnated with a water-resistant agent and/or printed as is common, especially with wet-waxing papers. What is needed, therefore, is a food-wrap base sheet that reduces the required amount of additives, while maintaining the desired physical properties.
Embodiments of the disclosure may provide an exemplary base sheet for food wrap products including a pulp-derived papermaking fiber and a fibrillated regenerated cellulose microfiber having a CSF value of less than about 175 mL. Embodiments of the disclosure may also provide an exemplary method for making a food wrap paper product. The exemplary method includes forming a base sheet including a pulp-derived papermaking fiber and a regenerated cellulose microfiber, and treating the base sheet with a water or grease resistant agent.
Such products can include so-called dry-waxing sheet, wet waxing sheet and sheet, particularly adapted for making oil and grease resistant (“OGR”) papers.
So that the manner in which the above recited features of the present invention can be understood in detail, a more particular description of the invention, briefly summarized above, may be had by reference to embodiments, some of which are illustrated in the appended drawings. It is to be noted, however, that the appended drawings illustrate only typical embodiments of this invention and are therefore not to be considered limiting of its scope, for the invention may admit to other equally effective embodiments.
A detailed description will now be provided. Each of the appended claims defines a separate invention, which for infringement purposes is recognized as including equivalents to the various elements or limitations specified in the claims. Depending on the context, all references below to the “invention” may in some cases refer to certain specific embodiments only. In other cases it will be recognized that references to the “invention” will refer to subject matter recited in one or more, but not necessarily all, of the claims. Each of the inventions will now be described in greater detail below, including specific embodiments, versions and examples, but the inventions are not limited to these embodiments, versions or examples, which are included to enable a person having ordinary skill in the art to make and use the inventions, when the information in this disclosure is combined with available information and technology.
Terminology used herein is given its ordinary meaning consistent with the exemplary definitions set forth immediately below; mils refers to thousandths of an inch; mg refers to milligrams and m2 refers to square meters, percent means weight percent (dry basis), “ton” means short ton (2,000 pounds), and so forth. Unless otherwise specified, the version of a test method applied is that in effect as of Jan. 1, 2008, and test specimens are prepared under standard TAPPI conditions; that is, conditioned in an atmosphere of 23° C.±1.0° C. (73.4° F.±1.8° F.) at 50% relative humidity for at least about 2 hours.
Unless otherwise specified, “basis weight,” “BWT,” “bwt,” and so forth, are used interchangeably and refer to the weight of a 3,000 square foot (ft2) ream of product. Consistency refers to percent 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 percent 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%.
The terms “cellulosic,” “cellulosic sheet,” and the like, are meant to include any product incorporating papermaking fiber having cellulose as a major constituent. “Papermaking fibers” include virgin pulps, recycle (secondary) cellulosic fibers, or fiber mixes including cellulosic fibers. Fibers suitable for making the webs can 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 naturally occurring pulp-derived fibers, as opposed to reconstituted fibers such as lyocell or rayon that are liberated from their source material by any one of a number of pulping processes familiar to one experienced in the art including sulfate, sulfite, polysulfide, soda pulping, etc. The pulp can be chemically bleached if desired. Suitable bleaching agents or chemical include, but are not limited to, chlorine, chlorine dioxide, oxygen, alkaline peroxide, and the like.
Naturally occurring pulp-derived fibers are referred to herein simply as “pulp-derived” papermaking fibers. “Furnishes” and like terminology refers to aqueous compositions including papermaking fibers, optionally wet strength resins, debonders, and the like, for making paper products. For purposes of calculating relative percentages of papermaking fibers, the fibrillated cellulose, e.g. lyocell, content is excluded as noted below.
Kraft softwood fiber is low yield fiber made by the well known Kraft (sulfate) pulping process from coniferous material and includes northern and southern softwood Kraft fiber, Douglas fir Kraft fiber and so forth. Kraft softwood fibers generally have a lignin content of less than about 5 percent by weight, a length weighted average fiber length of greater than about 2 mm, as well as an arithmetic average fiber length of greater than about 0.6 mm.
Kraft hardwood fiber is made by the Kraft process from hardwood sources, i.e., eucalyptus, and also generally has a lignin content of less than about 5 wt %. Kraft hardwood fibers are shorter than softwood fibers, typically having a length weighted average fiber length of less than about 1 mm and an arithmetic average length of less than about 0.5 mm or less than about 0.4 mm.
Recycle fiber may be added to the furnish in any amount. Any suitable recycle fiber may be used, including recycle fiber with relatively low levels of groundwood, for example, recycle fiber with less than about 15 wt % lignin content, or less than about 10 wt % lignin content may be used depending on the furnish mixture employed and the application.
Calipers and/or bulk reported herein may be referred to herein as 1, 8, or 16 sheet calipers, as specified. Hand sheet caliper and bulk is based on 5 sheets. 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° C.±1.0° C. (73.4° F.±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 descent rate. For finished product testing, each sheet of product to be tested should have the same number of plies as the product when 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 the winder. For base sheet testing off of the paper machine reel, single plies must be used. Sheets are stacked together aligned in the MD. On custom embossed or printed product, try to avoid taking measurements in these areas if at all possible. Bulk may also be expressed in units of volume/weight by dividing caliper by basis weight (specific bulk).
A creping adhesive may be used to secure the base sheet web to the Yankee drying cylinder. The creping adhesive can be a hygroscopic, re-wettable, substantially non-crosslinking adhesive. Examples of creping adhesives can include poly(vinyl alcohol) of the general class described in U.S. Pat. No. 4,528,316, the entirety of which is incorporated herein by reference to the extent not inconsistent with this disclosure. Other examples of suitable adhesives are disclosed in U.S. patent application Ser. No. 10/409,042, the entirety of which is incorporated herein by reference to the extent not inconsistent with this disclosure. Suitable adhesives can be provided with modifiers and so forth; however, crosslinkers and/or modifiers may be used sparingly, or not at all, in the adhesive.
“Freeness” or “Canadian Standard Freeness” (CSF) can be determined in accordance with TAPPI Standard T 227 M-94 (Canadian Standard Method). Any suitable method for preparing the regenerated cellulose microfiber for freeness testing may be employed, so long as the fiber is well-dispersed. For example, if the fiber is pulped at about 5% consistency for a few minutes or more, e.g., 5-20 minutes before testing, the fiber can be well dispersed for testing. Likewise, partially dried, fibrillated, regenerated cellulose microfiber can be treated for about 5 minutes in a British disintegrator at about 1.2% consistency to ensure proper dispersion of the fibers. All preparation and testing can be done at room temperature and either distilled or deionized water can be used throughout.
The fibers can be solvent spun cellulose fibers, which can be produced by extruding a solution of cellulose into a coagulating bath. Lyocell fiber, for example, is distinct from cellulose fiber made by other known processes, which rely on the formation of a soluble chemical derivative of cellulose and its subsequent decomposition to regenerate the cellulose, for example, the viscose process. Lyocell is generally defined herein to mean fibers spun directly from a solution of cellulose in an amine-containing medium. In one or more embodiments, the amine-containing medium can be a tertiary amine N-oxide. Examples of solvent-spinning processes for the production of lyocell fibers are described in U.S. Pat. Nos. 6,235,392; 6,042,769; and 5,725,821, the entirety of each being incorporated herein by reference to the extent not inconsistent with this disclosure.
Dry tensile strengths (MD and CD), stretch, ratios thereof, modulus, break modulus, stress, and strain can be measured with a standard INSTRON test device or other suitable elongation tensile tester. “MD” means machine direction and “CD” means cross-machine direction. Opacity is measured according to TAPPI test procedure T425-OM-91, or equivalent. The tensile tester may be configured in various ways, including using about 1 inch, about 3 inch, or about 15 mm wide strips of a specimen conditioned in an atmosphere of 23° C.±1° C. (73.4° F.±1° F.) at about 50% relative humidity for about 2 hours. The tensile test can be run at a crosshead speed of about 2 in/min. Tensile strength can also be referred to herein simply as “tensile,” and may be described in terms of breaking length (km), g/3″ or g/in.
GM Break Modulus is expressed in grams/3 inches/% strain, or grams/inch/% strain unless other units are indicated. Percent strain is dimensionless. Tensile values generally refer to break values unless otherwise indicated. Tensile strengths are reported in g/3″ or g/inch at break. GM Break Modulus is calculated as [(MD tensile/MD Stretch at break)×(CD tensile/CD Stretch at break)]½. Break Modulus for handsheets may also be measured on a 15 mm specimen and expressed in kg/mm2, if so desired. Tensile ratios can simply be ratios of the values determined by way of the foregoing methods. Unless otherwise specified, a tensile property is a dry sheet property.
Total Energy Absorbed (TEA) is a measure of toughness and is reported CD TEA, MD TEA, or GM TEA. TEA is calculated as the area under the stress-strain curve using a tensile tester as has been previously described above. The area is based on the strain value reached when the sheet is strained to rupture and the load placed on the sheet has dropped to 65 percent of the peak tensile load. Since the thickness of a paper sheet is generally unknown and varies during the test, it is common practice to ignore the cross-sectional area of the sheet and report the “stress” on the sheet as a load per unit length or typically in the units of grams per 3 inches of width. For the TEA calculation, the stress is converted to grams per millimeter and the area calculated by integration. The units of strain are millimeters per millimeter so that the final TEA units become g-mm/mm2.
Wet tensile is measured using a one or three-inch wide strip of material that is folded into a loop, clamped in a special fixture termed a Finch Cup, then immersed in water. The Finch Cup, which is commercially available from the Thwing-Albert Instrument Company of Philadelphia, Pa., is mounted onto a tensile tester equipped with a 2.0 pound 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 about 7.0±about 0.1 and the tensile is tested after about a 5 second immersion time. Values are divided by two, as appropriate, to account for the loop.
Wet/dry tensile ratios are expressed in percent by multiplying the ratio by 100. For towel products, the wet/dry CD tensile ratio is of heightened relevancy. Throughout this specification and claims which follow “wet/dry ratio” or like terminology refers to the wet/dry CD tensile ratio unless clearly specified otherwise. For handsheets, MD and CD values are approximately equivalent.
The pulp may be mixed with strength adjusting agents such as permanent wet strength agents (WSR), optionally dry strength agents, and the like, before the sheet is formed. Suitable permanent WSRs are known. Such WSRs can include urea-formaldehyde resins, melamine formaldehyde resins, glyoxylated polyacrylamide resins, polyamidoamine-epihalohydrin resins, and the like. Such WSRs can be 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. Examples of these materials are generally described in U.S. Pat. Nos. 3,556,932 and 3,556,933. Resins of this type are commercially available under the trade name PAREZ®. 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. Polyamidamine-epichlorohydrin permanent wet strength resins, can also be used, an example of which is sold under the trade names KYMENE® 557LX and 557H by Hercules, Inc. of Delaware and AMRES® by Georgia-Pacific Resins, Inc. These resins and the process for making the resins are described in U.S. Pat. Nos. 3,700,623 and 3,772,076. An extensive, non-limiting 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). A non-limiting list of wet strength resins is described by Westfelt in Cellulose Chemistry and Technology Volume 13, p. 813, 1979.
Suitable dry strength agents may include starch, guar gum, polyacrylamides, carboxymethyl cellulose (CMC) and the like. Of particular utility is carboxymethyl cellulose, an example of which is sold under the trade name HERCULES® CMC, by Hercules, Inc. of Delaware.
Regenerated cellulose fiber can be prepared from a cellulosic dope comprising cellulose dissolved in a solvent comprising tertiary amine N-oxides or ionic liquids. The solvent composition for dissolving cellulose and preparing underivatized cellulose dopes can include tertiary amine oxides such as N-methylmorpholine-N-oxide (NMMO) and similar compounds enumerated in U.S. Pat. No. 4,246,221. Cellulose dopes may also contain non-solvents for cellulose such as water, alkanols, or other solvents, as described in greater detail below.
Suitable cellulosic dopes are enumerated in Table 1, below; however, it will be appreciated that all numerical ranges shown are approximate.
Details with respect to preparation of cellulosic dopes including cellulose dissolved in suitable ionic liquids and cellulose regeneration therefrom can be found in U.S. Pat. No. 6,824,599. Here again, suitable levels of non-solvents for cellulose may be included.
There is described in this disclosure a process for dissolving cellulose in an ionic liquid without derivatization and regenerating the cellulose in a range of structural forms. It is reported that the cellulose solubility and the solution properties can be controlled by the selection of ionic liquid constituents with small cations and halide or pseudohalide anions favoring solution. Suitable ionic liquids for dissolving cellulose can include those with cyclic cations, such as: imidazolium; pyridinium; pyridazinium; pyrimidinium; pyrazinium; pyrazolium; oxazolium; 1,2,3-triazolium; 1,2,4-triazolium; thiazolium; piperidinium; pyrrolidinium; quinolinium; and isoquinolinium.
Exemplary processing techniques for ionic liquids/cellulose dopes, and the like, are also described in U.S. Pat. Nos. 6,808,557 and 6,808,557 and U.S. patent application Ser. Nos. 11/087,496; 11/406,620; 11/472,724; 11/472,729; 11/263,391; and 11/375,963. Some ionic liquids and quasi-ionic liquids which may be suitable are disclosed by Konig et al., Chem. Commun. 2005, 1170-1172.
“Ionic liquid” generally refers to a molten composition including an ionic compound that is preferably a stable liquid at temperatures of less than about 100° C. at ambient pressure. Such liquids can have low vapor pressure at 100° C.; specifically, the vapor pressure may be less than 75 mBar, less than 50 mBar, less than 25 mBar, less than about 10 mBar, or less than about 1 mBar. Moreover, suitable liquids can have a vapor pressure that is so low that it is negligible and is not easily measurable. Exemplary commercially available ionic liquids are BASIONIC™ ionic liquid products available from BASF and are listed in Table 2 below.
Exemplary cellulose dopes including ionic liquids having dissolved therein about 5 wt % underivatized cellulose are commercially available from Aldrich. These compositions utilize alkyl-methylimidazolium acetate as the solvent. It has been found that choline-based ionic liquids are not particularly suitable for dissolving cellulose.
After the cellulosic dope is prepared, it can be spun into fiber, fibrillated and incorporated into absorbent sheet as hereinafter described. A synthetic cellulose such as lyocell can be split into micro- and nano-fibers and added to conventional wood pulp. The fiber may be fibrillated, for example, in an unloaded disk refiner, or any other suitable technique including using a PFI mil. Relatively short fiber can be used and the consistency kept low during fibrillation. The beneficial features of fibrillated fibers include: biodegradability, hydrogen bonding, dispersibility, repulpability, and smaller microfibers than obtainable with meltspun fibers, for example.
Fibrillated cellulose, e.g. lyocell or its equivalents can have advantages over splittable meltspun fibers. Synthetic microdenier fibers come in a variety of forms. For example, a 3 denier nylon/PET fiber in a “pie wedge” configuration can be split into 16 or 32 segments, typically in a hydroentangling process. Each segment of a 16-segment fiber can have a coarseness of about 2 mg/100 m, versus eucalyptus pulp at about 7 mg/100 m. Unfortunately, a number of deficiencies have been identified with this approach for conventional wet laid applications. First, dispersibility can be less than optimal. Also, meltspun fibers often must be split before sheet formation, and an efficient method is lacking. Further, most available polymers for these fibers are not biodegradable. The coarseness is lower than wood pulp, but still high enough that they must be used in substantial amounts, and, therefore, can form a costly part of the furnish. Additionally, the lack of hydrogen bonding can require other methods of retaining the fibers in the sheet.
Fibrillated fibrils can be about 0.10 microns (μm) to about 0.25 microns in diameter, translating to a coarseness of about 0.0013 mg/100 m to about 0.0079 mg/100 m. Diameters can also range from a low of about 0.1 microns, 0.15 microns, or 0.20 to a high of about 0.25 microns, 0.3 microns, or 0.35 microns. In one or more embodiments, the fibrillated regenerated cellulose microfiber can have a coarseness value of from about 0.001 mg/100 m to about 0.6 mg/100 m. The fibrillated regenerated cellulose microfiber can also have a coarseness value of from about 0.01 mg/100 m to about 0.6 mg/100 m The fibrillated regenerated cellulose microfiber can also have a coarseness value that ranges from a low of about 0.001 mg/100 m, 0.01 mg/100 m, or 0.10 mg/100 m to a high of about 0.2 mg/100 m, 0.4 mg/100 m, or about 0.6 mg/100 m
In one or more embodiments, the weight average of the diameter can be about 0.1 to about 2 microns, less than about 2 microns, less than about 1 micron, less than about 0.5 microns, or less than about 0.25 microns. In one or more embodiments, the weight average of the diameter can be 0.1 microns to about 1.5 microns; 0.2 microns to about 1.2; or about 0.3 microns to about 0.9 microns. In one or more embodiments, the weight average of the length can be less than about 500 microns, less than about 400 microns, less than about 300 microns, or less than about 200 microns. In one or more embodiments, the weight average of the length can range from a low of about 50 microns, 75 microns, or 100 microns to a high of about 250 microns, 375 microns, or 500 microns. Assuming these fibrils are available as individual strands (i.e., separate from the parent fiber) the furnish fiber population can be increased at a low addition rate. Further, fibrils not separated from the parent fiber may also provide benefit. Dispersibility, repulpability, hydrogen bonding, and biodegradability remain product attributes since the fibrils are cellulose.
Fibrils from lyocell fiber have important distinctions from wood pulp fibrils, including the length of the lyocell fibrils. Wood pulp fibrils can be mere microns long, and therefore, can act in the immediate area of a fiber-fiber bond. Wood pulp fibrillation from refining can lead to stronger, denser sheets. Lyocell fibrils, however, may be as long as the parent fibers. These fibrils can act as independent fibers and can thereby improve the bulk while maintaining or improving strength. Southern pine and mixed southern hardwood (MSHW) are two examples of fibers that are disadvantaged relative to premium pulps with respect to softness. The term “premium pulps” as it is used herein generally refers to northern softwoods and eucalyptus pulps commonly used in the tissue industry for producing the softest bath, facial, and towel grades. Southern pine is coarser than northern softwood Kraft, and mixed southern hardwood is both coarser and higher in fines than market eucalyptus. The lower coarseness and lower fines content of premium market pulp leads to a higher fiber population, expressed as fibers per gram (N or Ni>0.2) in Table 3. Illustrative coarseness and length values, shown in Table 3, can be obtained with a commercially-available OpTest Fiber Quality Analyzer. Definitions are as follows:
Northern bleached softwood Kraft (NBSK) and eucalyptus have more fibers per gram than southern pine and hardwood. Lower coarseness leads to higher fiber populations and smoother sheets.
For comparison, the “parent” or “stock” fibers of lyocell can have a coarseness of about 16.6 mg/100 m before fibrillation and a diameter of about 11 μm to about 12 μm. The fibrils (i.e., fibers post-fibrillation) have a coarseness of from about 0.001 mg/100 m to about 0.2 mg/100 m. Thus, the fiber population can be increased at relatively low addition rates. Fiber length of the parent fiber can be selectable, and fiber length of the fibrils can depend on the starting length and the degree of cutting during the fibrillation process.
The dimensions of the fibers passing the 200 mesh screen are generally from about 0.2 μm in diameter by about 100 μm long. Using these dimensions, the fiber population can be calculated as about 200 billion fibers per gram. For perspective, southern pine can be three million fibers per gram and eucalyptus can be 20 million fibers per gram (see Table 3). Different fiber shapes with lyocell can result in approximately 0.2 μm diameter fibers that can be, for example, about 1,000 μm or more long. In one or more embodiments, the approximately 0.2 μm diameter fibers can have a length of less than about 500 μm, less than about 400 μm, less than about 300 μm, or less than about 200 μm. As noted above, fibrillated fibers of regenerated cellulose can be made by producing stock fibers having a diameter of about 10 μm to about 12 μm by fibrillating the parent fibers. Alternatively, fibrillated lyocell microfibers, for example, commercially available from Engineered Fibers Technology having suitable properties can be used.
In one or more embodiments, the freeness CSF value can be below about 150 mL, about 100 mL, about 50 mL, or about 25 mL. In one or more embodiments, the freeness CSF value can range from a low of about 4 mL, about 10 mL, or about 25 mL to a high of about 85 mL, about 115 mL, or about 150 mL. In one or more embodiments, at least about 50 wt %, about 60 wt %, about 70 wt %, or about 80 wt % of the fibrillated cellulose can be finer than 14 mesh. In one or more embodiments, of from about 50 wt %, 55 wt % or 60 wt % to a high of about 65 wt %, 75 wt %, or 80 wt % of the fibrillated cellulose can be finer than 14 mesh. Details as to fractionation using the Bauer-McNett Classifier appear in Gooding et al., “Fractionation in a Bauer-McNett Classifier”, Journal of Pulp and Paper Science; Vol. 27, No. 12, December 2001.
The fibrillated cellulose microfiber can be present in the base sheet in any suitable amount. In one or more embodiments, up to about 75 wt % regenerated cellulose microfiber can be used although one may, for example, employ up to 90 wt % or 95 wt % regenerated cellulose microfiber in some cases. In one or more embodiments, the amount of regenerated cellulose microfiber can range from a low of about 1 wt %, 5 wt %, or 15 wt % to a high of about 75 wt %, 85 wt %, or 95 wt %. The amount of regenerated cellulose microfiber can have a suitable maximum, i.e., 1+X(%) where X is any positive number up to about 50 or about 98. The following are some exemplary compositions, it being appreciated that all numbers presented are approximate:
Furthermore, lyocell fibrils are distinct from wood pulp fibrils. A wood pulp fiber is a complex structure of several layers (P, S1, S2, S3), as known in the art, each with cellulose strands arranged in spirals around the axis of the fiber. When subjected to mechanical refining, portions of the P and S1 layers peel away in the form of fines and fibrils. These fibrils are generally short, for example, less than about 20 microns. The fibrils can act in the immediate vicinity of the fiber at the intersections with other fibers. Thus, wood pulp fibrils can increase bond strength, sheet strength, sheet density, and sheet stiffness. The multilayered fiber wall structure with spiraled fibrils can make it difficult to split the wood fiber along its axis using commercial processes. By contrast, Lyocellfiber has a much simpler structure that allows the fiber to be split along its axis. The resulting fibrils can be about 0.1 microns to about 0.25 microns in diameter, as described above, and potentially as long as the original fiber. Fibril length is likely to be less than the “parent” fiber, and disintegration of many fibers can be incomplete. Nevertheless, a sufficient numbers of fibrils can act as individual fibers, thereby substantially raising the paper properties at a relatively low addition rate.
Considering the relative fiber coarsenesses of wood pulp furnishes, northern softwood (NBSK) has a coarseness of about 14 mg/100 m, and southern pine has a coarseness of about 20 mg/100 m. Mixed southern hardwood (MSHW) has a coarseness of 10 mg/100 m, and eucalyptus has a coarseness of about 6.5 mg/100 m. Lyocell fibrils with diameters between about 0.1 microns and 0.25 microns can have coarseness values between about 0.0013 mg/100 m and about 0.0079 mg/100 m, as described above. One way to express the difference between a premium furnish and southern furnish is fiber population, expressed as the number fibers per gram of furnish (N). N is inversely proportional to coarseness, so premium furnish has a larger fiber population than southern furnish. The fiber population of southern furnish can be increased to equal or exceed that of premium furnish by the addition of fibrillated lyocell.
Lyocell microfibers can have many attractive features including biodegradability, dispersibility, repulpability, low coarseness, and extremely low coarseness to length (C/L). The low C/L means that sheet strength can be obtained at a lower level of bonding, which makes the sheet more drapable (lower modulus as shown in
Integrated southern softwood and hardwood can have a lower cost than premium pulp, yet the ability of southern furnish to produce soft tissue can be less than desired for some applications. Mills producing premium products may be required to purchase premium fibers like northern softwood and eucalyptus for the highest softness grades, which can increase cost and negatively impact the mill fiber balance. Accordingly, refined lyocell fibers can be added to improve furnish quality.
At high levels of refining, the fibrils can be separated from the parent fiber and act as independent micro- or perhaps even nano-fibers. A high level of refining may produce a substantial impact at the lowest addition rate. More refining can produce a higher population of very low coarseness fibers, but may also reduce average fiber length. It is generally preferred to maximize production of low coarseness fibrils while minimizing the cutting of fibers. As discussed earlier, the 1.6 mm as measured by the FQA is not considered an accurate average value, but is included herein to show the directional decrease in length with refining. The fibrillated lyocell obtained for later examples began as 6 mm fibers with a coarseness of 16.7 mg/100 m before refining. The ideal fibrils are substantially less coarse than eucalyptus while maintaining adequate length. Refining can reduce the fibril length, but the fibrils can remain long enough to reinforce the fiber network.
A relatively modest amount of lyocell microfiber makes it possible to increase the fibers/gram of a furnish. Consider the calculations in Table 6, wherein fibrillated lyocell achieves fiber counts of greater than a billion fibers per gram. For comparison, eucalyptus fiber, which has a relatively large number of fibers, has only up to about 20 million fibers per gram.
As can be appreciated from Table 6, in one or more embodiments, the fibrillated regenerated cellulose microfiber can have a fiber count greater than about 50 million fibers/gram, about 400 million fibers/gram, about 2 billion fibers/gram, about 10 billion fibers/gram, about 50 billion fibers/gram, or about 200 billion fibers/gram, or more. In one or more embodiments, the fibrillated regenerated cellulose microfiber can have a fiber count ranging from a low of about 50 million fibers/gram, 75 million fibers/gram, or 100 million fibers/gram to a high of about 500 million fibers/gram, 1 billion fibers/gram, 100 billion fibers/gram, or 200 billion fibers/gram. In one or more embodiments, the fibrillated regenerated cellulose microfiber can have a fiber count ranging from a low of about 500 million fibers/gram, 800 million fibers/gram, or 1 billion fibers/gram to a high of about 10 billion fibers/gram, 80 billion fibers/gram, or 100 billion fibers/gram.
Another property, pore volume distribution (PVD) can be measured using liquid porosimetry techniques. For example, within a porous solid matrix. Each pore can be sized according to its effective radius, and the contribution of each size to the total free volume is the principal objective of the analysis. The data reveals useful information about the structure of a porous network, including absorption and retention characteristics of a material.
Liquid porosimetry generally requires quantitative monitoring of the movement of liquid either into or out of a porous structure. The effective radius R of a pore is operationally defined by the Laplace equation:
where γ is liquid surface tension, θ is advancing or receding contact angle of the liquid, and ΔP is pressure difference across the liquid/air meniscus. For liquid to enter or drain from a pore, an external pressure must be applied that is just enough to overcome the Laplace ΔP. Cos θ is negative when liquid must be forced in; cos θ is positive when it must be forced out. If the external pressure on a matrix having a range of pore sizes is changed, either continuously or in steps, filling or emptying will start with the largest pore and proceed in turn down to the smallest size that corresponds to the maximum applied pressure difference. Porosimetry involves recording the increment of liquid that enters or leaves with each pressure change and can be carried out in the extrusion mode; that is, liquid is forced out of the porous network rather than into it. The receding contact angle is the appropriate term in the Laplace relationship, and any stable liquid that has a known cos θr>0 can be used. If necessary, initial saturation with liquid can be accomplished by preevacuation of the dry material.
The addition of regenerated cellulose microfiber to a papermaking furnish of conventional papermaking fibers surprisingly provides increased smoothness to the surface of a sheet, which can be a highly desirable feature in a wiper, since this property promotes good surface to surface contact between the wiper and a substrate to be cleaned.
Another property that can be measured is Bendtsen Roughness, which is one method by which to characterize the surface of a sheet. Generally, Bendtsen Roughness is measured by clamping a test piece between a flat glass plate and a circular metal land and measuring the rate of airflow between the paper and land, wherein the air is supplied at a nominal pressure of 1.47 kPa. The measuring land has an internal diameter of about 31.5 mm±about 0.2 mm. and a width of about 150 μm±about 2 μm. The pressure exerted on the test piece by the land can be 1 kg pressure or 5 kg pressure.
The base sheet can have a MD tensile of greater than about 5 lbs/inch, such as greater than 10 lbs/inch, or greater than 20 lbs/inch, or greater than 30 lbs/inch, or greater than 50 lbs/inch, or greater than 100 lbs/inch. The base sheet can also have a MD tensile ranging from a low of about 5 lbs/inch, 25 lbs/inch, or 50 lbs/inch to a high of about 75 lbs/inch, 100 lbs/inch, or 200 lbs/inch.
The base sheet can further have a 1-sheet caliper of from about 1 mil to about 3 mils. Preferably, the base sheet can have a 1-sheet caliper of from about 1.2 mil to about 2.8 mils, about 1.2 mil to about 2.5 mils, about 1.5 mil to about 2.5 mils, or about 2.0 mil to about 3.0 mils. The base sheet can also have a 1-sheet caliper ranging from a low of about 1.0 mil, 1.4 mil, or 1.8 mil to a high of about 2.0 mil, 2.4 mil, or 3.0 mil.
Bendtsen Smoothness relative to a sheet without microfiber is calculated by dividing the Bendtsen Roughness of a sheet without microfiber by the Bendtsen Roughness of a like sheet with microfiber. Either like sides or both sides of the sheets may be used to calculate relative smoothness, depending upon the nature of the sheet. If both sides are used, it is referred to as an average value.
An illustrative base sheet for food wrap products can have the characteristics indicated in Tables 7 through 10, below. Such products made with regenerated cellulose microfiber generally contain less opacifier and less wet strength resin and optionally have lower roughness values.
As will be appreciated form Tables 7 through 10, a base sheet for food wrap products generally have basis weights of from about 5 lbs to about 25 lbs per 3000 ft2 and 1-sheet calipers of from about 1.25 mils to 2.5 mils. The base sheet can also have a basis weight of from about 5 lbs to about 25 lbs per 3,000 ft2. More preferably, the base sheet can have a basis weight of from about 10 lbs to about 20 lbs per 3,000 ft2. In one or more embodiments, the base sheet can have a basis weight ranging from a low of about 8 lbs, 14 lbs, or 17 lbs to a high of about 19 lbs, 22 lbs, or 25 lbs per 3,000 ft2.
Absorbencies are much lower than for absorbent products and tensiles much higher, distinguishing these products from tissue and towel base sheet. For example, absorbent products generally have SAT values of greater than 2 g/g, while these products have lower SAT values and higher tensiles.
In one or more embodiments, properties of a base sheet can be achieved through the addition of regenerated cellulose microfiber, which provides wet strength, opacity and smoothness. Basis weights and calipers may be reduced from the values shown in Tables 7 through 10, while maintaining tensile and opacity requirements. Still further advantages stem from the reduced pore size of the base sheet with the microfiber. The small pores help to hold a water and/or grease resistant coating on the surface where it is most effective and allow lower coatweights to be used, as further discussed below in connection with water and grease resistant agents which are applied to the base sheet.
In one or more embodiments, the base sheet can include one or more water and/or grease resistant agents. Such agents can include one or more polymers, waxes, and other sizes, which usually provide water and/or grease resistance. It will be appreciated that a combination of materials may be needed to achieve the desired level of both resistance to water and grease. These materials can be printed onto the base sheet or extruded onto the base sheet as appropriate and are preferably film-forming.
Aqueous barrier and/or grease resistance coatings can include one or more synthetic latexes with acrylic, styrenic, olefinic polymers, derivatives thereof, or mixtures thereof. Wax emulsions and the like can also be applied to the base sheet in coatweights of from about 0.3 lbs solids to about 3 lbs solids per 3,000 square foot ream; however, more barrier coatings may be used in the case of wax, as also noted below. Instead of a latex, the liquid coating may be a solution of polymer (e.g., aqueous polyvinyl alcohol), and may be applied in like amounts by like methods.
The coatings may be applied by press coating methods, i.e., gravure, coil coating, flexographic methods and so forth as opposed to extrusion methods which are used for thermoplastic resins and waxes usually at higher coatweights than aqueous coatings. The coating(s) can also be applied to the base sheet in water-borne form.
Suitable synthetic aqueous latexes can have the following physical properties. It being appreciated that all numbers presented are approximate:
Suitable polymers can include, but are not limited to, polyacrylates, polymethacrylates, polyamides, polystyrene/butadienes, polyolefins such as polypropylene or polyethylene, polyesters, polylactides, polyalkanoates, and the like, such as those described in U.S. Pat. No. 6,893,693. Suitable polymers listed in the '693 patent can include: poly(benzyl acrylate), poly(butyl acrylate)(s), poly(2-cyanobutyl acrylate), poly(2-ethoxyethyl acrylate), poly(ethyl acrylate), poly(2-ethylhexyl acrylate), poly(fluoromethyl acrylate), poly(5,5,6,6,7,7,7-heptafluoro-3-oxoheptyl acrylate), poly(heptafluoro-2-propyl acrylate), poly(heptyl acrylate), poly(hexyl acrylate), poly(isobornyl acrylate), poly(isopropyl acrylate), poly(3-methoxybutyl acrylate), poly(methyl acrylate), poly(nonyl acrylate), poly(octyl acrylate), poly(propyl acrylate), polyp-tolyl acrylate), poly(acrylic acid) and derivatives and salts thereof; polyacrylamides such as poly(acrylamide), poly(N-butylacrylamide), poly(N,N-dibutylacrylamide), poly(N-dodecylacrylamide), and poly(morpholylacrylamide); polymethacrylic acids and poly(methacrylic acid esters) such as poly(benzyl methacrylate), poly(octyl methacrylate), poly(butyl methacrylate), poly(2-chloroethyl methacrylate), poly(2-cyanoethyl methacrylate), poly(dodecyl methacrylate), poly(2-ethylhexyl methacrylate), poly(ethyl methacrylate), poly(1,1,1-trifluoro-2-propyl methacrylate), poly(hexyl methacrylate), poly(2-hydroxyethyl methacrylate), poly(2-hydroxypropyl methacrylate), poly(isopropyl methacrylate), poly(methacrylic acid), poly(methyl methacrylate) in various forms such as, atactic, isotactic, syndiotactic, and heterotactic; and poly(propyl methacrylate); polymethacrylamides such as poly(4-carboxyphenylmethacrylamide); other alpha- and beta-substituted poly(acrylics) and poly(methacrylics) such as poly(butyl chloroacrylate), poly(ethyl ethoxycarbonylmethacrylate), poly(methyl fluoroacrylate), and poly(methyl phenylacrylate). The latex applied to the base sheet can be any FDA-approved material, for example, a coating such as Plate Kote 982 Kosher available from Michelman.
Other suitable polymers can include polyethylene terephthalate (PET), or biopolymers such as polylactide (PLA) or polyhydroxyalkanoate (PHA). PLA and PHA are particularly preferred when a biodegradable product is desired. The polymers relating to latex coatings may be extrusion coated as well; however, many acrylics and styrene/butadiene polymers are more amenable to latex application.
The term “wax,” as used herein, refers to relatively low melting organic mixtures or compounds of relatively high molecular weight, solid at room temperature, and generally similar in composition to fats and oils, except that the waxes contain little or no glycerides. Some waxes can be hydrocarbons. Others can be esters of fatty acids and alcohols. Suitable waxes can be thermoplastic, but since they are not high polymers, are not considered in the family of plastics. Common properties include smooth texture, low toxicity, and freedom from objectionable odor and color. Waxes are typically combustible and have good dielectric properties. They are soluble in most organic solvents and insoluble in water. Typical classes of waxes are enumerated briefly below.
Natural waxes can include carnauba waxes, paraffin waxes, montan waxes, and microcrystalline waxes. Carnauba is a natural vegetable wax derived from fronds of Brazilian palm trees (Copernica cerifera). Carnauba is a relatively hard, brittle wax whose main attributes are lubricity, anti-blocking, and FDA compliance. Paraffins are low molecular weight waxes with melting points ranging from about 48 to about 74° C. They are relatively highly refined, have a low oil content, and are straight-chain hydrocarbons. Paraffins provide anti-blocking, slip, water resistance, and moisture vapor transmission resistance. Montan waxes are mineral waxes which, in crude form, are extracted from lignite formed decomposition of vegetable substances. Microcrystalline waxes come from the distillation of crude oil. Microcrystalline waxes have a molecular weight of from about 500 to 675 grams/mole and melting points of about 73 to about 94° C. These waxes are highly branched and have small crystals.
Synthetic waxes can include Fischer-Tropsch waxes, polyethylene waxes, and wax dispersions of various macromers. Fischer-Tropsch waxes are produced almost exclusively in South Africa by coal gasification. They include methylene groups which can have either even or odd numbers of carbons. These waxes have molecular weights of between about 300 and about 1400 gms/mole, and are used in various applications. Polyethylene waxes are made from ethylene produced from natural gas or by cracking petroleum naphtha. Ethylene is then polymerized to provide waxes with various melting points, hardnesses, and densities. Polyethylene wax molecular weights range from about 500 to about 3000 gms/mole. Oxidized polyethylenes are readily emulsifiable, whereas non-oxidized polyethylenes largely are not. However, some non-oxidized polyethylenes have been successfully emulsified. High density polyethylenes (HDPE) have a great deal of crystallinity and their molecules are tightly packed.
Wax dispersions are known and, for example, disclosed in U.S. Pat. Nos. 6,033,736; 5,431,840; and 4,468,254. In general, a wax dispersion includes from about 90 to about 50 percent water, from about 10 to about 50 percent wax solids, and minor amounts of an emulsifier. “Aqueous wax dispersion,” and like terminology, as it is used herein, generally refers to a stable mixture of wax, emulsifier, and water without a substantial solvent component. Wax may be applied to the base sheet in the form of a dispersion, but a melt application without water or other solvent may be required.
Wax coatings can be fortified with low density polyethylene (LDPE) for wet wax applications. These wax coatings may be applied generally by the same methods as aqueous coatings noted above, or may be extrusion coated onto the base sheet substrate. Wax coatweight typically ranges from 1 lb solids to 5 lbs solid per 3000 square foot ream for wet waxing and for dry waxing applications. Extrusion coating coatweights of wax or high polymer suitably range from about 2 lbs to about 10 lbs solid per 3000 square foot ream depending on the product.
In one or more embodiments, the aqueous barrier and/or grease resistance coatings can include a fluorochemical sizing agent or a chrome complex sizing agent, or both. An illustrative agent is QUILON® chrome complex surface treatment chemicals, commercially-available from Dupont Chemical. Such materials can be applied by the methods specified above, or similar methods, and in like amounts, whether in polymeric or lower molecular weight form.
The present disclosure can be more fully described according to the following non-limiting examples.
Hand Sheet Study #1
A hand sheet study was conducted with southern softwood and fibrillated lyocell fiber.
The dimensions of the fibers passing the 200 mesh screen can be between about 0.2 micron diameter by about 100 micron long, as described above. Using these dimensions, the fiber population can be calculated at about 200 billion fibers per gram, as described above. For perspective, southern pine can commonly be three million fibers per gram and eucalyptus can commonly be 20 million fibers per gram (as shown and described above in Table 1). Comparing the fine fraction with the 14 mesh pictures, the fibers may be the fibrils that are broken away from the original unrefined fibers. Different fiber shapes with lyocell can result in 0.2 micron diameter fibers that are perhaps 1000 microns or more long instead of 100, as described above.
Table 11, below, summarizes some of the significant effects derived from Hand Sheet Test #1, and shows the benefits of fibrillated lyocell. These benefits are also shown in
Table 12, below, compares the morphology of lyocell and softwood fibers as measured by the OpTest optical Fiber Quality Analyzer. The stock lyocell fibers (as shown in
Differences in fiber size are better appreciated by comparing
The degree of fibrillation is measured by Canadian Standard Freeness (csf). Unrefined lyocell has a freeness of about 800 mL, and trial quantities were obtained at about 400, 200, and 40 mL. As shown, 4 mm lyocell was refined to a freeness of only 22 mL with an average fiber length (Lw) of 1.6 mm.
Hand Sheet Study #2
This hand sheet study demonstrates that the benefit of fibrillated lyocell is obtained predominantly from short, low coarseness fibrils rather than partially refined parent fibers unintentionally persisting after the refining process. Six mm by 1.5 denier lyocell was refined to 40 freeness and fractionated in a Bauer McNett classifier using screens with meshes of 14, 28, 48, 100, and 200. Fiber length is a primary factor in determining the passage of fibers through each screen. The 14 and 28 mesh fractions were combined to form one fraction hereafter referred to as “Longs”. The 48, 100, 200 mesh fractions and the portion passing through the 200 mesh were combined to form a second fraction hereafter referred to as “Shorts”. Southern softwood was prepared by refining it 1000 revolutions in a PFI mill. Hand sheets were prepared at 15 lb/ream basis weight, pressed at 15 psi for five minutes, and dried on a steam-heated drum. Table 13 compares hand sheets made with different combinations of softwood and fibrillated lyocell. Softwood alone (Sample 1) has low opacity, low stretch, and low tensile. Twenty percent longs (Sample 2) improves opacity and stretch modestly, but not tensile. Twenty percent Shorts (Sample 3) greatly increases opacity, stretch, and tensile, more so than the whole lyocell (Sample 4). Sample 5 used recombined Longs and Shorts to approximate the original fibrillated lyocell. It can be appreciated from this example that the shorts are the dominant contributor to the present invention. Microfiber decreases the average pore size and increases smoothness of cellulosic sheet including foodwrap base sheet. Such are highly desirable attributes, especially for coated and printed end-products as is seen in the following porosity and roughness data.
The apparatus shown in
Sample A was a CWP base sheet prepared from 100% northern bleached softwood Kraft (NBSK) fiber. Sample B was a like CWP sheet made with 25% regenerated cellulose microfiber and sample C was also a like CWP sheet made with 50% regenerated cellulose microfiber and 50% NBSK fiber. Details and results appear in Table 13 below, and in
It is seen in Table 14, above, and
For purposes of convenience, the relative wicking ratio of a microfiber containing sheet is generally defined to be the ratio of the average pore effective sizes of a like sheet without microfiber to a sheet containing microfiber. Thus, the Sample B and C sheets had relative wicking ratios of approximately 2 and 3 as compared with the control Sample A. While the wicking ratio readily differentiates single ply CWP sheet made with cmf from a single ply sheet made with NBSK alone, more universal indicators of differences achieved with cmf fiber are high differential pore volumes at small pore radius (less than about 10-15 microns) as well as high capillary pressures at low saturation as is seen with two-ply wipers and handsheets
A series of two ply CWP sheets were prepared and tested for porosity, following the described procedures. Sample D was a control, prepared with NBSK fiber and without cmf, Sample E was a two ply sheet with 75% by weight NBSK fiber and 25% by weight cmf, and Sample F was a two ply sheet with 50% by weight NBSK fiber and 50% by weight cmf. Results appear in Table 10 and are presented graphically in
It is seen in Table 15 and
The porosity data for the cmf containing two ply sheet is nevertheless unique in that a relatively large fraction of the pore volume is at smaller radii pores, below about 15 microns. Similar behavior is seen in handsheets, discussed below.
Following the procedures noted above, handsheets were prepared and tested for porosity. Sample G was a NBSK handsheet without cmf, Sample J was 100% cmf fiber handsheet and sample K was a handsheet with 50% cmf fiber and 50% NBSK. Results appear in Table 16 and
Here again, it is seen that the sheets containing cmf had significantly more relative pore volume at small pore radii. The cmf containing two ply sheet had twice as much relative pore volume below 10-15 microns than the NBSK sheet; while the cmf and cmf containing handsheets had 3-4 times the relative pore volume below about 10-15 microns than the handsheet without cmf.
A Bendtsen smoothness and porosity tester (9 code SE 114), equipped with air compressor, 1 kg test head, 4 kg weight and clean glass plate was obtained from L&W USA, Inc., 10 Madison Road, Fairfield, N.J. 07004 and used in the tests which are described below. Tests were conducted in accordance with ISO Test Method 8791-2 (1990).
A series of handsheets were prepared with varying amounts of cmf and the conventional papermaking fibers listed in Table 16. The handsheets were prepared wherein one surface was plated and the other surface was exposed during the air drying process. Both sides were tested for Bendtsen Roughness at 1 kg pressure and 5 kg pressure. Table 17 presents the average values of Bendtsen Roughness at 1 kg pressure and at 5 kg pressure, as well as the relative average Bendtsen Smoothness as compared with cellulosic sheets made without regenerated cellulose microfiber.
Other embodiments can include:
1. A base sheet for food wrap products comprising:
a pulp-derived papermaking fiber and a fibrillated regenerated cellulose microfiber having a CSF value of less than about 175 mL.
2. The base sheet according to paragraph 1, wherein the base sheet has a 1-sheet caliper of from about 1 mil to about 3 mils, a basis weight of from about 5 lbs to about 25 lbs per 3,000 ft2, and an MD tensile of greater than about 5 lbs/inch.
3. The base sheet according to paragraphs 1 or 2, wherein the fibrillated regenerated cellulose microfiber has a CSF value of less than about 100 mL.
4. The base sheet according to any paragraph 1 to 3, wherein the fibrillated regenerated cellulose microfiber has a CSF value of less than about 25 mL.
5. The base sheet according to any paragraph 1 to 4, wherein the fibrillated regenerated cellulose microfiber has a number average diameter of from about 0.1 microns to about 2 microns.
6. The base sheet according to any paragraph 1 to 5, wherein the fibrillated regenerated cellulose microfiber has a coarseness value of from about 0.001 mg/100 m to about 0.6 mg/100 m.
7. The base sheet according to any paragraph 1 to 6, wherein the fibrillated regenerated cellulose microfiber has a weight average diameter of less than about 2 microns, a weight average length of less than about 500 microns, and a fiber count of greater than about 400 million fibers/gram.
8. The base sheet according to any paragraph 1 to 7, wherein the fibrillated regenerated cellulose microfiber has a fiber count greater than about 200 billion fibers/gram.
9. The base sheet according to any paragraph 1 to 8, wherein at least about 50 wt % of the fibrillated regenerated cellulose microfiber is finer than 14 mesh.
10. The base sheet according to any paragraph 1 to 9, wherein at least about 75% by weight of the fibrillated regenerated cellulose microfiber is finer than 14 mesh.
11. A method for making a food wrap paper product comprising:
forming a base sheet comprising pulp-derived papermaking fiber and regenerated cellulose microfiber; and
treating the base sheet with a water or grease resistant agent.
12. The method according to paragraph 11, wherein the water or grease resistant agent comprises a polyacrylate or polymethacrylate.
13. The method according to paragraphs 11 or 12, wherein the water or grease resistant agent comprises a polyamide or a styrene/butadiene polymer.
14. The method according to any paragraph 11 to 13, wherein the water or grease resistant agent comprises a polyolefin polymer or a polyester polymer.
15. The method according to any paragraph 11 to 14, wherein the water or grease resistant agent comprises a polylactide polymer or a polylalkanoate polymer.
16. The method according to any paragraph 11 to 15, wherein the water or grease resistant agent comprises a wax.
17. The method according to any paragraph 11 to 16, wherein the water or grease resistant agent comprises a fluorochemical sizing agent or a chrome complex sizing agent.
18. The method according to any paragraph 11 to 17, wherein the water resistant agent, the grease resistant agent, or both are applied to the base sheet in water-borne form.
19. The method according to any paragraph 11 to 18, wherein the water resistant agent, the grease resistant agent, or both are applied to the base sheet as a latex.
20. The method according to any paragraph 11 to 19, wherein the water resistant agent, the grease resistant agent, or both are applied to the base sheet in melt form.
Certain embodiments and features have been described using a set of numerical upper limits and a set of numerical lower limits. It should be appreciated that ranges from any lower limit to any upper limit are contemplated unless otherwise indicated. Certain lower limits, upper limits and ranges appear in one or more claims below. All numerical values are “about” or “approximately” the indicated value, and take into account experimental error and variations that would be expected by a person having ordinary skill in the art.
Various terms have been defined above. To the extent a term used in a claim is not defined above, it should be given the broadest definition persons in the pertinent art have given that term as reflected in at least one printed publication or issued patent. Furthermore, all patents, test procedures, and other documents cited in this application are fully incorporated by reference to the extent such disclosure(s) is not inconsistent with this application and for all jurisdictions in which such incorporation is permitted.
While the foregoing is directed to embodiments of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow.
This application claims priority to U.S. Provisional Patent Application having Ser. No. 61/192,159, and filed on Sep. 16, 2008, the entirety of which is incorporated herein by reference.
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