Patent Application
20100269995
This invention provides a method of improving the wet-strength of cellulosic paper while enhancing the repulpability.
Wet strength resins are often added to paper products including paperboard at the time of manufacture. In the absence of wet strength resins, paper normally retains only 3% to 5% of its strength after being wetted with water. However, paper made with wet strength resin generally retains at least 10%-50% of its strength when wet. Wet strength is useful in a wide variety of paper applications, some examples of which are toweling, milk and juice cartons, paper bags, and liner board for corrugated containers.
As stated in Handbook for Pulp and Paper Technologists, Gary A. Smook, Angus Wilde Publications, 1992 (which is incorporated herein by reference): “Paper has traditionally been defined as a felted sheet formed on a fine screen from a water suspension of fibers. Current paper products generally conform to this definition except that most products also contain non-fibrous additives. Dry forming methods are now utilized for the manufacture of a few specialty paper products. Pulp is the fibrous raw material for papermaking. Pulp fibers are usually of vegetable origin, but animal, mineral, or synthetic fibers may be used for special applications. The distinction between paper and paperboard is based on product thickness. Nominally, all sheets above 0.3 mm thickness are classed as paperboard; but enough exceptions are applied to make the distinction somewhat hazy.”
Because of increased commercial emphasis on developing paper products based on recovered or recycled cellulose, there is growing interest in developing paper which is readily repulpable. Paper and paperboard waste materials are difficult to repulp in aqueous systems without special chemical treatment when they contain wet strength resins.
Improving the repulpability of paper containing wet strength resins has generally been achieved by modifying the repulping conditions. However, many conventional repulping processes used for wet strength paper result in the formation of environmentally undesirable chlorine-containing degradation products, involve strong oxidizing agents, or proceed slowly.
There is a need for improved methods for making paper products that will be readily repulpable without significantly lowering the wet and dry strength properties of the paper.
The present invention relates to repulpable paper products comprising: papermaking fibers; cationic strength additives; and sulfopolyester thermoplastic resins.
The present invention also relates to methods of improving the wet-strength of paper which comprises adding to the paper during the papermaking process cationic strength additives; and sulfopolyester thermoplastic resins.
The present invention relates to paper products comprising: papermaking fibers; cationic strength additives; and sulfopolyester thermoplastic resins.
The present invention relates to methods of improving the wet-strength of cellulosic paper comprising adding to the papermaking fibers during the papermaking process cationic strength additives and sulfopolyester thermoplastic resins.
The present invention may be understood more readily by reference to the following detailed description of the invention and to the Examples included therein.
Before the present compositions of matter and methods are disclosed and described, it is to be understood that this invention is not limited to specific synthetic methods or to particular formulations, unless otherwise indicated, and, as such, may vary from the disclosure. It is also to be understood that the terminology used is for the purpose of describing particular embodiments only, and is not intended to limit the scope of the invention.
The singular forms “a”, “an”, and the the include plural referents, unless the context clearly dictates otherwise.
Optional or optionally means that the subsequently described events or circumstances may or may not occur. The description includes instances where the events or circumstances occur, and instances where they do not occur.
Unless otherwise indicated, all numbers expressing quantities of ingredients, properties such as molecular weight, reaction conditions, and so forth used in the specification and claims are to be understood as being modified in all instances by the term “about.” Ranges may be expressed herein as from about one particular value, and/or to about another particular value. When such a range is expressed, it is to be understood that another embodiment is from the one particular value and/or to the other particular value, along with all combinations within said range. Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and attached claims are approximations that may vary depending upon the desired properties sought to be obtained by the present invention. At the very least, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques. Further, the ranges stated in this disclosure and the claims are intended to include the entire range specifically and not just the endpoint(s). For example, a range stated to be 0 to 10 is intended to disclose all whole numbers between 0 and 10 such as, for example 1, 2, 3, 4, etc., all fractional numbers between 0 and 10, for example 1.5, 2.3, 4.57, 6.1113, etc., and the endpoints 0 and 10.
Throughout this application, where patents or publications are referenced, the disclosures of these references in their entireties are intended to be incorporated by reference into this application, in order to more fully describe the state of the art to which the invention pertains.
Some relevant technical terms as used in the context of the present invention are meant to be understood as follows (unless specifically indicated otherwise throughout the description).
“Papermaking fibers,” as used herein, include all known cellulosic fibers or fiber mixes comprising cellulosic fibers. Fibers suitable for making the webs of this invention comprise any natural or synthetic cellulosic fibers including, but not limited to non-woody fibers, such as cotton or cotton derivatives, abaca, kenaf, sabai grass, flax, esparto grass, straw, jute hemp, bagasse, milkweed floss fibers, and pineapple leaf fibers; and woody 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, and aspen. Woody fibers may be prepared in high-yield or low-yield forms and may be pulped in any known method, including kraft, sulfite, groundwood, thermomechanical pulp (TMP), chemithermomechanical pulp (CTMP), and bleached chemithermomechanical pulp (BCTMP), high-yield pulping methods and other known pulping methods. High brightness pulps, including chemically bleached pulps, may be used and unbleached or semi-bleached pulps may also be used. Recycled fibers are included within the scope of the present invention. Any known pulping and bleaching methods may be used. Fibers prepared from organosolv pulping methods may also be used. Suitable papermaking fibers may also include recycled fibers, virgin fibers, or mixes thereof.
Synthetic cellulose fibers are also suitable for use including rayon in all its varieties and other fibers derived from viscose or chemically modified cellulose. Chemically treated natural cellulosic fibers may be used such as mercerized pulps, chemically stiffened or crosslinked fibers, sulfonated fibers, and the like. Suitable synthetic polymeric fibers include rayon, polyolefin fibers, polyester fibers, polyamide fibers and the like. Suitable synthetic polymer fiber structures include monocomponent, bicomponent, and multi component fibers such as core-sheath, islands-in-the-sea, side-by-side, segmented pie, and the like.
In one embodiment of the present invention the papermaking fibers comprise woody fibers, softwood Kraft pulp, hardwood Kraft pulp, recycled fibers, non-woody fibers, synthetic polymeric fibers, glass fibers, or combinations thereof. In one embodiment the synthetic polymeric fibers have a mean fiber diameter of less than 5 microns. In another embodiment the synthetic polymeric fibers comprise greater than 50% of the total papermaking fiber or greater than 70% of the total papermaking fiber.
For good mechanical properties in using papermaking fibers, it may be desirable that the fibers be relatively undamaged and largely unrefined or only lightly refined. While recycled fibers may be used, virgin fibers are also useful for their mechanical properties and lack of contaminants. Mercerized fibers, regenerated cellulosic fibers, cellulose produced by microbes, rayon, and other cellulosic material or cellulosic derivatives may be used. Suitable papermaking fibers may also include recycled fibers, virgin fibers, or mixes thereof.
As used herein, “high yield Pulp fibers” are those papermaking fibers of pulps produced by pulping processes providing a yield of about 65 percent or greater. Yield is the resulting amount of processed fiber expressed as a percentage of the initial wood mass. High yield pulps include bleached chemithermomechanical pulp (BCTMP), chemithermomechanical pulp (CTMP) pressure/pressure thermomechanical pulp (PTMP), thermomechanical pulp (TMP), thermomechanical chemical pulp (TMCP), high yield sulfite pulps, and high yield Kraft pulps, all of which contain fibers having high levels of lignin. Characteristic high-yield fibers can have lignin content by mass of about 1 percent or greater. Suitable high yield pulp fibers, after being prepared by pulping and optional bleaching steps and prior to being formed into dry bales or webs, in one embodiment can also be characterized by being comprised of comparatively whole, relatively undamaged fibers, high freeness (250 Canadian Standard Freeness (CSF) or greater, and low fines content (less than 25 percent by the Britt jar test). In one embodiment, the high-yield fibers are predominately softwood, for example northern softwood.
As used herein, the term “cellulosic” is meant to include any material having cellulose as a major constituent, and specifically comprising about 50 percent or more by weight of cellulose or cellulose derivatives. Thus, the term includes cotton, typical wood pulps, non-woody cellulosic fibers, cellulose acetate, cellulose triacetate, rayon, viscose fibers, thermomechanical wood pulp, chemical wood pulp, debonded chemical wood pulp, lyocell and other fibers formed from solutions of cellulose in NMMO, milkweed, or bacterial cellulose. Fibers that have not been spun or regenerated from solution may be used exclusively, if desired, or at least about 80% of the web may be free of spun fibers or fibers generated from a cellulose solution.
One aspect of the present invention relates to the production of paper products including paper and paper board from an aqueous slurry of papermaking fibers. It was discovered that the paper products of the present invention containing a cationic strength additive and a sulfopolyester thermoplastic resin resulted in paper products with improved or maintained wet strength and dry strength and with significantly enhanced repulpability.
One embodiment of the present invention relates to repulpable paper product comprising: papermaking fibers; cationic strength additives; and thermoplastic sulfopolyester resins.
Another embodiment of the present invention relates to paper product comprising: papermaking fibers; cationic strength additives; and thermoplastic sulfopolyester resins. The paper products according the present invention provide enhance repulpability.
In addition to enhanced repulability the paper products according to the present invention also provide enhanced sheet strength, increased machine speed, and improved retention. The present invention also allows the papermakers to simplify the wet end by reducing or eliminating the use of certain wet end additives, including dry strength resins, cationic starches, drainage and retention aids, and coagulants. When the present invention is used as both a wet and dry strength aid, the absorbency of the paper product is not decreased. The present invention provides the following improvements in sheet performance: lower basis weight, increased recycle fiber utilization, the ability to provide dispersion at higher concentration or in solid form, extended shelf life, reduced Kraft utilization, immediate cure, improved print receptivity, improved surface strength, improved sheet processibility, improved machine runnability, increased production, higher sheet ash content and filler cost savings, improved fiber recovery, reduced whitewater solids and turbidity, increased retention of wet strength additive, reduced system deposition, provides high levels of controllable drainage, improved formation, increased machine speed, reduced dryer energy consumption, simplified and cleaner wet end resulting from fewer additives, cost-effective additive scheme, and wet end chemical efficiency gains.
It is common to include various inorganic and organic materials to the aqueous slurry of pulp or papermaking fibers for improving the paper products and the papermaking process. The process of making the paper products according to the present invention can be carried out on any conventional paper making apparatus.
In general, the process of the present invention includes providing a slurry of papermaking fibers, adding the components of the present invention to the slurry of pulp papermaking fibers, depositing the slurry of pulp papermaking fibers containing the components of the present invention on a forming fabric, and drying the slurry to form a paper web.
In one embodiment of the present invention, the fibrous web to be formed from the papermaking fibers treated in accordance with the present invention may be wet-laid, such as webs may be formed with known papermaking techniques wherein the dilute aqueous fiber slurry is disposed on a moving wire to filter out the fibers and form a paper web which is subsequently dewatered by combinations of units including suction boxes, wet presses, dryer units, and the like. Capillary dewatering may also be applied to remove water from the web.
Any conventional drying method or dryers may be used according to the present invention. Drying operations may include drum drying, through drying, steam drying such as superheated steam drying, displacement dewatering, Yankee drying, infrared drying, microwave drying, radio frequency drying in general, and impulse drying.
A moist fibrous web may also be formed by foam forming processes, wherein the treated fibers are entrained or suspended in a foam prior to dewatering, or wherein foam is applied to a paper web prior to dewatering or drying.
The fibrous web is generally a random plurality of papermaking fibers that can, optionally, be joined together with a binder. Any papermaking fibers, as herein defined, or mixtures thereof may be used, such as bleached fibers from a kraft or sulfite chemical pulping process. Recycled fibers may also be used, as may cotton linters or papermaking fibers comprising cotton. Both high-yield and low-yield fibers may be used. In one embodiment, the fibers may be predominantly hardwood, such as at least 50% hardwood or about 60% hardwood or greater or about 80% hardwood or greater or substantially 100% hardwood. In another embodiment, the web is predominantly softwood, such as at least about 50% softwood or at least about 80% softwood, or about 100% softwood. In another embodiment, the web is predominantly synthetic polymeric fiber, such as at least about 50% synthetic polymeric fiber or at least about 80% synthetic polymeric fiber, or about 100% synthetic polymeric fiber.
The fibrous web of the present invention may be formed from a single layer or multiple layers. Stratified webs may also be formed wherein at least one layer comprises softwood fibers while another layer comprises hardwood or other fiber types. Layered structures produced by any means known in the art are within the scope of the present invention. In the case of multiple layers, the layers are generally positioned in a juxtaposed or surface-to-surface relationship and all or a portion of the layers may be bound to adjacent layers. The paper web may also be formed from a plurality of separate paper webs wherein the separate paper webs may be formed from single or multiple layers.
One embodiment of the present invention provides a method of improving the wet-strength of a cellulosic paper which comprises adding to the paper during the papermaking process a cationic strength additive; and a sulfopolyester thermoplastic resin.
The process for manufacturing paper products or the repulpable paper products according to the present invention comprises a number of steps. One step comprises forming an aqueous slurry of papermaking fibers or pulp or which can be performed by conventional means, i.e., known mechanical, chemical and semi-chemical, etc., pulping processes. Another step comprises adding to the aqueous slurry of papermaking fibers or pulp cationic strength additives and thermoplastic sulfopolyester resins. This can be done at any point, before sheet formation or it can also be applied after sheet formation from a tub size or at a size press or from showers to the dried or partially dried sheet. Yet another step comprises sheeting and drying the aqueous slurry of papermaking or pulp fibers containing the cationic thermosetting resin. This can be done by any conventional means.
In one embodiment, the components of the present invention comprising the cationic strength additives and the thermoplastic sulfopolyester resins are added to the pulp slurry separately, though depending on desired strength characteristics of the web, either the cationic strength additives or the thermoplastic sulfopolyester resins may be added to the slurry before the other.
During the papermaking process, the cationic strength additive can be incorporated by various methods including addition in the pulp fiber slurry or incorporation at the pulp press. In one embodiment of the present invention, the cationic strength additives are added to the slurry before the sulfopolyester thermoplastic resin. Without being bound by any theory, the cationic strength additive bonds to the anionically charged cellulose pulp fibers which results in a positively charged pulp fiber. Subsequently, the anionically charged sulfopolyester thermoplastic resin is applied to pulp fiber which results in an ionic bond. The sulfopolyester resin can be applied by various methods including spray application.
In another embodiment, the process of the present invention includes providing a slurry of pulp or papermaking fibers, sequentially adding the components of the present invention to the aqueous slurry of pulp or papermaking fibers, depositing the slurry of pulp or papermaking fibers containing the components of the present invention on a forming fabric, and drying the slurry to form a paper web. Such components may also be sprayed, printed, or coated onto the web after formation, while wet, or added to the wet end of the papermaking machine prior to formation.
According to the present invention, the components comprising the cationic strength additives and the thermoplastic sulfopolyester resins may be added to the slurry in a ratio from about a 1:5 to about a 5:1, as desired.
The pH of the slurry may be adjusted during the process. For example, the pH of the slurry may be adjusted to an acidic pH, such as about 6 or less in one embodiment. In another embodiment, however, the pH may be adjusted to greater than about 6. When the desired viscosity is reached, sufficient water is then added to adjust the solids content of the resin solution to about 15% or less, the product cooled to about 25° C. and then stabilized by adding sufficient acid to reduce the pH at least to about 6 and preferably to about 5. Any suitable acid such as hydrochloric, sulfuric, nitric, formic, phosphoric and acetic acid may be used to stabilize the product.
The paper web of the present invention may have any conventional bulk weight. In one embodiment, the paper web of the present invention may have a bulk greater than about 2 cc/g. For example, the paper web may have a bulk greater than about 5 cc/g. The dry tensile index of the paper web may be any conventional value. For example, the dry tensile index of the paper web can be greater than about 20 Nm/g in one embodiment. In another embodiment, the dry tensile index of the paper web can be greater than about 22 Nm/g. In yet another embodiment, the dry tensile index can be greater than about 25 Nm/g. In general, the basis weight of the paper webs of the present invention can be any desired basis weight. For instance, in one embodiment, the paper web may have a basis weight between about 5 and about 200 gsm.
Other conventional chemical additives that can be used in the papermaking process according to the present invention are: rosin size, reactive size (alkenyl succinic anhydride or alkyl ketene dimer), surface size, starch, retention aids, drainage aids, formation aids, flocculants, creping aids (adhesives and release agents), dry strength resins (cationic starch, guar gums, polyacrylamides), defoamers, scavengers for anionic trash and stickies control, fillers (clay, calcium carbonate, titanium dioxide), optical brightening aids and dyes.
During papermaking and wet laid nonwovens hydraulic manufacturing processes, chemical additives are often incorporated to improve the wet strength and/or dry strength of paper and paperboard products. These chemical additives are commonly known as wet and dry strength additives and are available from a number of commercially available sources.
Examples of permanent wet strength additives include polyamide epichlorohydrin and polyamidoamine epichlorohydrin and are collectively known as PAE resins. Examples of wet strength additives are based on chemistries such as polyacrylamide and glyoxalated polyacrylamide (GPAM) resins.
According to the present invention, the cationic strength additives may consist of either wet strength or dry strength additives and include glyoxylated polyacrylamides, polyacrylamides, polyamide epichlorohydrins (PAEs), starches and other cationic additives well known to those skilled in the art.
Polyamide epichlorohydrin, polyamidoamine epichlorohydrin and polyamine epichlorohydrin resins and are collectively known as PAE resins. PAE resins are widely used in the papermaking industry due to their ability to impart a high degree of wet strength to numerous paper products, including tissue, towel, wipes and corrugated board. PAE resins do not improve the dry strength of paper or paperboard and products containing these resins are generally considered not to be repulpable. Paper products containing wet strength additives, although generally repulpable; often have insufficient wet strength for many applications. Upon complete wetting, paper products derived from wet strength additives typically degrade within minutes to hours.
Suitable cationic strength additives used in accordance with the present invention include PAE resins, glyoxylated polyacrylamide resins, starches, polyacrylamides, and other wet strength and dry strength additives commonly known to those skilled in the art.
Procedures for making PAE resins are well known in the literature and are described in more detail in U.S. Pat. No. 3,772,076, which is incorporated herein by reference. PAE resins are sold by Ashland, Inc., Wilmington, Del., under the trade name Kymene® and by Georgia Pacific, Inc., Atlanta, Ga., under the trade name Amres®. A typical procedure for synthesizing a PAE resin is as follows. A polyalkylene polyamine is reacted with an aliphatic dicarboxylic acid to form a polyamidoamine backbone. An example of a polyamidoamine is the reaction product of diethylenetriamine with an adipic acid or ester of a dicarboxylic acid derivative. The resulting polyamidoamine is then reacted with epichlorohydrin in aqueous solution. The resulting product is diluted and neutralized with a strong mineral acid to a pH below 3.0.
Acrylamide polymers modified with glyoxal are known as glyoxalated polyacrylamide resins. Procedures for synthesizing glyoxylated polyacrylamide are well known in the literature and are described in more detail in U.S. Pat. No. 3,556,932, which is incorporated herein by reference. Glyoxylated polyacrylamide resins are sold by Kemira, Inc., Kennesaw, Georgia, under the trade name Parez®. The acrylamide polymer may contain monomers to modify ionic properties. The acrylamide base polymer is reacted with sufficient glyoxal under aqueous alkaline conditions until a slight increase in viscosity occurs. The resulting product is then quenched with acid. Approximately half of the added glyoxyal remains unreacted and dissolved in the water. It is also possible to pre-blend the acrylamide polymer and glyoxal in a dry particulate state and subsequently add this blend to warm water to form a glyoxalated polyacrylamide resin.
Dry strength additives include materials such as starches that may be cationic, quaternary or nonionic in nature. Examples of dry strength additives suitable for use in the present invention include cationic derivatives of polysaccharides (such as starch, guar, cellulose, and chitin); polyamine; polyethyleneimine; vinylalcohol-vinylamine copolymers; cationic acrylic homo- and copolymers such as polyacrylamide, polydiallyldimethylammonium chloride and copolymers of acrylic acid, acrylic esters and acrylamide with diallyldimethylammonium chloride, acryloyloxyethyltrimethylammonium chloride, methacryloyloxyethyltrimethylammonium methylsulfate, methacryloyloxyethyltrimethylammonium chloride and methacrylamidopropyltrimethylammonium chloride.
Other cationic strength resins that may be used in the present invention are: aminopolyamide-epi resins (e.g. Kymene® 557H-resin); polyamine-epi resins (e.g. Kymene® 736 resin), epoxide resins (e.g. Kymene® 450 and Kymene® 2064 resins); polyethylenimine, ureaformaldehyde resins; melamine-formaldehyde resins; glyoxalated polyacrylamides (e.g. Hercobond® 1000 resin, Parez 631NC); polyisocyanates; and reactive starches (oxidized starch, dialdehyde starch, blocked reactive group starch).
The amount of cationic strength additive is generally from about 0.25 to about 3.00 weight % on a dry basis, based on the weight of the dried paper. For example in some embodiments of the present invention the amount of cationic strength additive is from about 0.25-3.00 weight percent, 0.25-2.00 weight percent, or 0.25-1.50 weight percent. In other embodiments, the cationic strength additive may be about 2 weight % on a dry basis, based on the weight of the dried paper, or about 1 weight %, or about 0.5 weight %. In one embodiment of the present invention similar amounts of wet strength additive and sulfopolyester are used.
The sulfopolyesters of the present invention comprisedicarboxylic acid monomer residues, sulfomonomer residues, diol monomer residues, and repeating units. The sulfomonomer may be a dicarboxylic acid, a diol, or hydroxycarboxylic acid. Thus, the term “monomer residue”, as used herein, means a residue of a dicarboxylic acid, a diol, or a hydroxycarboxylic acid. A “repeating unit”, as used herein, means an organic structure having 2 monomer residues bonded through a carbonyloxy group. The sulfopolyesters of the present invention contain substantially equal molar proportions of acid residues (100 mole %) and diol residues (100 mole %) which react in substantially equal proportions such that the total moles of repeating units is equal to 100 mole %. The mole percentages provided in the present disclosure, therefore, may be based on the total moles of acid residues, the total moles of diol residues, or the total moles of repeating units. For example, a sulfopolyeseter containing 30 mole % of a sulfomonomer, which may be a dicarboxylic acid, a diol, or hydroxycarboxylic acid, based on the total repeating units, means that the sulfopolyester contains 30 mole % sulfomonomer out of a total of 100 mole % repeating units. Thus, there are 30 moles of sulfomonomer residues among every 100 moles of repeating units. Similarly, a sulfopolyeseter containing 30 mole % of a dicarboxylic acid sulfomonomer, based on the total acid residues, means the sulfopolyester contains 30 mole % sulfomonomer out of a total of 100 mole % acid residues. Thus, in this latter case, there are 30 moles of sulfomonomer residues among every 100 moles of acid residues.
The sulfopolyesters described herein have an inherent viscosity, abbreviated hereinafter as “Ih.V.”, of at least about 0.1 dL/g, preferably about 0.2 to 0.3 dL/g, and most preferably greater than about 0.3 dL/g, measured in a 60/40 parts by weight solution of phenol/tetrachloroethane solvent at 25.degree. C. and at a concentration of about 0.5 g of sulfopolyester in 100 mL of solvent. The term “polyester”, as used herein, encompasses both “homopolyesters” and “copolyesters” and means a synthetic polymer prepared by the polycondensation of difunctional carboxylic acids with difunctional hydroxyl compound. As used herein, the term “sulfopolyester” means any polyester comprising a sulfomonomer. Typically the difunctional carboxylic acid is a dicarboxylic acid and the difunctional hydroxyl compound is a dihydric alcohol such as, for example glycols and diols. Alternatively, the difunctional carboxylic acid may be a hydroxy carboxylic acid such as, for example, p-hydroxybenzoic acid, and the difunctional hydroxyl compound may be a aromatic nucleus bearing 2 hydroxy substituents such as, for example, hydroquinone. The term “residue”, as used herein, means any organic structure incorporated into the polymer through a polycondensation reaction involving the corresponding monomer. Thus, the dicarboxylic acid residue may be derived from a dicarboxylic acid monomer or its associated acid halides, esters, salts, anhydrides, or mixtures thereof. As used herein, therefore, the term dicarboxylic acid is intended to include dicarboxylic acids and any derivative of a dicarboxylic acid, including its associated acid halides, esters, half-esters, salts, half-salts, anhydrides, mixed anhydrides, or mixtures thereof, useful in a polycondensation process with a diol to make a high molecular weight polyester.
The sulfopolyester of the present invention includes one or more dicarboxylic acid residues. Depending on the type and concentration of the sulfomonomer, the dicarboxylic acid residue may comprise from about 60 to about 100 mole % of the acid residues. Other examples of concentration ranges of dicarboxylic acid residues are from about 60 mole % to about 95 mole %, and about 70 mole % to about 95 mole %. Examples of dicarboxylic acids that may be used include aliphatic dicarboxylic acids, alicyclic dicarboxylic acids, aromatic dicarboxylic acids, or mixtures of two or more of these acids. Thus, suitable dicarboxylic acids include, but are not limited to succinic; glutaric; adipic; azelaic; sebacic; fumaric; maleic; itaconic; 1,3-cyclohexanedicarboxylic; 1,4-cyclohexanedicarboxylic; diglycolic; 2,5-norbornanedicarboxylic; phthalic; terephthalic; 1,4-naphthalenedicarboxylic; 2,5-naphthalenedicarboxylic; diphenic; 4,4′-oxydibenzoic; 4,4′-sulfonyldibenzoic; and isophthalic. The preferred dicarboxylic acid residues are isophthalic, terephthalic, and 1,4-cyclohexanedicarboxylic acids, or if diesters are used, dimethyl terephthalate, dimethyl isophthalate, and dimethyl-1,4-cyclohexane-dicarboxylate with the residues of isophthalic and terephthalic acid being especially preferred. Although the dicarboxylic acid methyl ester is the most preferred embodiment, it is also acceptable to include higher order alkyl esters, such as ethyl, propyl, isopropyl, butyl, and so forth. In addition, aromatic esters, particularly phenyl, also may be employed.
The sulfopolyester includes about 4 to about 40 mole %, based on the total repeating units, of residues of at least one sulfomonomer having 2 functional groups and one or more sulfonate groups attached to an aromatic or cycloaliphatic ring wherein the functional groups are hydroxyl, carboxyl, or a combination thereof. Additional examples of concentration ranges for the sulfomonomer residues are about 4 to about 35 mole %, about 8 to about 30 mole %, and about 8 to about 25 mole %, based on the total repeating units. The sulfomonomer may be a dicarboxylic acid or ester thereof containing a sulfonate group, a diol containing a sulfonate group, or a hydroxy acid containing a sulfonate group. The term “sulfonate” refers to a salt of a sulfonic acid having the structure “—SO.sub.3M” wherein M is the cation of the sulfonate salt. The cation of the sulfonate salt may be a metal ion such as Li.sup.+, Na.sup.+, K.sup.+, Mg.sup.++, Ca.sup.++, Ni.sup.++, Fe.sup.++, and the like. Alternatively, the cation of the sulfonate salt may be non-metallic such as a nitrogenous base as described, for example, in U.S. Pat. No. 4,304,901. Nitrogen-based cations are derived from nitrogen-containing bases, which may be aliphatic, cycloaliphatic, or aromatic compounds. Examples of such nitrogen containing bases include ammonia, dimethylethanolamine, diethanolamine, triethanolamine, pyridine, morpholine, and piperidine. Because monomers containing the nitrogen-based sulfonate salts typically are not thermally stable at conditions required to make the polymers in the melt, the method of this invention for preparing sulfopolyesters containing nitrogen-based sulfonate salt groups is to disperse, dissipate, or dissolve the polymer containing the required amount of sulfonate group in the form of its alkali metal salt in water and then exchange the alkali metal cation for a nitrogen-based cation.
When a monovalent alkali metal ion is used as the cation of the sulfonate salt, the resulting sulfopolyester is completely dispersible in water with the rate of dispersion dependent on the content of sulfomonomer in the polymer, temperature of the water, surface area/thickness of the sulfopolyester, and so forth. When a divalent metal ion is used, the resulting sulfopolyesters are not readily dispersed by cold water but are more easily dispersed by hot water. Utilization of more than one counterion within a single polymer composition is possible and may offer a means to tailor or fine-tune the water-responsivity of the resulting article of manufacture. Examples sulfomonomers residues include monomer residues where the sulfonate salt group is attached to an aromatic acid nucleus, such as, for example, benzene; naphthalene; diphenyl; oxydiphenyl; sulfonyldiphenyl; and methylenediphenyl or cycloaliphatic rings, such as, for example, cyclohexyl; cyclopentyl; cyclobutyl; cycloheptyl; and cyclooctyl. Other examples of sulfomonomer residues which may be used in the present invention are the metal sulfonate salt of sulfophthalic acid, sulfoterephthalic acid, sulfoisophthalic acid, or combinations thereof. Other examples of sulfomonomers which may be used are 5-sodiosulfoisophthalic acid and esters thereof. If the sulfomonomer residue is from 5-sodiosulfoisophthalic acid, typical sulfomonomer concentration ranges are about 0.4 to about 35 mole %, about 8 to about 30 mole %, and about 8 to 25 mole %, based on the total moles of acid residues.
The sulfomonomers used in the preparation of the sulfopolyesters are known compounds and may be prepared using methods well known in the art. For example, sulfomonomers in which the sulfonate group is attached to an aromatic ring may be prepared by sulfonating the aromatic compound with oleum to obtain the corresponding sulfonic acid and followed by reaction with a metal oxide or base, for example, sodium acetate, to prepare the sulfonate salt. Procedures for preparation of various sulfomonomers are described, for example, in U.S. Pat. Nos. 3,779,993; 3,018,272; and 3,528,947.
It is also possible to prepare the polyester using, for example, a sodium sulfonate salt, and ion-exchange methods to replace the sodium with a different ion, such as zinc, when the polymer is in the dispersed form. This type of ion exchange procedure is generally superior to preparing the polymer with divalent salts insofar as the sodium salts are usually more soluble in the polymer reactant melt-phase.
The sulfopolyester includes one or more diol residues which may include aliphatic, cycloaliphatic, and aralkyl glycols. The cycloaliphatic diols, for example, 1,3- and 1,4-cyclohexanedimethanol, may be present as their pure cis or trans isomers or as a mixture of cis and trans isomers. As used herein, the term “diol” is synonymous with the term “glycol” and means any dihydric alcohol. Examples diols include ethylene glycol; diethylene glycol; triethylene glycol; polyethylene glycols; 1,3-propanediol; 2,4-dimethyl-2-ethylhexane-1,3-diol; 2,2-dimethyl-1,3-propanediol; 2-ethyl-2-butyl-1,3-propanediol; 2-ethyl-2-isobutyl-1,3-propanediol; 1,3-butanediol; 1,4-butanediol; 1,5-pentanediol; 1,6-hexanediol; 2,2,4-trimethyl-1,6-hexanediol; thiodiethanol; 1,2-cyclohexanedimethanol; 1,3-cyclohexanedimethanol; 1,4-cyclohexanedimethanol; 2,2,4,4-tetramethyl-1,3-cyclobutanediol; p-xylylenediol, or combinations of one or more of these glycols.
The diol residues may include from about 25 mole % to about 100 mole %, based on the total diol residues, of residue of a poly(ethylene glycol) having a structure H—(OCH.sub.2-CH.sub.2).sub.n-OH wherein n is an integer in the range of 2 to about 500. Non-limiting examples of lower molecular weight polyethylene glycols, e.g., wherein n is from 2 to 6, are diethylene glycol, triethylene glycol, and tetraethylene glycol. Of these lower molecular weight glycols, diethylene and triethylene glycol are most preferred. Higher molecular weight polyethylene glycols (abbreviated herein as “PEG”), wherein n is from 7 to about 500, include the commercially available products known under the designation CARBOWAX®, a product of Dow Chemical Company (formerly Union Carbide). Typically, PEG's are used in combination with other diols such as, for example, diethylene glycol or ethylene glycol. Based on the values of n, which range from greater than 6 to 500, the molecular weight may range from greater than 300 to about 22,000 g/mol. The molecular weight and the mole % are inversely proportional to each other; specifically, as the molecular weight is increased, the mole % will be decreased in order to achieve a designated degree of hydrophilicity. For example, it is illustrative of this concept to consider that a PEG having a molecular weight of 1000 may constitute up to 10 mole % of the total diol, while a PEG having a molecular weight of 10,000 would typically be incorporated at a level of less than 1 mole % of the total diol.
Certain dimer, trimer, and tetramer diols may be formed in situ due to side reactions that may be controlled by varying the process conditions. For example, varying amounts of diethylene, triethylene, and tetraethylene glycols may be formed from ethylene glycol from an acid-catalyzed dehydration reaction which occurs readily when the polycondensation reaction is carried out under acidic conditions. The presence of buffer solutions, well-known to those skilled in the art, may be added to the reaction mixture to retard these side reactions. Additional compositional latitude is possible, however, if the buffer is omitted and the dimerization, trimerization, and tetramerization reactions are allowed to proceed.
The sulfopolyester of the present invention may include from 0 to about 25 mole %, based on the total repeating units, of residues of a branching monomer having 3 or more functional groups wherein the functional groups are hydroxyl, carboxyl, or a combination thereof. Non-limiting examples of branching monomers are 1,1,1-trimethylol propane, 1,1,1-trimethylolethane, glycerin, pentaerythritol, erythritol, threitol, dipentaerythritol, sorbitol, trimellitic anhydride, pyromellitic dianhydride, dimethylol propionic acid, or combinations thereof. Further examples of branching monomer concentration ranges are from 0 to about 20 mole % and from 0 to about 10 mole %. The presence of a branching monomer may result in a number of possible benefits to the sulfopolyester of the present invention, including but not limited to, the ability to tailor rheological, solubility, and tensile properties. For example, at a constant molecular weight, a branched sulfopolyester, compared to a linear analog, will also have a greater concentration of end groups that may facilitate post-polymerization crosslinking reactions. At high concentrations of branching agent, however, the sulfopolyester may be prone to gelation.
The sulfopolyesters of the present invention has a glass transition temperature, abbreviated herein as “Tg”, of at least 25.degree. C. as measured on the dry polymer using standard techniques, such as differentical scanning calorimetry (“DSC”), well known to persons skilled in the art. The Tg measurements of the sulfopolyesters of the present invention are conducted using a “dry polymer”, that is, a polymer sample in which adventitious or absorbed water is driven off by heating to polymer to a temperature of about 200.degree. C. and allowing the sample to return to room temperature. Typically, the sulfopolyester is dried in the DSC apparatus by conducting a first thermal scan in which the sample is heated to a temperature above the water vaporization temperature, holding the sample at that temperature until the vaporization of the water absorbed in the polymer is complete (as indicated by an a large, broad endotherm), cooling the sample to room temperature, and then conducting a second thermal scan to obtain the Tg measurement. Further examples of glass transition temperatures exhibited by the sulfopolyester are at least 30.degree. C., at least 35.degree. C., at least 40.degree. C., at least 50.degree. C., at least 60.degree. C., at least 65.degree. C., at least 80.degree. C., and at least 90.degree. C. Although other Tg's are possible, typical glass transition temperatures of the dry sulfopolyesters our invention are about 30.degree. C., about 48.degree. C., about 55.degree. C., about 65.degree. C., about 70.degree. C., about 75.degree. C., about 85.degree. C., and about 90.degree. C.
Our invention also provides sulfopolyesters which comprise: (i) about 50 to about 96 mole % of one or more residues of isophthalic acid or terephthalic acid, based on the total acid residues; (ii) about 4 to about 30 mole %, based on the total acid residues, of a residue of sodiosulfoisophthalic acid; (iii) one or more diol residues wherein at least 25 mole %, based on the total diol residues, is a poly(ethylene glycol) having a structure H—(OCH.sub.2-CH.sub.2).sub.n-OH wherein n is an integer in the range of 2 to about 500; (iv) 0 to about 20 mole %, based on the total repeating units, of residues of a branching monomer having 3 or more functional groups wherein the functional groups are hydroxyl, carboxyl, or a combination thereof.
The sulfopolyester may contain other concentrations of isophthalic acid residues, for example, about 60 to about 95 mole %, and about 75 to about 95 mole %. Further examples of isophthalic acid residue concentrations ranges are about 70 to about 85 mole %, about 85 to about 95 mole % and about 90 to about 95 mole %. The sulfopolyester also may comprise about 25 to about 95 mole % of the residues of diethylene glycol. Further examples of diethylene glycol residue concentration ranges include about 50 to about 95 mole %, about 70 to about 95 mole %, and about 75 to about 95 mole %. The sulfopolyester also may include the residues of ethylene glycol and/or 1,4-cyclohexanedimethanol, abbreviated herein as “CHDM”. Typical concentration ranges of CHDM residues are about 10 to about 75 mole %, about 25 to about 65 mole %, and about 40 to about 60 mole %. Typical concentration ranges of ethylene glycol residues are are about 10 to about 75 mole %, about 25 to about 65 mole %, and about 40 to about 60 mole %. In another embodiment, the sulfopolyester comprises is about 75 to about 96 mole % of the residues of isophthalic acid and about 25 to about 95 mole % of the residues of diethylene glycol.
The sulfopolyesters of the present invention are readily prepared from the appropriate dicarboxylic acids, esters, anhydrides, or salts, sulfomonomer, and the appropriate diol or diol mixtures using typical polycondensation reaction conditions. They may be made by continuous, semi-continuous, and batch modes of operation and may utilize a variety of reactor types. Examples of suitable reactor types include, but are not limited to, stirred tank, continuous stirred tank, slurry, tubular, wiped-film, falling film, or extrusion reactors. The term “continuous” as used herein means a process wherein reactants are introduced and products withdrawn simultaneously in an uninterrupted manner. By “continuous” it is meant that the process is substantially or completely continuous in operation and is to be contrasted with a “batch” process. “Continuous” is not meant in any way to prohibit normal interruptions in the continuity of the process due to, for example, start-up, reactor maintenance, or scheduled shut down periods. The term “batch” process as used herein means a process wherein all the reactants are added to the reactor and then processed according to a predetermined course of reaction during which no material is fed or removed into the reactor. The term “semicontinuous” means a process where some of the reactants are charged at the beginning of the process and the remaining reactants are fed continuously as the reaction progresses.
Alternatively, a semicontinuous process may also include a process similar to a batch process in which all the reactants are added at the beginning of the process except that one or more of the products are removed continuously as the reaction progresses. The process is operated advantageously as a continuous process for economic reasons and to produce superior coloration of the polymer as the sulfopolyester may deteriorate in appearance if allowed to reside in a reactor at an elevated temperature for too long a duration.
The sulfopolyesters of the present invention are prepared by procedures known to persons skilled in the art. The sulfomonomer is most often added directly to the reaction mixture from which the polymer is made, although other processes are known and may also be employed, for example, as described in U.S. Pat. Nos. 3,018,272, 3,075,952, and 3,033,822. The reaction of the sulfomonomer, diol component and the dicarboxylic acid component may be carried out using conventional polyester polymerization conditions. For example, when preparing the sulfopolyesters by means of an ester interchange reaction, i.e., from the ester form of the dicarboxylic acid components, the reaction process may comprise two steps. In the first step, the diol component and the dicarboxylic acid component, such as, for example, dimethyl isophthalate, are reacted at elevated temperatures, typically, about 150.degree. C. to about 250.degree. C. for about 0.5 to about 8 hours at pressures ranging from about 0.0 kPa gauge to about 414 kPa gauge (60 pounds per square inch, “psig”). Preferably, the temperature for the ester interchange reaction ranges from about 180.degree. C. to about 230.degree. C. for about 1 to about 4 hours while the preferred pressure ranges from about 103 kPa gauge (15 psig) to about 276 kPa gauge (40 psig). Thereafter, the reaction product is heated under higher temperatures and under reduced pressure to form sulfopolyester with the elimination of diol, which is readily volatilized under these conditions and removed from the system. This second step, or polycondensation step, is continued under higher vacuum and a temperature which generally ranges from about 230.degree. C. to about 350.degree. C., preferably about 250.degree. C. to about 310.degree. C. and most preferably about 260.degree. C. to about 290.degree. C. for about 0.1 to about 6 hours, or preferably, for about 0.2 to about 2 hours, until a polymer having the desired degree of polymerization, as determined by inherent viscosity, is obtained. The polycondensation step may be conducted under reduced pressure which ranges from about 53 kPa (400 torr) to about 0.013 kPa (0.1 torr). Stirring or appropriate conditions are used in both stages to ensure adequate heat transfer and surface renewal of the reaction mixture. The reactions of both stages are facilitated by appropriate catalysts such as, for example, alkoxy titanium compounds, alkali metal hydroxides and alcoholates, salts of organic carboxylic acids, alkyl tin compounds, metal oxides, and the like. A three-stage manufacturing procedure, similar to that described in U.S. Pat. No. 5,290,631, may also be used, particularly when a mixed monomer feed of acids and esters is employed.
To ensure that the reaction of the diol component and dicarboxylic acid component by an ester interchange reaction mechanism is driven to completion, it is preferred to employ about 1.05 to about 2.5 moles of diol component to one mole dicarboxylic acid component. Persons of skill in the art will understand, however, that the ratio of diol component to dicarboxylic acid component is generally determined by the design of the reactor in which the reaction process occurs.
In the preparation of sulfopolyester by direct esterification, i.e., from the acid form of the dicarboxylic acid component, sulfopolyesters are produced by reacting the dicarboxylic acid or a mixture of dicarboxylic acids with the diol component or a mixture of diol components. The reaction is conducted at a pressure of from about 7 kPa gauge (1 psig) to about 1379 kPa gauge (200 psig), preferably less than 689 kPa (100 psig) to produce a low molecular weight, linear or branched sulfopolyester product having an average degree of polymerization of from about 1.4 to about 10. The temperatures employed during the direct esterification reaction typically range from about 180.degree. C. to about 280.degree. C., more preferably ranging from about 220.degree. C. to about 270.degree. C. This low molecular weight polymer may then be polymerized by a polycondensation reaction.
The amount of thermoplastic sulfopolyester resin is generally from about 0.25 to about 3.00 weight % on a dry basis, based on the weight of the dried paper. For example in one embodiment the amount of sulfopolyester is from about 0.25-3.00 weight percent, 0.25-2.00 weight percent, or 0.25-1.50 weight percent. In another embodiment the amount of thermoplastic sulfopolyester can be about 0.05 weight % on a dry basis, or about 0.1 weight % or about 0.2 weight %. Typically the ratio of thermoplastic sulfopolyester resin to cationic strength additive is about 5:1 to about 1:5. In one embodiment the ratio of f sulfopolyester to cationic strength additive is about 1:1.
The repulping process may be carried out using any conventional method. Typically, the process of repulping the paper to obtain recycled pulp fibers can be carried out by any mechanical action that disperses dry pulp fibers into an aqueous pulp fiber suspension. Conditions for repulping, as well as equipment commercially used, are discussed in “Handbook for Pulp & Paper Technologists, Second Edition” by G. A. Smook, Angus Wilde Publications, 1992, pp 194-195 and 211-212, which reference is incorporated herein by reference in its entirety.
It was found that paper prepared by the process of the present invention can be repulped in substantially less time than is required to repulp the same paper at about the same level of wet-strength.
The paper products of the present invention are suitable for use in the following areas: paper towels; napkins; facial tissue; liquid packaging board (milk carton, juice carton); poultry boxes; produce boxes; carrierboard; butchers wrap; bleached bag; poster board; table cloth; wallboard tape; currency paper; map paper; tea bag; corrugating medium; paper plates; molded products (egg cartons); laminating grades; flooring felt; coffee filter; bread wrap; multiwall bag; shingle wrap, etc.
The recycled pulp fibers prepared by the repulping process of the present invention can be used to make paper by conventional paper making processes, which comprise providing an aqueous suspension of the recycled pulp fibers and then sheeting and drying the aqueous suspension to obtain paper.
The invention has been described in detail with particular reference to preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention.
This invention can be further illustrated by the following examples of potential embodiments thereof, although it will be understood that these examples are included merely for the purposes of illustration and are not intended to limit the scope of the invention unless otherwise specifically indicated. Parts and percentages mean parts by weight and percentages by weight, unless otherwise specified.
The examples were conducted using EastONE S85030 sulfopolyester dispersion to determine the effect of its addition on wet strength, dry strength and repulpability of paper in comparison to commercially available additives such as Kymene® and Hercobond® products from Hercules Incorporated, Wilmington, Del.
A 3 wt % solution of a sulfopolyester was prepared as follows. 500 grams of distilled water was placed into a beaker heated to approximately 88.degrees. C. on a hot plate. 15.5 grams of sulfopolyester pellets were added and continually stirred while maintaining a temperature of 88.degrees. C. F for 10-15 minutes or until all of the sulfopolyester had dissolved. The mixture was cooled and distilled water was added to achieve a total solution weight of 515.5 grams.
A 3 wt % solution of a PAE solution was prepared as follows. 500 grams of distilled water was placed into a beaker. 160 grams of a 12.5 wt % solution of a commercially available PAE solution was added to the beaker and stirred.
Each of the 3 wt % solutions was diluted, respectively, using distilled water such that when 3 ml of the solution was applied to the paper sheet, the target add-on concentration of 0.5 wt % was achieved.
3 drops of food coloring were added to each of the solutions as a visual aid to ensure uniform coverage of the solutions on the paper. An 8½″×11″ sheet of Lydall paper was placed on top of a larger piece of release paper. Lydall 18-½# Manning 514 saturating paper sheets weighing 1.87±0.01 grams were used. The release paper was parchment paper laminated to aluminum foil.
A control was prepared as follows. 5 ml of distilled water was added to the paper sheet using a 5 ml volumetric pipette. The water was gently rolled into the sheet using a 2 inch rubber hand roller. The paper sheet, with the release sheet attached, was dried for 5 minutes in a 93.degree. C. convection oven. The dried sheet was stored for 4 days under a 2 pound flat weight. This sample is referred to as the Control.
A sample containing 0.5 wt % PAE resin was prepared as follows. 5 ml of distilled water was added to the paper sheet using a 5 ml volumetric pipette. The water was gently rolled into the sheet using a hand roller. 3 ml of the diluted PAE solution was added with a 3 ml syringe to the pre-wetted paper. The solution was gently rolled into the sheet using a hand roller until uniform color was achieved. The paper sheet, with the release sheet attached, was dried for 5 minutes in a 93.degree. C. convection oven. The dried sheet was stored for 4 days under a 2 pound flat weight. This sample is referred to as Sample 1.
A sample containing 0.5 wt % sulfopolyester resin was prepared as follows. 5 ml of distilled water was added to the paper sheet using a 5 ml volumetric pipette. The water was gently rolled into the sheet using a hand roller. 3 ml of the diluted sulfopolyester solution was added with a 3 ml syringe to the pre-wetted paper. The solution was gently rolled into the sheet using a hand roller until uniform color was achieved. The paper sheet, with the release sheet attached, was dried for 5 minutes in a 93.degree. C. convection oven. The dried sheet was stored for 4 days under a 2 pound flat weight. This sample is referred to as Sample 2.
An example of the present invention containing 0.25 wt % PAE and 0.25 wt % sulfopolyester was prepared as follows. 5 ml of distilled water was added to the paper sheet using a 5 ml volumetric pipette. The water was gently rolled into the sheet using a hand roller. 3 ml of the diluted PAE solution was added with a 3 ml syringe to the pre-wetted paper. The solution was gently rolled into the sheet using a hand roller until uniform color was achieved. The sheet was allowed to sit for 2 minutes. 3 ml of the diluted sulfopolyester solution was subsequently added to the paper with a 3 ml syringe. The sulfopolyester solution was gently hand rolled into the paper. The paper sheet, with the release sheet attached, was dried for 5 minutes in a 93.degree. C. convection oven. The dried sheet was stored for 4 days under a 2 pound flat weight. This sample is referred to as Sample 3.
The control and Samples 1, 2 and 3 were evaluated for dry strength and wet strength using the following TAPPI test methods:
The repulpability of the paper samples was determined as follows. A brass hydropulper manufactured by Hermann Manufacturing Company was used for testing. The hydropulper was a 2 liter vessel with a 3000 rpm, ¾ horsepower tri-rotor. The hydropulper had a diameter of 6 inches and a height of 10 inches.
Samples were cut into two 1 inch squares. A 2 liter sample of water was maintained at 20.degrees. C. and poured into the hydropulper. The counter was set to zero and both samples were placed into the hydropulper. The samples were pulped at intervals of 500 revolutions. After each of the 500 revolutions, the hydropulper was temporarily stopped and a fluorescent inspection light was held over the basin to determine whether or not the samples had been fully pulped. The number of sets per 500 revolutions was recorded. After 15,000 revolutions, samples were considered not repulpable and testing was discontinued. The test results are shown below in Table 1.
This application claims priority to U.S. Provisional Application Ser. No. 61/172,257 filed Apr. 24, 2009, the disclosure of which is incorporated herein by reference in its entirety.
| Number | Date | Country | |
|---|---|---|---|
| 61172257 | Apr 2009 | US |
