Use of amphoteric emulsion polymers with strength resins as retention and drainage aids

Abstract

The present invention generally relates to methods and compositions for manufacture of tissue, paper, or board and for enhancing retention and drainage thereof. In particular, the disclosure provides methods for enhancing retention and drainage by addition of a retention and drainage aid comprising reactive cationic polymers (e.g., cationic strength resins), water-soluble amphoteric terpolymers, and optionally anionic organic or inorganic microparticles. Preparation of paper sheets under these conditions provides improved retention, drainage time, STFI and burst strength, and improved hydrophobic particle control.

Description

ArrY DocKErNo. I149704.062013CLIENTRPT NO. U52324USE OF AMPHOTERIC EMULSION POLYMERSWITH STRENGTH RESINSAS RETENTION AND DRAINAGEAIDS RELATED APPLICATIONStggoll Thepresentapplicationclaims benefit ofprioritytoUSProvisionalApplication No':63 / 5\0,759, filed on June28, 2023, and to Finnish ApplicationNumber 20236130 filed on October12,2023, the contentsof both of which are incorporatedby reference in their entireties.FIELD OF THE INVENTIONt00021 The present inventiongenerallyrelates tomethods and compositionsfor manufacture oftissue, paper, or board and for enhancing retentionand drainage thereof. ln particular, thedisclosure provides methods for enhancingretention and drainageby addition of a retention anddrainage aid comprisingreactive cationicpolymers (e.g.,cationicstrength resins), water-solubleamphoteric terpolymers, and optionally anionic organicor inorganic microparticles. Preparation ofpaper sheets under these conditionsprovidesimprovedretention, drainage time, STFI and burststrength,and improved hydrophobicparticle control.BACKGROUND OFTHE INVENTIONt00031 Glyoxylated polyacrylamide(GPAM)is generally usedin a variety of paper grades to enhancethe dry and temporary wet strength. lt is used for example toincrease the initial wet strength ofmany household tissues which come in contactwith water in use. Glyoxylated polyacrylamide is alsoapplied to increase the compression strengthand the dimensional stability of many board-gradepaperproducts.t96g4l ln the production ofpaperorpaperboard,adilute aqueous composition known as "furnish"or "stock" is sprayed onto a moving mesh knownas a "wire" or "wire screen". Solid components ofthis composition, such as cellulosicfibers, fines, and inorganicparticulate mineral fillers are drainedor filtered by the wire to forma paper sheet. Thepercentageofsolid material retained on the wire isknown as the"first pass retention" of thepapermaking process't00051 Paper and board manufacturers requirechemical additives that will effectively provideenhanced on-machine retention anddrainage while alsoprovidingadditionalbenefits, such asimprovedpaperstrength andwet pressability. These requirementsare especially challenging forpapermakingoperationsin millswithhigh recycledcontent.t0066l Retentionis a function of different mechanisms, such as filtration by mechanicalentrainment, electrostatic attraction,andbridgingbetween the fibers and the fillers in the furnish.Because both the cellulosicfibers and many common fillermaterials are negatively charged, they aremutually repellent.Generally, the only factor tending toenhance retention is mechanicalentrainment. Therefore, a retention aidis generally used to improve retention of the fibers andfillerson the wire.tO6O7l Drainage relatesto the rate of removal ofwater from the furnish as the paper sheet isformed. Drainage usually refers to only waterremoval which takes place in the "drainage zone"(gravity and vacuum sections) of thepaper machineprimarilybefore anypressing of the wet paperweb subsequent to formation ofthe web. Thus, drainageaids are used to improve the overallefficiency of dewateringin theproductionofpaperorpaperboard'Arrv DocrerNo. I 149704.062013CLIENTREP NO. U52324tooo8l lmprovements in retention and drainageof the final paper or paperboard sheet areparticularly desirable for several reasons,the most significant ofwhich is productivity' Goodretention and good drainage enable apapermachine to runfaster and to increase production.tggogl These improvementsare realized by the useof retention and drainage aids. These retentionand drainage aids aregenerallyadded to thefurnish asthefurnish approaches the headbox of thepaper machine and may comprisea coagulant / flocculant systemused in conjunction with one ormore shearing stages.t00101 A coagulantistypicallya low molecular weightcationic synthetic polymer that reduces thenegative surface charges on the fiber, fines, and / orfiller particles to accomplish agglomeration ofsuch particles. The flocculant, whichgenerally is a high molecular weightcationic, nonionic, oranionic syntheticpolymer,bridges theparticles and / or agglomerates,from one surface to another,thereby binding the particlesintolarger flocs. The largerflocs increase retention of the particles;however, as they are filtered out of the water onto thefiber web, the pores of the flocs are covered,thereby reducing the drainage efficiency ofthe fiber web. The largerflocs can be broken down byshearing which isprovidedby one ormore of the cleaning, mixing andpumping stages of thepapermakingprocess.tO011l Greater retention of fines and fillerspermits a reduction in the content of cellulosic fiber' Aspulpsof inferiorquality are employed toreduce papermaking costs, the retention aspect ofpapermaking becomes even moreimportant. This is due to thehigher level of fines found in lowerquality pulps, such as recycledfiberandcoatedbroke.Greaterretention of fines, fillers, and otherslurry components also reduces the amount of suchsubstances lost to the white water. This reducesthe amount of material wastes, the cost ofwaste disposal, and the adverse environmental effectstherefrom.t00121 There is a needinthe artto provide an improved coagulant / flocculantsystem which replacesthe cationic coagulant / high molecular weight anionicflocculant system of the prior art resulting in asubstantial improvement of the retentionand drainagepropertiesof thepaper furnish and thephysicalpropertiesof the formedpaper product such as formationand brightness. This isparticularly true for paper furnishes containing recycleddeinked fiber, groundwood, bleached fiberlinerboard and / or coated broke and either treated oruntreated fillers, higher levels of stickies,calcium ions, andconductivity.tOO13l Recycled fiber materialiscommonlyused as raw material for paper or board. The recycledfiber material comprisesinadditionto the fibers a numberof other substances. Particulate foreignmaterial is separated from the pulp in thepulperorat the screening. Some substances are naturallyretained on the fibers and do not disturbthe process. Other substances, such as stickies, may beseparated from thepulpat thescreening and at leastpartlyremovedfrom the process.tOO14l Use of recycledfiber material as raw materialisthemain source of hydrophobic substances,so called stickies, in paper and board making.While some or even most of these hydrophobicsubstances are removed during thepulpingofrecycled fiber rawmaterials, substantial amounts arestill carried over during thepaper or board makingprocess. Hydrophobic substances, which have notbeen removed in de-inking or other recycled fiberprocessing stages, e.g., which are not trapped bythe screens, enter the paper or board machineand circulate in the process waters. Due to theincreased environmental awareness andregulations,papermaking processes have become moreand more closed and useless fresh water. This resultsin heavy accumulation of interferingsubstances, including hydrophobic substances,in the fiber suspension and process waters. TheseArrY DocKEr No.1149704.062013 CLIENTREF NO. U52324substances may agglomerate into biggerhydrophobicparticles, which are capable of formingdeposits. Additionally, accumulationof dissolved saltsrenders traditional CPAMs less effective.Traditional CPAMs are not effectively reactivewith dissolved salts because traditional CPAMs are toobig inmolecular size and too low inpolymercationiccharge.tgoi.sl ln addition to the recycledfibermaterial, recycle of coated broke can also cause similarproblems as described abovefor the recycled fiber material.Coated broke contaminant depositionin papermaking systems can cause serious operationalproblems if left uncontrolled. Coated broke isrepulped and used as a furnish source atmost coated finepapermills. Themost difficult probleminvolved with recycling coated brokeis derived from the bindermaterials, sometimes in combinationwith pigments or fillers, since thesepolymers and the materialsto which they have been attached,are the origin of sticky deposits. Thesesticky depositscause difficulties when recycled back to thepaper machine operation. Formed deposits maycause web breakages, so as a precautionarymeasure the most affected surfaces, suchas drying cylinders, calendars,wires and felts, are beingregularly washed and cleaned, whichleads to downtime and loss of production.tog16l Considerable efforthas been directed toward developingimproved retention and drainageaids. PCT / U599 / 29L35discloses apolyampholyte coagulant, which is used as aretention / drainage / formation aid in apapermaking process. However, commercially availableretention and drainage aids remaininadequate for manufactureof paper and board with a highpercentage of recycled fiber content.tOO17l High molecular weightpolymericadditivesand retention aidpolymers added tend to holdwater during the firstpassesin thepress section, which dramaticallyincreases drain time andreduces wetpressabilityof thefibrous web. A retention and drainageaid that would allow for moreefficient dewateringinthepress section and faster dryingof the paper web in the dryer sectionwould lead to significant steam savings andfaster productivity for the paper manufacturer't001Sl Based on the foregoing thereis a need for improved polymer additives for use in themanufacturing ofpaper,tissue, towel,and / or board fromrecycled materials, which provideretention and drainage enhancement,whilealsocontrollinghydrophobic particles and agglomerates("stickies") in the furnish. Therefore, itisan objectof thepresentinventionto provide methods andcompositions for enhancing retentionand drainage(i.e.,retentionand drainage aids) which provideimproved retention, drainage time,paper strength, and improvedhydrophobic particle control.SUMMARY OFTHE INVENTIONtOO19l The present invention generally relates to methodsand compositions for manufacture oftissue, paper, or board and for enhancing retentionand drainage thereof. ln particular, thedisclosure provides methods for enhancingretention and drainage by addition of a retention anddrainage aid comprising reactive cationicpolymers (e.g.,cationic strengthresins), water-solubleamphoteric terpolymers, and optionallyanionic organic orinorganic microparticles. Preparation ofpaper sheets under these conditionsprovidesimprovedretention, drainage time, STFI and burststrength, andimproved hydrophobicparticle control'too2ol ln one aspect, thepresent inventionprovidesa methodfor manufacture of tissue, paper, orboard, the method comPrising:tO021l (a) formingor providingan aqueoussuspension comprising cellulosic fibers;l0122l(b)optionally dilutingthe aqueous suspension;Arrv Docrnr No.1149704.062013CLIENT REF NO. U52324I0O23l(c)flocculating theaqueous suspension to forma flocculated fiber suspension;lOO241(d)removing sufficient water from the flocculatedfiber suspension to form a wet fibrousweb, preferably by introducing theflocculated fiber suspension into aheadbox and draining theflocculated fiber suspension ona wire screen; andtOO25l(e) pressinganddrying the wet fibrous web toobtain a tissue, paper, or board;t00261 wherein the method further comprisesprior to step (c) treating the aqueous suspensioncomprisingcellulosic fibers with a retentionand drainage aid comprising:lOO27l(i)one or more reactive cationicpolymers; and

[0028] (ii)one or more water-solubleamphoteric polymers.t0o29l tn some exemplaryembodiments of the method saidretention and drainage aid optionallyfurther comprisesone or more anionic organicor inorganic microparticles.to030l ln some exemplary embodimentsof the method(i)saidone ormore reactive cationicpolymers, (ii) said one or more water-soluble amphotericpolymers, and optionally (iii) said one ormore anionic organic orinorganic microparticles:tOO31l (a) are added sequentially in any order, simultaneously,or premixed prior to addition; ort0632l (b) are added sequentiallyintheorder of(i), (ii),and then optionally(iii), wherein a mixingtime is allowed after each additionand said mixing timeranges from 0.01-10 min, 0.1-5 min, or I-2min.tOO33l ln some exemplary embodimentsofthemethod said one or more reactive cationic polymerscomprise:tOO34l(a)functionalgroupsthatare reactive to cellulosic orlignocellulosic fiber surfaces; andto035l(b)a cationiccharge density ranging from below5.0 mEq / g, 0.5-5'0 mEq / 8,I.O-4.O mEqf g, orL.5-2.5mEq / g as dry solids atpH7;

[0036] and further comprise oneofthefollowing;t0o37l(c)one or more cationicglyoxalatedpolyacrylamides (GPAMs);t003Sl(d)one ormore cationicpolyamidoamine-epichlorohydrin (PAE) resins; orto039l (e) a combination of one or more cationicGPAMs and one or more cationic PAE resins havinga ratio of PAE to GPAM ranging from1:99 to 99:1, 20:80 to 80:20,40:60 to 60:40, or 45:55, whereinsaid one or more cationicPAE resins and said one ormore cationic GPAMs are added sequentially inany order, simultaneously,or premixedpriorto additionto said aqueous suspension comprisingcellulosicfibers.too4ol ln some exemplary embodimentsof the method said one or more cationic GPAMs:

[0041] (a)are suitableforuseas a dry and / or wet strengthening agent;t9042l (b) are synthesized by reactingglyoxalwitha base polymer, wherein said base polymercomprises a weight average molecularweight ranging from 5-5000kDa, 50-2500 kDa, 80-2000 kDa,or 100-1000 kDa and comprisesnonionic monomers, cationicmonomers, and optional anionicmonomers,whereinArrvDocrBr No. 1149704.062013CLIENT REF NO. U52324to043l (i) said nonionic monomers areselected from thegroupofprimary amide-containingmonomers comprising acrylamide,methacrylamide, ethylacrylamide, crotonamide, N-methylacrylamide, N-butylacrylamide, N-ethyl methacrylamide,and any combination thereof;tOO44l (ii) said cationic monomers areselected from acryloyloxyethyltrimethyl ammonium chloride("AETAC" ), methacryloyloxyethyltrimethylammonium chloride ("MAETAC"),methacrylamidopropyltrimethylammoniumchloride ('MAPTAC"),acrylamidopropyltrimethylammoniumchloride("APTAC"), methacryloyloxyethyldimethylammoniumsulfate, diallyldimethylammoniumchloride("DADMAC"); dialkylaminoalkyl acrylates anddialkylaminoalkyl methacrylates and theirquaternary or acid salts, including but not limited to,dimethylaminoethyl acrylate("DMAEA"), dimethylaminoethylmethacrylate ("DMAEA"),dimethylaminoethylacrylate methyl chloridequaternary salt, dimethylaminoethyl acrylate methylsulfate quaternary salt, dimethylaminoethyl acrylatebenzyl chloride quaternary salt,dimethylaminoethyl acrylate sulfuric acidsalt,dimethylaminoethylacrylate hydrochloric acid salt,diethylaminoethyl acrylate methyl chloridequaternary salt, dimethylaminoethyl methacrylatemethyl chloridequaternarysalt, dimethylaminoethylmethacrylatemethyl sulfate quaternary salt,dimethylaminoethyl methacrylate benzyl chloridequaternary salt, dimethylaminoethyl methacrylatesulfuric acid salt, dimethylaminoethyl methacrylatehydrochloric acid salt, dimethylaminoethylmethacryloyl hydrochloric acid salt;dialkylaminoalkylacrylamidesand methacrylamides and theirquaternary or acid salts, includingbut not limited to, acryloylamidopropyltrimethylammoniumchloride, dimethylaminopropylacrylamide, dimethylaminopropylacrylamide methyl sulfatequaternary salt, dimethylaminopropyl acrylamidesulfuric acid salt, dimethylaminopropyl acrylamidehydrochloric acid salt, methacrylamidopropyltrimethylammoniumchloride, dimethylaminopropylmethacrylamide, dimethylaminopropylmethacrylamidemethyl sulfate quaternary salt,dimethylaminopropyl methacrylamide sulfuricacid salt, dimethylaminopropyl methacrylamidehydrochloric acidsalt, diethylaminoethylacrylate,diethylaminoethylmethacrylate; anddiallyldialkylammonium halides, includingbut not limited to, diallyldiethylammonium chloride anddiallyldimethylammoniumchloride("DADMAC"),andany combination thereof; andtOO45l (iii) said optional anionic monomers containfunctional groups selected from carboxylic acids,sulfonic acids, phosphonic acids, theircorresponding water solublesalts, their corresponding waterdispersible salts, and any combinationthereof, including but notlimited to, acrylic acid, methacrylicacid, maleic acid, itaconic acid,vinyl sulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid(AMpS), acrylamido methanesulfonic acid, acrylamidoethanesulfonic acid, 2-hydroxy-3-acrylamidepropane sulfonic acid, styrene sulfonic acid,vinyl benzene sulfonic acid,and vinyl phosphonic acid,their corresponding alkali metal, alkalineearth metal, and ammonium salts, and any combinationthereof;tOO46l (c) comprise a glyoxal:basepolymerweightratio ranging from 0.1:99.9 to 50:50, 5:95 to20:80, or5:95to10:90;t0947l(d)comprise a cationic chargedensity ranging from below5.0 mEq / g, 0.5-5.0 mEq / E,1.0-4.0mEq / g, or 1.5-2.5mEq / g as dry solids at pH 7;lOO48l (e) comprise apercentcationic monomercontentrangingfrom3-60% by weight, a percentanionic monomer content ranging from0-50% by weight, wherein theremainder of the monomercontent comprises nonionicmonomers;ArrY DocKErNo. 1149704.062013CLIENTREF NO. U52324to049l(f)are formulatedoptionally as a drypowder or as an aqueous composition comprising aGPAM solids percentage ranging from about0.5% to about 20%, optionallyfrom greater than about2% to about 1O%, further optionallyfrom aboutgreaterthan4% to about 8%'tg6s9l ln some exemplary embodimentsof the methodsaid one or more cationic PAE resins:

[0051] (a)are suitablefor use as a wet strengthening agenqtOO52l (b) are synthesized by reactingoneormore polyamidoamine backbones withepichlorohydrin, wherein said one ormore polyamidoamine backbonesare synthesized by reacting acarboxylic acid and / or a carboxylicacid derivative withanamine,wherein said one or morepolyamidoamine backbonescompriseamolar ratioof the amine to the carboxylic acid and / orcarboxylic acid derivativeranging from l-:L to2:L,1.05:1to2:I, or 1.5:L to2:I;t0o53l (c) comprise a molar ratio of epichlorohydrinto secondary amine groups of thepolyamidoamine backbone rangingfrom about 0.15 to about 1.7.t9054l ln some exemplaryembodiments of the methodsaid one or more water-soluble amphotericpolymers:IO055l (a) are comprised of acrylamide(AM) monomers, one ormore anionic monomers, and one ormore cationic monomers, wherein,t0o56l(i)said one or more anionicmonomers containfunctional groups selected from the groupconsisting of carboxylic acids, sulfonic acids,phosphonic acids, their corresponding water solublesalts, their corresponding water dispersiblesalts, and any combination thereof, including but notlimited to, acrylic acid, methacrylicacid, maleic acid, itaconicacid, vinyl sulfonic acid, 2-acrylamido-2-methylpropane sulfonicacid(AMPS),acrylamido methanesulfonicacid, acrylamido ethanesulfonicacid, 2-hydroxy-3-acrylamidepropanesulfonicacid, styrene sulfonic acid, vinyl benzene sulfonicacid, and vinyl phosphonic acid, their correspondingalkali metal, alkaline earth metal, andammonium salts, and any combinationthereof; andt9057l(ii)said one ormore cationic monomers are selectedfrom the group consisting ofacryloyloxyethyltrimethyl ammonium chloride("AETAC"), methacryloyloxyethyltrimethylammoniumchloride ("MAETAC"), methacrylamidopropyltrimethylammoniumchloride ("MAPTAC"),acrylamidopropyltrimethylammoniumchloride("APTAC"), methacryloyloxyethyldimethylammoniumsulfate, diallyldimethylammoniumchloride("DADMAC"); dialkylaminoalkyl acrylates anddialkylaminoalkyl methacrylates and theirquaternary or acid salts, including but not limited to,dimethylaminoethyl acrylate('DMAEA"), dimethylaminoethylmethacrylate ("DMAEA"),dimethylaminoethylacrylate methylchloridequaternarysalt,dimethylaminoethyl acrylate methylsulfate quaternary salt, dimethylaminoethyl acrylatebenzyl chloride quaternary salt,dimethylaminoethyl acrylate sulfuric acid salt,dimethylaminoethyl acrylate hydrochloric acid salt,diethylaminoethyl acrylate methylchloride quaternary salt, dimethylaminoethyl methacrylatemethyl chloridequaternarysalt,dimethylaminoethyl methacrylatemethyl sulfate quaternary salt,dimethylaminoethyl methacrylate benzyl chloridequaternary salt, dimethylaminoethyl methacrylatesulfuric acid salt, dimethylaminoethyl methacrylatehydrochloric acid salt, dimethylaminoethylmethacryloyl hydrochloric acid salt; dialkylaminoalkylacrylamidesand methacrylamides and theirquaternary or acid salts,including but not limited to,acryloylamidopropyltrimethylammoniumchloride, dimethylaminopropylacrylamide, dimethylaminopropylacrylamide methyl sulfatequaternary salt, dimethylaminopropylacrylamide sulfuric acidsalt, dimethylaminopropyl acrylamidehydrochloric acid salt, methacrylamidopropyltrimethylammoniumchloride, dimethylaminopropylmethacrylamide, dimethylaminopropyl methacrylamidemethyl sulfate quaternary salt,Arrv DocrErNo. I149704.062013CLIENTREFNO. U52324dimethylaminopropyl methacrylamide sulfuric acid salt,dimethylaminopropyl methacrylamidehydrochloric acidsalt, diethylaminoethylacrylate,diethylaminoethylmethacrylate; anddiallyldialkylammonium halides,including but not limited to, diallyldiethylammonium chloride anddiallyldimethylammonium chloride("DADMAC"),and any combinationthereof;tOO58] (b) comprise an inversephaseemulsion,a dry polymer, or an aqueous polymer solution,preferably an inversephaseemulsion;togsgl (c) comprise apolymerstandardviscosity (SV) rangingfrom<3.5 cPs, L-3.5 cPs, 2-3'5 cPs, or2.5-3.5 cPs;t0O6Ol(d)comprise amolecular weight ranging from1.5-9 million Daltons, 1.5-8 million Daltons, 2-8million Daltons,4-8 million Daltons, orpreferably 2-5 million Daltons;t0o6i.l (e) comprise an acrylamide(AM)monomercontent ranging from77-LOl wtYo,78-700 wtTo,80-100wt%, 90-L00 wt%o, or 95-100wt%;tOO62l (f) comprise an anionic monomer content ranging from(3wt%o, 42 wt%,0.01-3 wt%,0.5-2wtYo,I-2wt%o, t.5-2 wt%o, or L.8-2 wt%;tOO63l (g) comprise a cationic monomer content ranging from(20 wt%, I-2O wtYo,2-\6 wt%,4-12wl%o, or7-9 wt%; or

[0064] (h)any combination of theforegoing.tOO65l ln some exemplaryembodiments of the method saidone or more anionic organic orinorganic microparticles are selected from thegroupofmicroparticles and nanoparticles consistingof silica microparticles; colloidalsilica; aluminumphyllosilicate mineral particles, including but notlimited to bentonite, sodium bentonite,calcium bentonite, and montmorillonite; and anionicpolymer microparticles,including but not limited to highlystructured anionic polyacrylamides.t0o66l ln someexemplary embodiments of the method:t0067] (a) said one or more reactive cationicpolymers comprises said one or more cationic GPAMsand / orsaid one or more cationicPAE resins in aqueous form;10068l(b)said one ormore cationic GPAMs comprise saidbase polymer comprising cationicmonomers selected from DADMAC, AETAC,andcombinationsthereof; nonionic monomers selectedfrom acrylamide, methacrylamide, andcombinations thereof;and optionally anionic monomersselected from acrylic acid and / orcorresponding water solublesalts, water dispersible alkali metalsalts, alkaline earthmetal salts, ammonium salts, and combinationsthereof, or said base polymercomprises (i)acrylamide and DADMAC,(ii)acrylamide and AETAC, or(iii)acrylamide, DADMAC, andAETAC,

[0069] (c)said one or more water-solubleamphoteric polymerstOO7Ol (i) comprises an inverse emulsion of acrylamide(AM), acrylic acid (AA), and[2-(acryloyloxy)ethyll trimethylammonium chloride(Q9) monomers;tOO71l (ii) preferably comprisesan acrylic acid(AA)monomer contentof no more than 2 wt %; andlOO72l(iii) preferablycomprisesa ratio of AM:AA:Q9ranging from 89:2:9 to 9L:2:7; andtOO73l (d) said one or more anionic organic orinorganic microparticles comprise colloidal silica.lOO74l ln some exemplary embodimentsof the method,when added to said aqueous suspensioncomprising cellulosicfibers:ArrY DocKEr No.I 149704.062013CLIENT RBPNO. U52324t00751(a)said one ormore reactive cationicpolymersareadded at a dosage ranging from 0.1-15g / kg,0.5-5g / kg, or 0.5-a g / ke;t0976l (b) said one or more water-solubleamphotericpolymersareadded at a dosage ranging from0.05-5g / kg,O.L-4g / kg,or0.3-1e / kg;lOO77l(c)saidoneor more anionic organic or inorganicmicroparticles are added at a dosageranging from0.1-1g / kg,O.2-0.8g / kg,or0.a-0.6 g / ke't00781 ln some exemplary embodimentsof the method, said aqueous suspension comprisingcellulosic fibers comprises apH ranging from 4-8, 4-7.5,4-7,4.5-7,or 5-7 and further comprises:to079l(a)cellulosic fibersoptionally obtained from sourcesselected from softwood fiber, hardwoodfiber, recycled fiber, recycled old corrugated cardboard(OCC), recycled mixed office waste (MOW),recycled mixed officepaper,refinedfiber,millbroke fibers, coated broke, non-woodfibers, includingbut not limited to straw and wheatpulp, and a mixture of any of the foregoing;tOO86l(b) pulpselected fromKraft pulp, unbleached Kraftpulp, bleached pulp, unbleached pulp,process water from pulp, paper, and / or boardproduction, neutral sulfite semi chemical (NSSC) pulp,mechanicalpulp, non-woodpulp,and a mixture ofany of the foregoing; ort0081] (c) a stock selected fromathickstock, a thick stock dilutedwith chemical water, syntheticwater, white water , andf orprocess water, andathinstock, and a mixture of any of the foregoing.l9082l ln some exemplaryembodiments of themethod, when used for manufacture of tissue,paper,orboard,themethod resultsin:[OOS3](a)improved retention ofsaid cellulosic fibers; at0084l(b)improveddrainage of said flocculated fiber suspension;

[0085] (c)improvedSTFI and / or burst strength;tOOS6l (d) a reduced hydrophobicparticle and / or hydrophobic agglomerate counUt00871(e)an improved dry tensile,immediate wet tensile, and / orsoaked wet tensile strength; or[0088j(f)any combinationof (a)-(e)tOOSgl compared to a tissue,paper,or boardprepared by an identical method in the absence of (i)addition of said one or more reactivecationic polymers or(ii)additionof said one or more water-soluble amphotericpolymers.t009ol ln another aspect, thepresentinventionprovides a method for manufacture of tissue, paper,or board, the methodcomprising:tO091l (a) forming orprovidingan aqueoussuspension comprising cellulosic fibers;

[0092] (b)optionally diluting theaqueous suspension;[00931(c)flocculatingthe aqueous suspension to forma flocculated fiber suspension;t0o94l (d) removing sufficient water from theflocculated fiber suspension to form a wet fibrousweb, preferably by introducing theflocculated fiber suspension intoa headbox and draining theflocculated fiber suspensionon a wire screen;; andt6095l (e) pressing and drying the wet fibrousweb to obtain a tissue, paper, or board;ArrvDoc No. I 149704.062013CreLIrENTRETNO. U52324tOO96l wherein the method furthercomprisespriorto step(c)treatingthe aqueous suspensioncomprising cellulosicfibers with a retention and drainageaid comprising:tOO97] (i) one or more reactive cationicpolymers comprising functional groups that are reactive tocellulosic or lignocellulosic fiber surfacesand a cationic charge density ranging from below 5.0mEq / g,0.5-5.0 mEqlg, L.0-4.0mEq / g, or 1.5-2.5 mEq / gasdrysolids at pH 7, wherein said one ormore reactive cationic polymers comprise one or morecationic glyoxalated polyacrylamides(GpAMs); one or more cationicpolyamidoamine-epichlorohydrin(PAE)resins;or a combination ofone or more cationic GPAMs and one or morecationic PAE resins having a ratio of PAE to GPAMranging from L:99 to 99:1, 20:80 to80:20, 40:60 to 60:40, or45:55, wherein said one or morecationic PAE resins and saidoneormore cationic GPAMs areadded sequentially in any order,simultaneously, orpremixedpriorto addition to saidaqueous suspension comprising cellulosicfibers;to098l (ii) one or more water-solubleamphoteric polymers comprising an inverse emulsion ofacrylamide(AM),acrylic acid(AA), and[2-(acryloyloxy)ethyl]trimethylammonium chloride (Q9)monomers; preferably comprising an acrylic acid(AA) monomer content of no more lhan 2 wt%;andpreferablycomprisinga ratio of AM:AA:Q9ranging from 89:2:9 to9Li2i7; andt00991 (iii) optionally one or more anionicorganic or inorganic microparticles comprising silica'l01OOl ln another aspect, thepresent inventionprovides a fiber stock composition comprising:t01011(a)an aqueoussuspension comprising cellulosic fibers; and

[0102] (b)a retentionand drainage aid comprising

[0103] (i) one or more reactive cationicpolymers;to104l(ii)one or more water-solubleamphoteric polymers; andtQlosl(iii)optionallyone or more anionic organic orinorganic microparticles;t0L061 obtainableby a method according toany of the foregoing claims.t0107] ln another aspect, thepresent inventionprovidesa compositionfor use as a retention anddrainage aid in manufactureof tissue,paper,or board, thecomposition comprising:tOlOSl (a) one or more reactive cationicpolymers comprising a cationic charge density ranging frombelow 5.0 mEq / g,0.5-5.0 mEq / g, L.0-4.0mEq / g, or 1.5-2.5 mEq / gasdrysolids at pH 7, wherein saidone ormore reactive cationicpolymers compriset01O9l (i) one or more cationic glyoxalatedpolyacrylamides (GPAMs) synthesized by reacting glyoxalwith a base polymer, wherein said basepolymercomprisesa weight average molecular weightranging from 5-5000 kDa, 50-2500kDa, 80-2000 kDa, or 100-1000 kDa;(i) acrylamide and DADMAC,(ii) acrylamide and AETAC, or(iii)acrylamide,DADMAC, andAETAC and further wherein said one ormore GPAMs comprises a glyoxal:basepolymerweightratio ranging from 0.1:99.9 to 50:50, 5:95 to20:80, or 5:95 to 10:90; and a cationic charge densityranging from below 5.0 mEq / g, 0'5-5'0 mEq / E,1.0-4.0mEq / g, or 1.5-2.5 mEq / g as drysolids at pH 7;tO11Ol(ii)one or more cationicpolyamidoamine-epichlorohydrin(PAE) resins; orto111l(iii)a combinationof one or more cationicGPAMs and one or more cationic PAE resins havinga ratio of PAE to GPAM ranging from1:99to99:1, 20:80 to 80:20,40:60 to 60:40, or 45:55;ArrvDoc No. I 149704.062013CrsL,IrENTRgN NO. U52324t01121 (b) one or more water-solubleamphotericpolymerscomprisingacrylamide (AM), acrylic acid(AA),and [2-(acryloyloxy)ethyl]trimethylammonium chloride(Q9) monomers; wherein said one ormore water-soluble amphoteric emulsionpolymers preferably comprise an acrylic acid (AA)monomer contentof no more than2wt% and a ratio of AM:AA:Q9 ranging from 89:2:9 to 9L:2:7,wherein said one or more water-solubleamphotericpolymers is a an inverse emulsion, a drypolymer, an aqueous solution,preferably an inversephase emulsion; and[0i.13](c)optionallyone or more anionic organicor inorganic microparticles selected from thegroup of microparticles and nanoparticles consistingof silica microparticles; colloidal silica;aluminum phyllosilicate mineralparticles, including but not limited tobentonite, sodium bentonite,calcium bentonite, and montmorillonite;and anionicpolymer microparticles, including but notlimited to highly structuredanionic polyacrylamides.BRIEF DESCRIPTION OF THE DRAWINGStO114l The invention willbe described in more detailwithreference to appended drawings,described in detailbelow.DETAILEDDESCRIPTION OFTHE INVENTIONtO115l Before describing the invention,the following definitions are provided. Unless statedotherwise all terms are tobeconstruedas they would be by a person skilled in the art.toi.i.6l FIG 1provides an exemplary variability chart showingDDA drain time (sec) for recycledtowels prepared from LOO%OCC furnish treatedwith PAE and amphoteric emulsion polymers withor withoutsilica according to Example 1.t01i.7l FtG 2providesan exemplaryvariability chart showingfiltrate turbidity (NTU) for recycledtowels prepared from 1rOO% OCC furnish treatedwithPAE and amphoteric emulsion polymer with orwithout silicaaccording to Example 1.tO118l FtG 3providesan exemplaryvariability chart showingDDA drain time (sec) for recycledtowels prepared from LOO% OCC furnish treated with GPAMand amphoteric emulsion polymer withor without silica accordingto Example 1.tO1i.glFIG 4 provides an exemplary variabilitychart showing filtrate turbidity (NTU) for recycledtowels prepared from LOO% OCCfurnish treated with GPAM andamphoteric emulsion polymer withor without silica according toExample 1.t0129l FIG 5 provides an exemplarygraphof DDAdrain time (sec) vs. polymer dosage for apackaging grade furnish with conductivity3.84 mS / cm treated withreference cationicpolyacrylamide (CPAM, solid line)+GPAMand an amphotericemulsion polyacrylamide (amPAM,dashedline)+GPAM accordingto Example 3.IOI2I) FtG 5 provides an exemplarygraphofDDA drain time (sec) vs. polymer dosage for apackaging grade furnish with conductivity5.09 mS / cm treated withreference cationicpolyacrylamide (CPAM, solid line) + GPAM and an amphotericemulsion polyacrylamide (amPAM,dashed line)+GPAMaccording to Example 3.tO1,Z2l FtG 7 provides an exemplary bargraph of filtrate turbidity(NTU) vs. polymer dosage for areference cationic polyacrylamide (CPAM) and an amphotericemulsion polyacrylamide (amPAM)forpackaging grade liner sheets at three conductivitylevels according to Example 3.ArrY DocKEr No.I149704.062013CLIENT REF NO. U52324to123l FtG 8providesan exemplarygraph of strength(GM STFI) vs. GPAM dosage for packaginggradeliner sheetsprepared with amphoteric emulsionpolyacrylamide or dry amphotericpolyacrylamide according to Example 4.lOI24l FIG 9providesan exemplarybargraphof strengthproperties (STFI and Burst strength) ofhandsheetspreparedaccordingto Example 5.t01251 FIG 10 provides an exemplaryvariabilitychartshowing DDA drain time (sec) for towelspreparedfromLOO% recycled mixed officepaper according to Example 6.

[0126] FtG 11providesan exemplaryvariability chart showing filtrateturbidity (NTU) for towelsprepared from IOO% recycledmixed office paper according to Example 6.DEFINITIONSlOLZTl As used herein the singular forms"a","and",and "the" include plural referents unless thecontext clearlydictates otherwise.t01281 As used herein, the singularforms"a,""an," and"the" may mean "one" but also includeplural referents suchas "one or more" and "at least one"unless the context clearly dictatesotherwise. All technical and scientific terms usedherein have the same meaning as commonlyunderstood to one of ordinary skill in theart to which this inventionbelongs unless clearly indicatedotherwise.t0129] As used herein, theterm "or" in the claimsisusedto mean "andf or" unless explicitlyindicated to refer to alternativesonly or the alternativesare mutually exclusive, although thedisclosure supports a definition thatrefers to only alternatives and "and / or."t01301 As used herein the term"or combinations thereof'as used herein refers to all permutationsand combinations of thelisted itemsprecedingthe termunless stated otherwise.

[0131] PAPERMAKINGto132l As used herein, the term "paper"includesproductscomprisinga cellulosic sheet materialincludingpapersheet,paperboard, and the like.

[0133] As used herein, the terms "papermakingprocess" and "papermaking application" generallyrefers to any process in which any form ofpaper and / orpaperboard product may be produced' Forexample, suchprocessesincludemaking paperproductsfrompulp, such as methods comprisingforming an aqueous cellulosicpapermaking furnish, drainingthe furnish to form a sheet, and dryingthe sheet. The steps of forming thepapermakingfurnish,draining and drying may be carried out inany conventionalmannergenerallyknownin the art.

[0134] As used herein, the terms"wetendof a paper machine" or"wet end" generally refer to theparts of a papermaking process betweenpulping (orbleaching)and wet-pressing of the paper.t0135] As used herein, theterm "fiber" refers to thebasic structural unit of paper or board.t01361 As used herein, the terms"recycled fiber / ' and "recovered fiber",refer to paper, paperboard,and fibrous wastes from retail stores,office buildings, homes,manufacturing plants, and so forth,after they have passed through their end-usage as aconsumer item. Manufacturing wastes include:dry paper and paperboard wastegenerated after completion of thepapermaking process includingby way of example: envelope cuttings, binderytrimmings,andotherpaper and paperboard wasteresulting fromprinting,cutting,forming, and other convertingoperations; bag, box, and cartonmanufacturing wastes; mill wrappers, and rejectedunused stock; and repulped finished paper andL1.Arrv Docrsr No.1149704.062013 CLIENT Rgr NO. U52324paperboard from obsolete inventoriesofpaperandpaperboard manufacturers, merchants,wholesalers, dealers, printers, converters, or others.ln particular the term "recycled fibers" includesrecycled fibers derived byprocessingofpaper and other consumer cellulosicmaterials, e.9., paper,old corrugated containerboard(OCC),mixed office waste(MOW), old magazine (OMG), unbleachedkraftpulp,neutral sulphitesemi chemical(NCCS) pulp and / or mechanical pulp. Source materials forrecycled fibers may be selected from old corrugatedcontainerboard, mixed office waste, oldnewsprint, old magazines, double linerkraft, and any mixtures thereof.Mixed waste (MXW) denotesrecycled mixture of recycledboard, such as OCC, white lined chipboardand / or folding boxboard, andrecycled paper, such as old newsprint, old magazines and / oroffice waste papers. Mixed office wastedenotes recycled fiber material mainly containing copyingpapers, printer papers and offset papers.Double lined kraft denotes recycled fibermaterial comprising clean sorted unprinted corrugatedcardboard cartons, boxes, sheet or trimmings,e.g., of kraft orjuteliner.White lined chipboard(WLC)denotes multiply boardcomprising deinked fiber materialand / orun-deinked recycled fibermaterial originating e.g., from OCC, mixed office waste orold newspapers (ONP) in or more of thelayers. Presence of any of these recycled fiber materialsin the fiber suspension usually decreasesdrainage andpaperstrength andprovides a substantial load of starch,hydrophobic, and colloidalsubstancesto theprocess.t01371 As usedherein, the term "OCC" refers to old corrugatedcardboard and / or containerboard'Corrugated refers to those boxes where the materialsare made from three separate layers of paper,two liners and a corrugated, or wavy,layer sandwiched between them.Brown paper bags arecommonly accepted withOCC for recycling. The term OCC denotesrecycled fiber material whichhave liners of testliner,juteor kraft, and may cover alsodouble sorted corrugated containerboard(DSocc).tO13Sl As used herein, the terms"broke" or "mill broke" refer topaper, which during the papermakingprocessbecomes suitableonly for repulping e.g., trimmingsor paper that is out ofspecification. Broke is re-used material which never leftthe mill is not regarded as recycled orrecovered. Broke is a valuable source offiber and is recycled internally at the mill.t0139] As used herein, theterm"coatedbroke" refers to broke that contains coatings that areapplied to the base sheetof paper as it is being manufactured.When the broke contains thesecoatings, itpresents special problems in recycling torecover fiber values because the coatingsintroduce materials which would not normallybe present in the original stock of fiber used tomanufacture the basepapersheet.The coated broke may also containdyes and / or other additives.ln thepresentapplicationcoated broke includes surface-sized,dyed, and / or creped broke.to140j As usedherein, the term "recycled fiber composition"generally refers to a compositioncomprising recycled cellulosic fibers, typicallya composition wherein most or all are recycled fibers,e.g., at least 20,40, 50, 60,70,80,90or IO0%.t0141] As used herein,theterm"fiber suspension" is understoodas an aqueous suspension, whichcomprises fibers, preferably recycled fibers, and optionallyfillers. For example, the fiber suspensionmay comprise at least 5Yo,preferably 10-30 Yo, morepreferablytI- L9% ofmineral filler. Mineralfiller may be any filler conventionallyused inpaperand boardmanufacturing, such as groundcalcium carbonate, precipitated calcium carbonate, clay,talc, gypsum, titanium dioxide, syntheticsilicate, aluminum trihydrate, barium sulphate,magnesium oxide or their any of mixtures.ArrY DocKErNo. 1149704.062013CLIENTREP NO. U52324lOI42l As used herein the term "headbox"refers a receptacle in apapermaking machine that holdssuspended aqueous cellulosic solidsand which regulates the flow thereofonto a wire or screen thatprovidesfor the draining ofwater therefrom.to143l As used herein the term "lignocellulosic substrate"refers to a paper and / or paperboardproduct formed fromplantdry matterfrom any source, virgin or recycled,which may be coated,printed, and / or formed intoa packaging product. For example,suchsubstratesinclude paperproducts made frompulp,suchas by methods comprising formingan aqueous cellulosicpapermakingfurnish,draining the furnish to form asheet, and drying the sheet. The steps offorming the papermaking furnish, draining and dryingmay be carried out in any conventionalmanner generally known in the art.Thesubstratesmaycontainpolymericstrengtheningagents,such as wet strength and drystrength agents.lOL44l As used herein, theterm "slurry"generallyrefers toa mixture of water, dissolved paper pulp,and optionally othersoluble or insoluble componentsproduced or added during the stockpreparationphaseofpapermaking.toi.4sl As used herein, the terms "furnish"or "papermaking furnish" generally refers to a mixture ofcellulosic fibers,pulp,optionalfillers, dyes, and water fromwhich paper or board is made.to146l As used herein, the term "thick stock"generally refers to mixture of papermaking pulp andothermaterials with a consistency of about1.to5%.10L47l As used herein, the term "thinstock" generally refers toa mixture of papermaking pulp andother materials, after having been diluted to a consistencybelow 7%with whitewater or otherprocesswater ata fanpump.t0148] As used herein, the term"whitewate / 'generally refers to process water within a papermachine system, especially referringto water that is drained frompaper as the sheet is beingformed.t0149] As used herein, the terms "fixation","fixing" and "fix" means that a substance is associatedorattached onto the fibers atleasttemporarilyor permanently.tO15Ol As used herein, the term"flocculation"generallyrefersto the tendency for fibers to collecttogether in bunches in thepresenceof flow, and especiallyin the presence of retention aids; thesame word also refers to the action of high-masspolymers in forming bridges between suspendedcolloidalparticles, causing strong, relativelyirreversible agglomeration.t01511 The term "flocculant"may generally refer to a reagentthat may bridge neutralized orfacilitate coagulation ofparticles into larger agglomerates,typically resulting in more efficientsettling. Flocculationprocess generallyinvolvesaddition of a flocculantfollowedby mixing tofacilitate collisions betweenparticles,allowingfor the destabilizedparticles to agglomerate intolargerparticlesthat can beremoved bygravitythrough sedimentationor by other means, €.8.,centrifugation, filtration.t01521 As used herein the term"drystrength"generally refers to the force or energy required tobreak a paper sample, by one ofvarious procedures, after equilibrationin a standard atmosphere.to153l As usedherein theterm "wetstrength"generally refers to the strength of a sheet of paperafter it has been exposed to a standard solutionfor a standard length of time, but often expressedasa ratio vs. the dry strength.ArrYDocKEr No. I149704.062013CLIENTREFNO. U52324to154lpolymermolecular weights may be measuredby various methodsknown to persons of skill inthe art. For example, weight average molecularweight may be measuredusing gel permeationchromatography(GPC).Additionally,polymermolecularweights may be measured by GPC / LightScattering / Viscometryalso known as Triple DetectionGPC which employs Refractive lndex Detector(withor without UVDetector), Dilute SolutionViscometry and Light Scattering all in series todetermine molecularweights, distributionand related solution parameters.

[0155] RETENTION AND DRAINAGE AIDt0156] As used herein, the terms"polymer" or"polymeric additives" and similar terms are used intheir ordinary sense as understoodby one skilledintheart, and thus may be used herein to refer toor describe a large molecule(or groupof suchmolecules) that may comprise recurring units.polymersmay be formed in various ways, including bypolymerizing monomers and / or by chemicallymodifying one or more recurringunits ofaprecursor polymer. Unless otherwise specified, a polymermay comprise a "homopolymefthat may comprise substantiallyidentical recurring units that maybe formed by, for example,polymerizingaparticular monomer. Unless otherwise specified, apolymer may also comprise a "copolymer''that may comprise twoor more different recurring unitsthat may be formed by, for example,copolymerizing, twoor more different monomers, and / or bychemically modifying one ormore recurringunitsofa precursor polymer. Unless otherwisespecified, a polymer or copolymer may alsocomprise a "terpOlymer" ora "tetrapolyme / 'whichgenerally refer to polymers that comprise three,four, or more differentrecurring monomer units.The term "polyme / 'as used hereinis intended to include both theacid form of the polymer as wellas its various salts. Polymers may be amphoteric innature, that is, containing both anionic andcationic substituents,although not necessarilyin the same proportions.t0157] As used herein, the terms"polyacrylamide" or "PAM"generally refer to polymers and co-polymers comprising acrylamide moieties, and the termsencompass any polymers or copolymers,including terpolymers, comprisingacrylamide moieties,e.g., one or more acrylamide (co)polymers ofacrylamide and additional monomers capableof copolymerizing with acrylamide. Furthermore,pAMsmay comprise any of thepolymers or copolymers discussedherein. Additionally, the PAMSdescribed herein, e.g., one or more acrylamide(co)polymers, may be produced in one of variousforms, including, for example, dry(powder) form(e.g., DPAM), emulsion polyacrylamide (EPAM), orliquid polyacrylamide. Amphotericpolyacrylamides(AmPAM)may beformulated in dry (powder)form(e.g., AmDPAM), or emulsion form(AmEPAM)'t0158] As used herein, the term"amphotericpolymer" referstopolymers containing both anionicand cationic groups on the macromolecular chain.These polymers exhibit both attraction andrepulsion in their electrostatic intermolecularinteractions (resulting in anti-polyelectrolyteassociation called "Amphoteric Effect")and they exhibit excellentsalt tolerance, especially in highCa+2aqueouscompositions.to15gl As used herein, theterm"emulsionpolymer" generally refers to inverse emulsions (water-in-oil) in which water droplets containing thepolymer are suspended in an oil phase, also termed ahydrophobicphase.t0160] As used herein, theterm "inversephaseemulsion"refers to a liquid polymer composition ofpolymer dissolved in an aqueous solution whichis dispersed into an oil phase (e.g', hydrophobicliquid) to form an oil-continuousphase, which is then mixed withan aqueous solution so that thedispersed polymerphaseof theliquidpolymercompositionbecomes a substantially aqueous-continuous phase, and the hydrophobic liquidphase becomes a dispersed, discontinuous phase. Thet4Arrv DocrerNo. I149704.062013CLIENTREP NO. U52324inversion point can be characterized as thepointatwhich the viscosity of the inverted polymersolution has substantially reacheditsmaximumundera givenset of conditions.ln practice, this maybe determined for example bymeasuring viscosity of the compositionperiodically over time andwhen three consecutivemeasurements are within the standardof error for the measurement, thenthe solutionisconsideredinverted.to161l As used herein, the term"liquid polymer" refers to a combinationof at least one polymerand a liquid, typically an aqueousliquid. The polymer in a may be thoroughlydissolved or may be apartially dissolved suspension,dispersion, or slurry. An"aqueous polymer mixture" or "hydratedpolymer composition" refers to a combination of atleast one polymer and an aqueous liquid. Whena dry polymer is combined with an aqueousliquid, thepolymer isinitiallypartially hydrated at thepolymer-water interface. Polymers do notdissolve instantaneouslyin aqueous or non-aqueoussolvents. Dissolution is controlledby either the disentanglementof the polymer chains or by thediffusion of the chains througha boundary layer adjacent tothe polymer-solvent interface. Afterthorough mixing, the polymer may become fullyhydrated, at which point the wetting process iscomplete and the polymer may be eitherpartially dissolved or fully dissolved, depending on thenature and composition of thepolymer and solvent.

[0162] The term "water-soluble polymer"generallyrefersto any polymer that may dissolve and / ordisperse in water. Said polymers may modify thephysical propertiesofaqueous systems undergoinggelation, thickening, viscosification, or emulsification / stabilization.Said polymers may perform avariety of functions, including butnot limited to use as dispersing and suspending agents, stabilizers,thickeners, viscosifiers,gellants, flocculants and coagulants,film-formers, humectants, binders, andlubricants.10163l As used herein, the term "monomefgenerally refers tononionic monomers, anionicmonomers, cationic monomers,zwitterionic monomers,betaine monomers, and amphoteric ionpairmonomers.t01641 As used here "Q9 monomer"refersto2-(acryloyloxy)ethyll trimethylammoniumchloride(Q9) which has a molecular formulaof C8H16C|NO2 and a molecularweight of L93.67 g / mol.t0165] As used herein acrylamideor "AM" refers to a neutralmonomer of molecular formula:C3H5NO and a molecularweight of 71.08g / mol'to166l As used herein acrylic acidor "AA" refers toan anionic monomer of molecular formula:CH2CHCOOH and a molecular weightof 72.O6 g / mol.t0167] As used herein, the term "cationicmonomer"generally refers to a monomer that possesses apositivecharge. Examples thereofinclude acryloyloxy ethyltrimethylammonium chloride (Q9)monomers. Cationic monomers may also be selectedfrom acryloyloxyethyltrimethyl ammoniumchloride('AETAC"),methacryloyloxyethyltrimethylammoniumchloride ("MAETAC"),methacrylamidopropyltrimethylammoniumchloride ("MAPTAC"),acrylamidopropyltrimethylammoniumchloride('APTAC"), methacryloyloxyethyldimethylammoniumsulfate, diallyldimethylammoniumchloride("DADMAC"); dialkylaminoalkyl acrylates anddialkylaminoalkyl methacrylatesand theirquaternaryor acidsalts, including but not limited to,dimethylaminoethyl acrylate("DMAEA"),dimethylaminoethylmethacrylate ("DMAEA"),dimethylaminoethyl acrylate methyl chloridequaternary salt, dimethylaminoethyl acrylate methylsulfate quaternary salt, dimethylaminoethylacrylate benzyl chloride quaternary salt,dimethylaminoethyl acrylate sulfuricacid salt, dimethylaminoethylacrylate hydrochloric acid salt,diethylaminoethyl acrylate methyl chloridequaternary salt, dimethylaminoethyl methacrylateArrv Docrsr No.1149704.062013CLIENT REP NO, U52324methyl chloride quaternary salt, dimethylaminoethylmethacrylate methyl sulfate quaternary salt,dimethylaminoethyl methacrylate benzyl chloridequaternary salt, dimethylaminoethyl methacrylatesulfuric acid salt, dimethylaminoethylmethacrylate hydrochloric acidsalt, dimethylaminoethylmethacryloyl hydrochloricacid salt; dialkylaminoalkylacrylamidesand methacrylamides and theirquaternaryor acid salts,including but not limited to,acryloylamidopropyltrimethylammoniumchloride, dimethylaminopropylacrylamide,dimethylaminopropylacrylamidemethylsulfatequaternary salt, dimethylaminopropyl acrylamidesulfuric acid salt, dimethylaminopropyl acrylamidehydrochloric acid salt, methacrylamidopropyltrimethylammoniumchloride, dimethylaminopropylmethacrylamide, dimethylaminopropylmethacrylamide methylsulfate quaternary salt,dimethylaminopropyl methacrylamide sulfuric acid salt,dimethylaminopropyl methacrylamidehydrochloricacid salt, diethylaminoethylacrylate,diethylaminoethylmethacrylate; anddiallyldialkylammonium halides, includingbut not limited to, diallyldiethylammonium chloride anddiallyldimethylammonium chloride("DADMAC"),and any combinationthereof'

[0168] As used herein theterm"nonionicmonomer"generally refers to a monomer that possesses aneutral charge. Exemplary nonionic monomersmay comprise but are not limited to comprisingmonomers selected from thegroupconsistingof acrylamide("AMD"), methacrylamido, vinyl, allyl,ethyl, and the like, allof whichmay be substituted withasidechain selected from, forexample, analkyl, arylalkyl, dialkyl,ethoxyl, and / or hydrophobicgroup. ln an exemplary embodiment, a nonionicmonomer may comprise AMD. ln some embodiments,nonionic monomers may comprise but arenot limited to comprising vinyl amide(e.g., acrylamide, methacrylamide,N-methylacrylamide, N,N-dimethylacrylamide),4-acryloylmorpholine,maleic anhydride, N-vinylpyrrolidone, vinyl acetate, N-vinyl formamide and theirderivatives, such as hydroxyethyl(methyl(acrylate CH2=CR-COO-CH2CH2OH (t) and CH2=CR-CO-N(Z1XZ2)(2) N-substituted(methyl)acrylamide(ll), R=H or Me; Z1=5-15C alkyl; 1-3C alkyl substituted by1-3 phenyl,phenylor 6-72C cycloalkyl(both optionallysubstituted) andZ2=H; orZL andZ,2 are each 3-L0C alkyl;(ll) is N-tert. hexyl, tert. octyl,methylundecyl, cyclohexyl, benzyl, diphenylmethyl ortriphenyl acrylamide. Nonionic monomersinclude N-isopropylacrylamide, N-vinylformamide,methacrylamide;N-alkylacrylamides, includingbut not limited to, N-methylacrylamide,N-ethylacrylamide, N-propylacrylamide, and N-butylacrylamide; N,N-dialkylacrylamides,including, but notlimited to, N,N-dimethylacrylamide andN,N-diethylacrylamide;N-alkyl methacrylamides; alkylacrylates;hydroxyalkylacrylates andmethacrylates, including but not limited to,hydroxymethyl acrylate, 2-hydroxyethyl acrylate, 3-hydroxypropylacrylate,4-hydroxybutylacrylate,hydroxymethylmethacrylate,2-hydroxyethylmethacrylate, 3-hydroxypropylmethacrylate, and 4-hydroxybutylmethacrylate; dihydroxyalkylacrylates and methacrylates,including but not limitedto, 2,3-dihydroxypropyl acrylate, 3,4-dihydroxybutyl acrylate,2,3-dihydroxypropylmethacrylate (DHPMA), and 3,4-dihydroxybutylmethacrylate; alkyl acrylates, includingbut not limited to, methylmethacrylate; acrylonitrile; N-vinylmethylacetamide, N-vinylmethylformamide;N-vinylacetate, glyoxalated acrylamides, and vinylpyrrolidone. Nonionic monomers can be combinedfor example to form copolymers with acrylamidetg169l As used herein, the term "anionic monomers"may refer to either anionic monomers that aresubstantially anionic in whole or(in equilibrium) inpart,ata pH intherange of about 1.0 to about10.0. The "anionic monomers"may be neutral at lowpH (e.g., from a pH of about O-t, O-2, or 0-3)depending on the pKa values of acidicprotonscontainedtherein. Some anionic monomers areobtained in anionic form as alkali metal salts,alkaline earth metal salts,and ammonium salts, e'g.,sodium acetate and sodium2-acrylamido-2-methylpropane sulfonicacid (AMPS).tO17Ol Examples of anionic monomers whichmay be used herein include but are not limited tothose comprising acrylic, methacrylic,maleic monomers and thelike, sodium acrylate, calcium1,6ArrY DocKEr No.I 149704.062013CLIENT REF NO. U52324diacrylate, and / or any monomersubstituted withacarboxylicacid group or salt thereof. ln someembodiments,anionic monomers may be substitutedwith a carboxylic acid group and include, forexample, acrylic acid, and methacrylic acid.ln some embodiments,an anionic monomer which maybe used herein may be a(meth)acrylamide monomer whereinthe amide group has been hydrolyzedto a carboxyl group. Said monomer may be a derivativeor salt of a monomer according to otherembodiments. Additional examples of anionicmonomers comprise but are not limited to thosecomprising sulfonic acids or a sulfonic acidgroup, or both. ln some embodiments, the anionicmonomers which may be used hereinmay comprise a sulfonicfunction that may comprise, forexample, 2-acrylamido-2-methylpropanesulfonic acid(acrylamido tertiary butyl sulfonic acid or"ATBS"). ln some embodiments,anionic monomersmay comprise organic acids. ln someembodiments, anionic monomers may compriseacrylic acid,methacrylicacid, maleic acid, itaconicacid, acrylamido methylpropane sulfonicacid, vinylphosphonic acid,styrene sulfonic acid and theirsalts such as sodium, ammoniumandpotassium.ln other embodiments,anionic monomers maycomprise acrylic acid, methacrylic acid; sulfonic acids,phosphonic acids, maleic acid, itaconic acid,vinyl sulfonic acid, 2-acrylamido-2-methylpropane sulfonicacid (AMPS), acrylamido methanesulfonicacid, acrylamido ethanesulfonic acid,2-hydroxy-3-acrylamidepropane sulfonic acid, styrene sulfonicacid, vinyl benzene sulfonic acid, vinylphosphonicacid,and alkali metal salts, alkaline earth metalsalts, and ammoniumsalts thereof. Anionic monomerscan be combined for example to form aterpolymer of acrylamide ,acrylic acid and 2-acrylamido-2-methylpropanesulfonic acid (AMPS). lnan exemplary embodiment, one ormore acrylamide(co)polymers may comprise at least onemonoethylenically unsaturatedmonomer comprising acidgroups, for example monomers thatcomprise at least one group selected from-COOH,SO3H,or -PO3H2. Examples of such monomersmay include , but are not limited to, acrylic acid,methacrylic acid, vinyl sulfonic acid, allyl sulfonicacid or 2-acrylamido-2-methylpropane sulfonic acid,particularly preferably acrylic acid and / or 2-acrylamido-2-methylpropane sulfonicacid, and mostpreferred acrylic acid or the salts thereof. ln anexemplary embodiment, one or more acrylamide(co)polymers, or each of the one or moreacrylamide (co)polymers, may comprise acrylicacid and / or 2-acrylamido-2-methylpropanesulfonicacidor salts thereof.10177]RETENTION ANDDRAINAGE AIDl1172l As used herein, theterm "reactive cationicpolymers" refers to polymers that contain reactivemoieties (e.g., azetidinium rings, aldehydes,hemiacetals, and the like),which react with carboxylateand -OH moieties on cellulosic andlignocellulosic fibers to form covalentbonds. Exemplary reactivecationic polymers, including but not limited to, cationicglyoxalated polyacrylamides (GPAMs) andcationic polyamidoamine-epichlorohydrin(PAE)resinsare typically used as wet and / or dry strengthadditives in papermaking. Herein, GPAMsand PAE resins are used in combination with amphotericemulsion and drypolyacrylamides as retention and drainage aids.tO173l As used herein, the term"cationicglyoxalated polyacrylamides (GPAMs)" or "GPAM"generally refers to a polymer obtained by reactingglyoxal and apolyacrylamide base polymer.Methods for producingglyoxalated polyacrylamides are known in the art.(See e.g., U.S. Pat. No.3,556,932 which first disclosed thesynthesis of a GPAM compositionprepared by reacting glyoxalwith a cationic polyacrylamide). ln some instances, thepolyacrylamide backbone of the GPAM canincorporate a small amount of a cationic monomer,rendering thepolymer self-retaining on fibers. lngeneral, GPAM comprises a reactivepolymer that can covalently bindwith cellulose upondehydration. L7Arrv DocrerNo. I 149704.062013CLIENTRNP NO. U52324lOL74) ln some embodiments, cationicglyoxalated polyacrylamides(GPAMs) refers to an aldehydecontainingpolymer, preferablycationicglyoxalatedpolyacrylamide ("GPAM") suitable for use as adry and / or wet strengtheningagent, wherein said cationicGPAM comprises: A.) a base polymercomprising a cationic monomer, optionally wherein thecationic monomer comprises DADMACand / or acryloyloxyethyltrimethyl ammoniumchloride;B.) the base polymer comprises a weightaverage molecular weight of at least 5,000 Da,preferablyatleast 80,000 Da, more preferably 100-L000 kDa; C.) the cationic GPAM comprises aglyoxal:base polymer weight ratio of at least about5:95, optionally from about10:90; and D.) the GPAM optionally comprises a solids percentage offrom about OS% to about 2O%o, optionally fromgreater than about 2% to about 10%, furtheroptionallyfrom aboutgreaterlhan4%to about8%;t01751 ln some embodiments,cationic monomers may be selectedfrom the group consisting ofacryloyloxy ethyl trimethylammoniumchloride, methacryloyloxyethyltrimethylammoniumchloride,methacrylamidopropyltrimethylammoniumchloride,acrylamidopropyltrimethylammonium chloride,methacryloyloxyethyldimethylammoniumsulfate,dimethylaminoethylacrylate,dimethylaminopropylmethacrylamide,diallyldimethyla mmonium chloride(DADMAC);dialkylaminoalkyl acrylatesand methacrylates and theirquaternary or acid salts, including, but notlimited to, dimethylaminoethylacrylate methyl chloridequaternary salt, dimethylaminoethylacrylate methyl sulfatequaternarysalt, dimethyaminoethylacrylate benzylchloride quaternary salt,dimethylaminoethyl acrylate sulfuricacid salt, dimethylaminoethyl acrylate hydrochloric acid salt,diethylaminoethyl acrylate,methyl chloridequaternarysalt,dimethylaminoethyl methacrylatemethyl chloride quaternary salt, dimethylaminoethylmethacrylate methyl sulfate quaternary salt,dimethylaminoethyl methacrylate benzylchloride quaternary salt, dimethylaminoethyl methacrylatesulfuric acid salt, dimethylaminoethylmethacrylate hydrochloric acidsalt, dimethylaminoethylmethacryloyl hydrochloricacid salt, dialkylaminoalkylacrylamidesor methacrylamides and theirquaternaryoracid salts such as acrylamidopropyltrimethylammoniumchloride,dimethylaminopropyl acrylamidemethyl sulfate quaternary salt, dimethylaminopropyl acrylamidesulfuric acid salt, dimethylaminopropylacrylamide hydrochloric acid salt,methacrylamidopropyltrimethylammoniumchloride, dimethylaminopropylmethacrylamide methylsulfate quaternary salt, dimethylaminopropylmethacrylamide sulfuric acid salt,dimethylaminopropylmethacrylamide hydrochloricacid salt, diethylaminoethylacrylate,diethylaminoethylmethacrylate anddiallyldialkylammonium halides such as diallyldiethylammoniumchloride and diallyldimethyl ammoniumchloride.lnsome embodiments,said one or more cationicmonomers may comprise DADMAC. ln some embodiments,said one or more cationic monomersmay comprise acryloyloxyethyltrimethyl ammoniumchloride. ln some embodiments, said one ormore cationic monomers may compriseDADMAC and / or acryloyloxyethyltrimethyl ammoniumchloride. ln some embodiments,said one or more cationicmonomers may be selected from thegroup consisting of methacryloyloxyethyltrimethylammonium chloride, acryloyloxyethyltrimethylammonium chloride, 3-(methacrylamido) propyltrimethyl ammonium chloride,3-(acryloylamido)propyltrimethyl ammonium chloride,diallyldimethyl ammonium chloride,dimethylaminoethylacrylate, dimethylaminoethylmethacrylate, and dimethylaminopropylacrylamide,dimethylaminopropylmethacrylamide.t01761 ln some embodiments, the backbonepolymermay compriseone or more primary amide-containing monomers.ln some embodiments, the backbonepolymer may comprise one or moremonomers selected from thegroupconsisting ofacrylamide, methacrylamide, ethylacrylamide,crotonamide, N-methylacrylamide,N-butylacrylamide, N-ethylmethacrylamide, and anyArrYDocKEr No. I149704.062013CLIENTRNP NO. U52324combination thereof. ln someembodiments, the backbonepolymer may comprise one or moreacrylamide monomers.lOI77l ln some embodiments, the backbonepolymermay compriseone or more anionic monomers.preferablythe anionic monomers are selected from thegroup consisting of monomers containing acarboxylic acid functional group, a sulfonic acidfunctional group, phosphonic acid functional group,their corresponding water soluble or dispersiblesalts, and any combinations thereof; preferably theanionic monomers are selected from thegroup consisting of acrylicacid, methacrylic acid, maleicacid, itaconic acid, vinyl sulfonic acid,2-acrylamido-2-methylpropane sulfonic acid (AMPS),acrylamido methane sulfonicacid, acrylamido ethane sulfonicacid, 2-hydroxy-3-acrylamide propanesulfonic acid, styrene sulfonicacid, vinyl benzenesulfonic acid, and vinyl phosphonic acid, theircorresponding water soluble or dispersiblealkali metal, alkaline earthmetal, and ammonium salts,and any combinations thereof; morepreferably the anionicmonomers are selected from acrylicacid, its water soluble or dispersiblealkali metal, alkaline earthmetal, or ammonium salts, and anycombinationsthereof.t0178] As used herein, the term "glyoxylationpercentage" refers to the percentage of acrylamide-based monomers which areglyoxalated in apolymerof thecationic GPAM composition, e.g., thefirst base polymer and / or thesecond base polymer.tO17g] As used herein,the terms "cationicpolyamidoamine-epichlorohydrin (PAE) resins' , "PAEresin", or"PAE",generally refer to reactive cationicpolymers generally synthesized by reacting oneor more polyamidoamine backbonescomprising an acid value of betweenabout 35 to about 40 withepichlorohydrin. ln some embodiments,the molar ratioof epichlorohydrin: secondary amine groupsof the polyamidoamine backbone may be betweenabout0.L5to about t.7.lnsome embodiments,said method may comprise a low-temperaturehold time of less than 24 hours under a 30-35"Ctemperature range at the beginning ofthe synthesis reaction.ln some embodiments, said methodmay include the addition of astrong acid andaweakacid. ln some embodiments, said method maycomprise the addition of a weight ratio ofweak acid: strong acid of about 0.25 or more, 1.2 or more,1.6 or more, e.g., wherein said strong acidcomprisessulfuricacidand / orsaid weak acid comprisesformic acid. ln some embodiments,said method may furthercomprise sequential addition of formicacid and sulfuric acid. ln someembodiments, saidmethod may comprise one or more additions offormic acid and / or one or more additions of sulfuricacid. ln some embodiments, said method mayresult in a stable PAE resin comprising a solidspercentageranging aboutL0-30%,20-27% or about25%.ln some embodiments, said methodmay result in a stablePAE resin comprising final resin pHof about 2.5 to about 3.8.ln some embodiments, said stablePAE resin may comprise about 10,500ppm or more, about 10,500 ppm or less, about 5,000ppm or less, about L,000 ppm or less ofepichlorohydrinbyproducts following synthesisof said stable PAE resin.t01S0lpolyamidoamineepichlorohydrinresins(PAEresins)have been applied in the manufacture ofpaper for a variety of applications.For example,PAE resins are widely used as strength additives toincrease the paper wet strength. PAE resins arealso the most commonadhesives used in the crepingprocess for producing tissue and towelproducts. ConventionalPAE resins are typically produced in atwo-step reaction. ln the first step,apolyamidoamine is prepared by condensation of nearequimolar amounts of a polyamine and apolycarboxylic acid or polycarboxylic acid derivative. Thepolyamidoamine that is formed is thenreacted with epichlorohydrinin an aqueous solution toproduce the PAE resin. The detailedsynthesis is well knownand is documented in numerouspatents, e.g., US Pat. Nos.,2,926,1L6, and7,175,740'L9ArrYDocKEr No. I149704.062013CLIENTREFNO. U52324t0181] As used herein, the term "water-solubleamphoteric polymers" or "water-soluble amphotericterpolymers" generally refers topolymers comprised of acrylamide(AM) monomers, one or moreanionic monomers, and one ormore cationic monomers.Such polymers may be utilized in theinventive retention and drainage aids as amphoteric drypolymers (AmDPAM). Exemplary water-soluble amphoteric dry terpolymers(AmDPAM) aredocumented inEP325075281'. Water-solubleamphoteric polymers may alsobeutilizedin the inventive retentionand drainage aids as amphotericemulsionpolymers (AmEPAM).to182l Exemplary water-solubleamphotericpolymers comprise one or more anionic monomerscontaining functional groups selected from thegroup consisting of carboxylic acids, sulfonic acids,phosphonic acids, their corresponding watersoluble salts, their correspondingwater dispersiblesalts, and any combination thereof,including but not limited to,acrylic acid, methacrylic acid, maleicacid, itaconic acid, vinyl sulfonicacid, 2-acrylamido-2-methylpropanesulfonic acid (AMPS),acrylamido methanesulfonicacid, acrylamido ethanesulfonicacid, 2-hydroxy-3-acrylamide propanesulfonic acid, styrene sulfonic acid, vinyl benzenesulfonic acid, and vinyl phosphonic acid, theircorresponding alkali metal, alkaline earthmetal, and ammoniumsalts, and any combination thereof'to183l Exemplary water-solubleamphotericpolymerscompriseone or more cationic monomersselected from the group consisting of acryloyloxyethyltrimethylammonium chloride ("AETAC"),methacryloyloxyethyltrimethylammoniumchloride ('MAETAC"),methacrylamidopropyltrimethylammoniumchloride ("MAPTAC"),acrylamidopropyltrimethylammoniumchloride("APTAC"), methacryloyloxyethyldimethylammoniumsulfate, diallyldimethylammoniumchloride("DADMAC"); dialkylaminoalkyl acrylates anddialkylaminoalkyl methacrylates and theirquaternary or acid salts, including but not limited to,dimethylaminoethyl acrylate("DMAEA"), dimethylaminoethylmethacrylate ("DMAEA"),dimethylaminoethyl acrylatemethyl chloridequaternary salt, dimethylaminoethylacrylate methylsulfate quaternary salt, dimethylaminoethyl acrylatebenzyl chloride quaternary salt,dimethylaminoethyl acrylate sulfuric acidsalt, dimethylaminoethyl acrylate hydrochloric acid salt,diethylaminoethyl acrylate methylchloride quaternary salt, dimethylaminoethyl methacrylatemethyl chloridequaternarysalt,dimethylaminoethyl methacrylatemethyl sulfate quaternary salt,dimethylaminoethyl methacrylate benzyl chloridequaternary salt, dimethylaminoethyl methacrylatesulfuric acidsalt,dimethylaminoethylmethacrylatehydrochloric acid salt, dimethylaminoethylmethacryloyl hydrochloric acid salt;dialkylaminoalkylacrylamidesand methacrylamides and theirquaternary or acid salts, includingbut not limited to, acryloylamidopropyltrimethylammoniumchloride, dimethylaminopropylacrylamide, dimethylaminopropylacrylamidemethyl sulfatequaternary salt, dimethylaminopropyl acrylamidesulfuric acid salt, dimethylaminopropyl acrylamidehydrochloric acid salt, methacrylamidopropyltrimethylammoniumchloride, dimethylaminopropylmethacrylamide, dimethylaminopropylmethacrylamidemethylsulfate quaternary salt,dimethylaminopropyl methacrylamide sulfuricacid salt, dimethylaminopropyl methacrylamidehydrochloricacid salt, diethylaminoethylacrylate,diethylaminoethylmethacrylate; anddiallyldialkylammonium halides, includingbut not limited to, diallyldiethylammonium chloride andd iallyldimethylammoniumchloride('DADMAC"),andany com bination thereof.t01841preferredembodiments of water-soluble amphotericpolymers are synthesized from threedifferent monomers, i.e., acrylamide(AM)(nonionic),acrylic acid(AA) (anionic at higher pH levels),Q9 (cationic). ln exemplary embodimentsthe inventive emulsionamphoteric polymers: aresynthesized by inverse emulsion; comprise anacrylic acid anionic monomer content<2wl% and upto 20 wt%o Q9,>78 wt% acrylamide(AM) monomers; in morepreferred exemplary embodimentscomprise the following composition:AM: AA:Q9-89:2:9;possess a low SV value (<3.5 cPs) orArrY DocKEr No. I 149704.062013 CLIENTREF NO. U52324preferably from 2.5 to 3.5 cPs; and possess a MW-of at least 1.5 million Daltons to 9 millionDaltons, typically from 2 to 5 millionDaltons.t0185] As used herein, theterms "anionic microparticles","anionic organic or inOrganicmicroparticles",or "anionic additives"generally refers to anionic materials added to papermakingfurnish as part of drainage-aidprograms. Exemplary anionic organic orinorganic microparticles areselected from thegroupof microparticlesand nanoparticles consistingof silica microparticles;colloidal silica; aluminumphyllosilicate mineralparticles, including but not limited to bentonite,sodium bentonite,calcium bentonite, and montmorillonite;and anionic polymer microparticles,including but not limited to highly structured anionicpolyacrylamides. Preferred anionic organic orinorganic microparticles may includesilicaorcolloidalsilica. Thefunction ofthe colloidal silicaappears to involve (a) release of water frompolyelectrolytebridges,causing them to contract, and(b)acting as a link inbridges that involve macromolecules adsorbedon different fibers or fineparticles. These effects create more streamlinedpaths for water to flow around the fibers. Thetendency of microparticles to boost first-passretention also will tend to have a positive effect oninitial dewatering rates. lthasbeenreported thatpaper produced by means of a microparticleretention and drainage program has a more open,porous structure, though the effect may becomeobscured bysubsequent wet-pressing and calenderingoperations'

[0186] TERMS AND UNITStO1S7l As used herein, the term"aqueous solution" or "solution"generally refers to a mixture ofwater and a water-solublesolute or solutes which are completelydissolved with little to no residualundissolved polymergel.The solution may behomogenous. When mixed with excess of water, thepolymer product ispreferablyfully dissolvedand the obtainedpolymersolutionis preferably freefrom discretepolymer particlesorgranules or residualgel.16188l AS USed herein, the term "aqUeOuS SUSpenSiOn","aqUeOuS SlUrry", Or "Slurry" generally referto a heterogeneous mixture of a fluid that containsinsoluble or sparingly soluble solid particlessufficiently large for sedimentation.Suspensions and slurries of thepresent invention may alsocomprise some amount of solidparticles, often termed colloidalparticles, which do not completelysettle or take along time to settle completely.t018g]Asusedherein, the term "consistency"generally refers to percent oven dry mass in the stock,slurry,or furnish(i.e.,700% *oven dry mass / totalmass).t0190] The terms, "total solids" or"total suspended solids" areused interchangeably herein andgenerally refer the total amountor weight of suspendedsolids contained in oil sands or other sandscomprising dispersion. "Total solids" or"totalsuspendedsolids" generally does not include dissolvedsolids.tolg1l As used herein, the term"ppm" refers toparts permilliononthebasis of milligrams of soluteperliter of aqueous solutionor slurry (e.g., mg / L).to192l As used herein, the terms "lbs / ton"or "#ff" denote pounds of dry mass of added material(e.g.,additive, solute, and / orparticle) per ton of suspended solids(e.g., weight of AKD per total dryton of suspended solids).t0193] As used herein, the terms "kE / T" or "kgflon"denote kilograms of dry mass (additive, solute,and / orparticle)perton of slurry, stock, and / orfurnish.t6194l As used herein, thephrases "%o by wt." denotespounds of dry mass of additive per dry massof solidsintheformulation, solution, or slurry,multiplied by LOO%.2TArrYDocKEr No. I149704.062013CLIENT RBTNO. U52324 DESCRIPTION OF THE INVENTIONto195l A recently discoveredsynergy between a novel amphotericemulsion polymer and reactiveresins such as PAE and GPAM inpaperfurnish containinghigh amounts of recycled content showsunexpected performance efficiency for retentionand drainage andpotentially as a pressing aid. lnmills with high recycled content withhigher levels of calcium ionsand high conductivity, NorthAmericanpapermanufacturersare looking for effective chemistrythat will provide on-machineretention and drainagewhile maintaining strengthproperties.to196l Glyoxalated polyacrylamide(GPAM) products are widely used in the paper industry, often toincrease paper wet and dry strength. Additional benefitis to increase the drainage of fiber slurry.GPAM is typicallypreparedthrough thereaction betweenglyoxaland a cationic polyacrylamide basepolymer. The original GPAMwas reported in US Pat. No.3556932.The cationic polyacrylamide basepolymer has a molecular weight below 25,OOODaanda molar ratio of acrylamide to diallyldimethylammoniumchloride of 99:L to 75:1.l}tgTl Recentpatentshave reported severalapproaches to improveGPAM performance efficiency.US.patentsNo. 8222303, No. 8703847, No. 9644320 claimnew GPAM products prepared using acationic polyacrylamide with an average moleculeweight ranging from 30 kDa to 5 million Da. Thefinal GPAMproduct had a GPAM contentbelow 4%.t01g8l Polyamidoamine-epichlorohydrin(PAE)is thepredominantchemicaltoprovide wet strengthfor paper products. ltiscommonlyused forpapertowel, labels,and carrier board grade to providestrength while the paper products are wet. US PatentsNo. 2926L54 and29261'16 describe thesynthesis ofPAE samples.t01991 More recently an amphotericpolymer was designed toimprove the runnability of the papermachine. USpatent10,590,60482 claimanew amphotericpolymer with a mass average molecularweight MW of 1500000-6 000 OO0g / mol,and a totalionicity of 4-1-5 mol-To, whereby the polymerproduct has a polymer content of at least 60wt%.Evenmore recentlyan emulsion amphotericpolymer is reported(patentapplicationnumber: Docket No.: 1149704.048000)toimprove drainageand retention of apapermaking system.tO2OOl The present inventiongenerallyrelates tomethods and compositionsfor manufacture oftissue, paper, or board and for enhancingretention and drainage thereof. ln particular, thedisclosureprovidesmethods forenhancing retention and drainageby addition of a retention anddrainage aid comprisingreactive cationicpolymers (e.g.,cationicstrength resins), water-solubleamphoteric terpolymers, and optionally anionic organicor inorganic microparticles. Preparation ofpaper sheets under these conditionsprovides improved retention, drainage time, STFI and burststrength,and improved hydrophobicparticle control.to201l ln one aspect, thepresent inventionprovidesa methodfor manufacture of tissue, paper, orboard, the method comprising:tOZO2l (a)forming orprovidingan aqueoussuspension comprisingcellulosic fibers;

[0203] (b)optionally dilutingthe aqueous suspension;t6204l(c)flocculating theaqueous suspension to forma flocculated fiber suspension;t02051 (d) delivering the flocculatedfiber suspension to a headboxand draining on a wire screen toforma wet fibrous web; andt02o6l (e) pressing and dryingthewet fibrouswebtoobtain a tissue, paper, or board;ArrY DocKEr No.I149704.062013CLIENT RgTNO.U52324lO2O7l wherein the methodfurther comprisespriortostep (c) treating the aqueous suspensioncomprising cellulosicfibers with a retention and drainageaid comprising:

[0208] (i) one or more reactive cationicpolymers; and

[0209] (ii)oneor more water-solubleamphoteric polymers.tO21Ol ln some exemplaryembodiments of the methodsaid retention and drainage aid optionallyfurther comprisesone or more anionic organicor inorganic microparticles.t02111 ln some exemplary embodiments of themethod (i)said one or more reactive cationicpolymers, (ii) said one or morewater-soluble amphotericpolymers, and optionally (iii) said one ormoreanionic organicor inorganicmicroparticles:lO2I2l(a)are addedsequentially in any order, simultaneously,or premixed prior to addition; ortO213l (b) are added sequentially in the order of(i), (ii), and then optionally (iii), wherein a mixingtime is allowed after each additionand said mixing time ranges from0.01-10 min, 0.1-5 min, or L-2min.1021.4) ln some exemplary embodiments of the methodsaid one or more reactive cationic polymerscomprise:tO215l(a)functionalgroupsthatare reactive to cellulosic or lignocellulosicfiber surfaces; andt02161(b)a cationic chargedensity ranging from below5.0 mEq / g, 0.5-5.0 mEq / $,1.0-4.0 mEq / g, or1.5-2.5 mEq / e as drysolids atPH7;l}217l andfurther comprise one of thefollowing;t02181(c)one or more cationicglyoxalated polyacrylamides (GPAMs);t02L91(d)one or more cationicpolyamidoamine-epichlorohydrin (PAE) resins; orlO2ZOl (e) a combination of one or more cationic GPAMsand one or more cationic PAE resins havinga ratio of PAE to GPAM ranging from1-:99to99:1, 20:80 to 80:20,40:60to60:40, or 45:55, whereinsaid one or more cationicPAE resins and said one or more cationicGPAMs are added sequentially inany order, simultaneously, orpremixedpriorto addition tosaid aqueous suspension comprisingcellulosic fibers.tO2ZIl ln some exemplary embodiments ofthe method said one or more cationic GPAMs:t1222l(a)are suitable for useas a dry and / or wet strengthening agen!l}223l (b) are synthesized by reactingglyoxalwitha basepolymer, wherein said base polymercomprises a weight average molecular weightranging from 5-5000 kDa, 50-2500 kDa, 80-2000 kDa,or 100-1000 kDa and comprises nonionicmonomers, cationic monomers, and optional anionicmonomers,whereinlOZZ4l(i)said nonionic monomersare selected from thegroup of primary amide-containingmonomers comprisingacrylamide, methacrylamide,ethyl acrylamide, crotonamide, N-methylacrylamide, N-butyl acrylamide, N-ethylmethacrylamide, and any combination thereof;lOZ2Sl(ii)said cationic monomersare selected from acryloyloxyethyltrimethylammonium chloride('AETAC"), methacryloyloxyethyltrimethylammoniumchloride ("MAETAC"),methacrylamidopropyltrimethylammoniumchloride ("MAPTAC"),acrylamidopropyltrimethylammoniumchloride("APTAC"), methacryloyloxyethyldimethylammoniumsulfate, diallyldimethylammoniumchloride("DADMAC"); dialkylaminoalkyl acrylates andArrY DocKEr No.I 149704.062013CLIENT REPNO. U52324dialkylaminoalkyl methacrylates and theirquaternary or acid salts, including but not limited to,dimethylaminoethyl acrylate("DMAEA"),dimethylaminoethylmethacrylate ("DMAEA"),dimethylaminoethyl acrylatemethyl chloridequaternarysalt, dimethylaminoethylacrylate methylsulfate quaternary salt, dimethylaminoethyl acrylatebenzyl chloride quaternary salt,dimethylaminoethyl acrylate sulfuric acid salt,dimethylaminoethyl acrylate hydrochloric acid salt,diethylaminoethyl acrylate methyl chloridequaternary salt, dimethylaminoethyl methacrylatemethyl chloridequaternarysalt,dimethylaminoethyl methacrylatemethyl sulfate quaternary salt,dimethylaminoethyl methacrylatebenzyl chloridequaternarysalt,dimethylaminoethyl methacrylatesulfuric acid salt,dimethylaminoethyl methacrylatehydrochloric acid salt, dimethylaminoethylmethacryloylhydrochloric acid salt; dialkylaminoalkylacrylamidesand methacrylamides and theirquaternary or acid salts, including butnot limited to, acryloylamidopropyltrimethylammoniumchloride, dimethylaminopropylacrylamide, dimethylaminopropylacrylamidemethyl sulfatequaternary salt, dimethylaminopropyl acrylamide sulfuricacid salt, dimethylaminopropyl acrylamidehydrochloricacid salt, methacrylamidopropyltrimethylammoniumchloride, dimethylaminopropylmethacrylamide, dimethylaminopropylmethacrylamide methyl sulfatequaternary salt,dimethylaminopropyl methacrylamidesulfuric acid salt, dimethylaminopropylmethacrylamidehydrochloric acidsalt,diethylaminoethylacrylate,diethylaminoethylmethacrylate; anddiallyldialkylammonium halides, including butnot limited to, diallyldiethylammonium chloride anddiallyldimethylammoniumchloride("DADMAC"), and any combination thereof; and10226l(iii)said optional anionicmonomers contain functionalgroupsselected from carboxylic acids,sulfonic acids,phosphonic acids, their correspondingwatersolublesalts, their corresponding waterdispersible salts, and any combination thereof,including but not limited to, acrylic acid, methacrylicacid, maleic acid, itaconic acid, vinyl sulfonicacid, 2-acrylamido-2-methylpropane sulfonic acid(AMPS),acrylamidomethanesulfonic acid, acrylamido ethanesulfonicacid, 2-hydroxy-3-acrylamidepropane sulfonic acid, styrene sulfonic acid, vinyl benzenesulfonic acid, and vinyl phosphonic acid,their corresponding alkali metal, alkaline earthmetal, and ammonium salts, and any combinationthereof;l1227l(c)comprisea glyoxal:base polymer weight ratioranging from 0.1:99.9 to 50:50, 5:95 to20:80, or 5:95 to10:90;l1228l (d) comprise a cationic charge densityranging from below 5.0 mEq / g, 0.5-5.0 mEq / E,1'0-4'0mEq / g, or 1.5-2.5 mEq / g as dry solidsat pH 7;l122gl(e)comprise apercent cationic monomer content rangingfrom 3-60% by weight, a percentanionic monomercontentrangingfrom0-50% byweight, wherein the remainder of the monomercontentcomprises nonionic monomers;tO23Ol(f)are formulated optionallyas a dry powder or as an aqueous composition comprising aGPAM solids percentage ranging from about 0.5% to about20%o, optionally from greater than about2Yoto aboutl-0%,furtheroptionally from aboutgreaterlhan4% to about 8%.t0231-l ln some exemplary embodiments ofthe method said one or more cationic PAE resins:l1232l(a)are suitable foruse as a wet strengthening agen|t9233l(b)are synthesizedby reacting one or morepolyamidoamine backbones withepichlorohydrin, wherein said one or morepolyamidoamine backbones are synthesized by reacting acarboxylic acid and / or a carboxylicacid derivative with an amine,wherein said one or morepolyamidoamine backbones comprise a molar ratio oftheamineto the carboxylic acid and / orcarboxylicacid derivative ranging fromL:Lto2:L,1.05:1to 2:L, or 1.5:1 to2:t;ArrYDocKEr No. I 149704.062013CLIENTRET NO. U52324102341(c)comprise a molar ratio of epichlorohydrinto secondary amine groups of thepolyamidoamine backbonerangingfromabout 0'15toabout L.7't6235l ln some exemplaryembodiments of themethod said one or more water-soluble amphotericpolymers:t02361(a)are comprised of acrylamide(AM) monomers, one ormore anionic monomers, and one ormore cationic monomers,wherein,lOZ37l(i) said one ormore anionic monomers containfunctional groups selected from the groupconsisting of carboxylic acids, sulfonic acids,phosphonic acids, their corresponding water solublesalts, their corresponding water dispersiblesalts, and any combination thereof, including but notlimited to, acrylic acid, methacrylicacid, maleic acid, itaconic acid,vinyl sulfonic acid, 2-acrylamido-2-methylpropane sulfonicacid(AMPS),acrylamido methanesulfonicacid, acrylamido ethanesulfonicacid, 2-hydroxy-3-acrylamidepropane sulfonic acid,styrene sulfonic acid, vinyl benzene sulfonicacid, and vinyl phosphonic acid, their correspondingalkali metal, alkaline earth metal, andammoniumsalts, and any combinationthereof; andto238l(ii)said one ormore cationic monomers are selectedfrom the group consisting ofacryloyloxyethyltrimethylammonium chloride("AETAC"), methacryloyloxyethyltrimethylammoniumchloride("MAETAC"), methacrylamidopropyltrimethylammoniumchloride ("MAPTAC"),acrylamidopropyltrimethylammoniumchloride ("APTAC"), methacryloyloxyethyldimethylammoniumsulfate, diallyldimethylammoniumchloride("DADMAC");dialkylaminoalkylacrylates anddialkylaminoalkyl methacrylates and theirquaternary or acid salts, including but not limited to,dimethylaminoethylacrylate("DMAEA"),dimethylaminoethylmethacrylate ("DMAEA"),dimethylaminoethylacrylatemethylchloridequaternary salt,dimethylaminoethylacrylate methylsulfatequaternarysalt, dimethylaminoethylacrylate benzylchloride quaternary salt,dimethylaminoethylacrylatesulfuric acid salt, dimethylaminoethylacrylate hydrochloric acid salt,diethylaminoethyl acrylate methylchloridequaternary salt, dimethylaminoethyl methacrylatemethyl chloridequaternarysalt,dimethylaminoethyl methacrylatemethyl sulfate quaternary salt,dimethylaminoethyl methacrylate benzyl chloridequaternary salt, dimethylaminoethyl methacrylatesulfuric acid salt, dimethylaminoethylmethacrylatehydrochloric acid salt, dimethylaminoethylmethacryloyl hydrochloric acid salt; dialkylaminoalkylacrylamidesand methacrylamides and theirquaternary or acid salts, including butnot limited to, acryloylamidopropyltrimethylammoniumchloride, dimethylaminopropylacrylamide, dimethylaminopropylacrylamide methyl sulfatequaternarysalt, dimethylaminopropylacrylamide sulfuricacid salt, dimethylaminopropyl acrylamidehydrochloric acid salt, methacrylamidopropyltrimethylammoniumchloride, dimethylaminopropylmethacrylamide, dimethylaminopropylmethacrylamide methylsulfate quaternary salt,dimethylaminopropylmethacrylamide sulfuric acid salt,dimethylaminopropyl methacrylamidehydrochloricacid salt, diethylaminoethylacrylate, diethylaminoethylmethacrylate;anddiallyldialkylammonium halides, including butnot limited to, diallyldiethylammonium chloride anddiallyldimethylammonium chloride("DADMAC"), and any combination thereof;tg239l (b) comprise an inversephaseemulsion, a drypolymer, or an aqueous polymer solution,preferablyaninversephaseemulsion;lO24Ol (c) comprise apolymerstandardviscosity (SV) rangingfrom<3.5 cPs, 1-3.5 cPs, 2-3'5 cPs, or2.5-3.5 cPs;IO247l (d) comprise a molecular weightranging from L.5-9 million Daltons, 1.5-8 million Daltons, 2-8million Daltons,4-8 million Daltons,or preferably 2-5 million Daltons;Arrv Docrer No. 1149704.062013 CLIENT REF NO. U52324t1242l(e)compriseanacrylamide(AM)monomer contentranging from 77-100 wt%o,78-LOOwl%,80-100wt%, 90-100 wt%o, or 95-100 wt%;

[0243] (f)comprise an anionic monomer content ranging from(3wtYo, 42wt%,0.01-3 wt%,0.5-2wt%o,1--2wtyo,L.5-2 wt%o, or 1',8-2 wl%;t1244l (g)comprise a cationic monomer content ranging from(20wt%o,L-2OwtYo,2-16w|%o,4-L2wt%o, or 7-9 wt%; or102451(h)anycombinationof the foregoing.10246l ln some exemplary embodiments ofthe method said one or more anionic organic orinorganic microparticles are selectedfrom the group of microparticles andnanoparticles consistingof silica microparticles; colloidalsilica; aluminumphyllosilicate mineral particles, including but notlimited to bentonite, sodiumbentonite, calcium bentonite,and montmorillonite; and anionicpolymer microparticles, including but notlimitedtohighly structured anionic polyacrylamides.l}247lln some exemplary embodimentsof the method:102481(a) said one ormore reactive cationicpolymerscomprisessaid one or more cationic GPAMsand / or said one ormore cationic PAE resins in aqueousform;l124gl (b) said one or more cationic GPAMscomprise said base polymer comprising cationicmonomers selected from DADMAC,AETAC, and combinations thereof;nonionic monomers selectedfrom acrylamide, methacrylamide,and combinations thereof;and optionally anionic monomersselected from acrylic acid and / or corresponding watersoluble salts, water dispersible alkali metalsalts, alkaline earth metal salts, ammoniumsalts, and combinations thereof, or said base polymercomprises(i)acrylamide and DADMAC,(ii) acrylamide and AETAC, or(iii) acrylamide, DADMAC, andAETAC,

[0250] (c)said oneor more water-soluble amphoteric polymerstQ251l (i) comprises an inverse emulsion of acrylamide(AM), acrylic acid (AA), and[2-(acryloyloxy)ethyll trimethylammonium chloride (Q9) monomers;10252) (ii) preferably comprises an acrylic acid(AA)monomercontent of no more than 2 wt%; andt02531(iii) preferably comprises a ratio of AM:AA:Q9ranging from 89:2:9 to 97:2:7; andlO2S4l (d)said one or more anionic organicor inorganic microparticles comprise colloidalsilica't0255] ln some exemplary embodimentsof the method, whenadded to said aqueous suspensioncomprising cellulosic fibers:t02561(a)said one ormore reactive cationicpolymers are added at a dosage ranging from 0.1-15g / kg,0.5-5g / kg, or 0.5-a glkg;

[0257] (b)said one or more water-solubleamphotericpolymersareadded at a dosage ranging from0.05-5g / kg,0.I-4 g / kg, or 0.3-1' g / kg;to258l (c) said one or more anionic organic orinorganic microparticles are added at a dosagerangingfrom0.1-1g / kg,O.2-0.8g / kg, or 0.a-0.6e / kg.t02591 ln some exemplaryembodiments of the method, saidaqueous suspension comprisingcellulosic fibers comprises apHranging from4-8, 4-7 .5, 4-7,4.5-7,or 5-7 and further comprises:ArrYDocKEr No. 1149704.062013CLIENT RErNO. U52324t0260l(a)cellulosicfibers optionally obtainedfrom sources selectedfrom softwood fiber, hardwoodfiber, recycled fiber,recycled old corrugated cardboard(OCC), recycled mixed office waste (MOW),recycled mixed officepaper,refined fiber, mill brokefibers, coated broke, non-wood fibers, includingbut not limited to straw and wheatpulp, and a mixture of any of the foregoing;t9261l(b) pulpselectedfrom Kraft pulp, unbleached Kraftpulp,bleachedpulp, unbleached pulp,process water from pulp, paper, andf or boardproduction, neutral sulfite semi chemical (NSSC) pulp,mechanicalpulp, non-woodpulp,and a mixture of anyof the foregoing; or10262l(c)a stock selected from a thick stock,athickstock diluted with chemical water, syntheticwater, white water, andf orprocess water, and a thin stock, and a mixtureof any of the foregoing.t0263] ln some exemplary embodimentsof the method, whenused for manufacture of tissue,paper,or board,the method results in:[02641(a)improved retention of said cellulosic fibers; a

[0265] (b)improved drainage ofsaidflocculated fiber suspension;

[0265] (c)improvedSTFIand / orburst strength;10267l(d)a reduced hydrophobic particle and / or hydrophobicagglomerate counUtO26Sl (e) an improved dry tensile, immediatewet tensile, and / or soaked wet tensile strength; or

[0269] (f)any combination of(a)-(e)lO27Ol compared toatissue,paper, or boardpreparedby anidentical method in the absence of (i)addition of said one or more reactive cationicpolymersor(ii) addition of said one or more water-solubleamphotericpolymers.lO27Ll ln another aspect, thepresent invention provides a method formanufacture of tissue, paper,or board, the methodcomprising:lo272l(a)formingor providing an aqueous suspension comprisingcellulosic fibers;l}273l(b) optionally diluting the aqueous suspension;lO274l(c)flocculating the aqueous suspensionto form a flocculated fiber suspension;l1275l(d)deliveringthe flocculated fiber suspension to aheadbox and draining on a wire screen toforma wet fibrous web; and10276l(e) pressingand drying the wet fibrousweb to obtain a tissue, paper, or board;lo277l wherein the methodfurther comprisespriorto step(c)treatingthe aqueous suspensioncomprising cellulosic fiberswith a retention and drainage aid comprising:l1278l (i) one or more reactive cationicpolymerscomprisingfunctional groups that are reactive tocellulosic or lignocellulosic fiber surfacesand acationiccharge density ranging from below 5.0mEqlg,0.5-5.0 mEq / g,1.0-4.0mEq / g, or 1.5-2.5 mEq / g as dry solids atpH 7, wherein said one ormore reactive cationicpolymers comprise one or more cationicglyoxalated polyacrylamides(GPAMs); one or more cationicpolyamidoamine-epichlorohydrin(PAE)resins; oracombinationofone or more cationic GPAMs and one ormore cationic PAE resins havinga ratio of PAE to GPAMranging from 1:99 to99:1, 20:80 to 80:20, 40:60 to 60:4O, or45:55, wherein said one or morecationic PAE resins and said one or more cationic GPAMsare added sequentially in any order,simultaneously, orpremixed priorto additionto said aqueous suspension comprising cellulosicfibers;ArrY DocKEr No. I 149704.062013 CLIENTREF NO. U52324l}27gl(ii)oneor morewater-soluble amphotericpolymerscomprisingan inverse emulsion ofacrylamide(AM), acrylic acid(AA),and[2-(acryloyloxy)ethyl]trimethylammonium chloride (Q9)monomers;preferablycomprising an acrylicacid(AA)monomer content ofno more than 2 wtYo;andpreferablycomprisinga ratio of AM:AA:Q9 ranging from 89:2:9 to9'J':2:7; andt028ol(iii)optionallyone or more anionic organic or inorganicmicroparticles comprising silica.tO2S1l ln another aspect,thepresentinventionprovides a fiber stock composition comprising:l1282l(a) an aqueous suspension comprisingcellulosic fibers; and[02831(b)a retention and drainageaidcomprising

[0234] (i)one or morereactive cationic polymers;

[0285] (ii)one ormore water-soluble amphotericpolymers; andtO2S6l(iii) optionally one or more anionic organicor inorganic microparticles;l1287lobtainable by a method accordingto any of the foregoing claims.t0288] ln another aspect, thepresent inventionprovidesa compositionfor use as a retention anddrainage aid in manufactureof tissue,paper,or board, thecomposition comprising:t62Sgl (a) one or more reactive cationicpolymers comprising a cationic charge density ranging frombelow 5.0 mEq / g,0.5-5.0 mEq / g,1.0-4.0mEq / g, or 1.5-2.5 mEq / gasdry solidsat pH 7, wherein saidone or more reactive cationicpolymers comprisetO29Ol (i) one or more cationicglyoxalated polyacrylamides(GPAMs)synthesized byreacting glyoxalwith a base polymer, wherein said basepolymer comprises a weight average molecular weightranging from 5-5000 kDa, 50-2500kDa, 80-2000 kDa, or L00-1000 kDa;(i) acrylamide and DADMAC,(ii)acrylamide andAETAC,or(iii) acrylamide, DADMAC, andAETACandfurther wherein said one ormore GPAMs comprises aglyoxal:base polymer weight ratio ranging from 0.1:99.0 to 50:50, 5:95 to20:80, or 5:95 to 10:90; and a cationic charge densityranging from below 5.0 mEq / g, 0.5-5.0 mEq / g,1.0-4.0 mEq / 9, or 1.5-2.5 mEq / gas dry solids at pH 7;tO291l(ii)one or more cationicpolyamidoamine-epichlorohydrin (PAE) resins; orl12gzJ (iii) a combination of one or more cationicGPAMs and one or more cationic PAE resins havinga ratio of PAE to GPAM ranging from 1:99 to99:L, 20:80 to 80:20, 40:60 to 60:40, or 45:55;t6293l(b)one or more water-solubleamphotericpolymerscomprising acrylamide(AM), acrylic acid(AA),and [2-(acryloyloxy)ethyl]trimethylammonium chloride(Q9) monomers; wherein said one ormore water-soluble amphotericemulsionpolymers preferably comprise an acrylic acid (AA)monomer content of no more than 2 wt%anda ratio of AM:AA:Q9 ranging from 89:2:9 to 9t:227 ,wherein said one or more water-solubleamphotericpolymersis a an inverseemulsion, a drypolymer,an aqueous solution,preferably an inversephaseemulsion;andl12g41(c)optionallyone or more anionic organic orinorganic microparticles selected from thegroup of microparticles and nanoparticlesconsisting of silica microparticles; colloidal silica;aluminumphyllosilicatemineralparticles, including but not limited tobentonite, sodium bentonite,calcium bentonite,and montmorillonite; and anionicpolymer microparticles, including but notlimitedto highly structured anionicpolyacrylamides.to295l The methods and compositionsillustratively disclosed herein suitablymay be practiced in theabsence of any elementwhich is not specifically disclosedherein and / or any element specificallyArrvDocrnr No. 1149704.062013CLIENTREF NO. U52324disclosed herein. Exemplary embodimentsof the invention and its advantagesare further disclosedin the following examples. EXAMPLESt02961 The examples provided herein are for illustrativepurposes so that the invention may be morefully understood. These examples should notbe construed as limiting the invention in any way'102971EXPERT M ENTALPROCEDU RES

[0298] Determination ofdrainage time by DDA Screeningtg2ggl Cellulosicfibrous webs werepreparedand drainage timeswere analyzed by dynamicdrainage analyzer(DDA)testing according to thefollowing. An aliquot of cellulosic stock (500 mL)with a consistency of 0.4 to 0J%by wt(Totalsuspended solids, TSS)was mixed with chemicaladditives for 45 seconds while agitating.After mixing, the flocculated stockwas drained through a 60mesh screen under vacuum(250 mBar). Drainage time was determinedby measuring the timeneeded to show a vacuum break(i.e.,a rapidincrease in vacuumpressure).The fiber matleft on theDDAscreenand the filtrate were used for additionaltesting.[03001Determination of filtrate turbiditytO3O1l Turbidity testingwas performed on the filtrates fromDDA screening as an indication ofretention. Turbidity of treated filtrates wasperformed using a Hach 2100Q turbidimeter. The Model2100Q Portable Turbidimeter operates onthe nephelometricprincipleof turbiditymeasurement.The optical systemincludes atungsten-filamentlamp, a 90" detector tomonitor scattered light anda transmitted light detector. The instrument's microprocessorcalculates the ratio of the signals fromthe 90'andtransmittedlight detectors, which correctsfor interferences from color and / or light-absorbing materials. The instrumentrange is 0to1000 NTU. A lower turbidity level generally trendswith an increase in retention offiller, fines, and / or contaminants in thefurnish in the fiber mat.Example 1: Evaluation of amphoteric emulsionpolymers with reactive strength resins andsilica as retention and drainageaids in recycled OCC furnish

[0302] Amphotericemulsion terpolymers with reactivestrength resins were evaluated with andwithout silica as retention and drainageaids for L00% recycled old corrugated cardboard (OCC)stock. Retention and drainage aidadditives are shown in Table 1.t03031 A NATissue machine was used for formation ofrecycledtowelsusing the recycled OCCcellulosic fiber stock. ThepHof the stock was about7.3 and the conductivity of the white water was1.4 mS / cm. The total white waterhardness was1"40ppm as CaCO: and alkalinitywas 360 ppm asCaCOe. The consistency was O.60%,measured as totalsuspended solids (TSS)'t03o4l Table1:Chemicalandpolymeric additives testedasretentionand drainage aids in Examplest-7. Monomer Composition, IDAdditiSVArrYDocKEr No. 1149704.062013CLIENT RgTNO. U52324 AmphotericAmphoteric EmulsionPAM(AmEPAMA) 3.0-3.47%Q9,2%AA,9L% AMDPolymerAA P AAPCCASt6PAM-Poyacryam etO3O6lpreparationof sheets and determinationof drainage time by DDA screeningtO3O7l Sheets(i.e.,cellulosic fibrousmats) wereprepared and drainage times were analyzed bydynamic drainage analyzer(DDA)testing accordingto the following. An aliquot of cellulosic stock(500 mL) was combined with reactive strengthresin(GPAMorPAE, 3 kg / t, where T=metric ton)and mixed for up to 2 minutes, followedbyaddition ofpolymeric additive (AmEPAM A, AmEPAM B,or ANMicro).Where indicated,silica was added last.tO3O8l After agitating for 45 seconds, the flocculatedstock was drained through a 60 mesh screenunder vacuum (250 mBar) to form a fibermat. Drainage timewasdeterminedby measuring the timeneeded to show a vacuum break(i.e., a rapid increasein vacuum pressure). Filtrates were collectedand used for determinationof filtrate turbidity asa measure of fiber retention.

[0309] Determination offiltrate turbidityt03101 Turbidity testing wasperformed on the filtrates from DDA screening as an indication ofretention of cellulosic fiber materialfrom the fiber stockin the fiber mat. Turbidity of treatedfiltrates was performed usinga Hach 2L00Q turbidimeter.The Model 2100Q Portable Turbidimeteroperates on the nephelometricprincipleof turbiditymeasurement. The optical system includes atungsten-filament lamp, a 90" detector tomonitor scattered lightand a transmitted light detector.The instrument's microprocessor calculatesthe ratio of thesignals from the 90' and transmittedlight detectors, which correctsfor interferences fromcolor and / or light-absorbing materials. Theinstrument range is 0 to1000 NTU. A lower turbiditylevel generally trends with an increase inretention of filler,fines, and / or contaminantsin the furnish in the fiber mat.to311l Additives, dosages, and retentionand drainage results are shown in FIGS 1-4.t03121 The results indicate that the inventiveretention and drainage aids (e.g., reactive strengthresin with amphoteric emulsion terpolymer)significantly improvethe drainage and retention (i.e.,shorter drainage time and lowerturbidity) of sheetsprepared from a 1-00% recycled furnish overGpAM or PAE alone. The inventiveretention and drainageaids improve both drainage and turbidityin a dose dependentmanner as the AmEPAMpolymer dosage increased.Arrv DocrBrNo. I 149704.062013CLIENTRENNO.U52324103131 Addition of silica alone to a cellulosic fibersuspension is known to have no effect ordetrimental effects on both retentionand drainage in the absence of PAE, GPAM and / or AmEPAM.Addition of silica to the inventiveretention and drainage aidsprovided a synergistic improvement inboth retention and drainage, with the shortestdrainage times and lowest turbidities observed in thepresenceof 0.5kg / T silica,t03141 These resultsprovide proofofconcept that the inventive retentionand drainage aids (e.g.,reactive strength resin+amphotericpolymer)providesynergisticenhancements in retention anddrainage over reactive strengthresin alone. The optional additionof silica adds additional synergisticbenefit. Example 2: Evaluation of AmEPAM andAmDPAM with reactive strength resins and silica asretention and drainageaids in recycled MOW furnishtO315l Amphoteric emulsion terpolymersand amphoteric drypolymers were evaluated withreactive strength resin(PAE),with andwithout silica or ANMicro,as retention and drainage aids forrecycled mixed officewaste (MOW) furnish. The inventiveretention and drainage aids wereevaluated against chemical additives(polyamines and CPAMs) that are knownfor their performanceon wet pulp pressability. Retention anddrainage aid additives are shown in Table 1.tO316l A NA Tissue machine was usedfor formation of recycledwhite towels using the recycledMOW cellulosic fiber stock. ThepHof headbox furnishwas 6.28 and the conductivity measurementof the white water was 1.5 mS / cm. The totalhardness of white water was 600 ppm as CaCOE andalkalinity was 360ppmas CaCOe.The consistency was 0.63%, measuredas total suspended solids(rss).t03171 Towel fibermats were prepared and evaluatedfor drainage time by DDA screening and theresulting filtrates were evaluated for turbidityaccording to Example 1. An aliquot of cellulosic stock(5OO mL) was combined with reactive strengthresin (PAE) or control resin (CPAM2) and mixed for upto 2 minutes, followed by additionof amphotericpolymericadditive(AmEPAM or AmDPAM) orcontrol polymer (CPAM1 or Polyamine). Where indicated,anionic additive (silica or ANMicro) wasadded last. Additionally, the hydrophobicparticle (HP) count and HP agglomerate count weredetermined.tO318l Conditions, dosages,and results are summarized in Table 2.t03191Table2:Additivesand results for recycled towelsHP Polymer Resin Anionic Drain Filtrate3tArrY DocKErNo. I149704,062013CLIENTREFNO.U52324CPAMl tnone 0 Silica 0.5 24.58 71.3 44.t% 58.Oo / oA AAA A A AtOpo. .,lower turbidity) of a recycled MOW furnish over commonlyused additives (CPAM1 or polyamine)and an anionic additive. Optional addition ofan anionicadditive(e.g., silicaor ANMicro)providesadditionalbenefits to drainage andretention.tO321l Results alsoindicatethatboth amphoteric emulsionpolymers (AmEPAM) and amphoteric drypolymers (AmDPAM) significantly improve the drainage andretention when used with PAE or acationicpolyacrylamide(CPAM2)and an anionic additive.l1322l These resultsprovidefurtherproof of concept that the inventiveretention and drainage aids(e.g., amphoteric polymer + PAE + anionic additive)provide synergistic enhancements in retentionand drainage overpolymeric additive + anionic additive.Example 3: Evaluation of AmEPAMvs. CPAM with GPAM as retention anddrainage aids inpackaging gradefurnishto323l Amphoteric emulsion terpolymers(AmEPAM)+ GPAM were evaluated against a cationicpolyacrylamide(CPAM) + GPAM as retention and drainage aid alongwith common additives (e'g',rosin and alum) in a commercialpackaging grade furnish at different conductivity levels.l1324l NA Packaging Liner sheets wereprepared and evaluated for drainage time by DDA screeningand the resulting filtrates were evaluatedfor turbidity according to Example 1.to325l Liner sheets wereprepared using furnish comprised of69% unbleached kraft and 31%recycled OCC. Thick stock was collected from themachine chest prior to the introduction of anypapermaking additives. Tray water was collectedand was used to dilute the thick stock to headboxconsistency(O.6%1,measuredastotalsuspended solids(TSS). Theresultingthin stock furnish hadthe following characteristics:pH 6.02, conductivity 3.84gS / cm, alkalinity 32O mg / L as CaCOa andtotal hardness 800 mg / L as CaCOs. Aportionof thestock was also treated with a L0% CaClz solutionand a IO% Na2SO4 solution to increase the conductivityof the system. Total conductivity wasmeasured at three distinctlevels: 3.84 mS / cm, 5.09 mS / cm and 8.01mS / cm.t03261 A commercialchemical additive sequence and dosagewas followed, with the polymer beingthe independent variable. The sequence was comprisedof 1.5 kg / ton GPAM, 0.1 kg / ton rosin, 5kg / ton alum, andpolymer,where thepolymer was either a cationicpolyacrylamide (CPAM) or theinventive amphotericpolyacrylamide(AmEPAM)at dosagesranging from 0.L-0.3 kg / T.Arrv DocnErNo. 1149704.062013CLIENTREFNO.U52324l1327l Conditions, dosages, and drainage timeresults for two conductivity levels are shown in FIGS5-6. Conditions, dosages, and filtrate turbidityresults for three conductivity levels are shown in FIG7.to328l Results from FIG 5 indicate thatpackaging grade furnish at conductivity 3.84 mS / cm, whentreated with AmEPAMprovidessignificantlybetter drainage time than theCPAM. Results from FIG 6indicate that AmEPAM continues to outperformthe CPAM asa drainage aid for packaging gradefurnish at conductivity 5.09mS / cm. Results from FIG 7 indicatethat AmEPAM outperforms CPAM infiltrate turbidity testresults across all three conductivitylevels at all dosages.

[0329] These resultsprovide proofof concept thatthe inventive retention and drainage aid system(AmEPAM+GPAM) outperforms a conventionalcombination(CPAM +GPAM)in packaging gradefurnish with rosin and alum acrossseveral conductivity levels andpolymer dosages.Example 4: Evaluationof strength ofpackagingliner sheetsmade with AmEPAM vs. AmDPAMwithGPAMt03301 NA packaging liner sheets werepreparedusingamphoteric emulsion terpolymers (AmEPAM)or amphoteric dry polymers(AmDPAM)across severalGPAM dosages (1.5-4.5 kg / T) according toExample 3. The resulting sheetswere evaluated using a standard strengthtest, e.9., Short SpanCompressive Test(STFI).Geometricmean STFI results are shown in FIG 8.t03311 Theseresults indicate that, when used withGPAM, both AmEPAM and AmDPAM provide astrength benefit over GPAM alone. Theseresults also indicate that, when used with GPAM, theamphoteric emulsionpolymers (AmEPAM) provide a strength benefitover amphoteric dry polymer(AmDPAM). Example5:Evaluation of strength of handsheetsmade with AmEPAM vs. CPAM with GPAMand silica as retentionand drainage aids in recycledOCC furnishto332l NA Handsheets werepreparedusingretention and drainage aids consisting of amphotericemulsion terpolymers(AmEPAM)+GPAM+silica or cationicpolyacrylamide (CPAM) + GPAM + silicaaccording to Example1.to333l This exampleused L00% recycled OCC. Thick stockwas collected from the machine chestprior to the introduction of anypapermaking additives. Tray water was collectedand was used todilutethe thick stock to headbox consistency(0.6%), measured as total suspended solids (TSS). Theresulting thin stock furnishhad the following characteristics:pH 6.3, conductivity 2.9 mS / cm,alkalinity 300 mg / Las CaCOg andtotalhardness 900 mg / L as CaCO:.t03341 GPAM was added at 4 kg / ton.AmEPAMorCPAM was added at 0.125 kg / ton as activepolymer. Silica was added at 0.125kg / ton. NA Handsheets wereprepared and tested for strengthusing standard STFI and burststrength tests. STFI and burst strengthresults are shown in FIG 9.t03351 Theseresults indicate that, when used with GPAMand silica, the amphoteric emulsionpolymers(AmEPAM) providea strength benefitover CPAM. Without being boundto theory, it canbe rationalized that the amphotericpolymer allows for better retentionof GPAM treated fines thanCPAM when used withsilica. This results in better strengthproperties of paper.t03361 These resultsprovidefurtherproofof conceptthat the inventive retention and drainage aidsystem (AmEPAM+GPAM)outperformsa conventionalcombination(CPAM + GPAM).Arrv Docrr,r No.1149704.062013CLIENT REF NO. U52324 Example 6: Evaluation of amphotericemulsionpolymerswithreactive strength resins andsilica as retention and drainage aidsin recycled towel grade OCC furnishto337l Amphoteric emulsionterpolymers(Amphoteric EPAM) were evaluated against othercommonly used polymers(ANMicroor CPAM),along with reactive strength resin (PAE or GPAM),with and without silica, as retentionand drainage aids for 100%recycled towel grade OCC stock.Retention and drainage aid additivesare shown in Table1. The backbone MW for GPAM A is 10-50kDa, and backbone MWfor GPAM B is 100-200 kDa.lO33Sl This exampleused IOO%OCCfor brown towelgrade.Thick stock was collected from themachine chest prior to the introduction ofany papermaking additives.Tray water was collected andwas used to dilute the thick stock toheadbox consistency(0.5% TSS). The resulting thin stock furnishhad the following characteristics:pH 6.45, conductivity1.9 mS / cm, total hardness 600 mg / L asCaCOs.to33gl Towel fiber mats werepreparedand evaluatedfor drainage time by DDA screening and theresulting filtrateswere evaluated for turbidity according to Example 1. Conditions, dosages, andresultsshown in FIGS 10-11.to340l These resultsindicate that, the combination ofGPAM A or B with amphoteric PAM, with orwithout silica, showed better drainage andretention than the combination of GPAM with anionicpolymer (ANMicro) or cationicpolymer(CPAM)with or without silica.The combination of GPAM Bwith amphoteric PAM with silicashowed the best retentionand drainage't03411 These results provide furtherproofof conceptthat the inventive retention and drainage aidsconsisting of reactive strength resin(GPAMorPAE) + amphoteric PAM provide synergisticenhancements in retention and drainageoverpolymer (e.g.,amphotericPAM or ANMicro) aloneand over reactive strengthresin (GPAM or PAE) alone.Theoptionaladdition of silica providesadditional synergistic enhancementto the retentionand drainage aids.lO34Z) Without being bound to theory, it canbe rationalized that the observed synergism may resultfrom a mechanism wherein(i)reactivestrength resins(GPAM, PAE), which are cationic and highlyreactive, efficiently bind to anioniccellulosic fiber andfinesthatwould otherwise be lost, therebyproviding better retentionbecause;(ii)thesimultaneouspresence of the amphoteric PAM, which isa terpolymer containing anionic and cationicmonomers (see Table 1), causes flocculation to occurand allows for the reactive strengthresintoreact with the anionicmonomers of the amphotericterpolymer, thereby forminglarge and stable flocs comprisingfiber, fines, amphoteric PAM, andstrength resin, and causing a synergistic increasein retention and drainage; and (iii) the optionaladdition of silica causes the flocs to shrink bycollapsing bonds betweenstrength resin and polymerand extruding water, thereby forminga higher density floc structurewhich allows for additionalsynergistic increase in retention,faster drainage, and likely betterwet pressability.to343l Taken together, the results of Examples1-5 indicate that synergistic increase in retention anddrainage haspotential to greatly improveretention, drainage, and hydrophobicparticle / agglomerate incorporation intosheet formation fromrecycled fibers' These result alsoprove that optional addition ofsilicaprovidesadditionaldrainage and retention benefits.Example 7: Evaluation of amphoteric emulsionpolymers with reactive strength resins (PAEand DpAM) and silicaasretentionand drainage aidsin recycled mixed office paper furnishto344l Amphoteric emulsion terpolymers(AmphotericPAM)wereevaluated with a combination ofreactive strength resins(PAE and GPAM), with and withoutsilica, as retention and drainage aids for100% recycledmixed officepaperstock.ArrY DocKEr No.I 149704.062013CLIENTREP NO. U52324to345l ln this example, L00%recycled mixed officepaper was used to make recycled white towel.The thick stock was diluted with white water toconsistency of 0.83%. Towel fiber mats wereprepared and evaluated for drainagetime by DDA screening and theresulting filtrates wereevaluated for turbidity accordingto Example 1. Conditions,dosages, and results are shown in Table3.to346l Table3: Additives, dosage, and resultsfor recycled towelsAdditive ProgramDrain Time, sec Turbidity, NTUB12221101 1k1Sl1both PAE and GPAM with silica.The best results were achievedby addition of both GPAM and PAE.These results provide proof of concept that GPAM andPAE may be added together to the inventiveretention and drainageaids to enhance drain timeand turbidity.

Claims

ATTY DOCKET NO.1149704.062013 CLIENT REF NO. US2324 CLAIMS  What is claimed is:

1. A method for manufacture of tissue, paper, or board, the method comprising:  (a) forming or providing an aqueous suspension comprising cellulosic fibers;  (b) optionally diluting the aqueous suspension;   (c) flocculating the aqueous suspension to form a flocculated fiber suspension;   (d) removing sufficient water from the flocculated fiber suspension to form a wet fibrous  web, preferably by introducing the flocculated fiber suspension into a headbox and  draining the flocculated fiber suspension on a wire screen; and   (e) pressing and drying the wet fibrous web to obtain a tissue, paper, or board;  wherein the method further comprises prior to step (c) treating the aqueous suspension  comprising cellulosic fibers with a retention and drainage aid comprising:  (i) one or more reactive cationic polymers; and  (ii) one or more water‐soluble amphoteric polymers.

2. The method of claim 1, said retention and drainage aid optionally further comprises one or more  anionic organic or inorganic microparticles.

3. The method of claim 1 or 2, wherein (i) said one or more reactive cationic polymers, (ii) said one  or more water‐soluble amphoteric polymers, and optionally (iii) said one or more anionic organic  or inorganic microparticles:  (a) are added sequentially in any order, simultaneously, or premixed prior to addition; or   (b) are added sequentially in the order of (i), (ii), and then optionally (iii), wherein a mixing  time is allowed after each addition and said mixing time ranges from 0.01‐10 min, 0.1‐5  min, or 1‐2 min.

4. The method of any of the foregoing claims, wherein said one or more reactive cationic polymers  comprise:  (a) functional groups that are reactive to cellulosic or lignocellulosic fiber surfaces; and   (b) a cationic charge density ranging from below 5.0 mEq / g, 0.5‐5.0 mEq / g, 1.0‐4.0 mEq / g,  or 1.5‐2.5 mEq / g as dry solids at pH 7;   and further comprise one of the following;   (c) one or more cationic glyoxalated polyacrylamides (GPAMs);   (d) one or more cationic polyamidoamine‐epichlorohydrin (PAE) resins; or   (e) a combination of one or more cationic GPAMs and one or more cationic PAE resins  having a ratio of PAE to GPAM ranging from 1:99 to 99:1, 20:80 to 80:20, 40:60 to 60:40,  or 45:55, wherein said one or more cationic PAE resins and said one or more cationic  GPAMs are added sequentially in any order, simultaneously, or premixed prior to  addition to said aqueous suspension comprising cellulosic fibers.

5. The method of claim 4, wherein said one or more cationic GPAMs:  ATTY DOCKET NO.1149704.062013 CLIENT REF NO. US2324 (a) are suitable for use as a dry and / or wet strengthening agent;   (b) are synthesized by reacting glyoxal with a base polymer, wherein said base polymer  comprises a weight average molecular weight ranging from 5‐5000 kDa, 50‐2500 kDa,  80‐2000 kDa, or 100‐1000 kDa and comprises nonionic monomers, cationic monomers,  and optional anionic monomers, wherein  (i) said nonionic monomers are selected from the group of primary amide‐containing  monomers comprising acrylamide, methacrylamide, ethyl acrylamide, crotonamide,  N‐methyl acrylamide, N‐butyl acrylamide, N‐ethyl methacrylamide, and any  combination thereof;   (ii) said cationic monomers are selected from acryloyloxyethyltrimethyl ammonium  chloride (“AETAC”), methacryloyloxyethyltrimethylammonium chloride (“MAETAC”),  methacrylamidopropyltrimethylammonium chloride (“MAPTAC”),  acrylamidopropyltrimethylammonium chloride (“APTAC”),  methacryloyloxyethyldimethylammonium sulfate, diallyldimethylammonium  chloride (“DADMAC”); dialkylaminoalkyl acrylates and dialkylaminoalkyl  methacrylates and their quaternary or acid salts, including but not limited to,  dimethylaminoethyl acrylate (“DMAEA”), dimethylaminoethyl methacrylate  (“DMAEA”), dimethylaminoethyl acrylate methyl chloride quaternary salt,  dimethylaminoethyl acrylate methyl sulfate quaternary salt, dimethylaminoethyl  acrylate benzyl chloride quaternary salt, dimethylaminoethyl acrylate sulfuric acid  salt, dimethylaminoethyl acrylate hydrochloric acid salt, diethylaminoethyl acrylate  methyl chloride quaternary salt, dimethylaminoethyl methacrylate methyl chloride  quaternary salt, dimethylaminoethyl methacrylate methyl sulfate quaternary salt,  dimethylaminoethyl methacrylate benzyl chloride quaternary salt,  dimethylaminoethyl methacrylate sulfuric acid salt, dimethylaminoethyl  methacrylate hydrochloric acid salt, dimethylaminoethyl methacryloyl hydrochloric  acid salt; dialkylaminoalkylacrylamides and methacrylamides and their quaternary or  acid salts, including but not limited to, acryloylamidopropyltrimethylammonium  chloride, dimethylaminopropyl acrylamide, dimethylaminopropyl acrylamide methyl  sulfate quaternary salt, dimethylaminopropyl acrylamide sulfuric acid salt,  dimethylaminopropyl acrylamide hydrochloric acid salt,  methacrylamidopropyltrimethylammonium chloride, dimethylaminopropyl  methacrylamide, dimethylaminopropyl methacrylamide methyl sulfate quaternary  salt, dimethylaminopropyl methacrylamide sulfuric acid salt, dimethylaminopropyl  methacrylamide hydrochloric acid salt, diethylaminoethylacrylate,  diethylaminoethylmethacrylate; and diallyldialkylammonium halides, including but  not limited to, diallyldiethylammonium chloride and diallyldimethylammonium  chloride (“DADMAC”), and any combination thereof; and  (iii) said optional anionic monomers contain functional groups selected from carboxylic  acids, sulfonic acids, phosphonic acids, their corresponding water soluble salts, their  corresponding water dispersible salts, and any combination thereof, including but  not limited to, acrylic acid, methacrylic acid, maleic acid, itaconic acid, vinyl sulfonic  acid, 2‐acrylamido‐2‐methylpropane sulfonic acid (AMPS), acrylamido  methanesulfonic acid, acrylamido ethanesulfonic acid, 2‐hydroxy‐3‐acrylamide  propane sulfonic acid, styrene sulfonic acid, vinyl benzene sulfonic acid, and vinyl ATTY DOCKET NO.1149704.062013 CLIENT REF NO. US2324 phosphonic acid, their corresponding alkali metal, alkaline earth metal, and  ammonium salts, and any combination thereof;   (c) comprise a glyoxal:base polymer weight ratio ranging from 0.1:99.9 to 50:50, 5:95 to  20:80, or 5:95 to 10:90;   (d) comprise a cationic charge density ranging from below 5.0 mEq / g, 0.5‐5.0 mEq / g, 1.0‐4.0  mEq / g, or 1.5‐2.5 mEq / g as dry solids at pH 7;   (e) comprise a percent cationic monomer content ranging from 3‐60% by weight, a percent  anionic monomer content ranging from 0‐50% by weight, wherein the remainder of the  monomer content comprises nonionic monomers;   (f) are formulated optionally as a dry powder or as an aqueous composition comprising a  GPAM solids percentage ranging from about 0.5% to about 20%, optionally from greater  than about 2% to about 10%, further optionally from about greater than 4% to about  8%.

6. The method of claim 4, wherein said one or more cationic PAE resins:   (a) are suitable for use as a wet strengthening agent;   (b) are synthesized by reacting one or more polyamidoamine backbones with  epichlorohydrin, wherein said one or more polyamidoamine backbones are synthesized  by reacting a carboxylic acid and / or a carboxylic acid derivative with an amine, wherein  said one or more polyamidoamine backbones comprise a molar ratio of the amine to the  carboxylic acid and / or carboxylic acid derivative ranging from 1:1 to 2:1, 1.05:1 to 2:1, or  1.5:1 to 2:1;   (c) comprise a molar ratio of epichlorohydrin to secondary amine groups of the  polyamidoamine backbone ranging from about 0.15 to about 1.

7.

7. The method of any of the foregoing claims, wherein said one or more water‐soluble amphoteric  polymers:  (a) are comprised of acrylamide (AM) monomers, one or more anionic monomers, and one  or more cationic monomers, wherein,   (i) said one or more anionic monomers contain functional groups selected from the  group consisting of carboxylic acids, sulfonic acids, phosphonic acids, their  corresponding water soluble salts, their corresponding water dispersible salts, and  any combination thereof, including but not limited to, acrylic acid, methacrylic acid,  maleic acid, itaconic acid, vinyl sulfonic acid, 2‐acrylamido‐2‐methylpropane sulfonic  acid (AMPS), acrylamido methanesulfonic acid, acrylamido ethanesulfonic acid, 2‐ hydroxy‐3‐acrylamide propane sulfonic acid, styrene sulfonic acid, vinyl benzene  sulfonic acid, and vinyl phosphonic acid, their corresponding alkali metal, alkaline  earth metal, and ammonium salts, and any combination thereof; and   (ii) said one or more cationic monomers are selected from the group consisting of  acryloyloxyethyltrimethyl ammonium chloride (“AETAC”),  methacryloyloxyethyltrimethylammonium chloride (“MAETAC”),  methacrylamidopropyltrimethylammonium chloride (“MAPTAC”),  acrylamidopropyltrimethylammonium chloride (“APTAC”),  methacryloyloxyethyldimethylammonium sulfate, diallyldimethylammonium ATTY DOCKET NO.1149704.062013 CLIENT REF NO. US2324 chloride (“DADMAC”); dialkylaminoalkyl acrylates and dialkylaminoalkyl  methacrylates and their quaternary or acid salts, including but not limited to,  dimethylaminoethyl acrylate (“DMAEA”), dimethylaminoethyl methacrylate  (“DMAEA”), dimethylaminoethyl acrylate methyl chloride quaternary salt,  dimethylaminoethyl acrylate methyl sulfate quaternary salt, dimethylaminoethyl  acrylate benzyl chloride quaternary salt, dimethylaminoethyl acrylate sulfuric acid  salt, dimethylaminoethyl acrylate hydrochloric acid salt, diethylaminoethyl acrylate  methyl chloride quaternary salt, dimethylaminoethyl methacrylate methyl chloride  quaternary salt, dimethylaminoethyl methacrylate methyl sulfate quaternary salt,  dimethylaminoethyl methacrylate benzyl chloride quaternary salt,  dimethylaminoethyl methacrylate sulfuric acid salt, dimethylaminoethyl  methacrylate hydrochloric acid salt, dimethylaminoethyl methacryloyl hydrochloric  acid salt; dialkylaminoalkylacrylamides and methacrylamides and their quaternary or  acid salts, including but not limited to, acryloylamidopropyltrimethylammonium  chloride, dimethylaminopropyl acrylamide, dimethylaminopropyl acrylamide methyl  sulfate quaternary salt, dimethylaminopropyl acrylamide sulfuric acid salt,  dimethylaminopropyl acrylamide hydrochloric acid salt,  methacrylamidopropyltrimethylammonium chloride, dimethylaminopropyl  methacrylamide, dimethylaminopropyl methacrylamide methyl sulfate quaternary  salt, dimethylaminopropyl methacrylamide sulfuric acid salt, dimethylaminopropyl  methacrylamide hydrochloric acid salt, diethylaminoethylacrylate,  diethylaminoethylmethacrylate; and diallyldialkylammonium halides, including but  not limited to, diallyldiethylammonium chloride and diallyldimethylammonium  chloride (“DADMAC”), and any combination thereof;   (b) comprise an inverse phase emulsion, a dry polymer, or an aqueous polymer solution,  preferably an inverse phase emulsion;   (c) comprise a polymer standard viscosity (SV) ranging from <3.5 cPs, 1‐3.5 cPs, 2‐3.5 cPs, or  2.5‐3.5 cPs;   (d) comprise a molecular weight ranging from 1.5‐9 million Daltons, 1.5‐8 million Daltons, 2‐ 8 million Daltons, 4‐8 million Daltons, or preferably 2‐5 million Daltons;   (e) comprises an acrylamide (AM) monomer content ranging from 77‐100 wt%, 78‐100 wt%,  80‐100 wt%, 90‐100 wt%, or 95‐100 wt%;   (f) comprise an anionic monomer content ranging from ≤3 wt%, ≤2 wt%, 0.01‐3 wt%, 0.5‐2  wt%, 1‐2 wt%, 1.5‐2 wt%, or 1.8‐2 wt%;   (g) comprise a cationic monomer content ranging from ≤20 wt%, 1‐20 wt%, 2‐16 wt%, 4‐12  wt%, or 7‐9 wt%; or   (h) any combination of the foregoing.

8. The method of any of claims 2‐7, wherein said one or more anionic organic or inorganic  microparticles are selected from the group of microparticles and nanoparticles consisting of silica  microparticles; colloidal silica; aluminum phyllosilicate mineral particles, including but not limited  to bentonite, sodium bentonite, calcium bentonite, and montmorillonite; and anionic polymer  microparticles, including but not limited to highly structured anionic polyacrylamides.

9. The method of any of the foregoing claims, wherein  ATTY DOCKET NO.1149704.062013 CLIENT REF NO. US2324 (a) said one or more reactive cationic polymers comprises said one or more cationic GPAMs  and / or said one or more cationic PAE resins in aqueous form;   (b) said one or more cationic GPAMs comprise said base polymer comprising cationic  monomers selected from DADMAC, AETAC, and combinations thereof; nonionic  monomers selected from acrylamide, methacrylamide, and combinations thereof; and  optionally anionic monomers selected from acrylic acid and / or corresponding water  soluble salts, water dispersible alkali metal salts, alkaline earth metal salts, ammonium  salts, and combinations thereof, or said base polymer comprises (i) acrylamide and  DADMAC, (ii) acrylamide and AETAC, or (iii) acrylamide, DADMAC, and AETAC,   (c) said one or more water‐soluble amphoteric polymers  (i) comprises an inverse emulsion of acrylamide (AM), acrylic acid (AA), and [2‐ (acryloyloxy)ethyl] trimethylammonium chloride (Q9) monomers;   (ii) preferably comprises an acrylic acid (AA) monomer content of no more than 2 wt %;  and  (iii) preferably comprises a ratio of AM:AA:Q9 ranging from 89:2:9 to 91:2:7; and  (d) said one or more anionic organic or inorganic microparticles comprise colloidal silica.

10. The method of any of the foregoing claims, wherein when added to said aqueous suspension  comprising cellulosic fibers:  (a) said one or more reactive cationic polymers are added at a dosage ranging from 0.1‐15  g / kg, 0.5‐5 g / kg, or 0.5‐4 g / kg;   (b) said one or more water‐soluble amphoteric polymers are added at a dosage ranging  from 0.05‐5 g / kg, 0.1‐4 g / kg, or 0.3‐1 g / kg;   (c) said one or more anionic organic or inorganic microparticles are added at a dosage  ranging from 0.1‐1 g / kg, 0.2‐0.8 g / kg, or 0.4‐0.6 g / kg.

11. The method of any of the foregoing claims, wherein said aqueous suspension comprising  cellulosic fibers comprises a pH ranging from 4‐8, 4‐7.5, 4‐7, 4.5‐7, or 5‐7 and further comprises:  (a) cellulosic fibers optionally obtained from sources selected from softwood fiber,  hardwood fiber, recycled fiber, recycled old corrugated cardboard (OCC), recycled mixed  office waste (MOW), recycled mixed office paper, refined fiber, mill broke fibers, coated  broke, non‐wood fibers, including but not limited to straw and wheat pulp, and a mixture  of any of the foregoing;   (b) pulp selected from Kraft pulp, unbleached Kraft pulp, bleached pulp, unbleached pulp,  process water from pulp, paper, and / or board production, neutral sulfite semi chemical  (NSSC) pulp, mechanical pulp, non‐wood pulp, and a mixture of any of the foregoing; or   (c) a stock selected from a thick stock, a thick stock diluted with chemical water, synthetic  water, white water, and / or process water, and a thin stock, and a mixture of any of the  foregoing.

12. The method of any of the foregoing claims, wherein when used for manufacture of tissue, paper,  or board, the method results in:   (a) improved retention of said cellulosic fibers; a ATTY DOCKET NO.1149704.062013 CLIENT REF NO. US2324 (b) improved drainage of said flocculated fiber suspension;  (c) improved STFI and / or burst strength;  (d) a reduced hydrophobic particle and / or hydrophobic agglomerate count;   (e) an improved dry tensile, immediate wet tensile, and / or soaked wet tensile strength; or   (f) any combination of (a)‐(e)  compared to a tissue, paper, or board prepared by an identical method in the absence of (i)  addition of said one or more reactive cationic polymers or (ii) addition of said one or more  water‐soluble amphoteric polymers.

13. A method for manufacture of tissue, paper, or board, the method comprising:  (a) forming or providing an aqueous suspension comprising cellulosic fibers;  (b) optionally diluting the aqueous suspension;   (c) flocculating the aqueous suspension to form a flocculated fiber suspension;   (d) delivering the flocculated fiber suspension to a headbox and draining on a wire screen to  form a wet fibrous web; and   (e) pressing and drying the wet fibrous web to obtain a tissue, paper, or board;  wherein the method further comprises prior to step (c) treating the aqueous suspension  comprising cellulosic fibers with a retention and drainage aid comprising:  (i) one or more reactive cationic polymers comprising functional groups that are  reactive to cellulosic or lignocellulosic fiber surfaces and a cationic charge density  ranging from below 5.0 mEq / g, 0.5‐5.0 mEq / g, 1.0‐4.0 mEq / g, or 1.5‐2.5 mEq / g as  dry solids at pH 7, wherein said one or more reactive cationic polymers comprise one  or more cationic glyoxalated polyacrylamides (GPAMs); one or more cationic  polyamidoamine‐epichlorohydrin (PAE) resins; or a combination of one or more  cationic GPAMs and one or more cationic PAE resins having a ratio of PAE to GPAM  ranging from 1:99 to 99:1, 20:80 to 80:20, 40:60 to 60:40, or 45:55, wherein said one  or more cationic PAE resins and said one or more cationic GPAMs are added  sequentially in any order, simultaneously, or premixed prior to addition to said  aqueous suspension comprising cellulosic fibers;   (ii) one or more water‐soluble amphoteric polymers comprising an inverse emulsion of  acrylamide (AM), acrylic acid (AA), and [2‐(acryloyloxy)ethyl] trimethylammonium  chloride (Q9) monomers; preferably comprising an acrylic acid (AA) monomer  content of no more than 2 wt %; and preferably comprising a ratio of AM:AA:Q9  ranging from 89:2:9 to 91:2:7; and  (iii) optionally one or more anionic organic or inorganic microparticles comprising silica.

14. A fiber stock composition comprising:  (a) an aqueous suspension comprising cellulosic fibers; and  (b) a retention and drainage aid comprising   (i) one or more reactive cationic polymers;   (ii) one or more water‐soluble amphoteric polymers; and  ATTY DOCKET NO.1149704.062013 CLIENT REF NO. US2324 (iii) optionally one or more anionic organic or inorganic microparticles;  obtainable by a method according to any of the foregoing claims.

15. A composition for use as a retention and drainage aid in manufacture of tissue, paper, or board,  the composition comprising:   (a) one or more reactive cationic polymers comprising a cationic charge density ranging  from below 5.0 mEq / g, 0.5‐5.0 mEq / g, 1.0‐4.0 mEq / g, or 1.5‐2.5 mEq / g as dry solids at  pH 7, wherein said one or more reactive cationic polymers comprise   (i) one or more cationic glyoxalated polyacrylamides (GPAMs) synthesized by reacting  glyoxal with a base polymer, wherein said base polymer comprises a weight average  molecular weight ranging from 5‐5000 kDa, 50‐2500 kDa, 80‐2000 kDa, or 100‐1000  kDa; (i) acrylamide and DADMAC, (ii) acrylamide and AETAC, or (iii) acrylamide,  DADMAC, and AETAC and further wherein said one or more GPAMs comprises a  glyoxal:base polymer weight ratio ranging from 0.1:99.9 to 50:50, 5:95 to 20:80, or  5:95 to 10:90; and a cationic charge density ranging from below 5.0 mEq / g, 0.5‐5.0  mEq / g, 1.0‐4.0 mEq / g, or 1.5‐2.5 mEq / g as dry solids at pH 7;   (ii) one or more cationic polyamidoamine‐epichlorohydrin (PAE) resins; or   (iii) a combination of one or more cationic GPAMs and one or more cationic PAE resins  having a ratio of PAE to GPAM ranging from 1:99 to 99:1, 20:80 to 80:20, 40:60 to  60:40, or 45:55;   (b) one or more water‐soluble amphoteric polymers comprising acrylamide (AM), acrylic  acid (AA), and [2‐(acryloyloxy)ethyl] trimethylammonium chloride (Q9) monomers;  wherein said one or more water‐soluble amphoteric emulsion polymers preferably  comprise an acrylic acid (AA) monomer content of no more than 2 wt % and a ratio of  AM:AA:Q9 ranging from 89:2:9 to 91:2:7, wherein said one or more water‐soluble  amphoteric polymers is a an inverse emulsion, a dry polymer, an aqueous solution,  preferably an inverse phase emulsion; and  (c) optionally one or more anionic organic or inorganic microparticles selected from the  group of microparticles and nanoparticles consisting of silica microparticles; colloidal  silica; aluminum phyllosilicate mineral particles, including but not limited to bentonite,  sodium bentonite, calcium bentonite, and montmorillonite; and anionic polymer  microparticles, including but not limited to highly structured anionic polyacrylamides;  optionally obtainable by a method according to any of the foregoing claims.

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