CN103201426B - Improve the method for the behavior in service of wet web, purposes and the paper of solution - Google Patents

Improve the method for the behavior in service of wet web, purposes and the paper of solution Download PDF

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Publication number
CN103201426B
CN103201426B CN201180047192.6A CN201180047192A CN103201426B CN 103201426 B CN103201426 B CN 103201426B CN 201180047192 A CN201180047192 A CN 201180047192A CN 103201426 B CN103201426 B CN 103201426B
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paper
wet web
anionic
solution
polymer
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CN103201426A (en
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克里斯蒂安·萨尔米宁
埃利亚斯·雷图莱宁
扬内·卡塔亚-阿霍
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Camiro Head Office
Stora Enso Oyj
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Stora Enso Oyj
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    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
    • D21H17/24—Polysaccharides
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/41—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
    • D21H17/42—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups anionic
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/18—Reinforcing agents
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
    • D21H17/24—Polysaccharides
    • D21H17/25—Cellulose
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
    • D21H17/24—Polysaccharides
    • D21H17/31—Gums
    • D21H17/32—Guar or other polygalactomannan gum
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/41—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
    • D21H17/44—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups cationic
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H23/00—Processes or apparatus for adding material to the pulp or to the paper
    • D21H23/02—Processes or apparatus for adding material to the pulp or to the paper characterised by the manner in which substances are added
    • D21H23/22—Addition to the formed paper
    • D21H23/50—Spraying or projecting

Abstract

The present invention relates to the method for the behavior in service for improving wet web and analog. Described method comprises in fibre stuff adds cation type polymer, forms wet web, and anionic polymer solution is applied to described wet web by this fibre stuff. The invention still further relates to the paper by using the method to make, and relate to the purposes of the solution that comprises anionic polymer.

Description

Improve the method for the behavior in service of wet web, purposes and the paper of solution
According to the preamble of claims, the present invention relates to improve the behavior in service of wet webThe purposes of method, solution and paper.
Background of invention
Produce economically paper and need the behavior in service that paper machine is good. Paper machine behavior in service is passed through conventionallyWeb breaks number proportional to speed of production assessed. In order to obtain good behavior in service, paper mustMust in the each subprocess along whole paper machine line, move well with low web breaks number. ?In practice, commonly one of subprocess causes most web breaks, causes very poor gross efficiency.Have been noted that many runnability problems occur in when paper web is during still in wet condition, especiallyIn the process from press section to drying section. Thus, if obtain the Gao Sheng of whole paper production lineProduce efficiency, in the time that paper is still wet, the good operation performance of the beginning of paper machine is favourable.
Can improve by improving the intensity of wet web the behavior in service of l Water Paper. Known have many solutionsScheme is for improving the intensity of wet web, as the entirety in beating degree, the change process of raising paper pulp is joinedSlurry composition or web tension. But many these solutions cause the property of the paper finally making simultaneouslyShoddyization or significantly improve production cost. For example, improve beating degree can improve curling, and shadow adverselyRing the character of final paper.
Traditional wet strength additives (it is for improving the wet strength of dry final paper web) does not improveThe intensity of wet web, that is, and from the intensity of undried wet web. This is because wet strength additives existsThey conventionally require heating and solidify (curing) before showing improved strength.
Manufacturing the paper machine that its dry front intensity is the paper product kind (papergrades) of key factor hasHigh efficiency, but their average speed of production may be significantly lower than their normal speed. IfCan improve the intensity of wet web, can improve the speed of these paper machines.
Filler, as clay, calcium carbonate, calcium sulfate or talcum are used for papermaking to reduce the cost of paper and to changeThe optical property of kind paper. Filler is added in paper machine slurry (stock) before. For being coated withThe paper product kind of cloth, coating pigment (it comprises identical mineral) can enter paper by breaking portion,Paper-making process is got back in its recirculation. The content of filler and coating pigment is conventionally by burning at 525 DEG CSlurry or pattern product and the content of ashes measurement carried out record.
For uncoated cultural paper and for the body paper of the cultural paper that is coated with by cork and hardwoodMake, its content of ashes is generally 18-24%. Use for the uncoated culture based on 100% corkContent of ashes paper and conventionally there is 10-17% for the body paper of the cultural paper that is coated with. Prevent cultureThe important limiting factor that in paper using, filer content improves is wet web behavior in service.
One object of the present invention is to minimize or even eliminate the shortcoming existing in prior art.
One object of the present invention be to provide a kind of intensity of improving wet web and analog effectively andSimple method.
One object of the present invention is that the filer content that improves paper is to reduce papermaking cost.
Employing has the method for the feature proposing in the characteristic of independent claims below and establishesPut and realize these objects.
The typical method of the present invention that is used for the behavior in service of improving wet web and analog comprises:
-in fibre stuff, add cation type polymer,
-form wet web by this fibre stuff, and
-anionic polymer solution is applied to described wet web.
Typical paper of the present invention is that the method for the application of the invention makes.
The solution of the anionic polymer that conventionally, comprises dissolved form is by being applied to described solutionPaper web and for improving the behavior in service of wet web.
Find surprisingly now, when anionic polymer solution is by (preferably by spraying)While being applied to wet web (fiber that it comprises the surface charge with at least part of cationic), fibreInteraction between dimension and the intensity of wet web improve. Do not wish to be bound by theory, suppose and executeThe electron interaction that the anionic polymer adding is had on the fiber surface of cationic charge adsorbsOr adhere to. Can interact to affect wet web by the molecular level between chemicals and fiber strongThe raising of degree. This can promote the strong of the key that forms between the amount of fiber-fiber interaction and fiberDegree. Further infer, between the fiber of raising, molecular level interacts, be no matter electrostatic property orBe chemical property, explained that the intensity of wet web improves, instead of formed covalent bond. Thus willAnionic polymer solution is applied to wet web to improve fiber interaction and l Water Paper each otherThe tensile strength of width and/or residual tensions.
Also observe, anionic polymer solution is applied to the filler that wet web can improve paper and containsAmount. When adopting the present invention to improve paper web wet strength after strain or tension force, can useHigh filler content in body paper, for the uncoated cultural paper being made by cork and hardwood mixtureWith the cultural paper body paper of coating, corresponding to the content of ashes that for example exceedes 25%. Correspondingly, forUncoated cultural paper based on 100% cork and the cultural paper body paper of coating, can use formerHigh filler content in paper, this high filler content is corresponding to the content of ashes that exceedes 18%. In initial wetThe improvement of paper web intensity and dry strength aspect contains the ash content that also can improve other paper and cardboard kindAmount, for example, for newsprint kind, content of ashes is increased to 5-17%, or for SC and LWCBody paper, content of ashes is increased to 8-14%.
The improvement of initial wet web strength also can be used for changing into more cheap mixture of raw material for slurryMaterial. For example, less OCC (OCC) and the paper more collected from family for the manufacture ofBoxboard (testliner) or corrugated paper (flutingboard) kind. Reclaim based on fiber wattThe content of ashes of stupefied paper or boxboard can improve and exceedes 15%.
The another kind of mode of utilizing the initial wet web strength of improving is that the line that is reduced in squeezer place is bornLotus, this improves the dry strength of paper and reduces porosity. This can be of value to printability.
Anionic polymer solution can be applied to wet fiber web, and can be with any suitableMode apply described in carrying out, for example, by spraying or applying. Can also by use film transfer (asFilm transfer is to expelling belt), froth bed applies or molten from independent head box charging anionic polymerLiquid applies anionic polymer solution. Preferably apply anionic polymer solution by spraying.Have been found that and provide many surprising by anionic polymer solution spraying to fiber webAdvantage. The spraying of polymer solution does not affect the formation of paper web, does not have thus in final paper propertiesThe negative effect of noting. On the other hand, have been noted that anionic polymer solution is in webReservation be better than polymer solution added in slurry. This means the use of anionic polymerIt is lower that amount can keep, and can make the loss of chemicals minimize. Observe, when passing throughWhen anionic polymer solution is added in spraying, this polymer is uniformly distributed in whole web. At widthBetween the surface of material and core segment, do not observe the difference of amount of polymers.
Preferably, anionic polymer being applied to wet web does not produce the density of final dry paperImpact. This may show, applies anionic polymer and has improved the strong of fiber-fiber key in wet webSpend, still may not increase the number of these keys. Also surprisingly, spraying anionic polymerizationThing can improve the gas permeability of final dry paper, even on average improves 35%.
Anionic polymer solution is to comprise the anionic being dissolved in solvent (being generally water) to gatherThe solution of compound. The anionic that anionic polymer solution can comprise dissolving and discrete form gathersCompound, as long as the amount of the anionic polymer dissolving is enough to obtain required effect. According to thisA bright embodiment, can be containing discrete not gathering for anionic polymer solution of the present inventionCompound particle. Anionic polymer solution can comprise a kind of anionic polymer, or it canFor example, with the mixture of the anionic polymer that comprises different dissolvings, two or three anionicThe mixture of polymer. This embodiment means to wet web and applies anionic polymer solution,The mixture that this solution comprises different anionic polymers, for example two or three anionic is poly-The mixture of compound. The anionic that comprises multiple different dissolving at anionic polymer solution is poly-In the situation of compound, the anionic property of polymer (anionicity) can differ from one another. In other words,Solution can comprise two or more and have the anionic polymer of the dissolving of different anions.
According to an embodiment, two or more anionic polymer solution orders can be appliedOn wet web, preferably by spraying. This means the first anionic polymer solution is applied toWet web, subsequently by second and optional anionic polymer solution be thereafter applied to wet web.This applies preferably and is undertaken by spraying.
According to one embodiment of the invention, anionic polymer solution comprises synthetic anionicPolymer, as anion-polyacrylamide, or carboxymethyl cellulose (CMC) or other anionType heavy polymer, as anionic starch, anion guar gum or alginates. By this moon fromSubtype polymer solution is applied on wet web. Carboxymethyl cellulose is by carboxymethyl is introduced to fiberElement chain and the anionic polymer that makes, the substitution value of cellulosic backbone and chain length affect its character.In the time that substitution value exceedes 0.3, carboxymethyl cellulose becomes water miscible.
According to one embodiment of the invention, can also be by using amphiphilic polymers to obtain anionType polymer solution, as long as its net charge under the pH of paper-making process is negative.
Conventionally, the concentration of anionic polymer solution is < 1 % by weight, is more typically 0.05-1 weight%, then be more typically 0.2-0.6 % by weight.
According to one embodiment of the invention, using the solution of synthetic anionic polymer as the moon fromSubtype polymer solution is applied to wet web. Synthetic anionic polymer can for example be selected from completely orThe polyacrylamide of partial hydrolysis, or the homopolymers that comprises at least one anionic monomer or copolymer,Described anionic monomer for example (methyl) acrylic acid, maleic acid, crotonic acid, itaconic acid, vinyl sulfonic acid,2-acrylamide-2-methyl propane sulfonic, styrene sulfonic acid, vinyl phosphonate or Ethylene Glycol Methyl acrylic acidEster phosphate. Also can comprise uncharged monomer. Preferably propylene of synthetic anionic polymerThe copolymer of acid amides and one or more anionic copolymerization monomers. Glyoxalated anion acrylamide altogetherPolymers is also applicable to the present invention. Synthetic anionic polymer can be sour form or salt form, andIt can be straight chain, side chain or slightly crosslinked.
In this application, copolymer refers to such polymer, and it is by least two kinds of different monomersComposition. The number that forms the different monomers of copolymer can be greater than two kinds, for example three kinds or four kinds.
The weight average molecular weight (MW) of synthetic anionic polymer is generally > 100,000g/mol, moreBe generally 1,000,000g/mol.
According to one embodiment of the invention, anionic polymer solution applying on wet webThe synthetic anionic polymer solution that can be 0.3-0.5 % by weight by spraying concentration carries out. ExcellentSelection of land, by the solution spraying of synthetic anionic polymer to wet web. Be applicable to solution of the present inventionCan be for example by synthetic anionic polymer powder being dissolved in water to form 0.3-0.5%w/wSolution obtain. Can also obtain by the emulsion or the dispersion liquid that dissolve synthetic anionic polymerObtain solution.
Can be preferably by spraying by anionic polymer with≤2g/m2, common 0.05-1.5g/m2、More generally≤1g/m2, the most common 0.05-1g/m2, preferred 0.05-0.5g/m2, more preferably 0.05-0.3g/m2Amount be applied to wet web.
Be used for the table of natural unmodified fibers cellulose fiber, lignocellulose fiber or the wood fibre of papermakingNormally anionic of surface charge. According to one embodiment of the invention, the surface charge of fiberBe controlled as at least part of cationic, that is to say, fiber can have band cationic electric chargeSurf zone, even if they can have other surf zone with anionic property electric charge. This canBy at least a portion modification of fiber is obtained to change at least in part their surface charge. For example, can be by add cation in slurry for the manufacture of the surface charge of the fiber of paper webType polymer and modification partially or completely.
The cation type polymer adding in slurry can be any cation that is suitable for being used in slurryType polymer. The cation type polymer adding in fibre stuff can be selected from shitosan, cationThe polysaccharide of changing, as cationic starch or cation guar gum, or cation synthesising copolymer, as sun fromSub-acrylamide copolymer, vinyl amine copolymer or polyamidoamines amine. Glyoxalated cationic polyAcrylamide also can be as the cation type polymer in the present invention. Cation type polymer is all rightTo be described in for example US7, the cationic starch graft copolymer in 786,238B2. Add in slurryPreferably cationic starch of cation type polymer.
When the cation type polymer adding in fibre stuff is cationic acrylamide polymerTime, it can be by water-soluble ethylenically unsaturated monomers or by the grams of monomer blend that comprises cationic monomerForm. Cationic acrylamide polymer preferably has at least 1.0dl/g, more preferably 1.5dl/g at leastApparent characteristic viscosity.
According to one embodiment of the invention, cation type polymer can be amphiphilic polymers, onlyTo under the pH of paper-making process, its net charge be cationic.
Therein synthesizing cationic type polymer is added in the embodiment of the present invention in slurry,Preferably add to and have > 2%, preferably in the thick slurry of the denseness of 3-5%. Synthesizing cationic type polymerConventionally and preferably add in thick slurry with the amount of 0.5-5kg/t. Add the synthesizing cationic in slurry toType copolymer preferably has low charge density, and for example Cationic Acrylamide Copolymers is normally at pHThe cationic acrylamide of low electric charge of the electric charge of 4 times have < 1.7meq/g, preferably < 1.2meq/g altogetherPolymers.
According to one embodiment of the invention, by by the polysaccharide of cationization (as cationic starchOr cation guar gum) add in fibre stuff and make the surface charge modification of fiber. CationizationPolysaccharide (as cationic starch or cation guar gum) preferably in paper pulp storage column and the short circulatory systemBetween add in the thick slurry of the denseness with for example 2-5%. Cationic starch can be any being suitable forIn the cationic starch of papermaking, as potato, rice, corn, waxy corn, wheat, barleyOr tapioca. Amylopectin content > 75% starch is favourable. Conventionally, cationic starch comprisesCation group, as quaternary ammonium group, its substitution value (DS)---be illustrated in average every grape in starchThe number of the cation group on sugar unit---be generally 0.01-0.20, preferably 0.01-0.06. Sun fromSub-starch has the electric charge of 0.06-1.04meq/g, preferred 0.06-0.35meq/g conventionally. Starch canWith 2-20kg/ ton paper pulp, the amount use of 7-12kg/ ton paper pulp conventionally.
When the aridity of paper web is < 50%, conventionally < 40%, more generally < 30%, the most common 8-15%Time anionic polymer solution can be applied to wet web. When pulp suspension enters head box alsoWhile entering paper machine thus, its dryness level is more than or equal to 0.3% and be less than 2% conventionally. Work as widthMaterial removes and anhydrates first in the time that head box enters wet end (wiresection) under weight-driven from web.While further advancing in wet end along with paper, dewater by different vacuum units is auxiliary. Wet end itAfter, the aridity of paper is generally 20%. In wet pressing process, the aridity of paper is increased to 40-50%.Preferably before the last region of no pressure of wet end, preferably carry out executing of anionic polymer solution by sprayingAdd.
According to one embodiment of the invention, before the press section of paper machine by anionic polymerizationThing solution is applied to wet web.
When manufacture containing the uncoated of wood pulp and coating paper product kind time, the present invention is for improving l Water PaperThe intensity of width is favourable. The present invention be also suitable for when manufacture include but not limited to super calendering (SC) paper,When ultra-light-weight coating (ULWC) paper, light weight are coated with the paper product kind of (LWC) paper and newsprintImprove the intensity of wet web. The magazine paper of typical coating, as LWC, comprises about 40-60 % by weightThe bleached softwood slurry of mechanical pulp, about 25-40 % by weight and filler and/or the painting of about 20-35 % by weightCloth agent. SC paper bag is containing the mechanical pulp of about 70-90 % by weight and the long fibre cellulose paper of about 10-30%Slurry. Be particularly suited for according to method processing of the present invention with the paper web that records substrate for the manufacture of inkjet printing.Paper web can comprise the combination from the fiber of palohierror or softwood trees or two kinds of fibers. Fiber can lead toCross and be generally used for any suitable slurrying of papermaking or purification techniques obtains, as thermomechanical slurrying (TMP),Chemical-mechanical pulping (CMP), chemi thermo mechanical slurrying (CTMP), defibrillation, alkaline sulfuric acidSalt method (kraft) slurrying, acid sulfite process and half chemical pulping. Paper web can only wrapContaining pristine fibre or recycled fiber or the combination of the two. The weight of final paper web is 30-800g/m2, logicalNormal is 30-600g/m2, be more typically 50-500g/m2, preferably 60-300g/m2, more preferably 60-120g/m2, more more preferably 70-100g/m2。
In some embodiments, paper web can comprise and is derived from non-wooden material, as bamboo, bagasse,The fiber of hemp, wheat straw or rice straw.
According to another embodiment, before or after applying cationic or amphiphilic polymers solutionCarry out anionic polymer solution applying to wet web. Such polymer order is applied toThe remarkable improvement that wet web (preferably by spraying) can produce dry and wet web strength. AnionicAlso can before being preferably applied to wet web by spraying, it mix in advance with cation type polymer solutionBe combined. In this embodiment, cation type polymer is added in fibre stuff notBe necessary, but can implement.
For example,, before or after anionic polymer solution is applied to wet web, at press sectionOn wet web, apply carboxymethyl cellulose (CMC), polyvinyl alcohol (PVA), the poly-second of modification beforeThe polymer solution of enol, guar gum and/or shitosan. Carboxymethyl cellulose, polyvinyl alcohol, modificationPolyvinyl alcohol, guar gum or shitosan can once apply one, or they two or three canOrder applies. In the time that web has higher than about 55% aridity, CMC and shitosan improve wet widthMaterial intensity, and PVA also improves wet web strength under lower web dryness level. AnionicThe molecular contact that improves fiber-fiber joint with the polyelectrolyte multilayer of cation type polymer is long-pending,And improve thus the intensity of dry paper. Have been noted that now the layering of polymer, for example two-layer,Also can significantly improve the intensity of wet web. This shows, the layering of polymer can improve under wet conditionInteraction between fiber. By anionic polymer spray to outermost layer can reduce wet web withAdhesion on paper machine between anion central roll, this seems is also rational. By being sprayed on papermakingOn machine, generate in the process of polymer bilayer or multilayer, advantageously make the amount of the polymer of spraying minimize.
According to another embodiment, before press section or drying section by molten one or more layers chemicalsLiquid is applied to wet web. In fibre stuff, add cation type polymer nonessential, but canImplement. Cation type polymer as hereinbefore defined. As described in the present application, chemical solutions is preferably logicalCross spraying and be applied to wet web, but they can apply by coating, film transfer, froth bed orApply from independent head box charging. For example be applied to the chemical solutions of paper web by spraying passableThe solution of carboxymethyl cellulose (CMC), polyvinyl alcohol (PVA), shitosan or guar gum. MelonYou are interpreted as galactomannans here by glue. It is a kind of polysaccharide that comprises galactolipin and mannose.The skeleton of guar gum is the straight chain of β Isosorbide-5-Nitrae-connection mannose residue, every second mannose place 1 on it, 6-Be connected with galactose residue and form short side chain. Guar gum can be with natural guars, anion melon thatThe form of glue or cation guar gum is applied to web. For example, natural guars, cation guar gumOr anion guar gum can be applied to wet web, described wet web not to add in slurry sun fromIn the situation of subtype polymer, form. In another example, natural guars or anion guar gum canTo be applied to wet web, described wet web is by being added with wherein cation type polymer (as cationGuar gum) slurry form.
Test
Embodiment 1
Commercially available starching and being used as raw material from undried bleached softwood kraft from Finland paper mill.Canadian Standard Freeness (CSF) value that records paper pulp according to standard SCAN-C21:65 is 500ml.
Use the standard SCAN-CM64:00 formation gram of recirculation plain boiled water preparation experiment chamber page by employingBe heavily 60g/m2Wet handmade paper (handsheet). For every page of paper, will boiling at T=97 DEG CThe cationic starch of 30 minutes adds to separately in the batching in sheet former. The cation adding forms sedimentThe amount of powder is 10kg/t(Raisamyl135 starch DS0.035, BASF). In contrast, do not makeUse cationic starch.
By anionic polymer solution spraying, to the handmade paper of moulding, described handmade paper sticks to netUpper, below applies vacuum. In vacuum enhancing spraying process, anionic polymer solution is in l Water Paper pageInfiltration. The PAMA (from the FennopolA8500R of KemiraOyj) of sprayingConcentration be 0.3%w/w denseness, and before spraying at room temperature mix whole night. Water spraying contrastPage.
After spraying, by handmade paper wet pressing. At two kinds of different stress levels (50kPa and 350kPa)Under carry out wet pressing, to reach two kinds of different aridity of wet handmade paper. The sample that will wet cuts into width20mm, sample length 100mm. Wet sample is stored in and moulds under air tight condition at the temperature of 7 DEG CIn pocket with degree of keeping dry level.
Percussion mechanism (the VTT that uses 1.0m/s speed for the engineering properties of dry pattern product and l Water Paper sampleFinland, FASTTENSILETESTRIGIMPACT) measure. Percussion mechanism and method of testingBe described in following document: Kurki, M., Kouko, J., Kekko, P., Saari, T., Laboratoryscalemeasurementprocedureofpapermachinewetwebrunnability:Part1,PaperijaPuu, 86 (2004) 4; And Kouko, J., Salminen, K., Kurki, M., Laboratoryscalemeasurementprocedureofpapermachinewetwebrunnability:Part2,PaperijaPuu,89(2007)7-8。
Result is presented in Fig. 1, shows the impact of the initial wet intensity of studied applying method on paper.In Fig. 1, use following abbreviation:
CS=cationic starch
A-PAM=PAMA
Even invention has been described with reference to it seems at present the most practical and preferred embodiment,But it being understood that and the invention is not restricted to above-mentioned embodiment, the present invention is also intended to cover appended rightDifference amendment and equivalent technical solutions in claimed range.

Claims (21)

1. for improving the method for behavior in service of wet web, comprising:
-in fibre stuff, add cation type polymer,
-form wet web by described fibre stuff,
It is characterized in that,
In the time that the aridity of described paper web is < 50%, before the press section of paper machine, anionic is poly-Compound solution is applied to described wet web, and described anionic polymer solution comprises:
-carboxymethyl cellulose (CMC),
-anionic starch,
-anion guar gum,
-alginates, or
-synthetic anionic polymer, it is selected from the polyacrylamide of hydrolysis wholly or in part; Or
The homopolymers that comprises at least one anionic monomer or copolymer.
2. method according to claim 1, is characterized in that, described anionic monomer is selected from (firstBase) acrylic acid, maleic acid, crotonic acid, itaconic acid, vinyl sulfonic acid, 2-acrylamide-2-methyl-propSulfonic acid, styrene sulfonic acid, vinyl phosphonate and glycolmethacrylate phosphate.
3. method according to claim 1, is characterized in that, described synthetic anionic polymerizationThing is the copolymer of acrylamide and one or more anionic copolymerization monomers.
4. method according to claim 1, is characterized in that, described synthetic anionic polymerizationThe weight average molecular weight (MW) of thing is > 100,000g/mol.
5. according to the method described in any one in aforementioned claim 1 to 4, it is characterized in that, with≤2g/m2Amount described anionic polymer is applied to described wet web.
6. method according to claim 1, is characterized in that, described anionic polymer is moltenApplying by spraying, by coating, by using film transfer, applying or lead to by froth bed of liquidCross from anionic polymer solution described in independent headbox charging and carry out.
7. method according to claim 6, is characterized in that, described anionic polymer is moltenLiquid applying on described wet web is that the synthetic anionic of 0.3-0.5 % by weight is poly-by spraying concentrationCompound solution carries out.
8. method according to claim 1, is characterized in that, by anionic polymer solutionBe applied to described wet web, described anionic polymer solution comprises different anions type polymerMixture.
9. method according to claim 1, is characterized in that, by spraying two or moreAnionic polymer solution order is applied on described wet web.
10. method according to claim 1, is characterized in that, when the aridity of described paper webDuring for 8-15%, described anionic polymer solution is applied to described wet web.
11. methods according to claim 1, is characterized in that, in the last region of no pressure of wet endDescribed anionic polymer solution is applied to described wet web before.
12. methods according to claim 1, is characterized in that, add described fibre stuff toIn described cation type polymer be selected from shitosan; The polysaccharide of cationization, as cationic starch orCation guar gum; Or cation synthesising copolymer, as cation acrylamide copolymer, vinylAmine copolymer thing or polyamidoamines amine.
13. methods according to claim 12, is characterized in that, by the polymerization of synthesizing cationic typeThing adds to and has with the amount of 0.5-5kg/t > in the thick slurry of 2% denseness.
14. according to the method described in claim 12 or 13, it is characterized in that, by cationic thirdAlkene amide polymer adds in fibre stuff, and described cationic acrylamide polymer is by water-solubleEthylenically unsaturated monomers or formed by the grams of monomer blend that comprises cationic monomer, described cationicAcrylamide polymer has at least apparent characteristic viscosity of 1.0dl/g.
15. methods according to claim 12, is characterized in that, by the polysaccharide of cationization,As cationic starch or cation guar gum add in fibre stuff.
16. methods according to claim 15, is characterized in that, paper pulp storage column and short followingBetween loop systems, taking the amount of 7-12kg/ ton paper pulp, substitution value (DS) is formed sediment as the cation of 0.01-0.06Powder adds in the thick slurry that denseness is 2-5%.
17. methods according to claim 1, is characterized in that, by cationic or both sexesPolymer solution carries out described anionic polymerization by spraying before or after being applied to described wet webThing solution applies to described wet web.
18. methods according to claim 15, is characterized in that, described anionic is poly-Before or after compound solution is applied to described wet web, before press section, on described wet web, executeAdd the polymer solution of polyvinyl alcohol (PVA), modified polyvinylalcohol, guar gum and/or shitosan.
19. require by right to use the paper that in 1 to 18, the method described in any one makes.
20. solution that comprise anionic polymer are for by being applied to wet web by described solutionImprove the purposes of the behavior in service of described wet web.
21. purposes according to claim 20, is characterized in that, when manufacturing not containing wood pulp notCoated paper, the coated paper that does not contain wood pulp, super calendering (SC) paper, ultra-light-weight coating (ULWC)When being coated with (LWC) paper or newsprint, paper, light weight improve the intensity of described wet web.
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